JP2019163449A - Resin modifier - Google Patents

Abstract

To provide a resin modifier that imparts excellent scratch resistance and the long-lasting effect to a thermoplastic resin without impairing mechanical strength.SOLUTION: A resin modifier (Y) contains (X) a block polymer having as constitutional units a block of (a) polyolefin having 30 mol% or more of a constitutional unit derived from propylene and a block of (b) polysiloxane and having a molecular structure being any of structures (1) to (3) as given below: (1) a linear (a)-(b) diblock type structure; (2) a linear (b)-(a)-(b) triblock type structure; and (3) a branched type structure having two to three blocks of polysiloxane (b) bonded to one terminal of the block of polyolefin (a).SELECTED DRAWING: None

Description

  The present invention relates to a resin modifier. In detail, it is related with the resin modifier which provides abrasion resistance, without impairing the mechanical physical property of a thermoplastic resin composition.

Thermoplastic resins, such as polyolefin resins, are excellent in moldability, rigidity, heat resistance, chemical resistance, light weight and electrical insulation, and are widely used as molded products in films, fibers, hollow fiber membranes, and other various shapes. Has been.
On the other hand, polyolefin resins have problems in scratch resistance, wear resistance, and the like. For example, when used for automobile interior parts, there is a problem that the appearance is easily damaged due to scratches.
Conventionally, as a method for improving scratch resistance, there is a method of adding a lubricant such as silicone oil (for example, see Patent Document 1) or a surfactant (for example, see Patent Document 2) to a thermoplastic resin, for example, a polyolefin resin. Are known.

Japanese Patent Application Laid-Open No. 09-043408 JP-A-10-237235

However, in the method of adding silicone oil or a surfactant to the polyolefin resin composition, the mechanical strength (tensile modulus and resistance) inherent to the original molded polyolefin resin product can be obtained by adding an amount sufficient to exert the modification effect. Impact properties, etc., the same applies hereinafter) are impaired or bleed out from the molded product, and there is a problem in sustainability, and it has been desired to solve it.
An object of the present invention is to provide a resin modifier that imparts excellent scratch resistance to a thermoplastic resin and durability of its effect without impairing mechanical strength.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have reached the present invention. That is, the present invention has, as constitutional units, a block of polyolefin (a) having a constitutional unit derived from propylene of 30 mol% or more and a block of polysiloxane (b), and has a molecular structure of the following (1) to (3 ) A resin modifier (Y) containing a block polymer (X) having a structure of any of the above; a resin composition (Z) containing the resin modifier (Y) and a thermoplastic resin (C) ); A molded article formed by molding the resin composition (Z).
(1) a linear (a)-(b) diblock structure;
(2) linear (b)-(a)-(b) triblock structure;
(3) A branched structure in which 2 to 3 blocks of polysiloxane (b) are bonded to one end of a block of polyolefin (a).

The molded article of the thermoplastic resin composition containing the resin modifier of the present invention and the resin modifier of the present invention has the following effects.
(1) The resin modifier of the present invention can impart scratch resistance to a thermoplastic resin without impairing the original mechanical strength (mechanical properties), and is excellent in sustainability of the effect.
(2) The molded article of the thermoplastic resin composition of the present invention is excellent in scratch resistance and excellent in sustainability of the effect.

The resin modifier (Y) of the present invention has a block of polyolefin (a) having a structural unit derived from propylene of 30 mol% or more and a block of polysiloxane (b) as structural units, and has a molecular structure. The block polymer (X) which is the structure in any one of following (1)-(3) is contained.
(1) a linear (a)-(b) diblock structure;
(2) linear (b)-(a)-(b) triblock structure;
(3) A branched structure in which 2 to 3 blocks of polysiloxane (b) are bonded to one end of a block of polyolefin (a).

<Polyolefin (a)>
The polyolefin (a) includes a polyolefin (a1-1) having a carboxyl group or a carboxylic anhydride group at both ends of the polymer, a polyolefin (a1-2) having a hydroxyl group at both ends of the polymer, and an amino group at both ends of the polymer. Polyolefin (a1-3) having an end group and polyolefin (a1-4) having an isocyanate group at both ends of the polymer, Polyolefin (a1-5) having both a carboxyl group and a hydroxyl group at both ends of the polymer, a carboxyl group or a carboxyl group Polyolefin (a2-1) having an acid anhydride group at one end of the polymer, polyolefin (a2-2) having a hydroxyl group at one end of the polymer, polyolefin (a2-3) having an amino group at one end of the polymer, and isocyanate Having a group at one end of the polymer (A2-4), and polyolefin (a2-5), and the like having both carboxyl group and a hydroxyl group at one terminal of the polymer. Among these, (a1-1) and (a2-1) having a carboxyl group or a carboxylic acid anhydride group at the terminal are preferable from the viewpoint of ease of modification and heat resistance during molding.
In addition, the terminal in this invention means the terminal part which the repeating structure of the monomer unit which comprises a polymer interrupts. Moreover, both ends mean both ends in the main chain of the polymer, and one end means any one end in the main chain of the polymer.

  The polyolefin (a1-0) whose main component is a polyolefin that can be modified at both ends is one or more of olefins having 2 to 30 carbon atoms (preferably 2 to 12, more preferably 2 to 10 carbon atoms). (Co) polymerization of the mixture [(co) polymerization means polymerization or copolymerization. The same applies below. And a polyolefin containing 30 mol% or more of a structural unit derived from propylene in a polyolefin (polymerization method) and degraded polyolefin {high molecular weight [preferably number average molecular weight (hereinafter abbreviated as Mn) 10,000 To 150,000] a product obtained by mechanically, thermally or chemically degrading polyolefin (degradation method)}.

  Among these, a degraded polyolefin is preferable from the viewpoint of ease of modification and availability when introducing a carboxyl group, a carboxylic anhydride group, a hydroxyl group, an amino group, or an isocyanate group. Further preferred is a thermally degraded polyolefin. According to thermal degradation, a low molecular weight polyolefin having 1 to 2 terminal double bonds per molecule can be easily obtained as described later, and the low molecular weight polyolefin has a carboxyl group, a carboxylic acid anhydride group, a hydroxyl group, It is easy to modify by introducing an amino group or an isocyanate group.

Mn of the polymer in the present invention can be measured under the following conditions using gel permeation chromatography (GPC).
Apparatus (example): “HLC-8120” [manufactured by Tosoh Corporation]
Column (example): “TSKgelGMHXL” [manufactured by Tosoh Corporation] (two)
“TSKgelMultiporeHXL-M” [manufactured by Tosoh Corporation] (1 pc.)
Sample solution: 0.3 wt% orthodichlorobenzene solution Solution injection amount: 100 μl
Flow rate: 1 ml / min Measurement temperature: 135 ° C
Detection device: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE)
12 points (molecular weight: 500, 1,050, 2,800, 5,970,
9, 100, 18, 100, 37, 900, 96, 400,
190,000, 355,000, 1,090,000,
2,890,000) [manufactured by Tosoh Corporation]

  The heat-degraded polyolefin is not particularly limited, and is obtained by heating a high molecular weight polyolefin in an inert gas (at 300 to 450 ° C. for 0.5 to 10 hours, for example, JP-A-3-62804). Obtained by the method described in the gazette), and heat-degraded by heating in air.

The high molecular weight polyolefin used in the thermal degradation method is a (co) polymer of one or a mixture of two or more olefins having 2 to 30 carbon atoms (preferably 2 to 12, more preferably 2 to 10 carbon atoms). Mn is preferably 10,000 to 150,000, more preferably 15,000 to 70,000: Melt flow rate (hereinafter abbreviated as MFR: unit is g / 10 min), preferably 0.5 to 150, more preferably 1 to 100] having 30 mol% or more of a structural unit derived from propylene in the polyolefin. Here, MFR is a numerical value representing the melt viscosity of the resin, and the larger the numerical value, the lower the melt viscosity. The measurement of MFR conforms to the method defined in JIS K7210-1 (2014). For example, in the case of polypropylene, it is measured under conditions of 230 ° C. and a load of 2.16 kgf.
Examples of the olefin having 2 to 30 carbon atoms include α-olefins having 2 to 30 carbon atoms and dienes having 4 to 30 carbon atoms.

Examples of the α-olefin having 2 to 30 carbon atoms include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-icocene and 1-icosene. Tetracocene etc. are mentioned.
Examples of the diene having 4 to 30 carbon atoms include butadiene, isoprene, cyclopentadiene and 1,11-dodecadiene.
Of the olefins having 2 to 30 carbon atoms, ethylene, propylene, α-olefins having 4 to 12 carbon atoms, butadiene, isoprene and a mixture thereof are preferable from the viewpoint of controlling the molecular weight, and ethylene, Propylene, α-olefins having 4 to 10 carbon atoms, butadiene and mixtures thereof, particularly preferred are ethylene, propylene and mixtures thereof.

  Mn of the polyolefin (a1-0) is preferably from 800 to 20,000, more preferably from 1,000 to 10,000, particularly from the viewpoint of scratch resistance of the molded product described later and the sustainability of the effect. Preferably, it is 1,200 to 6,000.

  The average number of terminal double bonds per molecule of (a1-0) is the viewpoint of the scratch resistance of the molded product and the durability of its effect, the ease of structure control of the block polymer (X) described later, and the thermoplasticity. From this viewpoint, the number is preferably 1.1 to 2.5, more preferably 1.3 to 2.2, and particularly preferably 1.5 to 2.0.

  When a method of obtaining a low molecular weight polyolefin by a thermal degradation method is used, the average number of terminal double bonds per molecule is 1.1 to 2.5 (a1-0) in the range of Mn 800 to 20,000. Is easily obtained.

  Polyolefin (a2-0) whose main component is a polyolefin whose one end can be modified can be obtained in the same manner as (a1-0), and Mn in (a2-0) is the scratch resistance of the molded product described later. From the viewpoint of the property and sustainability of the effect, it is preferably 800 to 20,000, more preferably 1,000 to 10,000, and particularly preferably 1,200 to 6,000.

  The average number of double bonds per molecule of (a2-0) is determined in terms of the scratch resistance of the molded product and the sustainability of its effect, the ease of structural control of the block polymer (X) described later, and the thermoplasticity. From the viewpoint, it is preferably 0.5 to 1.4, more preferably 0.6 to 1.3, particularly preferably 0.7 to 1.2, and most preferably 0.8 to 1.1. It is a piece.

  When a method for obtaining a low-molecular-weight polyolefin by a thermal degradation method is used, the average number of terminal double bonds per molecule is 0.5 to 1.4 (M2) in the range of Mn from 800 to 20,000. 0) is easily obtained.

  Since the low molecular weight polyolefin obtained by the thermal degradation method has the average number of the terminal double bonds, it may be modified by introducing a carboxyl group, a carboxylic anhydride group, a hydroxyl group, an amino group or an isocyanate group. Is easy.

  (A1-0) and (a2-0) are generally obtained as a mixture of these, but the mixture may be used as it is or after purification and separation. Among these, a mixture is preferable from the viewpoint of production cost and the like.

  Hereinafter, (a1-1) to (a1-5) having a carboxyl group, a carboxylic anhydride group, a hydroxyl group, an amino group, or an isocyanate group at both ends of the polyolefin (a1-0) will be described. (A2-1) to (a2-5) having these groups at one end of (0), (a1-1) to (a1) in which (a1-0) is replaced with (a2-0) It can be obtained in the same manner as in -5).

