JP7202217B2 - Resin modifier - Google Patents

Description

The present invention relates to resin modifiers. More particularly, it relates to a resin modifier that imparts scratch resistance without impairing the mechanical properties of a thermoplastic resin composition.

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

JP-A-09-043408 JP-A-10-237235

However, in the method of adding silicone oil or surfactant to the polyolefin resin composition, if the amount of additive that sufficiently exerts the modification effect is added, the original mechanical strength (tensile modulus and resistance) of the original polyolefin resin molded product can be improved. Impact resistance, etc. (the same shall apply hereinafter) is impaired, and bleeding out from the molded article causes a problem of sustainability, and a solution to this problem has been desired.
SUMMARY OF THE INVENTION An object of the present invention is to provide a resin modifier that imparts excellent scratch resistance and durability of the effect to thermoplastic resins without impairing mechanical strength.

The present inventors arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention has a block of polyolefin (a) having 30 mol% or more of structural units derived from propylene and a block of polysiloxane (b) as structural units, and has a molecular structure of the following (1) to (3) ); a resin modifier (Y) containing a block polymer (X) having any of the structures of: a resin composition (Z ); a molded article obtained by molding the resin composition (Z).
(1) a linear (a)-(b) diblock structure;
(2) a 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 of the present invention and a molded article of a thermoplastic resin composition containing the resin modifier of the present invention exhibit the following effects.
(1) The resin modifier of the present invention can impart scratch resistance to a thermoplastic resin without impairing its original mechanical strength (mechanical properties), and its effect is excellent in sustainability.
(2) Molded articles of the thermoplastic resin composition of the present invention are excellent in scratch resistance and excellent in durability of the effect.

The resin modifier (Y) of the present invention has a block of polyolefin (a) having 30 mol% or more of structural units derived from propylene and a block of polysiloxane (b) as structural units, and has a molecular structure of It contains a block polymer (X) having any one of the following structures (1) to (3).
(1) a linear (a)-(b) diblock structure;
(2) a 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)>
Examples of the polyolefin (a) include polyolefins (a1-1) having carboxyl groups or carboxylic anhydride groups at both ends of the polymer, polyolefins (a1-2) having hydroxyl groups at both ends of the polymer, and amino groups at both ends of the polymer. A polyolefin (a1-3) having a terminal and a polyolefin (a1-4) having an isocyanate group at both ends of the polymer, a polyolefin (a1-5) having both a carboxyl group and a hydroxyl group at both ends of the polymer, a carboxyl group or a carboxylic 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 Examples include polyolefin (a2-4) having a group at one end of the polymer and polyolefin (a2-5) having both a carboxyl group and a hydroxyl group at one end of the polymer. Among these, (a1-1) and (a2-1) having a terminal carboxyl group or carboxylic anhydride group are preferred from the viewpoint of ease of modification and heat resistance during molding.
In the present invention, the terminal means the terminal portion where the repeating structure of the monomer units constituting the polymer is interrupted. Moreover, both ends mean both ends in the main chain of the polymer, and one end means either one end in the main chain of the polymer.

The polyolefin (a1-0) mainly composed of a polyolefin that can be modified at both ends contains one or more olefins having 2 to 30 carbon atoms (preferably 2 to 12, more preferably 2 to 10 carbon atoms). (Co)polymerization of mixtures [(Co)polymerization means polymerization or copolymerization. Same below. ], Polyolefin containing 30 mol% or more of structural units derived from propylene in polyolefin (polymerization method) and degraded polyolefin {high molecular weight [preferably number average molecular weight (hereinafter abbreviated as Mn) 10,000 ~150,000] obtained by mechanically, thermally or chemically degrading polyolefin (degradation method)}.

Among these, degraded polyolefins are preferred 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. More preferred are thermally degraded polyolefins. 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. It is easy to modify by introducing an amino group, an isocyanate group, or the like.

Mn of the polymer in the present invention can be measured using gel permeation chromatography (GPC) under the following conditions.
Apparatus (example): "HLC-8120" [manufactured by Tosoh Corporation]
Column (one example): "TSKgelGMHXL" [manufactured by Tosoh Corporation] (2 columns)
"TSKgel Multipore HXL-M" [manufactured by Tosoh Corporation] (1 piece)
Sample solution: 0.3% by weight ortho-dichlorobenzene solution Solution injection volume: 100 μl
Flow rate: 1 ml/min Measurement temperature: 135°C
Detection device: refractive index detector Reference material: standard polystyrene (TSKstandard 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 thermally degraded polyolefin is not particularly limited, but is obtained by heating a high-molecular-weight polyolefin in an inert gas (at 300 to 450° C. for 0.5 to 10 hours, e.g. JP-A-3-62804 obtained by the method described in the publication) and those thermally degraded by heating in air.

High-molecular-weight polyolefins used in the thermal degradation method include (co)polymers of one or a mixture of two or more olefins having 2 to 30 carbon atoms (preferably 2 to 12 carbon atoms, 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/10min) is preferably 0.5 to 150, more preferably 1 to 100] and having 30 mol % or more of structural units derived from propylene in the polyolefin. Here, the MFR is a numerical value representing the melt viscosity of a resin, and the larger the numerical value, the lower the melt viscosity. Measurement of MFR conforms to the method specified 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 olefins 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 α-olefins having 2 to 30 carbon atoms include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-icosene and 1- and tetracosene.
Examples of dienes having 4 to 30 carbon atoms include butadiene, isoprene, cyclopentadiene and 1,11-dodecadiene.
Among the olefins having 2 to 30 carbon atoms, ethylene, propylene, α-olefins having 4 to 12 carbon atoms, butadiene, isoprene and mixtures thereof are preferable from the viewpoint of molecular weight control, and ethylene, Propylene, α-olefins having 4 to 10 carbon atoms, butadiene and mixtures thereof, particularly preferably ethylene, propylene and mixtures thereof.

Mn of the polyolefin (a1-0) is preferably 800 to 20,000, more preferably 1,000 to 10,000, particularly It is preferably 1,200 to 6,000.

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

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

Polyolefin (a2-0) mainly composed of polyolefin that can be modified at one end can be obtained in the same manner as (a1-0), and Mn of (a2-0) is the scratch resistance of the molded article described later. It is preferably from 800 to 20,000, more preferably from 1,000 to 10,000, and particularly preferably from 1,200 to 6,000, from the viewpoint of durability and durability of its effect.

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

When using the method of obtaining low molecular weight polyolefin by thermal degradation, the average number of terminal double bonds per molecule is 0.5 to 1.4 (a2- 0) is easily obtained.

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

(a1-0) and (a2-0) are generally obtained as a mixture thereof, and the mixture may be used as it is or after purification and separation. Among these, a mixture is preferred 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. 0) having these groups at one end of (a2-1) to (a2-5), (a1-1) to (a1 -5) can be obtained in the same manner.

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 an α,β-unsaturated carboxylic acid (anhydride) (α,β-unsaturated A polyolefin (a1-1-1) having a structure modified with a saturated carboxylic acid or an anhydride thereof; polyolefin (a1-1-2) having a structure modified by oxidation or hydroformylation of (a1-0), polyolefin (a1-1-3) (a1-1-3) with a lactam or aminocarboxylic acid, A polyolefin (a1-1-4) having a submodified structure, a mixture of two or more thereof, and the like can be used.
The 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 α,β-unsaturated carboxylic acids (anhydrides) used for modification include monocarboxylic acids, dicarboxylic acids and mono- or dicarboxylic anhydrides, specifically (meth)acrylic acid [(meth) Acrylic acid means acrylic acid or methacrylic acid. Same below. ], maleic acid (anhydride), fumaric acid, itaconic acid (anhydride) and citraconic acid (anhydride).
Among these, from the viewpoint of ease of modification, preferred are dicarboxylic acids and mono- or dicarboxylic acid anhydrides, more preferred are maleic acid (anhydride) and fumaric acid, and particularly preferred is maleic acid ( anhydride).

The amount of the α,β-unsaturated carboxylic acid (anhydride) used for modification is based on the weight of the polyolefin (a1-0), the scratch resistance of the molded product, the ease of structural control of the block polymer (X) and From the viewpoint of the 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, and particularly preferably 2 to 10% by weight. %.
Modification with an α,β-unsaturated carboxylic acid (anhydride) is performed, for example, on the terminal double bond of (a1-0) by either a solution method or a melt method, and an α,β-unsaturated carboxylic acid (Anhydride) can be subjected 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 aminocarboxylic acid.
Lactams used for secondary modification include lactams having 6 to 12 carbon atoms (preferably 6 to 8, more preferably 6), and specific examples include caprolactam, enantholactam, laurolactam and undecanolactam. is mentioned.
Examples of aminocarboxylic acids include aminocarboxylic acids having 2 to 12 carbon atoms (preferably 4 to 12, more preferably 6 to 12 carbon atoms). Specifically, amino acids (glycine, alanine, valine, leucine, isoleucine, and phenylalanine, etc.), 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, preferred are caprolactam, laurolactam, glycine, leucine, ω-aminocaprylic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, more preferred are caprolactam, laurolactam, ω-Aminocaprylic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, particularly preferred are caprolactam and 12-aminododecanoic acid.

The amount of the lactam or aminocarboxylic acid used for the secondary modification is based on the weight of the material to be modified (a1-1-1), the scratch resistance of the molded article, the ease of structural control of the block polymer (X) and From the viewpoint of the 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, and particularly preferably 2 to 25% by weight. %.

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

Further, 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 structural control of the block polymer (X), and thermoplasticity. to 50 mg KOH/g, particularly preferably 5 to 30 mg KOH/g.
The acid value in the present invention is measured by titration using a KOH/methanol solution containing phenolphthalein as an indicator. Measured as oxidation number.

The polyolefin (a1-2) having hydroxyl groups at both ends of the polymer is obtained by modifying the polyolefin (a1-1) having carboxyl groups or carboxylic anhydride groups at both ends of the polymer with amines having hydroxyl groups. and mixtures of two or more of these can be used.
Amines having a hydroxyl group that can be used for modification include amines having a hydroxyl group having 2 to 10 carbon atoms, specifically 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, 4-amino butanol, 5-aminopentanol, 6-aminohexanol, 3-aminomethyl-3,5,5-trimethylcyclohexanol and the like.
Among these, amines having a hydroxyl group of 2 to 6 carbon atoms (2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol and 6-amino hexanol, etc.), more preferred are 2-aminoethanol and 4-aminobutanol, and particularly preferred is 2-aminoethanol.

The amount of the amine having a hydroxyl group used for modification is determined based on the weight of the material to be modified (a1-1), the scratch resistance of the molded article, the ease of structural control of the block polymer (X), and the resin composition ( 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, 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 structural control of the block polymer (X), and thermoplasticity. to 50 mg KOH/g, particularly preferably 5 to 30 mg KOH/g.

The polyolefin (a1-3) having amino groups at both ends of the polymer is a polyolefin having amino groups obtained by modifying the 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 of these can be used.
Diamines having 2 to 12 carbon atoms can be used as the diamine, and specific examples include ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine and decamethylenediamine.
Among these, preferred from the viewpoint of ease of modification are diamines having 2 to 8 carbon atoms (ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, etc.), and more preferred are ethylenediamine and hexamethylenediamine. Ethylenediamine is particularly preferred.

The amount of diamine used for modifying (a1-1) is determined by the scratch resistance of the molded product, the ease of structural 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 sexuality, it is preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight, particularly preferably 2 to 10% by weight, based on the weight of (a1-1). Modification of (a1-1) with diamine is preferably 0.5 to 1,000% by weight, more preferably 0.5 to 1,000% by weight, 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 removing unreacted diamine 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 structural control of the block polymer (X), and thermoplasticity. to 50 mg KOH/g, particularly preferably 5 to 30 mg KOH/g.

Examples of the polyolefin (a1-4) having isocyanate groups at both ends include polyolefins having isocyanate groups obtained by modifying (a1-2) with poly(2 to 3 or more) isocyanates, and mixtures of two or more thereof. be done.
Polyisocyanates include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding the carbon atoms in the isocyanate NCO group; the same shall apply hereinafter), aliphatic polyisocyanates having 2 to 18 carbon atoms, and alicyclic compounds having 4 to 15 carbon atoms. formula polyisocyanates, 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, bis(2-isocyanatoethyl)fumarate, bis(2-isocyanatoethyl)carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate and the like.

Alicyclic polyisocyanates include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocyanatoethyl )-4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

Aroaliphatic polyisocyanates include m- or p-xylylene diisocyanate (XDI) and α,α,α',α'-tetramethylxylylene diisocyanate (TMXDI).

Examples of modified polyisocyanate include urethane modified, urea modified, carbodiimide modified and uretdione modified.
Preferred among the polyisocyanates are TDI, MDI and HDI, more preferred is HDI.

The reaction between the polyisocyanate and (a1-2) can be carried out in the same manner as a general urethanization reaction.
The equivalent ratio (NCO:OH) between the isocyanate groups of the polyisocyanate and the hydroxyl groups of (a1-2) is preferably 1.8:1 to 3:1, more preferably 2:1.
In order to accelerate the urethanization reaction, a catalyst generally used for the urethanization reaction may be used, if necessary. As catalysts, metal catalysts {tin catalysts [dibutyltin dilaurate and stannus octoate, etc.], lead catalysts [lead 2-ethylhexanoate, lead octoate, etc.], other metal catalysts [metal naphthenate (cobalt naphthenate etc.) and phenylmercuric propionate etc.]}; amine catalyst {triethylenediamine, diazabicycloalkene [1,8-diazabicyclo[5,4,0]undecene-7 etc.], dialkylaminoalkylamine (dimethylaminoethylamine and dimethylaminooctylamine, etc.), carbonates or organic acid (formic acid, etc.) salts of heterocyclic aminoalkylamines [2-(1-aziridinyl)ethylamine and 4-(1-piperidinyl)-2-hexylamine, etc.], N -methyl or ethylmorpholine, triethylamine and diethyl- or dimethylethanolamine, etc.}; and combined systems of two or more of these.
The amount of catalyst used is preferably 3% by weight or less, preferably 0.001 to 2% by weight, based on the total weight of polyisocyanate and (a1-2).