As the polyolefin (a1-1) having a carboxyl group or a carboxylic anhydride group at both ends of the polymer, the end of (a1-0) is α, β-unsaturated carboxylic acid (anhydride) (α, β-unsaturated). A structure obtained by secondary modification of a polyolefin (a1-1-1) or (a1-1-1) having a structure modified with a saturated carboxylic acid or an anhydride thereof (the same shall apply hereinafter) with a lactam or an aminocarboxylic acid. Polyolefin (a1-1-2) having a structure in which (a1-0) is modified by oxidation or hydroformylation (a1-1-3), (a1-1-3) is a lactam or aminocarboxylic acid. Polyolefin (a1-1-4) having a second modified structure and a mixture of two or more of these can be used.
In addition, α, β-unsaturated carboxylic acid (anhydride) means α, β-unsaturated carboxylic acid or its anhydride.

(A1-1-1) can be obtained by modifying (a1-0) with an α, β-unsaturated carboxylic acid (anhydride).
Examples of the α, β-unsaturated carboxylic acid (anhydride) used for modification include monocarboxylic acid, dicarboxylic acid, and mono- or dicarboxylic acid anhydride. Specifically, (meth) acrylic acid [(meth) Acrylic acid means acrylic acid or methacrylic acid. The same applies below. ], Maleic acid (anhydride), fumaric acid, itaconic acid (anhydride), citraconic acid (anhydride), and the like.
Of these, dicarboxylic acid and mono- or dicarboxylic acid anhydride are preferable from the viewpoint of ease of modification, maleic acid (anhydride) and fumaric acid are more preferable, and maleic acid (maleic acid is particularly preferable). Anhydride).

The amount of α, β-unsaturated carboxylic acid (anhydride) used for modification is based on the weight of the polyolefin (a1-0), and the scratch resistance of the molded product, the ease of structure control of the block polymer (X), and From the viewpoint of dispersibility of the block polymer (X) in the resin composition (Z) described later, it is preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight, particularly preferably 2 to 10% by weight. %.
The modification with α, β-unsaturated carboxylic acid (anhydride) is performed by, for example, converting the α, β-unsaturated carboxylic acid to the terminal double bond of (a1-0) by either a solution method or a melting method. The reaction can be carried out by subjecting (anhydride) to an addition reaction (ene reaction), and the reaction temperature is preferably 170 to 230 ° C.

(A1-1-2) can be obtained by secondary modification of (a1-1-1) with a lactam or an aminocarboxylic acid.
Examples of the lactam used for the secondary modification include lactams having 6 to 12 carbon atoms (preferably 6 to 8, more preferably 6), and specifically include caprolactam, enantolactam, laurolactam, undecanolactam, and the like. Is mentioned.
Examples of the aminocarboxylic acid include aminocarboxylic acids having 2 to 12 carbon atoms (preferably 4 to 12 and more preferably 6 to 12), and specifically include amino acids (glycine, alanine, valine, leucine, isoleucine). And phenylalanine), ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.
Among the lactams and aminocarboxylic acids, caprolactam, laurolactam, glycine, leucine, ω-aminocaprylic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid are preferred, and caprolactam, laurolactam, Omega-aminocaprylic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, particularly preferred are caprolactam and 12-aminododecanoic acid.

  The amount of lactam or aminocarboxylic acid used for the secondary modification is based on the weight of the object to be modified (a1-1-1), and the scratch resistance of the molded product, the ease of structure control of the block polymer (X), and From the viewpoint of dispersibility of the block polymer (X) in the resin composition (Z) described later, it is preferably 0.5 to 100% by weight, more preferably 1 to 50% by weight, particularly preferably 2 to 25% by weight. %.

(A1-1-3) can be obtained by introducing a carboxyl group by a method of oxidizing (a1-0) with oxygen and / or ozone (oxidation method) or hydroformylation by an oxo method.
The introduction of the carboxyl group by the oxidation method can be performed by a known method, for example, the method described in US Pat. No. 3,692,877. Introduction of the carbonyl group by hydroformylation can be carried out by various methods including known methods, for example, Macromolecules, VOL. 31, 5943 page.
(A1-1-4) can be obtained by secondary modification of (a1-1-3) with a lactam or an aminocarboxylic acid.
Examples of the lactam and aminocarboxylic acid include those exemplified as the lactam and aminocarboxylic acid used for the secondary modification of the above (a1-1-1), and preferred ranges and use amounts thereof are also the same. .

The acid value of (a1-1) is preferably 4 to 100 mgKOH / g, more preferably 4 from the viewpoints of reactivity with (b), ease of structure control of the block polymer (X) and thermoplasticity. -50 mgKOH / g, particularly preferably 5-30 mgKOH / g.
The acid value in the present invention is measured by titration using a KOH / methanol solution containing phenolphthalein as an indicator. When the acid group is a carboxylic acid anhydride group, the half ester after being half esterified with methanol Measured as acid value.

The polyolefin (a1-2) having a hydroxyl group at both ends of the polymer is a hydroxyl group obtained by modifying a polyolefin (a1-1) having a carboxyl group or a carboxylic acid anhydride group at both ends of the polymer with an amine having a hydroxyl group. The polyolefin which has and the mixture of these 2 or more types can be used.
Examples of the amine having a hydroxyl group that can be used for modification include amines having a hydroxyl group having 2 to 10 carbon atoms, and specifically include 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, 4-amino. Examples include butanol, 5-aminopentanol, 6-aminohexanol, and 3-aminomethyl-3,5,5-trimethylcyclohexanol.
Of these, amines having a hydroxyl group having 2 to 6 carbon atoms (2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol and 6-amino are preferred from the viewpoint of ease of modification. Hexanol and the like), 2-aminoethanol and 4-aminobutanol are more preferable, and 2-aminoethanol is particularly preferable.

  The amount of the amine having a hydroxyl group used for modification is determined based on the weight of the object to be modified (a1-1), the scratch resistance of the molded article, the ease of structure control of the block polymer (X), and the resin composition (described later). From the viewpoint of dispersibility of the block polymer (X) in Z), it is preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight, and particularly preferably 2 to 10% by weight.

  The hydroxyl value of (a1-2) is preferably 4 to 100 mgKOH / g, more preferably 4 from the viewpoints of reactivity with (b), ease of structure control of block polymer (X) and thermoplasticity. -50 mgKOH / g, particularly preferably 5-30 mgKOH / g.

The polyolefin (a1-3) having amino groups at both ends of the polymer is a polyolefin having an amino group obtained by modifying a polyolefin (a1-1) having carboxyl groups or carboxylic anhydride groups at both ends of the polymer with a diamine. And mixtures of two or more thereof.
Examples of the diamine include C2-C12 diamines, and specific examples include ethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, and decamethylene diamine.
Of these, diamines having 2 to 8 carbon atoms (ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, etc.) are preferable from the viewpoint of ease of modification, and ethylenediamine and hexamethylenediamine are more preferable. Particularly preferred is ethylenediamine.

  The amount of the diamine used for the modification of (a1-1) is the scratch resistance of the molded product, the ease of structure control of the block polymer (X), and the dispersion of the block polymer (X) in the resin composition (Z) described later. From the viewpoint of properties, it is preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight, and particularly preferably 2 to 10% by weight based on the weight of (a1-1). The modification of (a1-1) with diamine is preferably 0.5 to 1,000% by weight, more preferably based on the weight of (a1-1), from the viewpoint of preventing cross-linking reaction between polymer molecules. Is preferably 1 to 500% by weight, particularly preferably 2 to 300% by weight of diamine, and then the unreacted diamine is removed at 120 to 230 ° C. under reduced pressure.

  The amine value of (a1-3) is preferably 4 to 100 mgKOH / g, more preferably 4 from the viewpoints of reactivity with (b), ease of structure control of block polymer (X) and thermoplasticity. -50 mgKOH / g, particularly preferably 5-30 mgKOH / g.

Examples of the polyolefin (a1-4) having an isocyanate group at both ends include a polyolefin having an isocyanate group obtained by modifying (a1-2) with poly (2-3 or more) isocyanate and a mixture of two or more of these. It is done.
Examples of the polyisocyanate include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding carbon atoms in the isocyanate NCO group; the same shall apply hereinafter), aliphatic polyisocyanates having 2 to 18 carbon atoms, and alicyclic rings having 4 to 15 carbon atoms. These include polyisocyanates of the formula, araliphatic polyisocyanates having 8 to 15 carbon atoms, modified products of these polyisocyanates, and mixtures of two or more thereof.

  Aromatic polyisocyanates include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- or 4,4'-diphenylmethane Diisocyanate (MDI), 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane and 1 , 5-naphthylene diisocyanate and the like.

  Aliphatic polyisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, Examples thereof include bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, and 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

  Examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis (2-isocyanatoethyl). ) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

  Examples of the araliphatic polyisocyanate include m- or p-xylylene diisocyanate (XDI) and α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI).

Examples of modified polyisocyanates include urethane-modified products, urea-modified products, carbodiimide-modified products, and uretdione-modified products.
Of the polyisocyanates, TDI, MDI and HDI are preferred, and HDI is more preferred.

The reaction between polyisocyanate and (a1-2) can be carried out in the same manner as a general urethanization reaction.
The equivalent ratio (NCO: OH) of the isocyanate group of the polyisocyanate to the hydroxyl group of (a1-2) is preferably 1.8: 1 to 3: 1 and more preferably 2: 1.
In order to accelerate the urethanization reaction, a catalyst generally used in the urethanization reaction may be used as necessary. Catalysts include metal catalysts {tin catalysts [dibutyltin dilaurate and stannous octoate, etc.], lead catalysts [lead 2-ethylhexanoate, lead octenoate, etc.], other metal catalysts [metal naphthenate (cobalt naphthenate) Etc.) and phenylmercurypropionate etc.}; amine catalysts {triethylenediamine, diazabicycloalkenes [1,8-diazabicyclo [5,4,0] undecene-7 etc.], dialkylaminoalkylamines (dimethylaminoethylamine and Dimethylaminooctylamine etc.), heterocyclic aminoalkylamine [2- (1-aziridinyl) ethylamine and 4- (1-piperidinyl) -2-hexylamine etc.] carbonate or organic acid (formic acid etc.) salt, N Methyl or ethylmorpholine, triethylamine and diethyl or dimethyl Ethanolamine}; and use of two or more types of system thereof.
The amount of the catalyst used is preferably 3% by weight or less, and preferably 0.001 to 2% by weight, based on the total weight of the polyisocyanate and (a1-2).

As (a1-5), a polyolefin having a structure in which one end of (a1-0) is modified with an α, β-unsaturated carboxylic anhydride and further modified with a diolamine (a1) -5-1) can be used.
Examples of the diol amine used for the secondary modification include diethanolamine.

  Mn of the polyolefin (a) is preferably 1000 to 25,000, more preferably 1 from the viewpoints of dispersibility of the block polymer (X), mechanical properties of the molded article, scratch resistance and durability of the effect. , 500 to 12,000, particularly preferably 2,000 to 7,000.