As (a1-5), a polyolefin having a structure obtained by modifying one end of (a1-0) with an α,β-unsaturated carboxylic acid anhydride, and a polyolefin having a structure obtained by secondary modification with diolamine (a1 -5-1) can be used.
Diolamine used for secondary modification includes, for example, diethanolamine.

Mn of the polyolefin (a) is preferably 1000 to 25,000, more preferably 1 , 500 to 12,000, particularly preferably 2,000 to 7,000.

The amount of structural units derived from propylene in the polyolefin (a) is 30 to 30 from the viewpoint of the mechanical properties and scratch resistance of the resin composition (Z) (especially when polypropylene resin is used) and the durability of the effect. 100 mol %, preferably 35 to 100 mol %, more preferably 50 to 100 mol %, particularly preferably 80 to 100 mol %, most preferably 96 to 100 mol %.
Polyolefin (a) containing a predetermined amount of propylene is obtained by using (a1-0) and (a2-0) having 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 preferably 90 to 100% from the viewpoint of the dispersibility of the block polymer (X), the mechanical properties of the molded product, the scratch resistance, and the durability of the effect. preferable.

Isotacticity in the present invention can be calculated using, for example, ¹³ C-NMR (nuclear magnetic resonance spectroscopy). In general, side-chain methyl groups can be It is known that peaks are observed at different chemical shifts under the influence of the steric configuration (meso or racemo) with the methyl group. The isotacticity at can also be calculated based on the Pentad estimate.
That is, among the carbon peaks (H) derived from the side chain methyl groups in propylene obtained by ¹³ C-NMR, among the peaks, the carbon peaks derived from the methyl groups in isotactic propylene in which the pentad is formed only by the meso structure When peak (Ha) is used, isotacticity is calculated by the following formula.
Isotacticity (%) = [(H _a )/Σ(H)] x 100 (1)
In the formula, H _a is the peak height of the isotactic (pentad is formed only by the mesostructure) signal, and H is each peak height of the pentad.

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

As the polysiloxane (b1), from the viewpoint of structural control of the block polymer (X), polysiloxane monool (b1-1), polysiloxane diol (b1-2), polysiloxane monoamine (b1-3), polysiloxane Diamines (b1-4) and modified products thereof (b1-5) are preferably used.

Then, 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, preferably a methyl group and a butyl group, more preferably a butyl group from the viewpoint of scratch resistance and durability of the effect.
R ² to R ⁵ 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 an aliphatic hydrocarbon group, from the viewpoint of scratch resistance and continuation of its effect. are methyl groups and butyl groups, particularly preferably methyl groups.
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, more preferably a methylene group, an ethylene group and propylene A group, particularly preferably a propylene group.
R ⁷ represents an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group and a propylene group, more preferably an ethylene group, from the viewpoint of industrialization.
When there are a plurality of (OR ⁷ ), they may be the same or different, and their binding form may be block form or random form.
n is an integer of 1-500, a is 0 or 1, and b is an integer of 0-30.

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 article described later and the continuity of the effect. 0.8% by weight, more preferably 70 to 99.6% by weight, particularly preferably 90 to 98% by weight.
Therefore, the preferred range of n in the general formula (1) is the range in which the content of (SiR ² R ³ O) is within the preferred range.

Q in general formula (2) represents a hydroxyl group or an amino group.
R ⁸ and R ¹⁵ each independently represent an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group and a propylene group, more preferably an ethylene group from the viewpoint of industrialization.
When there are a plurality of (OR ⁸ ) and (OR ¹⁵ ), they may be the same or different, and their binding form may be block form or 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, more preferably methylene radicals, ethylene radicals and propylene radicals, particularly preferred is the propylene radical.
Each of R ¹⁰ to R ¹³ independently represents a hydrocarbon group having 1 to 6 carbon atoms, preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms, more preferably an aliphatic hydrocarbon group, from the viewpoint of scratch resistance and continuation of its effect. are methyl groups and butyl groups, particularly preferably methyl groups.
c and f each independently represent an integer of 0-30, d and e each independently represent 0 or 1, and m is an integer of 1-500.

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 article described below and the continuity of the effect. 0.8% by weight, more preferably 70 to 99.6% by weight, particularly preferably 90 to 98% by weight.
Therefore, the preferred range of n in the general formula (2) is the range in which the content of (SiR ¹⁰ R ¹¹ O) is within the preferred range.

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

R ¹⁶ in the general formula (3) represents an alkyl group having 1 to 4 carbon atoms, preferably a methyl group and a butyl group, more preferably a butyl group, from the viewpoint of scratch resistance and durability of the effect.
Each of R ¹⁷ to R ²⁰ independently represents a hydrocarbon group having 1 to 6 carbon atoms, preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms, more preferably an aliphatic hydrocarbon group, from the viewpoint of scratch resistance and continuation of its effect. are methyl groups and butyl groups, particularly preferably methyl groups.
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, more preferably a methylene group, an ethylene group and propylene A group, particularly preferably a propylene group.
R ²² represents an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group and a propylene group, more preferably an ethylene group from the viewpoint of industrialization.
When there are a plurality of (OR ²² ), they may be the same or different, and their binding form may be block form or random form.
n' is an integer of 1-500, a' is 0 or 1, and b' is an integer of 0-30.

Polysiloxane monool (b1-1) is obtained by anionic polymerization of a cyclic polysiloxane such as 1,3,5,7-tetramethylcyclotetrasiloxane using an organic alkali metal compound as an initiator, and one terminal is an alkali metal silanolate. A method of obtaining a polysiloxane (so-called living polymer) and reacting it with an alkylchlorosilane compound having a hydroxyl group to introduce a functional group at one end, or anion polymerization of a cyclic polysiloxane using an organic alkali metal compound as an initiator. , to obtain a polysiloxane (so-called living polymer) with one terminal being an alkali metal silanolate, reacting this with a dialkylchlorosilane compound to synthesize a polysiloxane containing a SiH group at one terminal, and adding a double It can be obtained by, for example, a method of reacting an alcohol having one bond with a platinum-based catalyst.
In addition, (OR ²² ) in 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 added with an alkylene oxide having 2 to 4 carbon atoms. can.

Examples of organic alkali metal compounds include alkyllithium having 1 to 4 carbon atoms (methyllithium, ethyllithium, propyllithium and butyllithium). Among these, butyllithium 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 5 to 99.0% from the viewpoint of the scratch resistance of the molded article described below and the continuity of its effect. 8% by weight, more preferably 70 to 99.6% by weight, particularly preferably 90 to 98% by weight.
Therefore, the preferred range of n' in the general formula (3) is the range in which the content of (SiR ¹⁷ R ¹⁸ O) is within the preferred range.

Examples of the polysiloxane diol (b1-2) include polysiloxanes represented by 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, preferably an ethylene group and a propylene group, more preferably an ethylene group from the viewpoint of industrialization.
When there are a plurality of (OR ²³ ) and (OR ³⁰ ), they may be the same or different, and their binding form may be block form or random form.
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, more preferably methylene radicals, ethylene radicals and propylene radicals, particularly preferred is the propylene radical.
Each of R ²⁵ to R ²⁸ independently represents a hydrocarbon group having 1 to 6 carbon atoms, preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms, more preferably an aliphatic hydrocarbon group, from the viewpoint of scratch resistance and continuation of its effect. are methyl groups and butyl groups, particularly preferably methyl groups.
c' and f' each independently represent an integer of 0 to 30, d' and e' each independently represent 0 or 1, and m' represents an integer of 1 to 500;

Polysiloxane diol (b1-2) can be obtained, for example, by reacting dimethylpolysiloxane having Si—H groups at both ends with alcohol having one double bond at the molecular end in the presence of a platinum-based catalyst, or bis(hydroxyethyl ) It can be produced by, for example, a method in which tetramethyldisiloxane and a cyclic siloxane are subjected to 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 article described below and the continuity of the effect. % by weight, more preferably 70 to 99.6% by weight, particularly preferably 90 to 98% by weight.
Therefore, the preferred range of m' in formula (4) is the range in which the content of (SiR ²⁵ R ²⁶ O) is within the preferred range.

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

R ³¹ in the general formula (5) represents an alkyl group having 1 to 4 carbon atoms, preferably a methyl group and a butyl group, more preferably a butyl group, from the viewpoint of scratch resistance and durability of the effect.
R ³² to R ³⁵ 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 an aliphatic hydrocarbon group, from the viewpoint of scratch resistance and continuation of its effect. are methyl groups and butyl groups, particularly preferably methyl groups.
R ³⁶ 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, more preferably a methylene group, an ethylene group and a propylene group. A group, particularly preferably a propylene group.
R ³⁷ represents an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group or a propylene group, more preferably an ethylene group, from the viewpoint of industrialization.
When there are a plurality of (OR ³⁷ ), they may be the same or different, and their binding form may be block form or random form.
n'' is an integer of 1-500, a'' is 0 or 1, and b'' is an integer of 0-30.

The polysiloxane monoamine (b1-3) anionically polymerizes 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, which is combined with an amino group. A method of introducing a functional group at one end by reacting with an alkylchlorosilane compound having Polymer) is obtained, reacted with a dialkylchlorosilane compound to synthesize a polysiloxane containing a single terminal SiH group, and an amine having one double bond at the molecular terminal such as allylamine is reacted with a platinum catalyst. can be obtained by

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 article described below and the continuity of the effect. % by weight, more preferably 70 to 99.6% by weight, particularly preferably 90 to 98% by weight.
Therefore, the preferred range of n'' in the general formula (5) is the range in which the content of (SiR ³² R ³³ O) is within the preferred range.
Further, a'' in the general formula (5) 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, preferably an ethylene group and a propylene group, more preferably an ethylene group from the viewpoint of industrialization.
When there are a plurality of (OR ³⁸ ) and (OR ⁴⁵ ), they may be the same or different, and their binding form may be block form or random form.
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 from the viewpoint of industrialization, more preferably methylene radicals, ethylene radicals and propylene radicals, particularly preferred is the propylene radical.
R ⁴⁰ to R ⁴³ 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 an aliphatic hydrocarbon group, from the viewpoint of scratch resistance and continuation of its effect. are methyl groups and butyl groups, particularly preferably methyl groups.
c″ and f″ each independently represent an integer of 0 to 30, d″ and e″ each independently represent 0 or 1, and m″ represents an integer of 1 to 500.

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

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 article described below and the continuity of the effect. % by weight, more preferably 70 to 99.6% by weight, particularly preferably 90 to 98% by weight.
Therefore, the preferred range of m'' in the general formula (6) is the range in which the content of (SiR ⁴⁰ R ⁴¹ O) is within the preferred range.

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

Polysiloxane esteramide (b2-1) is composed of polyamide [12 nylon, 6 nylon, etc.] having carboxyl groups at both ends and polysiloxane monool (b1-1).
Examples of polyamides having carboxyl groups at both ends include ring-opening polymers of lactams, polycondensates of aminocarboxylic acids, polyamides of diamines and dicarboxylic acids having 2 to 12 linear hydrocarbon carbon atoms, and the like.
Among 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, ring-opening polymers of caprolactam and 12-aminododecanoic acid are preferred. They are polycondensates and polyamides of adipic acid and hexamethylenediamine, more preferably ring-opening polymers of caprolactam.

The polysiloxane amideimide (b2-2) is composed of a polyamideimide having at least one imide ring and a polysiloxane monool (b1-1).
As the polyamideimide, a lactam and a polymer composed of a trivalent or tetravalent aromatic polycarboxylic acid capable of forming at least one imide ring, an aminocarboxylic acid and a trivalent or tetravalent aromatic poly carboxylic acid, polymers comprising polyamide and trivalent or tetravalent aromatic polycarboxylic acid, and mixtures thereof.

Examples of polysiloxane ester (b2-3) include those composed of polyester and polysiloxane monool (b1-1) or polysiloxane diol (b1-2).
Polyesters include polyesters of dicarboxylic acids and diols.

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

The polysiloxane urethane (b2-9) includes a diisocyanate among the above polyisocyanates, a polysiloxane monool (b1-1) or a polysiloxane monoamine (b1-3) and, if necessary, a chain extender [having 2 to 12 carbon atoms Linear or branched aliphatic diols (ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol, etc.) and the above diamines] What is done is mentioned.

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), from the viewpoint of the scratch resistance of the molded article. ~99% by weight.

Among the polysiloxane (b1) and the polysiloxane-containing polymer (b2), the polysiloxane (b1) is preferable from the viewpoint of the scratch resistance of the molded article described below and the continuity of the effect.

Mn of the polysiloxane (b) is preferably 500 to 10,000, more preferably 1,000 to 6,000, from the viewpoint of the scratch resistance of the molded article described later and the reactivity with the polyolefin (a). , particularly preferably 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 structural units derived from propylene and a block of polysiloxane (b) as structural units, and has the following molecular structure ( 1) to any one of the structures of (3).
(1) a linear (a)-(b) diblock structure;
(2) a 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), the (a)-(b) diblock type structure is preferable from the viewpoint of the scratch resistance of the molded article and the dispersibility of the block polymer (X) in the resin composition (Z) described later. and (b)-(a)-(b) triblock structures, particularly preferred are (a)-(b) diblock structures.