The amount of the structural unit derived from propylene in the polyolefin (a) is 30 to 30 from the viewpoint of mechanical properties and scratch resistance of the resin composition (Z) (particularly when a polypropylene resin is used) and durability of its effect. It is 100 mol%, preferably 35 to 100 mol%, more preferably 50 to 100 mol%, particularly preferably 80 to 100 mol%, and most preferably 96 to 100 mol%.
Polyolefin (a) containing a predetermined amount of propylene is obtained by using (a1-0) and (a2-0) that have a content of structural units derived from propylene in the polyolefin of 30 to 100 mol%. Obtainable.

  In the polyolefin (a), the isotacticity of the propylene portion is 90 to 100% from the viewpoint of dispersibility of the block polymer (X), mechanical properties of the molded article, scratch resistance, and durability of the effect. preferable.

The isotacticity in the present invention can be calculated using, for example, ¹³ C-NMR (nuclear magnetic resonance spectroscopy). In general, the side chain methyl group is located on both sides (triplet, triad), on both sides of the triplet (pentad, pentad), and on both sides of the quintuplet (triplet, heptad). It is known that peaks are observed at different chemical shifts under the influence of the configuration with a methyl group (meso or racemo), and the evaluation of stereoregularity is generally performed for pentads. The isotacticity in can also be calculated based on the pentad evaluation.
That is, about the carbon peak (H) derived from the side chain methyl group in propylene obtained by ¹³ C-NMR, among the peaks, the pentad is derived from the methyl group in propylene of the isotactic propylene formed only by the mesostructure. In the case of a peak (Ha), isotacticity is calculated by the following equation.
Isotacticity (%) = [(H _a ) / Σ (H)] × 100 (1)
However, where the H _a peak signal of isotactic (pentad is formed only in the mesostructure) height, H is a the peak height of the pentad.

<Polysiloxane (b)>
Examples of the polysiloxane (b) in the present invention include polysiloxane (b1) and polysiloxane-containing polymer (b2).

  As the polysiloxane (b1), from the viewpoint of controlling the structure of the block polymer (X), polysiloxane monool (b1-1), polysiloxane diol (b1-2), polysiloxane monoamine (b1-3), polysiloxane It is preferable to use diamine (b1-4) and these modified products (b1-5).

  And the block of polysiloxane (b) is a block represented by the following general formula (1) or general formula (2) introduced by using (b1-1) to (b1-5). preferable.

R ¹ in the general formula (1) represents an alkyl group having 1 to 4 carbon atoms, and a methyl group and a butyl group are preferable from the viewpoint of scratch resistance and durability of the effect, and a butyl group is more preferable.
R ^{2 to} R ⁵ each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and an aliphatic hydrocarbon group having 1 to 4 carbon atoms is more preferable from the viewpoint of scratch resistance and continuity of the effect, and more preferable. Are methyl and butyl, particularly preferably methyl.
R ⁶ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms from the viewpoint of industrialization, and more preferably a methylene group, an ethylene group and propylene. Groups, particularly preferred are propylene groups.
R ⁷ represents an alkylene group having 2 to 4 carbon atoms. From the viewpoint of industrialization, R ⁷ is preferably an ethylene group and a propylene group, and more preferably an ethylene group.
When there are a plurality of (OR ⁷ ), they may be the same or different, and the combination form may be a block form or a random form.
n is an integer of 1 to 500, a is 0 or 1, and b represents an integer of 0 to 30.

The content of (SiR ² R ³ O) based on the weight of the block represented by the general formula (1) is preferably 5 to 99 from the viewpoint of the scratch resistance of the molded product described later and the continuity of the effect. 0.8 wt%, more preferably 70 to 99.6 wt%, and particularly preferably 90 to 98 wt%.
Therefore, a preferable range of n in the general formula (1) is a range in which the content ratio of (SiR ² R ³ O) is in a preferable range.

Q in the general formula (2) represents a hydroxyl group or an amino group.
R ⁸ and R ¹⁵ each independently represents an alkylene group having 2 to 4 carbon atoms, and from the viewpoint of industrialization, preferred are an ethylene group and a propylene group, and more preferred is an ethylene group.
When there are a plurality of (OR ⁸ ) and (OR ¹⁵ ), they may be the same or different, and the combination form may be a block form or a random form.
R ⁹ and R ¹⁴ each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms from the viewpoint of industrialization, and more preferably methylene. Groups, ethylene groups and propylene groups, particularly preferred are propylene groups.
R ^{10 to} R ¹³ each independently represents a hydrocarbon group having 1 to 6 carbon atoms, and an aliphatic hydrocarbon group having 1 to 4 carbon atoms is more preferable from the viewpoint of scratch resistance and the continuity of the effect. Are methyl and butyl, particularly preferably methyl.
c and f each independently represents an integer of 0 to 30, d and e are each independently 0 or 1, and m is an integer of 1 to 500.

The content of (SiR ¹⁰ R ¹¹ O) based on the weight of the block represented by the general formula (2) is preferably 5 to 99 from the viewpoint of the scratch resistance of the molded product described later and the continuity of the effect. 0.8 wt%, more preferably 70 to 99.6 wt%, and particularly preferably 90 to 98 wt%.
Therefore, a preferable range of n in the general formula (2) is a range in which the content ratio of (SiR ¹⁰ R ¹¹ O) is in a preferable range.

  Examples of the polysiloxane monool (b1-1) include polysiloxane represented by the general formula (3).

R ¹⁶ in the general formula (3) represents an alkyl group having 1 to 4 carbon atoms, and a methyl group and a butyl group are preferable from the viewpoint of scratch resistance and durability of the effect, and a butyl group is more preferable.
R ^{17 to} R ²⁰ each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and an aliphatic hydrocarbon group having 1 to 4 carbon atoms is more preferable from the viewpoint of scratch resistance and continuity of the effect, and more preferable. Are methyl and butyl, particularly preferably methyl.
R ²¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms from the viewpoint of industrialization, and more preferably a methylene group, an ethylene group or propylene. Groups, particularly preferred are propylene groups.
R ²² represents an alkylene group having 2 to 4 carbon atoms. From the viewpoint of industrialization, R ²² is preferably an ethylene group and a propylene group, and more preferably an ethylene group.
When there are a plurality of (OR ²² ), they may be the same or different, and the combination form may be a block form or a random form.
n ′ is an integer of 1 to 500, a ′ is 0 or 1, and b ′ represents an integer of 0 to 30.

Polysiloxane monool (b1-1) is an anionic polymerization of a cyclic polysiloxane such as 1,3,5,7-tetramethylcyclotetrasiloxane using an organic alkali metal compound as an initiator, and one end is an alkali metal silanolate. Obtain a polysiloxane (so-called living polymer) and react it with an alkylchlorosilane compound having a hydroxyl group to introduce a functional group at one end, or anionic polymerization of cyclic polysiloxane using an organic alkali metal compound as an initiator A polysiloxane (so-called living polymer) whose one end is an alkali metal silanolate is obtained, and this is reacted with a dialkylchlorosilane compound to synthesize a one-end SiH group-containing polysiloxane, which is doubled at the end of a molecule such as allyl alcohol. Alcohol with one bond is platinum-based It may be obtained by methods such as reacting the.
In addition, (OR ²² ) in the general formula (3) can be introduced by using an alkylchlorosilane compound having a hydroxyl group or an alcohol having a double bond at the molecular end to which an alkylene oxide having 2 to 4 carbon atoms is added. it can.

  Examples of the organic alkali metal compound include alkyl lithium having 1 to 4 carbon atoms (methyl lithium, ethyl lithium, propyl lithium, and butyl lithium). Of these, butyl lithium is preferable from the viewpoint of industrialization.

The content of (SiR ¹⁷ R ¹⁸ O) based on the weight of the polysiloxane monool (b1-1) is preferably from 5 to 99. 5 from the viewpoint of scratch resistance of the molded product described later and continuity of the effect. It is 8% by weight, more preferably 70 to 99.6% by weight, and particularly preferably 90 to 98% by weight.
Therefore, a preferable range of n ′ in the general formula (3) is a range in which the content ratio of (SiR ¹⁷ R ¹⁸ O) is in a preferable range.

  Examples of the polysiloxane diol (b1-2) include polysiloxane represented by the general formula (4).

R ²³ and R ³⁰ in the general formula (4) each independently represent an alkylene group having 2 to 4 carbon atoms, and from the viewpoint of industrialization, an ethylene group and a propylene group are preferable, and an ethylene group is more preferable.
When there are a plurality of (OR ²³ ) and (OR ³⁰ ), they may be the same or different, and the coupling format may be a block format or a random format.
R ²⁴ and R ²⁹ each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms from the viewpoint of industrialization, and more preferably methylene. Groups, ethylene groups and propylene groups, particularly preferred are propylene groups.
R ^{25 to} R ²⁸ each independently represent a hydrocarbon group having 1 to 6 carbon atoms, preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms, more preferably from the viewpoint of scratch resistance and the continuity of the effect. Are methyl and butyl, particularly preferably methyl.
c ′ and f ′ each independently represents an integer of 0 to 30; d ′ and e ′ are each independently 0 or 1; and m ′ is an integer of 1 to 500.

  Polysiloxane diol (b1-2) can be prepared by, for example, reacting dimethylpolysiloxane having Si-H groups at both ends with alcohol having one double bond at the molecular ends in the presence of a platinum catalyst, or bis (hydroxyethyl). ) Tetramethyldisiloxane and cyclic siloxane can be produced by a condensation reaction using an acidic catalyst to obtain a carbinol-modified polysiloxane at both ends.

The content of (SiR ²⁵ R ²⁶ O) based on the weight of the polysiloxane diol (b1-2) is preferably 5 to 99.8 from the viewpoint of the scratch resistance of the molded product described later and the continuity of the effect. % By weight, more preferably 70 to 99.6% by weight, and particularly preferably 90 to 98% by weight.
Therefore, a preferable range of m ′ in the general formula (4) is a range in which the content ratio of (SiR ²⁵ R ²⁶ O) is in a preferable range.

  Examples of the polysiloxane monoamine (b1-3) include polysiloxane represented by the general formula (5).

R ³¹ in the general formula (5) represents an alkyl group having 1 to 4 carbon atoms, and a methyl group and a butyl group are preferable from the viewpoint of scratch resistance and durability of the effect, and a butyl group is more preferable.
R ^{32 to} R ³⁵ each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and from the viewpoint of scratch resistance and continuity of the effect, an aliphatic hydrocarbon group having 1 to 4 carbon atoms is more preferable. Are methyl and butyl, particularly preferably methyl.
R ³⁶ represents a divalent hydrocarbon group having 1 to 20 carbon atoms. From the viewpoint of industrialization, R ³⁶ is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and more preferably a methylene group, an ethylene group and propylene. Groups, particularly preferred are propylene groups.
R ³⁷ represents an alkylene group having 2 to 4 carbon atoms. From the viewpoint of industrialization, R ³⁷ is preferably an ethylene group and a propylene group, and more preferably an ethylene group.
When there are a plurality of (OR ³⁷ ), they may be the same or different, and the combination form may be a block form or a random form.
n ″ is an integer of 1 to 500, a ″ is 0 or 1, and b ″ represents an integer of 0 to 30.