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

A block polymer having a linear (a)-(b) diblock structure is, 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 by reacting with polysiloxane monoamine (b1-3) at a molar ratio of 1:1, or by reacting polyolefin (a1-1) having carboxyl groups or carboxylic anhydride groups at both ends of the polymer with polysiloxane monoamine Reaction with all (b1-1) or polysiloxane monoamine (b1-3) at a molar ratio of 1:1, or polyolefin (a2-1) having a carboxyl group or carboxylic anhydride group at one end of the polymer and polysiloxane diol (b1-2) or polysiloxane diamine (b1-4) at a molar ratio of 1:1.

A block polymer having a linear (b)-(a)-(b) triblock structure is, for example, a polyolefin (a1-1) having a carboxyl group or a carboxylic 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 anhydride group at one end of the polymer and a poly It can be obtained by reacting with siloxane monool (b1-1) at a molar ratio of 1:2.
In the above, an example of the combination of polyolefin (a) and polysiloxane (b) when obtaining the block polymer (X) having each structure is shown, but as described above, (a) and (b) are various Therefore, any combination can be employed as long as the functional group of (a) and the functional group of (b) can react with each other.

The block polymer (X) preferably has a structure in which a polyolefin (a) block and a polysiloxane (b) block 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, an ester bond and an imide bond are more preferable, and an imide bond is particularly preferable.

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

The weight ratio of the block of the polysiloxane (b) to the block polymer (X) [(b)/(X)] is determined from the viewpoint of 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 (a) and the block (b) are bonded via an ester bond, an amide bond, or an imide bond, for example, (a) and ( b) is put into a reaction vessel, and under stirring, at a reaction temperature of 100 to 250° C. and a pressure of 0.003 to 0.1 MPa, water produced by an esterification reaction, amidation reaction or imidization reaction (hereinafter abbreviated as produced water ) is removed from the reaction system, it can be produced by a method of reacting for 1 to 50 hours.

For the esterification reaction, it is preferred to use 0.05 to 0.5% by weight of catalyst based on the weight of (a) and (b) in order to promote the reaction. Catalysts include inorganic acids (sulfuric acid, hydrochloric acid, etc.), organic sulfonic acids (methanesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, naphthalenesulfonic acid, etc.), antimony catalysts (antimony trioxide, etc.), tin catalysts (monobutyltin oxide and dibutyl tin oxide, etc.), titanium catalysts (tetrabutyl titanate, bistriethanolamine titanate, potassium oxalate titanate, etc.), zirconium catalysts (tetrabutyl zirconate, zirconyl acetate, etc.), zinc catalysts (zinc acetate, etc.), etc. mentioned. When a catalyst is used, the catalyst can be neutralized, if necessary, and treated with an adsorbent to remove and purify the catalyst after the completion of the esterification reaction.
Methods for removing the generated water out of the reaction system include the following methods.
[1] A method of using an organic solvent that is incompatible with water (e.g., toluene, xylene, cyclohexane, etc.) and azeotroping the organic solvent and generated water under reflux to remove only the generated water from the reaction system. .
[2] A method of blowing a carrier gas (for example, air, nitrogen, helium, argon, carbon dioxide, etc.) into the reaction system to remove the generated water out of the reaction system together with the carrier gas.
[3] A method of reducing the pressure in the reaction system to remove the generated water out of the reaction system.

When (X) has a structure in which a block of (a) and a block of (b) are bonded via a urethane bond or a urea bond, for example, (b) is put into a reaction vessel and stirred. It can be produced by heating to 30 to 100° C., then adding (a), and reacting at the same temperature for 1 to 20 hours.
To promote the reaction, it is preferred to use 0.001 to 5% by weight of catalyst based on the weight of (a) and (b). Examples of catalysts include organometallic compounds (dibutyltin dilaurate, dioctyltin dilaurate, lead octanoate, bismuth octanoate, etc.), tertiary amines {triethylenediamine, trialkylamines having an alkyl group having 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 block polymer (X) described above.
The resin modifier (Y) can be suitably used as a resin modifier for the thermoplastic resin (C) described below.
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), and Additives (D) such as compatibilizers (D7), fillers (D8) and transesterification inhibitors (D9) may be included.

<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 to 50:50, more preferably 1:99 to 20:80, particularly preferably 2:98 to 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 vinyl group-containing aromatic hydrocarbon alone and a copolymer containing a vinyl group-containing aromatic hydrocarbon and at least one selected from the group consisting of butadiene as structural units; polystyrene], etc.; and mixtures of two or more of these.
Among these, PVDF of (C1) and (C2) is preferable, (C1) is more preferable, and particularly preferable from the viewpoint of the mechanical properties and scratch resistance of the molded article described later and the durability of the effect. Among (C1) polypropylenes (homotype polypropylene, block type polypropylene and ethylene/propylene copolymer), most preferred is homotype polypropylene.

The resin composition (Z) may optionally contain a colorant (D1), a release agent (D2), an antioxidant (D3), a flame retardant (D4), and an ultraviolet absorber as long as the effects of the present invention are not impaired. Additives (D) such as (D5), antibacterial agents (D6), compatibilizers (D7), fillers (D8) and transesterification inhibitors (D9) can be included. Each additive may be used alone or in combination of two or more.

Examples of the coloring agent (D1) include inorganic pigments [white pigments, cobalt compounds, iron compounds and sulfides, etc.], 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.] and the like.

Release agents (D2) include lower alcohol esters of higher fatty acids (having 1 to 4 carbon atoms) (butyl stearate, etc.), and polyvalent (divalent to tetravalent or higher) fatty acids (having 2 to 18 carbon atoms). Examples thereof include alcohol esters (hardened castor oil, etc.), glycol (C2-8) esters of fatty acids (2-18 carbon atoms) (ethylene glycol monostearate, etc.), and liquid paraffin.

Examples of antioxidants (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 phenols [1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, etc.], sulfur compounds (dilauryl 3 , 3'-thiodipropionate, etc.), phosphorus compounds (triphenylphosphite, etc.), amine compounds (octylated diphenylamine, etc.), and the like.

Flame retardants (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 UV absorbers (D5) include benzotriazole [2-(2'-hydroxy-5'-methylphenyl)benzotriazole, etc.], benzophenone (2-hydroxy-4-methoxybenzophenone, etc.), salicylate (phenylsalicylate etc.) and acrylates (2-ethylhexyl-2-cyano-3,3-diphenyl acrylate etc.).

Antibacterial agents (D6) include benzoic acid, sorbic acid, halogenated phenols, organic iodine, nitriles (2,4,5,6-tetrachloroisophthalonitrile, etc.), thiocyano (methylenebisthianocyanate), N-halo Alkylthioimides, copper agents (8-oxyquinoline copper, etc.), benzimidazoles, benzothiazoles, trihaloallyls, triazoles, organic nitrogen-sulfur compounds (Suraof 39, etc.), quaternary ammonium compounds and pyridine compounds.

Examples of the compatibilizer (D7) include modified vinyl polymers having at least one functional group (polar group) selected from the group consisting of carboxyl groups, epoxy groups, amino groups, hydroxyl groups and polyoxyalkylene groups; , a polymer described in JP-A-3-258850, and a block polymer having a modified vinyl polymer having a sulfonic acid group and a polyolefin portion and an aromatic vinyl polymer portion described in JP-A-6-345927. A coalescence etc. are mentioned.

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

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 effects of each additive and the mechanical properties of the molded product. , More preferably 0.01 to 35% by weight; From the same viewpoint, the content of each (D) is preferably 0.1 to 3% by weight, more preferably 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) is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight; (D8) is preferably 0.5-10% by weight, more preferably 1-5% by weight; (D9) is 0.01-3% by weight, more preferably 0.05-1% 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 melt-mixing, in general, pelletized or powdered components are mixed in an appropriate mixer (Henschel mixer, etc.), and then melt-mixed in an extruder to pelletize. can.
There are no particular restrictions on the order of addition of each component during melt mixing, but for example,
[1] A method of melt-mixing (C) and (Y) and then, if necessary, adding (D) all at once and melt-mixing;
[2] When melt-mixing (C) and (Y), part of (C) is melt-mixed in advance to prepare a high-concentration composition (masterbatch resin composition) of (Y), and then the remaining A method of melt mixing (C) and optionally (D) (masterbatch 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 in (C) efficiently.

<Molded product>
The molded article of the present invention is obtained by molding the resin composition (Z) of the present invention. Examples of molding methods include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding and film molding (cast method, tenter method, inflation method, etc.). It can be molded by any method including means such as molding, multi-layer molding or foam molding.

INDUSTRIAL APPLICABILITY The molded article of the present invention has excellent mechanical properties, scratch resistance and durability thereof, and a molded article 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 the scratch resistance of other polyolefin-based resin moldings used for interior and exterior parts of automobiles, industrial products such as precision equipment and home electric appliances, and plumbing (toiletries, bathrooms, kitchens, etc.).

Examples of the present invention will be described below, but the present invention is not limited to these. In the following, parts indicate parts by weight. In the following, Examples 8, 11, 12, 15, 35, 38, 39, and 42 are referred to as Reference Examples 1 to 8, respectively.

<Production Example 1>
[Single-end acid-modified ethylene-propylene random copolymer (a-1)]
A low-molecular-weight ethylene-propylene random copolymer obtained by a thermal degradation method [ethylene-propylene random copolymer Obtained by thermal degradation of the coalescence (propylene content=32 mol %) at 410±0.1° C. for 16 minutes under nitrogen. Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, 10 parts of maleic anhydride and 30 parts of xylene were charged, mixed uniformly, then replaced with nitrogen, and sealed. The mixture was heated to 200° C. with stirring to melt, and 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 (a-1) having a carboxylic anhydride group at one end of the polymer. 95 parts were obtained.
The Mn of (a-1) was 4,000, the propylene content was 32 mol %, and the isotacticity of the propylene portion was 40%.

<Production Example 2>
[Single-end acid-modified ethylene-propylene random copolymer (a-2)]
A low-molecular-weight ethylene-propylene random copolymer obtained by a thermal degradation method [ethylene-propylene random copolymer Obtained by thermally degrading a polymer (propylene content=52 mol %) at 410±0.1° C. for 16 minutes under a stream of nitrogen. Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, 10 parts of maleic anhydride and 30 parts of xylene were charged, mixed uniformly, then replaced with nitrogen, and sealed. The mixture was heated to 200° C. with stirring to melt, and 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 (a-2) having a carboxylic anhydride group at one end of the polymer. 95 parts were obtained.
The Mn of (a-2) was 4,000, the propylene content was 52 mol %, and the isotacticity of the propylene portion was 60%.

<Production Example 3>
[Single-end acid-modified 1-butene-propylene random copolymer (a-3)]
A low molecular weight 1-butene-propylene random copolymer [1-butene- Obtained by thermally degrading a propylene random copolymer (propylene content=82 mol %) at 410±0.1° C. for 16 minutes under a nitrogen stream. Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, 10 parts of maleic anhydride and 30 parts of xylene were charged, mixed uniformly, then replaced with nitrogen, and sealed. The mixture was heated to 200° C. with stirring to melt, and 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 (a-3) having a carboxylic anhydride group at one end of the polymer. 95 parts were obtained.
The Mn of (a-3) was 4,000, the propylene content was 82 mol %, and the isotacticity of the propylene portion was 80%.

<Production Example 4>
[Single-end acid-modified ethylene-propylene random copolymer (a-4)]
A low-molecular-weight ethylene-propylene random copolymer obtained by a thermal degradation method [ethylene-propylene random copolymer Obtained by thermal degradation of the 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, 10 parts of maleic anhydride and 30 parts of xylene were charged, mixed uniformly, then replaced with nitrogen, and sealed. The mixture was heated to 200° C. with stirring to melt, and 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 (a-4) having a carboxylic anhydride group at one end of the polymer. 95 parts were obtained.
(a-4) had an Mn of 4,000, a propylene content of 96 mol %, and an isotacticity of the propylene portion of 90%.

<Production Example 5>
[Single-end acid-modified homotype polypropylene (a-5)]
A low-molecular-weight homotype polypropylene obtained by a thermal degradation method [homotype polypropylene at 410 ± 0.1 ° C , obtained by thermal degradation for 16 minutes under nitrogen bubbling. Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, 10 parts of maleic anhydride and 30 parts of xylene were charged, mixed uniformly, then replaced with nitrogen, and sealed. The mixture was heated to 200° C. with stirring to melt, and 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 (a-5) having a carboxylic anhydride group at one end of the polymer. 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 obtained by a thermal degradation method [ethylene-propylene random copolymer Obtained by thermal degradation of the 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, 20 parts of maleic anhydride and 30 parts of xylene were charged, mixed uniformly, then replaced with nitrogen, and sealed. The mixture was heated to 200° C. with stirring to melt, and 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 (a-6) having carboxylic anhydride groups at both ends of the polymer. 95 parts were obtained.
The Mn of (a-6) was 4,000, the propylene content was 96 mol%, and the isotacticity of the propylene portion was 90%.

<Production Example 7>
[Single-end acid-modified ethylene-propylene random copolymer (a-7)]
A low-molecular-weight ethylene-propylene random copolymer obtained by a thermal degradation method [ethylene-propylene random copolymer Obtained by thermal degradation of the 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, 10 parts of maleic anhydride and 30 parts of xylene are charged, mixed uniformly, then replaced with nitrogen, and sealed. The mixture was heated to 200° C. with stirring to melt, and 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 (a-7) having a carboxylic anhydride group at one end of the polymer. 95 parts were obtained.
The 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>
[Single-end acid-modified ethylene-propylene random copolymer (a-8)]
A low-molecular-weight ethylene-propylene random copolymer obtained by a thermal degradation method [ethylene-propylene random copolymer Obtained by thermal degradation of the 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, 10 parts of maleic anhydride and 30 parts of xylene were added, mixed uniformly, then replaced with nitrogen, and sealed. The mixture was heated to 200° C. with stirring to melt, and 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 (a-8) having a carboxylic anhydride group at one end of the polymer. 95 parts were obtained.
The Mn of (a-8) was 2,500, the propylene content was 96 mol%, and the isotacticity of the propylene portion was 90%.