  The polysiloxane monoamine (b1-3) is obtained by anionic polymerization of a cyclic polysiloxane using the above organic alkali metal compound as an initiator to obtain a polysiloxane (so-called living polymer) having an alkali metal silanolate at one end and an amino group. A method in which a functional group is introduced at one end by reacting with an alkylchlorosilane compound having an alkyl group, or a polysiloxane in which a cyclic polysiloxane is anionically polymerized using an organic alkali metal compound as an initiator and an alkali metal silanolate at one end (so-called living Polymer), this is reacted with a dialkylchlorosilane compound to synthesize one-terminal SiH group-containing polysiloxane, and an amine having one double bond at the molecular terminal, such as allylamine, is reacted with a platinum-based catalyst, etc. Can be obtained.

The content of (SiR ³² R ³³ O) based on the weight of the polysiloxane monoamine (b1-3) is preferably 5 to 99.8 from the viewpoint of the scratch resistance of the molded product described later and the continuity of the effect. % By weight, more preferably 70 to 99.6% by weight, and particularly preferably 90 to 98% by weight.
Therefore, a preferable range of n ″ in the general formula (5) is a range in which the content ratio of (SiR ³² R ³³ O) is within a preferable range.
In the general formula (5), a ″ is 0 or 1, preferably 0.

R ³⁸ and R ⁴⁵ in the general formula (6) each independently represent an alkylene group having 2 to 4 carbon atoms, and from the viewpoint of industrialization, an ethylene group and a propylene group are preferable, and an ethylene group is more preferable.
When there are a plurality of (OR ³⁸ ) and (OR ⁴⁵ ), they may be the same or different, and the coupling format may be a block format or a random format.
R ³⁹ and R ⁴⁴ each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably methylene from the viewpoint of industrialization. Groups, ethylene groups and propylene groups, particularly preferred are propylene groups.
R ^{40 to} R ⁴³ each independently represents a hydrocarbon group having 1 to 6 carbon atoms, and an aliphatic hydrocarbon group having 1 to 4 carbon atoms is more preferable from the viewpoint of scratch resistance and the continuity of the effect. Are methyl and butyl, particularly preferably methyl.
c ″ and f ″ each independently represents an integer of 0 to 30; d ″ and e ″ each independently represents 0 or 1; and m ″ represents an integer of 1 to 500.

  Polysiloxane diamine (b1-4) can be prepared by reacting, for example, a dimethylpolysiloxane having Si-H groups at both ends and an amine having one double bond at the molecular end in the presence of a platinum catalyst, or bis (aminopropyl). ) Tetramethyldisiloxane and cyclic siloxane can be produced by a condensation reaction using an alkaline catalyst to obtain an amino-modified polysiloxane at both ends.

The content of (SiR ⁴⁰ R ⁴¹ O) based on the weight of the polysiloxane diamine (b1-4) is preferably 5 to 99.8 from the viewpoint of the scratch resistance of the molded product described later and the continuity of the effect. % By weight, more preferably 70 to 99.6% by weight, and particularly preferably 90 to 98% by weight.
Therefore, a preferable range of m ″ in the general formula (6) is a range in which the content ratio of (SiR ⁴⁰ R ⁴¹ O) is within a preferable range.

  Examples of the polysiloxane-containing polymer (b2) include polysiloxane ester amide (b2-1) having a segment of polysiloxane monool (b1-1) and polysiloxane amideimide (b2-2) having a segment of (b1-1). ), Polysiloxane ester (b2-3) having a segment of (b1-1), polysiloxane ester amide (b2-4) having a segment of polysiloxane diol (b1-2), and a segment of (b1-2) Polysiloxane amide imide (b2-5), polysiloxane ester (b2-6) having a segment of (b1-2), polysiloxane amide (b2-7) having a segment of polysiloxane monoamine (b1-3), Poly having segments of polysiloxane diamine (b1-4) Rokisan'amido (b2-8) and (b1-1), (b1-2), and the like (b1-3) or polysiloxane urethane having a segment of (b1-4) (b2-9).

The polysiloxane ester amide (b2-1) is composed of a polyamide [12 nylon, 6 nylon, etc.] having a carboxyl group at both ends and a polysiloxane monool (b1-1).
Examples of the polyamide having a carboxyl group at both ends include a ring-opening polymer of lactam, a polycondensate of aminocarboxylic acid, and a polyamide of a diamine and a dicarboxylic acid having 2 to 12 linear hydrocarbon carbon atoms.
Of the polyamides having carboxyl groups at both ends, from the viewpoint of dispersibility of the block polymer (X) in the resin composition (Z) described later, a ring-opening polymer of caprolactam, preferably 12-aminododecanoic acid, Polycondensates and polyamides of adipic acid and hexamethylenediamine are preferred, and caprolactam ring-opening polymers are more preferred.

The polysiloxane amide imide (b2-2) is composed of a polyamideimide having at least one imide ring and a polysiloxane monool (b1-1).
Polyamideimide includes a polymer comprising lactam and a trivalent or tetravalent aromatic polycarboxylic acid capable of forming at least one imide ring, an aminocarboxylic acid and a trivalent or tetravalent aromatic polycarboxylic acid. Examples thereof include a polymer composed of carboxylic acid, a polymer composed of polyamide and trivalent or tetravalent aromatic polycarboxylic acid, and a mixture thereof.

As polysiloxane ester (b2-3), what is comprised from polyester and polysiloxane monool (b1-1) or polysiloxane diol (b1-2) is mentioned.
Examples of the polyester include a polyester of a dicarboxylic acid and a diol.

  Examples of the polysiloxane amide (b2-7) include those composed of polyamide and polysiloxane monoamine (b1-3).

  As polysiloxane urethane (b2-9), diisocyanate among the above polyisocyanates, polysiloxane monool (b1-1) or polysiloxane monoamine (b1-3) and optionally a chain extender [2-12 carbon atoms] Linear or branched aliphatic diol (ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc.) and the diamine described above] What is done.

  From the viewpoint of scratch resistance of the molded product, the content of the polysiloxane moiety segment in the polysiloxane-containing polymer (b2) is preferably 70 to 99% by weight, more preferably 90%, based on the weight of (b2). ~ 99% by weight.

  Of the polysiloxane (b1) and the polysiloxane-containing polymer (b2), polysiloxane (b1) is preferable from the viewpoint of the scratch resistance of the molded product described later and the continuity of the effect.

  The Mn of the polysiloxane (b) is preferably 500 to 10,000, more preferably 1,000 to 6,000, from the viewpoint of scratch resistance of the molded product described later and reactivity with the polyolefin (a). Particularly preferred is 2,000 to 5,000.

<Block polymer (X)>
The block polymer (X) in the present invention has a block of polyolefin (a) having 30 mol% or more of a structural unit derived from propylene and a block of polysiloxane (b) as structural units, and the molecular structure is as follows ( The structure is any one of 1) to (3).
(1) a linear (a)-(b) diblock structure;
(2) linear (b)-(a)-(b) triblock structure;
(3) A branched structure in which 2 to 3 blocks of polysiloxane (b) are bonded to one end of a block of polyolefin (a).

  As the structure of (X), (a)-(b) diblock structure is preferable from the viewpoint of scratch resistance of the molded product and dispersibility of the block polymer (X) in the resin composition (Z) described later. And (b)-(a)-(b) triblock type structures, particularly preferred are (a)-(b) diblock type structures.

  The block polymers having the molecular structures (1) to (3) are not particularly limited, but can be obtained by the following method, for example.

  The linear (a)-(b) block polymer having a diblock structure includes, for example, a polyolefin (a2-1) having a carboxyl group or a carboxylic anhydride group at one end of the polymer and a polysiloxane monool (b1- 1) or reacting polysiloxane monoamine (b1-3) at a molar ratio of 1: 1, or polyolefin (a1-1) having a carboxyl group or a carboxylic acid anhydride group at both ends of the polymer and polysiloxane mono Polyolefin (a2-1) having a molar ratio of 1: 1 with all (b1-1) or polysiloxane monoamine (b1-3), or having a carboxyl group or carboxylic anhydride group at one terminal of the polymer And polysiloxane diol (b1-2) or polysiloxane diamine (b1-4) in a 1: 1 molar ratio. It can be obtained in.

  The linear (b)-(a)-(b) block polymer having a triblock structure includes, for example, a polyolefin (a1-1) having a carboxyl group or a carboxylic acid anhydride group at both ends of the polymer and a polysiloxane mono It can be obtained by reacting all (b1-1) or polysiloxane monoamine (b1-3) at a molar ratio of 1: 2.

A block polymer having a branched structure in which two polysiloxane (b) blocks are bonded to one end of a polyolefin (a) block is, for example, a polyolefin having a carboxylic acid anhydride group at one end of the polymer It can be obtained by reacting siloxane monool (b1-1) with a molar ratio of 1: 2.
In the above, an example of the combination of the polyolefin (a) and the polysiloxane (b) when obtaining the block polymer (X) having each structure has been shown. As described above, (a) and (b) are various. Since the functional group of (a) and the functional group of (b) can react, any combination can be adopted.

  The block polymer (X) preferably has a structure in which a block of the polyolefin (a) and a block of the polysiloxane (b) are bonded via an ester bond, an amide bond, an imide bond, a urethane bond or a urea bond. From the viewpoints of heat resistance and ease of production, ester bonds and imide bonds are more preferable, and imide bonds are particularly preferable.

  The Mn of the block polymer (X) is preferably from 3,000 to 14,000, more preferably from 4,000 to 11,000, particularly preferably 5,000, from the viewpoint of scratch resistance of the molded product described later. ~ 9,000.

  The weight ratio [(b) / (X)] of the block of the polysiloxane (b) to the block polymer (X) is based on the mechanical properties and scratch resistance of the molded product, and the dispersibility of the block polymer in the resin composition. From the viewpoint, it is preferably 10 to 60% by weight, more preferably 15 to 60% by weight, and particularly preferably 20 to 60% by weight.

  When the block polymer (X) has a structure in which the block of (a) and the block of (b) are bonded via an ester bond, an amide bond, or an imide bond, for example, (a) and ( b) is charged into a reaction vessel, and water produced by esterification reaction, amidation reaction or imidization reaction at a reaction temperature of 100 to 250 ° C. and a pressure of 0.003 to 0.1 MPa under stirring (hereinafter abbreviated as produced water). ) Is removed from the reaction system while being reacted for 1 to 50 hours.

In the case of the esterification reaction, it is preferable to use 0.05 to 0.5% by weight of catalyst based on the weight of (a) and (b) in order to accelerate the reaction. Catalysts include inorganic acids (such as sulfuric acid and hydrochloric acid), organic sulfonic acids (such as methanesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, and naphthalenesulfonic acid), antimony catalysts (such as antimony trioxide), and tin catalysts (monobutyltin). Oxide and dibutyltin oxide), titanium catalyst (tetrabutyl titanate, bistriethanolamine titanate, potassium oxalate titanate, etc.), zirconium catalyst (tetrabutyl zirconate, zirconyl acetate, etc.) and zinc catalyst (zinc acetate, etc.) Can be mentioned. When a catalyst is used, the catalyst can be neutralized as necessary after completion of the esterification reaction and treated with an adsorbent to remove and purify the catalyst.
Examples of the method for removing the produced water from the reaction system include the following methods.
[1] A method of removing only the produced water from the reaction system by azeotropically boiling the organic solvent and the produced water under reflux using an organic solvent incompatible with water (for example, toluene, xylene, cyclohexane, etc.) .
[2] A method in which carrier gas (for example, air, nitrogen, helium, argon, carbon dioxide, etc.) is blown into the reaction system, and the generated water is removed from the reaction system together with the carrier gas.
[3] A method of removing the generated water from the reaction system by reducing the pressure in the reaction system.

When (X) has a structure in which the block of (a) and the block of (b) are bonded via a urethane bond or a urea bond, for example, (b) is put into a reaction vessel and stirred. After heating to 30-100 degreeC below, (a) is thrown in and it can manufacture by the method made to react at the same temperature for 1 to 20 hours.
In order to promote the reaction, it is preferable to use 0.001 to 5% by weight of catalyst based on the weight of (a) and (b). Catalysts include organometallic compounds (dibutyltin dilaurate, dioctyltin dilaurate, lead octoate, bismuth octoate, etc.), tertiary amines {triethylenediamine, trialkylamines having an alkyl group of 1 to 8 carbon atoms (trimethylamine, tributylamine) And trioctylamine etc.), diazabicycloalkenes [1,8-diazabicyclo [5,4,0] undecene-7] etc.]; and combinations of two or more thereof.

<Resin modifier (Y)>
The resin modifier (Y) of the present invention contains the above-mentioned block polymer (X).
The resin modifier (Y) can be suitably used as a resin modifier for the thermoplastic resin (C) described later.
The resin modifier (Y) includes a colorant (D1), a release agent (D2), an antioxidant (D3), a flame retardant (D4), an ultraviolet absorber (D5), an antibacterial agent (D6), which will be described later. An additive (D) such as a compatibilizing agent (D7), a filler (D8), and a transesterification inhibitor (D9) can be contained.

<Resin composition (Z)>
The resin composition (Z) of the present invention contains the resin modifier (Y) of the present invention and a thermoplastic resin (C).
The weight ratio [(Y) :( C)] of the resin modifier (Y) and the thermoplastic resin (C) is preferably 0.5 from the viewpoint of mechanical properties, scratch resistance, and durability of the effect. : 99.5-50: 50, more preferably 1: 99-20: 80, and particularly preferably 2: 98-10: 90.

The thermoplastic resin (C) includes polyolefin resin (C1) [polypropylene (PP), ethylene / propylene copolymer, polyethylene (PE), etc.]; fluororesin (C2) [PTFE (polytetrafluoroethylene), ETFE ( Ethylene-tetrafluoroethylene copolymer), PFA (perfluoroalkoxyalkane (copolymer of tetrafluoroethylene (C ₂ F ₄ ) and perfluoroalkoxyethylene) and PVDF (polyvinylidene fluoride resin))]; polystyrene resin (C3) [A copolymer containing vinyl group-containing aromatic hydrocarbons alone and vinyl group-containing aromatic hydrocarbons and at least one selected from the group consisting of butadiene; for example, polystyrene (PS) and impact resistance And a mixture of two or more thereof.
Among these, from the viewpoint of the mechanical properties and scratch resistance of the molded product described later and the durability of the effect, PVDF among (C1) and (C2) is preferable, and (C1) is particularly preferable. Of (C1), polypropylene (homotype polypropylene, block type polypropylene and ethylene / propylene copolymer) is the most preferred, and homotype polypropylene is most preferred.

  In the resin composition (Z), if necessary, the colorant (D1), the release agent (D2), the antioxidant (D3), the flame retardant (D4), and the ultraviolet absorber as long as the effects of the present invention are not impaired. Additives (D) such as (D5), antibacterial agent (D6), compatibilizer (D7), filler (D8), and transesterification agent (D9) can be contained. Each additive may be used alone or in combination of two or more.

  Examples of the colorant (D1) include inorganic pigments [white pigments, cobalt compounds, iron compounds, sulfides, and the like], organic pigments [azo pigments and polycyclic pigments, etc.], dyes [azo-based, indigoid-based, sulfide-based, alizarin]. System, acridine system, thiazole system, nitro system, aniline system, etc.].

  As the release agent (D2), higher fatty acid lower (1 to 4 carbon) alcohol ester (such as butyl stearate), polyvalent fatty acid (2 to 18 carbon) (divalent to tetravalent or higher) Examples include alcohol esters (hardened castor oil and the like), glycols (2 to 8 carbon atoms) of fatty acids (carbon numbers 2 to 18) (ethylene glycol monostearate and the like), liquid paraffin, and the like.

  Examples of the antioxidant (D3) include phenol compounds [monocyclic phenol (2,6-di-t-butyl-p-cresol, etc.), 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 compounds (dilauryl 3) , 3'-thiodipropionate etc.), phosphorus compounds (triphenyl phosphite etc.), amine compounds (octylated diphenylamine etc.) and the like.

  Examples of the flame retardant (D4) 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 ultraviolet absorber (D5) include benzotriazole [2- (2′-hydroxy-5′-methylphenyl) benzotriazole and the like], benzophenone (2-hydroxy-4-methoxybenzophenone and the like), salicylate (phenyl salicylate). Etc.) and acrylates (2-ethylhexyl-2-cyano-3,3-diphenyl acrylate etc.) and the like.

  As the antibacterial agent (D6), benzoic acid, sorbic acid, halogenated phenol, organic iodine, nitrile (2,4,5,6-tetrachloroisophthalonitrile, etc.), thiocyano (methylene bisthianocyanate), N-halo Examples include alkylthioimides, copper agents (such as 8-oxyquinoline copper), benzimidazoles, benzothiazoles, trihaloallyls, triazoles, organic nitrogen sulfur compounds (such as Suraoff 39), quaternary ammonium compounds, and pyridine compounds.

  Examples of the compatibilizer (D7) include 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: A polymer described in JP-A-3-258850, a modified vinyl polymer having a sulfonic acid group described in JP-A-6-345927, and a block weight having a polyolefin part and an aromatic vinyl polymer part. Examples include coalescence.

Examples of the filler (D8) include inorganic fillers (such as calcium carbide, talc and clay) and organic fillers (such as urea and calcium stearate).
Examples of the transesterification inhibitor (D9) include phosphate esters [bisphenol A bis (diphenyl phosphate), monooctadecyl phosphate, dioctadecyl phosphate, etc.] and phosphite [tris (2,4-di-t-butylphenyl). ) Phosphite etc.].

  The total content of (D) based on the weight of the thermoplastic resin (C) is generally 45% by weight or less, preferably 0.001 to 40% by weight from the viewpoint of the effect of each additive and the mechanical properties of the molded product. The content of each (D) is preferably (D1) from 0.1 to 3% by weight, more preferably from 0.2 to 2% by weight; (D2) is preferably 0.01 to 3 wt%, more preferably 0.05 to 1 wt%; (D3) is preferably 0.01 to 3 wt%, more preferably 0.05 to 1 wt%; (D4) is preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight; (D5) is preferably 0.01 to 3% by weight, more preferably 0.05 to 1% by weight; ) Is preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight; (D7) Preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight; (D8) preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight; (D9) 0.01 to 3% by weight, more preferably 0.05 to 1% by weight.

The resin composition (Z) of the present invention can be obtained by melt-mixing the resin modifier (Y) of the present invention, the thermoplastic resin (C) and, if necessary, the additive (D).
At this time, the same additive (D) as the additive (D) contained in the resin modifier (Y) may be added to the resin composition (Z).
As a method of melting and mixing, generally, a method of mixing each component in pellet form or powder form with an appropriate mixer (Henschel mixer etc.) and then melt mixing and pelletizing with an extruder is applied. it can.
There is no particular limitation on the order of addition of each component during melt mixing, for example,
[1] A method in which (C) and (Y) are melt-mixed, and then (D) is added all at once and melt-mixed if necessary;
[2] When (C) and (Y) are melt-mixed, a part of (C) is melt-mixed in advance to prepare a high-concentration composition (masterbatch resin composition) of (Y), and then the remaining (C) and a method of melt-mixing (D) as necessary (master batch method or master pellet method);
Etc.
The concentration of (Y) in the masterbatch resin composition in the method [2] is preferably 20 to 80% by weight, more preferably 50 to 70% by weight.
Of the methods [1] and [2], the method [2] is preferable from the viewpoint that (Y) is easily dispersed efficiently in (C).

<Molded product>
The molded product of the present invention is obtained by molding the resin composition (Z) of the present invention. 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 or foam molding can be used for any molding method.

  The molded product of the present invention has excellent mechanical properties, scratch resistance and durability thereof, and a molded product having good scratch resistance can be obtained.

The resin modifier (Y) of the present invention is suitably used as a scratch resistance improver.
Since the molded article of the present invention containing (Y) has excellent scratch resistance, it can be suitably used for the following applications. That is, it is suitable for improving scratch resistance of automobile interior / exterior products, industrial products such as precision instruments and home appliances, and other polyolefin-based resin molded products used in water-related areas (toiletries, bathrooms, kitchens, etc.).

  Examples of the present invention will be described below, but the present invention is not limited thereto. Below, a part shows a weight part.

<Production Example 1>
[One-end acid-modified ethylene-propylene random copolymer (a-1)]
A low molecular weight ethylene-propylene random copolymer [ethylene-propylene random copolymer obtained by a thermal degradation method] in a stainless steel pressure-resistant reaction vessel equipped with a stirrer, a thermometer, a heating / cooling device, a nitrogen introduction tube and a decompression device. What was obtained by thermally degrading a coalescence (propylene content = 32 mol%) at 410 ± 0.1 ° C. under nitrogen flow for 16 minutes. Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, maleic anhydride 10 parts and xylene 30 parts were added, mixed uniformly, then purged with nitrogen, While stirring, the temperature was raised to 200 ° C. to melt, and the mixture was reacted at the same temperature for 10 hours. Then, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to obtain a polyolefin having a carboxylic anhydride group at one end of the polymer (a-1) 95 parts were obtained.
Mn of (a-1) was 4,000, propylene content was 32 mol%, and isotacticity of the propylene portion was 40%.

<Production Example 2>
[One-end acid-modified ethylene-propylene random copolymer (a-2)]
A low molecular weight ethylene-epylene random copolymer obtained by a thermal degradation method [ethylene-propylene random copolymer] A polymer (propylene content = 52 mol%) obtained by heat degradation at 410 ± 0.1 ° C. for 16 minutes under nitrogen flow. Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, maleic anhydride 10 parts and xylene 30 parts were added, mixed uniformly, then purged with nitrogen, While stirring, the temperature was raised to 200 ° C. to melt, and the mixture was reacted at the same temperature for 10 hours. Then, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to give a polyolefin having a carboxylic anhydride group at one end of the polymer (a-2) 95 parts were obtained.
Mn of (a-2) was 4,000, propylene content was 52 mol%, and isotacticity of the propylene portion was 60%.

<Production Example 3>
[One-end acid-modified 1-butene-propylene random copolymer (a-3)]
A low molecular weight 1-butene-propylene random copolymer [1-butene-] obtained by a thermal degradation method in a stainless steel pressure-resistant reaction vessel equipped with a stirrer, a thermometer, a heating / cooling device, a nitrogen introduction tube and a decompression device. A product obtained by thermally degrading a propylene random copolymer (propylene content = 82 mol%) at 410 ± 0.1 ° C. under nitrogen flow for 16 minutes. Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, maleic anhydride 10 parts and xylene 30 parts were added, mixed uniformly, then purged with nitrogen, While stirring, the temperature was raised to 200 ° C. to melt, and the mixture was reacted at the same temperature for 10 hours. Then, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to obtain a polyolefin having a carboxylic anhydride group at one end of the polymer (a-3) 95 parts were obtained.
Mn of (a-3) was 4,000, propylene content was 82 mol%, and isotacticity of the propylene portion was 80%.