<Production Example 9>
[Single-end acid-modified ethylene-propylene random copolymer (a-9)]
A low-molecular-weight ethylene-propylene random copolymer obtained by a thermal degradation method [ethylene-propylene random copolymer Obtained by thermal degradation of the 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, 10 parts of maleic anhydride and 30 parts of xylene are charged, mixed uniformly, then replaced with nitrogen, and sealed. The mixture was heated to 200° C. with stirring to melt, and 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 (a-9) having a carboxylic anhydride group at one end of the polymer. 95 parts were obtained.
The 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)]
A low-molecular-weight ethylene-propylene random copolymer obtained by a thermal degradation method [ethylene-propylene random copolymer Obtained by thermal degradation of the 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, 20 parts of maleic anhydride and 30 parts of xylene are charged, mixed uniformly, then replaced with nitrogen, and sealed. The mixture was heated to 200° C. with stirring to melt, and 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 (a-10) having carboxylic anhydride groups at both ends of the polymer. 95 parts were obtained.
The 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)]
A low-molecular-weight ethylene-propylene random copolymer obtained by a thermal degradation method [ethylene-propylene random copolymer Obtained by thermal degradation of the 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, 20 parts of maleic anhydride and 30 parts of xylene are charged, mixed uniformly, replaced with nitrogen, and stirred while sealed. The temperature was raised to 200° C. while melting, 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 (a-11) having carboxylic anhydride groups at both ends of the polymer. 95 parts were obtained.
The 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>
[Single-terminal amino-modified ethylene-propylene random copolymer (a-12)]
A low-molecular-weight ethylene-propylene random copolymer obtained by a thermal degradation method [ethylene-propylene random copolymer Obtained by thermal degradation of the 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, 10 parts of maleic anhydride and 30 parts of xylene were charged, mixed uniformly, then replaced with nitrogen, and sealed. The mixture was heated to 200° C. with stirring to melt, and 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 a polyolefin having a carboxylic anhydride group at one end of the polymer. .
Next, 90 parts of the above-mentioned polyolefin having a carboxylic anhydride group at one end of the polymer and 10 parts of bis(2-aminoethyl) ether were charged into the same pressure-resistant reaction vessel as in Production Example 1, and under a nitrogen gas atmosphere, The temperature was raised to 200° C. while 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 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 a linear polydimethylsiloxane (Mn = 400) having one end blocked with a butyl group and the other end having a SiH bond, and 72 parts of allylamine A suspension of 0.3 parts of platinum oxide was added to the solution, and the mixture was reacted 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 matter. 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 a linear polydimethylsiloxane (Mn = 900) having one end blocked with a butyl group and the other end having a SiH bond, and 28.8 parts of allylamine. A suspension in which 0.12 part of platinum oxide was suspended in 1 part was charged, and the reaction was allowed to proceed at 105° C. for 16 hours while 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 matter. Thereafter, excess allylamine contained in the filtrate was removed under reduced pressure to obtain α-butyl-ω-amino-modified polydimethylsiloxane (b-2) having Mn of 1,000.

<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 a linear polydimethylsiloxane (Mn = 1900) having one end blocked with a butyl group and the other end having a SiH bond, and 14 parts of allylamine A suspension of 0.060 part of platinum oxide was added to the solution, and the mixture was reacted 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 insolubles. Thereafter, excess allylamine contained in the filtrate was removed under reduced pressure to obtain α-butyl-ω-amino-modified polydimethylsiloxane (b-3) having 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 a linear polydimethylsiloxane (Mn = 4900) having one end blocked with a butyl group and the other end having a SiH bond, and 5.8 parts of allylamine. A suspension in which 0.022 part of platinum oxide was suspended in 1 part was charged, and the mixture was reacted with stirring at 105° C. 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 matter. Thereafter, excess allylamine contained in the filtrate was removed under reduced pressure to obtain α-butyl-ω-amino-modified polydimethylsiloxane (b-4) having Mn of 5,000.

<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 tube, 100 parts of a linear polydimethylsiloxane (Mn = 4900) having one end blocked with a butyl group and the other end having a SiH bond, and ethylene glycol monoallyl A suspension of 0.024 parts of platinum oxide suspended in 10 parts of ether was charged, and the reaction was allowed to proceed at 105° C. for 16 hours while stirring. After cooling to room temperature, the reaction mixture was passed through a membrane filter (polytetrafluoroethylene [PTFE], pore size 0.45 μm) to remove insolubles. 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) with Mn of 5,000.

<Production Example 18>
[Carbinol-modified polydimethylsiloxane at both ends (Mn = 4000) (b-8)]
100 parts of linear polydimethylsiloxane (Mn=3900) having SiH bonds at both ends and 0.30 of platinum oxide in 13 parts of ethylene glycol monoallyl ether were placed in a reaction vessel equipped with a stirrer, thermometer and cooling tube. A suspension of the two parts was charged and reacted with stirring at 105° C. 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 insolubles. Thereafter, excess ethylene glycol monoallyl ether contained in the filtrate was removed under reduced pressure to obtain a polydimethylsiloxane (b-8) modified with carbinol at both ends and having an Mn of 4,000.

<Production Example 19>
[Amine-modified polydimethylsiloxane at both ends (Mn = 4000) (b-9)]
In a reactor equipped with a stirrer, a thermometer and a cooling tube, 100 parts of linear polydimethylsiloxane (Mn = 3900) having SiH bonds at both ends and 0.030 parts of platinum oxide in 7.2 parts of allylamine were added. The suspended suspension was charged and reacted with stirring at 105° C. 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 insolubles. Thereafter, excess allylamine contained in the filtrate was removed under reduced pressure to obtain polydimethylsiloxane (b-9) modified with amines at both ends and having an Mn of 4,000.

<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 cooling tube, 100 parts of a linear polydiethylsiloxane (Mn = 1900) having one end blocked with a butyl group and the other end having a SiH bond, and 14 parts of allylamine A suspension of 0.060 part of platinum oxide was added to the solution, and the mixture was reacted 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 insolubles. Thereafter, excess allylamine contained in the filtrate was removed under reduced pressure to obtain α-butyl-ω-amino-modified polydiethylsiloxane (b-10) with 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 a linear polydibutylsiloxane (Mn = 1900) having one end blocked with a butyl group and the other end having a SiH bond, and 14 parts of allylamine A suspension of 0.060 part of platinum oxide was added to the solution, and the mixture was reacted 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 matter. Thereafter, excess allylamine contained in the filtrate was removed under reduced pressure to obtain α-butyl-ω-amino-modified polydibutylsiloxane (b-11) with Mn of 2000.