<Production Example 4>
[One-end acid-modified ethylene-propylene random copolymer (a-4)]
Low molecular weight ethylene-propylene random copolymer obtained by thermal degradation method [ethylene-propylene random copolymer] A product obtained by thermally degrading a coalescence (propylene content = 96 mol%) at 410 ± 0.1 ° C. for 16 minutes under nitrogen flow. Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, maleic anhydride 10 parts and xylene 30 parts were added, mixed uniformly, then purged with nitrogen, While stirring, the temperature was raised to 200 ° C. to melt, and the mixture was reacted at the same temperature for 10 hours. Next, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to give a polyolefin having a carboxylic anhydride group at one end of the polymer (a-4) 95 parts were obtained.
In (a-4), Mn was 4,000, the propylene content was 96 mol%, and the isotacticity of the propylene portion was 90%.

<Production Example 5>
[One-end acid-modified homotype polypropylene (a-5)]
Low-molecular-weight homotype polypropylene obtained by a thermal degradation method [410 ± 0.1 ° C. of homotype polypropylene] in a stainless steel pressure-resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen introduction tube and decompression device , Obtained by heat degradation for 16 minutes under nitrogen flow. Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, maleic anhydride 10 parts and xylene 30 parts were added, mixed uniformly, then purged with nitrogen, While stirring, the temperature was raised to 200 ° C. to melt, and the mixture was reacted at the same temperature for 10 hours. Then, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to give a polyolefin having a carboxylic anhydride group at one end of the polymer (a-5) 95 parts were obtained.
The Mn of (a-5) was 4,000, the propylene content was 100 mol%, and the isotacticity of the propylene portion was 99%.

<Production Example 6>
[Both-terminal acid-modified ethylene-propylene random copolymer (a-6)]
A low molecular weight ethylene-propylene random copolymer [ethylene-propylene random copolymer obtained by a thermal degradation method] in a stainless steel pressure-resistant reaction vessel equipped with a stirrer, a thermometer, a heating / cooling device, a nitrogen introduction tube and a decompression device. A product obtained by thermally degrading a coalescence (propylene content = 96 mol%) at 410 ± 0.1 ° C. for 16 minutes under nitrogen flow. Mn: 3,900, average number of double bonds per molecule: 2.0] 90 parts, maleic anhydride 20 parts and xylene 30 parts were added, mixed uniformly, then purged with nitrogen, While stirring, the temperature was raised to 200 ° C. to melt, and the mixture was reacted at the same temperature for 10 hours. Next, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to give a polyolefin (a-6) having carboxylic anhydride groups at both ends of the polymer. 95 parts were obtained.
In (a-6), Mn was 4,000, the propylene content was 96 mol%, and the isotacticity of the propylene portion was 90%.

<Production Example 7>
[One-end acid-modified ethylene-propylene random copolymer (a-7)]
Low molecular weight ethylene-propylene random copolymer obtained by thermal degradation method [ethylene-propylene random copolymer] A product obtained by thermally degrading a coalescence (propylene content = 96 mol%) at 410 ± 0.1 ° C. for 16 minutes under nitrogen flow. Mn: 1,400, average number of double bonds per molecule: 1.0] 90 parts, maleic anhydride 10 parts and xylene 30 parts were added, mixed uniformly, then purged with nitrogen, While stirring, the temperature was raised to 200 ° C. to melt, and the mixture was reacted at the same temperature for 10 hours. Subsequently, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to give a polyolefin having a carboxylic anhydride group at one end of the polymer (a-7) 95 parts were obtained.
Mn of (a-7) was 1,500, the propylene content was 96 mol%, and the isotacticity of the propylene portion was 90%.

<Production Example 8>
[One-end acid-modified ethylene-propylene random copolymer (a-8)]
Low molecular weight ethylene-propylene random copolymer obtained by thermal degradation method [ethylene-propylene random copolymer] A product obtained by thermally degrading a coalescence (propylene content = 96 mol%) at 410 ± 0.1 ° C. for 16 minutes under nitrogen flow. Mn: 2,400, average number of double bonds per molecule: 1.0] 90 parts, maleic anhydride 10 parts and xylene 30 parts were added, mixed uniformly, then purged with nitrogen, While stirring, the temperature was raised to 200 ° C. to melt, and the mixture was reacted at the same temperature for 10 hours. Then, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to give a polyolefin having a carboxylic anhydride group at one end of the polymer (a-8) 95 parts were obtained.
Mn of (a-8) was 2,500, propylene content was 96 mol%, and isotacticity of the propylene portion was 90%.

<Production Example 9>
[One-end acid-modified ethylene-propylene random copolymer (a-9)]
Low molecular weight ethylene-propylene random copolymer obtained by thermal degradation method [ethylene-propylene random copolymer] A product obtained by thermally degrading a coalescence (propylene content = 96 mol%) at 410 ± 0.1 ° C. for 16 minutes under nitrogen flow. Mn: 10,000, average number of double bonds per molecule: 1.0] 90 parts, maleic anhydride 10 parts and xylene 30 parts were added, mixed uniformly, then purged with nitrogen, While stirring, the temperature was raised to 200 ° C. to melt, and the mixture was reacted at the same temperature for 10 hours. Then, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to give a polyolefin having a carboxylic anhydride group at one end of the polymer (a-9) 95 parts were obtained.
Mn of (a-9) was 10,000, the propylene content was 96 mol%, and the isotacticity of the propylene portion was 90%.

<Production Example 10>
[Both-terminal acid-modified ethylene-propylene random copolymer (a-10)]
Low molecular weight ethylene-propylene random copolymer obtained by thermal degradation method [ethylene-propylene random copolymer] A product obtained by thermally degrading a coalescence (propylene content = 96 mol%) at 410 ± 0.1 ° C. for 16 minutes under nitrogen flow. Mn: 10,000, average number of double bonds per molecule: 2.0] 90 parts, maleic anhydride 20 parts and xylene 30 parts were added, mixed uniformly, and then purged with nitrogen. While stirring, the temperature was raised to 200 ° C. to melt, and the mixture was reacted at the same temperature for 10 hours. Subsequently, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to give a polyolefin (a-10) having carboxylic anhydride groups at both ends of the polymer 95 parts were obtained.
Mn of (a-10) was 10,000, the propylene content was 96 mol%, and the isotacticity of the propylene portion was 90%.

<Production Example 11>
[Both-terminal acid-modified ethylene-propylene random copolymer (a-11)]
Low molecular weight ethylene-propylene random copolymer obtained by thermal degradation method [ethylene-propylene random copolymer] A product obtained by thermally degrading a coalescence (propylene content = 96 mol%) at 410 ± 0.1 ° C. for 16 minutes under nitrogen flow. Mn: 1,400 Average number of double bonds per molecule: 2.0] 90 parts, maleic anhydride 20 and 30 parts of xylene were added, mixed uniformly, purged with nitrogen, and stirred under sealing While heating to 200 ° C., the mixture was melted and reacted at the same temperature for 10 hours. Next, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to obtain a polyolefin having a carboxylic anhydride group at both ends of the polymer (a-11) 95 parts were obtained.
Mn of (a-11) was 1,500, the propylene content was 96 mol%, and the isotacticity of the propylene portion was 90%.

<Production Example 12>
[One-terminal amino-modified ethylene-propylene random copolymer (a-12)]
Low molecular weight ethylene-propylene random copolymer obtained by thermal degradation method [ethylene-propylene random copolymer] A product obtained by thermally degrading a coalescence (propylene content = 96 mol%) at 410 ± 0.1 ° C. for 16 minutes under nitrogen flow. Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, maleic anhydride 10 parts and xylene 30 parts were added, mixed uniformly, then purged with nitrogen, While stirring, the temperature was raised to 200 ° C. to melt, and the mixture was reacted at the same temperature for 10 hours. Then, excess maleic anhydride and xylene were distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to obtain 95 parts of polyolefin having a carboxylic anhydride group at one end of the polymer. .
Next, 90 parts of the above-mentioned polyolefin having a carboxylic acid anhydride group at one end of the polymer and 10 parts of bis (2-aminoethyl) ether are put into a pressure-resistant reaction vessel similar to Production Example 1, and under a nitrogen gas atmosphere, The temperature was raised to 200 ° C. with stirring, and the reaction was carried out at the same temperature for 2 hours. Excess bis (2-aminoethyl) ether was distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 2 hours to obtain a modified polyolefin (a-12) having an amino group at one end.
The Mn of (a-12) was 4,000, the propylene content was 96 mol%, and the isotacticity of the propylene portion was 90%.

<Production Example 13>
[Α-Butyl-ω-amino-modified polydimethylsiloxane (Mn = 500) (b-1)]
In a reaction vessel equipped with a stirrer, a thermometer and a cooling tube, 100 parts of linear polydimethylsiloxane (Mn = 400) having one end blocked with a butyl group and having a SiH bond at the other end, in 72 parts of allylamine A suspension in which 0.3 part of platinum oxide was suspended was charged and reacted at 105 ° C. with stirring for 16 hours. After cooling to room temperature, the reaction mixture was passed through a membrane filter (polytetrafluoroethylene [PTFE], pore size 0.45 μm) to remove insoluble matters. Thereafter, excess allylamine contained in the filtrate was removed under reduced pressure to obtain α-butyl-ω-amino-modified polydimethylsiloxane (b-1) having Mn of 500.

<Production Example 14>
[Α-Butyl-ω-amino-modified polydimethylsiloxane (Mn = 1000) (b-2)]
In a reaction vessel equipped with a stirrer, a thermometer and a cooling tube, 100 parts of linear polydimethylsiloxane (Mn = 900) having one end blocked with a butyl group and having an SiH bond at the other end, 28.8 allylamine A suspension obtained by suspending 0.12 part of platinum oxide in a part was charged and reacted at 105 ° C. with stirring for 16 hours. After cooling to room temperature, the reaction mixture was passed through a membrane filter (polytetrafluoroethylene [PTFE], pore size 0.45 μm) to remove insoluble matters. Thereafter, excess allylamine contained in the filtrate was removed under reduced pressure to obtain α-butyl-ω-amino-modified polydimethylsiloxane (b-2) having a Mn of 1000.

<Production Example 15>
[Α-Butyl-ω-amino-modified polydimethylsiloxane (Mn = 2000) (b-3)]
In a reaction vessel equipped with a stirrer, a thermometer and a cooling tube, 100 parts of linear polydimethylsiloxane (Mn = 1900) having one end blocked with a butyl group and having a SiH bond at the other end, in 14 parts of allylamine And a suspension in which 0.060 part of platinum oxide was suspended were allowed to react at 105 ° C. with stirring for 16 hours. After cooling to room temperature, the reaction mixture was passed through a membrane filter (polytetrafluoroethylene [PTFE], pore size 0.45 μm) to remove insoluble matters. Thereafter, excess allylamine contained in the filtrate was removed under reduced pressure to obtain α-butyl-ω-amino-modified polydimethylsiloxane (b-3) having a Mn of 2000.

<Production Example 16>
[Α-Butyl-ω-amino-modified polydimethylsiloxane (Mn = 5000) (b-4)]
In a reaction vessel equipped with a stirrer, a thermometer and a cooling tube, 100 parts of linear polydimethylsiloxane (Mn = 4900) having one end blocked with a butyl group and having a SiH bond at the other end, and allylamine 5.8 A suspension obtained by suspending 0.022 part of platinum oxide in the part was charged and reacted at 105 ° C. with stirring for 16 hours. After cooling to room temperature, the reaction mixture was passed through a membrane filter (polytetrafluoroethylene [PTFE], pore size 0.45 μm) to remove insoluble matters. Thereafter, excess allylamine contained in the filtrate was removed under reduced pressure to obtain α-butyl-ω-amino-modified polydimethylsiloxane (b-4) having a Mn of 5000.

<Production Example 17>
[Α-Butyl-ω-carbinol-modified polydimethylsiloxane (Mn = 5000) (b-6)]
In a reaction vessel equipped with a stirrer, a thermometer and a cooling pipe, 100 parts of linear polydimethylsiloxane (Mn = 4900) having one end blocked with a butyl group and having a SiH bond at the other end, ethylene glycol monoallyl A suspension in which 0.024 part of platinum oxide was suspended in 10 parts of ether was charged and reacted at 105 ° C. with stirring for 16 hours. After cooling to room temperature, the reaction mixture was passed through a membrane filter (polytetrafluoroethylene [PTFE], pore size 0.45 μm) to remove insoluble matters. Thereafter, excess ethylene glycol monoallyl ether contained in the filtrate was removed under reduced pressure to obtain α-butyl-ω-carbinol-modified polydimethylsiloxane (b-6) having a Mn of 5000.

<Production Example 18>
[Both ends carbinol-modified polydimethylsiloxane (Mn = 4000) (b-8)]
In a reaction vessel equipped with a stirrer, a thermometer and a cooling tube, 100 parts of linear polydimethylsiloxane (Mn = 3900) having SiH bonds at both ends and platinum oxide of 0.30 in 13 parts of ethylene glycol monoallyl ether. The suspension in which the part was suspended was charged and reacted at 105 ° C. with stirring for 16 hours. After cooling to room temperature, the reaction mixture was passed through a membrane filter (polytetrafluoroethylene [PTFE], pore size 0.45 μm) to remove insoluble matters. Thereafter, excess ethylene glycol monoallyl ether contained in the filtrate was removed under reduced pressure to obtain a carbinol-modified polydimethylsiloxane (b-8) having both ends Mn of 4000.

<Production Example 19>
[Both-terminal amine-modified polydimethylsiloxane (Mn = 4000) (b-9)]
In a reaction vessel equipped with a stirrer, a thermometer and a cooling pipe, 100 parts of linear polydimethylsiloxane (Mn = 3900) having SiH bonds at both ends and 0.030 part of platinum oxide in 7.2 parts of allylamine The suspended suspension was charged and reacted at 105 ° C. with stirring for 16 hours. After cooling to room temperature, the reaction mixture was passed through a membrane filter (polytetrafluoroethylene [PTFE], pore size 0.45 μm) to remove insoluble matters. Thereafter, excess allylamine contained in the filtrate was removed under reduced pressure to obtain a both-end amine-modified polydimethylsiloxane (b-9) having a Mn of 4000.

<Production Example 20>
“Α-Butyl-ω-amino-modified polydiethylsiloxane (Mn = 2000) (b-10)”
In a reaction vessel equipped with a stirrer, a thermometer and a condenser tube, 100 parts of linear polydiethylsiloxane (Mn = 1900) having one end blocked with a butyl group and having a SiH bond at the other end, in 14 parts allylamine And a suspension in which 0.060 part of platinum oxide was suspended were allowed to react at 105 ° C. with stirring for 16 hours. After cooling to room temperature, the reaction mixture was passed through a membrane filter (polytetrafluoroethylene [PTFE], pore size 0.45 μm) to remove insoluble matters. Thereafter, excess allylamine contained in the filtrate was removed under reduced pressure to obtain α-butyl-ω-amino-modified polydiethylsiloxane (b-10) having a Mn of 2000.

<Production Example 21>
“Α-butyl-ω-amino-modified polydibutylsiloxane (Mn = 2000) (b-11)”
In a reaction vessel equipped with a stirrer, a thermometer and a cooling tube, 100 parts of linear polydibutylsiloxane (Mn = 1900) having one end blocked with a butyl group and having a SiH bond at the other end, in 14 parts of allylamine And a suspension in which 0.060 part of platinum oxide was suspended were allowed to react at 105 ° C. with stirring for 16 hours. After cooling to room temperature, the reaction mixture was passed through a membrane filter (polytetrafluoroethylene [PTFE], pore size 0.45 μm) to remove insoluble matters. Thereafter, excess allylamine contained in the filtrate was removed under reduced pressure to obtain α-butyl-ω-amino-modified polydibutylsiloxane (b-11) having a Mn of 2000.

<Production Example 22>
“Α-Butyl-ω-amino-modified poly (dimethylsiloxane / dibutylsiloxane) random copolymer (Mn = 2000, weight ratio of dimethylsiloxane / dibutylsiloxane = 80: 20) (b-12)”
A linear poly (dimethylsiloxane / dibutylsiloxane) random copolymer (Mn = 1900) having a butyl group at one end and a SiH bond at the other end in a reaction vessel equipped with a stirrer, thermometer and cooling pipe ) 100 parts and a suspension obtained by suspending 0.060 parts of platinum oxide in 14 parts of allylamine were allowed to react at 105 ° C. for 16 hours with stirring. After cooling to room temperature, the reaction mixture was passed through a membrane filter (polytetrafluoroethylene [PTFE], pore size 0.45 μm) to remove insoluble matters. Thereafter, excess allylamine contained in the filtrate was removed under reduced pressure to obtain an α-butyl-ω-amino-modified poly (dimethylsiloxane / dibutylsiloxane) random copolymer (b-12) having a Mn of 2000. .

<Production Example 23>
“Α-Butyl-ω-Polyethylene Glycol (Mn = 1000) Modified Polydimethylsiloxane (Mn = 5000) (b-13)”
In a reaction vessel equipped with a stirrer, a thermometer and a cooling tube, 100 parts of linear polydimethylsiloxane (Mn = 4000) having one end blocked with a butyl group and having a SiH bond at the other end, polyethylene glycol monoallyl A solution prepared by dissolving 125 parts of ether (Mn = 1000) and 0.030 part of platinum oxide in 200 parts of toluene was reacted at 105 ° C. with stirring for 16 hours. After cooling to room temperature, the reaction mixture was passed through a membrane filter (polytetrafluoroethylene [PTFE], pore size 0.45 μm) to remove insoluble matters. Thereafter, excess polyethylene glycol monoallyl ether (Mn = 1000) contained in the filtrate is removed by washing with water, toluene is removed under reduced pressure, and α-butyl-ω-polyethylene glycol having a Mn of 5000 (Mn = 1000). ) Modified polydimethylsiloxane (b-13) was obtained.

<Production Example 24>
“Α-butyl-ω-poly (oxyethylene / oxypropylene) = 50/50 mol%) random copolymer (Mn = 1000) modified polydimethylsiloxane (Mn = 5000) (b-14)”
In a reaction vessel equipped with a stirrer, a thermometer and a cooling tube, 100 parts of linear polydimethylsiloxane (Mn = 4000) having one end blocked with a butyl group and having an SiH bond at the other end, poly (oxyethylene) / Oxypropylene len = 50/50 mol%) random copolymer (Mn = 1000) 125 parts, solution of 0.030 part platinum oxide dissolved in 200 parts toluene, and stirred at 105 ° C. for 16 hours Reacted. After cooling to room temperature, the reaction mixture was passed through a membrane filter (polytetrafluoroethylene [PTFE], pore size 0.45 μm) to remove insoluble matters. Then, excess poly (oxyethylene / oxypropylene = 50/50 mol%) random copolymer contained in the filtrate is removed by washing with water, and toluene is removed under reduced pressure to obtain α-butyl having a Mn of 5000. -Ω-poly (oxyethylene / oxypropylene) = 50/50 mol% random copolymer (Mn = 1000) modified polydimethylsiloxane (b-14) was obtained.

<Production Example 25>
“Α-methyl-ω-terminated carbinol-modified polydimethylsiloxane (Mn = 5000) (b-15)”
In a reaction vessel equipped with a stirrer, a thermometer and a cooling pipe, 100 parts of linear polydimethylsiloxane (Mn = 4900) having one end blocked with a methyl group and having a SiH bond at the other end, ethylene glycol monoallyl A suspension in which 0.024 part of platinum oxide was suspended in 10 parts of ether was charged and reacted at 105 ° C. with stirring for 16 hours. After cooling to room temperature, the reaction mixture was passed through a membrane filter (polytetrafluoroethylene [PTFE], pore size 0.45 μm) to remove insoluble matters. Thereafter, excess ethylene glycol monoallyl ether contained in the filtrate was removed under reduced pressure to obtain α-methyl-ω-carbinol-modified polydimethylsiloxane (b-15) having a Mn of 5000.

<Comparative Production Example 1>
[One-end acid-modified ethylene-propylene random copolymer (a′-1)]
Low molecular weight ethylene-propylene random copolymer obtained by thermal degradation method [ethylene-propylene random copolymer] What was obtained by thermally degrading a coalescence (propylene content = 20 mol%) for 16 minutes at 410 ± 0.1 ° C. under nitrogen aeration (80 mL / min). Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, maleic anhydride 10 parts and xylene 30 parts were added, mixed uniformly, then purged with nitrogen, While stirring, the temperature was raised to 200 ° C. to melt, and the mixture was reacted at the same temperature for 10 hours. Then, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to obtain a polyolefin having a carboxylic anhydride group at one end of the polymer (a′-1 ) 95 parts were obtained.
Mn of (a′-1) was 4,000, propylene content was 20 mol%, and isotacticity of the propylene portion was 10%.

<Comparative Production Example 2>
[Graft acid-modified ethylene-propylene random copolymer (a′-2)]
A low molecular weight ethylene-propylene random copolymer [ethylene-propylene random copolymer obtained by a thermal degradation method] in a stainless steel pressure-resistant reaction vessel equipped with a stirrer, a thermometer, a heating / cooling device, a nitrogen introduction tube and a decompression device. A product obtained by thermally degrading a coalescence (propylene content = 96 mol%) for 16 minutes at 410 ± 0.1 ° C. under nitrogen aeration (80 mL / min). Mn: 10,000, average number of double bonds per molecule: 2.0] 90 parts, maleic anhydride 20 parts and xylene 100 parts were charged, and after nitrogen substitution, heated to 140 ° C. under nitrogen flow And dissolved uniformly. A solution prepared by dissolving 2.0 parts of dicumyl peroxide [trade name “Park Mill D” manufactured by NOF Corporation] in 10 parts of xylene was added dropwise over 10 minutes, and stirring was continued for 3 hours under reflux of xylene. It was. Thereafter, xylene and unreacted maleic anhydride were distilled off under reduced pressure (1.5 kPa, the same shall apply hereinafter) to obtain 95 parts of polyolefin (a′-2) in which a carboxylic anhydride group was grafted to the polymer. It was.
Mn of (a′-2) was 10,000, propylene content was 96 mol%, and isotacticity of the propylene portion was 90%.

<Example 1>
In a reaction vessel equipped with a stirrer, a thermometer and a heating / cooling device, 100 parts of (a-1) obtained in Production Example 1, α-butyl-ω-amino-modified polydimethylsiloxane (Mn = 2000) (b-4) 125 parts and 0.3 parts of the antioxidant “Irganox 1010” were added, the temperature was raised to 210 ° C. with stirring, and the reaction was carried out at the same temperature for 8 hours under reduced pressure (0.013 MPa or less). As a result, a resin modifier (Y-1) containing a block polymer (X-1) having a Mn of 9000 was obtained.

Table 1 shows a list of raw material symbols and compositions used in the examples.
The polysiloxane (b-5) in Table 1 was obtained by reacting cyanonitrile with α-butyl-ω-carbinol-modified polydimethylsiloxane (Mn = 2000), then hydrogenating the nitrile group. -A carboxyethyl group is introduced.
The polysiloxane (b-7) is an α-butyl-ω-amino modified polydimethylsiloxane (Mn = 5000) (b-4) reacted with ethylene diisocyanate to introduce 2-isocyanatoethyl group. It is.

<Examples 2-27 and Comparative Examples 1-2>
Resin modifiers (Y-2) to (Y-27) and (RY-1) were carried out in the same manner as in Example 1 except that the raw materials used and the amounts used thereof were changed to those shown in Table 2 or Table 3. To (RY-2).

  Table 2 shows the physical properties and compositions of the resin modifiers (Y-1) to (Y-27) and (RY-1) to (RY-2) obtained in Examples 1-27 and Comparative Examples 1-2. Table 3 shows.

<Examples 28 to 64, Comparative Examples 3 to 9>
According to the formulation (parts) shown in Table 4 and Table 5, after blending each compounding component for 3 minutes with a Henschel mixer, it was melt-kneaded in a twin screw extruder with a vent at 100 rpm, 220 ° C. and a residence time of 5 minutes. Resin compositions (Z-1) to (Z-37) and (RZ-1) to (RZ-7) were obtained.

The contents of the thermoplastic resins described in Tables 4 and 5 are as follows.
(C-1): Homotype polypropylene [trade name “Sun Allomer PM900A”, manufactured by Sun Allomer Co., Ltd.]
(C-2): Block type polypropylene ["PM771M", manufactured by Sun Allomer Co., Ltd.]
(C-3): ethylene-propylene copolymer [trade name “Sun Allomer PB222A”, manufactured by Sun Allomer Co., Ltd.]
(C-4): Polyethylene [trade name “Novatec HJ490”, manufactured by Nippon Polyethylene Co., Ltd.]
(C-5): Impact-resistant polystyrene resin [“HIPS 433”, manufactured by PS Japan Ltd.]
(C-6): Polyvinylidene fluoride resin [“KYNAR741”, manufactured by Arkema Co., Ltd.]

  About each obtained resin composition, using an injection molding machine [“PS40E5ASE”, manufactured by Nissei Plastic Industry Co., Ltd.], a molding test piece was prepared at a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C., and the following performance test was performed. Table 4 and Table 5 show the results evaluated by the above.

<Performance test>
(1) Appearance The appearance of the surface of the test piece (80 × 80 × 2 mm) was visually observed and evaluated according to the following criteria.
○: Good without abnormality (equivalent to thermoplastic resin not containing resin modifier)
X: Surface roughness, swelling, etc. are recognized.

(2) Decreasing rate of mechanical strength (Izod impact strength and flexural modulus) The decreasing rate of mechanical strength when the resin modifier (Y) of the present invention is blended with the thermoplastic resin (C) is expressed as Izod impact. The strength and flexural modulus were evaluated. In addition, since the rate of decrease in mechanical strength varies depending on the blending amount of the resin modifier (Y), in order to clarify the rate of decrease depending on the type of the resin modifier (Y), the rate of decrease at a specific blending amount. Was evaluated using a value obtained by dividing by the blending weight% of the resin modifier (Y).
That is, evaluation was performed according to the following <Evaluation Criteria> using the reduction rate (% / weight%) of the mechanical strength obtained by the following formula.
[Decrease rate of mechanical strength (% / wt%)] = {[Mechanical strength before blending]-[Mechanical strength after blending]} / [Mechanical strength before blending] / [Resin modifier] Blending weight] x 100 (%)
For example, when homopolymer polypropylene (Izod impact strength = 2.0 J / m) is blended with 10% by weight of resin modifier (Y) and the Izod impact strength after blending is 1.8 J / m, calculation is performed. The formula is as follows.
[Decrease rate of mechanical strength (% / wt%)] = [2.0 (J / m) −1.8 (J / m)] / 2.0 (J / m) / 10 (wt%) × 100 (%) = 1.0 (% / weight%)

<Evaluation criteria>
A: [Decrease rate] ≦ 0.5
○: 0.5 <[reduction rate] ≦ 1.5
○ ^- : 1.5 <[reduction rate] ≦ 2.5
Δ: 2.5 <[reduction rate] ≦ 5.5
×: 5.5 <[decreasing rate]

(2-1) Izod impact strength (unit: J / m)
Measured according to ASTM D256 Method A (notched, 3.2 mm thickness).
(2-2) Flexural modulus (unit: MPa)
Measured according to ASTM D638.

(3) Scratch resistance A test piece having a thickness of 1.0 mm was reciprocated at 23 ° C. under a jig load of 3 kg and 100 reciprocations with a cotton canvas No. 3 mounted on a wear tester manufactured by Daiei Kagaku Seiki Seisakusho. Abrasion was performed under conditions of a speed of 30 times / min and a stroke of 100 mm. The gloss change rate before and after abrasion was determined by the following formula, and scratch resistance was evaluated according to the following <evaluation criteria>. If the rate of change in gloss is small, it indicates that the material has good scratch resistance.
Gloss change rate (%) = 100 × (Gloss before wear−Gloss after wear) / (Gloss before wear)

<Evaluation criteria>
A: 0 ≦ [gross change rate] ≦ 20
○: 20 <[gross change rate] ≦ 25
○ ^- : 25 <[gross change rate] ≦ 30
Δ: 30 <[gross change rate] ≦ 40
×: 40 <[gross change rate] ≦ 100

(4) Persistence of scratch resistance A test piece having a thickness of 1.0 mm was immersed in toluene at 25 ° C. for 10 minutes, washed with a cotton cloth, and then the humidity was kept at 50 RH% and the temperature was kept at 23 ° C. The temperature was controlled in a humidifier for 24 hours, and an abrasion test was performed in the same manner as described above, and the durability of scratch resistance was evaluated according to the following <Evaluation Criteria>.

<Evaluation criteria>
A: The increase in the gloss change rate is less than 5 compared to the gloss change rate before the wiping treatment with toluene.
○: The increase in the gloss change rate is 5 or more and less than 10 compared with the gloss change rate before the wiping treatment with toluene.
Δ: Gross change rate increment of 10 or more and less than 15 compared to the gloss change rate before wiping with toluene.
X: The gloss change rate increment is 15 or more compared with the gloss change rate before the wiping treatment with toluene.
-: In the above (3), the evaluation of the durability of the scratch resistance was not made for those of Δ and ×.

  From Table 4 and Table 5, it can be seen that the resin modifier of the present invention can impart excellent scratch resistance and durability to a thermoplastic resin without impairing its mechanical properties as compared with a comparative one.

Since the resin modifier (Y) of the present invention can impart excellent scratch resistance and durability to the molded product without impairing the mechanical strength and good appearance of the thermoplastic resin molded product, the scratch resistance is improved. Especially useful as an agent, suitable for improving the scratch resistance of automotive interior and exterior products, industrial products such as precision equipment and home appliances, and other polyolefin resin molded products used in water areas (toiletries, bathrooms, kitchens, etc.) is there.
Since the resin composition (Z) using the resin modifier (Y) of the present invention has good scratch resistance, various molding methods [injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion Housing products (for home appliances / OA equipment, game machines, office equipment, etc.) molded by molding, blow molding, foam molding and film molding (casting method, tenter method and inflation method), plastic container materials [used in clean rooms Trays (IC trays, etc.) and other containers, etc.], various cushioning materials, covering materials (wrapping film, protective film, etc.), flooring sheets, artificial grass, mats, tape base materials (for semiconductor manufacturing processes, etc.) ) And various molded products (automobile parts, etc.), and is extremely useful.
According to the present invention, a molded article having excellent mechanical properties and excellent scratch resistance can be obtained.

Claims (12)

It has a block of polyolefin (a) having a structural unit derived from propylene of 30 mol% or more and a block of polysiloxane (b) as structural units, and the molecular structure is any of the following (1) to (3) Resin modifier (Y) containing block polymer (X) which is a structure.
(1) a linear (a)-(b) diblock structure;
(2) linear (b)-(a)-(b) triblock structure;
(3) A branched structure in which 2 to 3 blocks of polysiloxane (b) are bonded to one end of a block of polyolefin (a).   The resin modifier according to claim 1, wherein the isotacticity of the propylene moiety in the polyolefin (a) is 90 to 100%.   The resin modifier according to claim 1 or 2, wherein the block polymer (X) has a number average molecular weight of 3,000 to 14,000.   The resin modifier according to any one of claims 1 to 3, wherein a weight ratio [(b) / (X)] of the block of the polysiloxane (b) to the block polymer (X) is 10 to 60% by weight.   The block polymer (X) is obtained by bonding the block of the polyolefin (a) and the block of the polysiloxane (b) through an ester bond, an amide bond, an imide bond, a urethane bond or a urea bond. The resin modifier in any one of 1-4.   The resin modifier according to any one of claims 1 to 5, wherein the block polymer (X) is a (a)-(b) diblock type polymer. The resin modifier according to any one of claims 1 to 6, wherein the block of the polysiloxane (b) is a block represented by the general formula (1) or the general formula (2).

[Wherein, R ¹ represents an alkyl group having 1 to 4 carbon atoms; R ^{2 to} R ⁵ each independently represents a hydrocarbon group having 1 to ⁶ carbon atoms; R ⁶ represents a divalent group having 1 to 20 carbon atoms; R ⁷ represents an alkylene group having 2 to 4 carbon atoms; when there are a plurality of (OR ⁷ ), they may be the same or different, and the bonding form may be a block form or a random form N is an integer of 1 to 500; a is 0 or 1; b represents an integer of 0 to 30; ]

[Wherein, Q represents a hydroxyl group or an amino group; R ⁸ and R ¹⁵ each independently represents an alkylene group having 2 to 4 carbon atoms; and a plurality of (OR ⁸ ) and (OR ¹⁵ ) may be the same. R ⁹ and R ¹⁴ each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms; and R ^{10 to} R ¹³ are each independently selected. Represents a hydrocarbon group having 1 to 6 carbon atoms; c and f each independently represents an integer of 0 to 30; d and e are each independently 0 or 1; and m is an integer of 1 to 500. . ]   The resin modifier according to any one of claims 1 to 7, which is used as an abrasion resistance improver.   A resin composition (Z) comprising the resin modifier (Y) according to any one of claims 1 to 8 and a thermoplastic resin (C).   The resin composition according to claim 9, wherein the thermoplastic resin (C) is a polyolefin resin (C1).   The weight ratio [(Y) :( C)] of the resin modifier (Y) and the thermoplastic resin (C) is 0.5: 99.5 to 50:50. Resin composition.   The molded product formed by shape | molding the resin composition (Z) in any one of Claims 9-11.