<Production Example 22>
"α-butyl-ω-amino-modified poly(dimethylsiloxane/dibutylsiloxane) random copolymer (Mn = 2000, dimethylsiloxane/dibutylsiloxane weight ratio = 80:20) (b-12)"
A linear poly(dimethylsiloxane/dibutylsiloxane) random copolymer (Mn = 1900 ) and a suspension of 0.060 part of platinum oxide suspended in 14 parts of allylamine, and reacted with stirring at 105° C. 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 insolubles. 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 an 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 a linear polydimethylsiloxane (Mn = 4000) having one end blocked with a butyl group and having a SiH bond at the other end, polyethylene glycol monoallyl 125 parts of ether (Mn=1000) and a solution prepared by dissolving 0.030 parts of platinum oxide in 200 parts of toluene were charged and reacted with stirring at 105° C. 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 matter. Thereafter, excess polyethylene glycol monoallyl ether (Mn = 1000) contained in the filtrate was removed by washing with water, toluene was removed under reduced pressure, and α-butyl-ω-polyethylene glycol (Mn = 1000) with Mn of 5000 was removed. ) A modified polydimethylsiloxane (b-13) was obtained.

<Production Example 24>
"α-butyl-ω-poly(oxyethylene/oxypropyleneene = 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 a linear polydimethylsiloxane (Mn = 4000) having one end blocked with a butyl group and the other end having a SiH bond, and poly(oxyethylene /oxypropyleneene = 50/50 mol%) 125 parts of a random copolymer (Mn = 1000) and a solution of 0.030 parts of platinum oxide dissolved in 200 parts of toluene were charged 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 insolubles. Thereafter, excess poly(oxyethylene/oxypropyleneene = 50/50 mol%) random copolymer contained in the filtrate was removed by washing with water, toluene was removed under reduced pressure, and α-butyl having Mn of 5000 was removed. A -ω-poly(oxyethylene/oxypropyleneene=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 tube, 100 parts of a linear polydimethylsiloxane (Mn = 4900) having one end blocked with a methyl group and the other end having a SiH bond, and ethylene glycol monoallyl A suspension of 0.024 parts of platinum oxide suspended in 10 parts of ether was charged, and the reaction was allowed to proceed at 105° C. for 16 hours while 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 matter. 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) with Mn of 5,000.

<Comparative Production Example 1>
[Single-end acid-modified ethylene-propylene random copolymer (a'-1)]
A low-molecular-weight ethylene-propylene random copolymer obtained by a thermal degradation method [ethylene-propylene random copolymer Obtained by thermal degradation of the coalescence (propylene content=20 mol %) at 410±0.1° C. under nitrogen gas (80 mL/min) for 16 minutes. Mn: 3,900, average number of double bonds per molecule: 1.0] 90 parts, 10 parts of maleic anhydride and 30 parts of xylene were charged, mixed uniformly, then replaced with nitrogen, and sealed. The mixture was heated to 200° C. with stirring to melt, and 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 (a'-1 ) to give 95 parts.
The Mn of (a′-1) was 4,000, the propylene content was 20 mol %, and the 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 obtained by a thermal degradation method [ethylene-propylene random copolymer Obtained by thermal degradation of the coalescence (propylene content=96 mol %) at 410±0.1° C. under nitrogen flow (80 mL/min) for 16 minutes. Mn: 10,000, average number of double bonds per molecule: 2.0] 90 parts, 20 parts of maleic anhydride and 100 parts of xylene are charged, and after purging with nitrogen, the temperature is raised to 140°C under nitrogen ventilation. and uniformly dissolved. A solution prepared by dissolving 2.0 parts of dicumyl peroxide [trade name “Percumyl D”, manufactured by NOF Corporation] in 10 parts of xylene was added dropwise thereto over 10 minutes, and then stirring was continued for 3 hours while refluxing xylene. rice field. Thereafter, xylene and unreacted maleic anhydride are distilled off under reduced pressure (1.5 kPa, hereinafter the same) to obtain 95 parts of polyolefin (a'-2) in which carboxylic anhydride groups are grafted onto the polymer. rice field.
(a′-2) had an Mn of 10,000, a propylene content of 96 mol %, and an isotacticity of the propylene portion of 90%.

<Example 1>
100 parts of (a-1) obtained in Production Example 1 and α-butyl-ω-amino-modified polydimethylsiloxane (Mn= 2000) (b-4) 125 parts and antioxidant "Irganox 1010" 0.3 parts were added, the temperature was raised to 210°C while stirring, and the reaction was carried out at the same temperature under reduced pressure (0.013 MPa or less) for 8 hours. Then, a resin modifier (Y-1) containing a block polymer (X-1) having an Mn of 9,000 was obtained.

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

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

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

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

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

For each resin composition obtained, 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. Tables 4 and 5 show the results of evaluation by .

<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 containing no resin modifier)
x: Rough surface, blisters, etc. are observed.

(2) Decrease rate of mechanical strength (Izod impact strength and flexural modulus) The strength and flexural modulus were evaluated. In addition, since the rate of decrease in mechanical strength varies depending on the amount of resin modifier (Y) blended, in order to clarify the rate of decrease depending on the type of resin modifier (Y), the rate of decrease at a specific amount was divided by the blended weight % of the resin modifier (Y) at that time.
That is, evaluation was made according to the following <Evaluation Criteria> using the rate of decrease in mechanical strength (%/% by weight) obtained by the following formula.
[Degradation rate of mechanical strength (% / wt%)] = {[mechanical strength before blending] - [mechanical strength after blending]} / [mechanical strength before blending] / [resin modifier Compounding weight] × 100 (%)
For example, when homotype polypropylene (Izod impact strength = 2.0 J / m) is blended with 10% by weight of the resin modifier (Y), and the Izod impact strength after blending is 1.8 J / m, the calculation The formula is as follows.
[Mechanical strength reduction rate (%/wt%)] = [2.0 (J/m) - 1.8 (J/m)]/2.0 (J/m)/10 (wt%) x 100 (%) = 1.0 (%/% by weight)

<Evaluation Criteria>
◎: [decrease rate] ≤ 0.5
○: 0.5 < [decrease rate] ≤ 1.5
○ ^- : 1.5 < [decrease rate] ≤ 2.5
△: 2.5 < [decrease rate] ≤ 5.5
×: 5.5 < [decrease rate]

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

(3) Scratch resistance A test piece with a thickness of 1.0 mm was subjected to a cotton canvas No. 3 attached to an abrasion tester manufactured by Daiei Kagaku Seiki Seisakusho at 23 ° C. under a jig load of 3 kg. Abrasion was performed at a speed of 30 times/min and a stroke of 100 mm. The gloss change rate before and after abrasion was obtained from the following formula, and the scratch resistance was evaluated according to the following <evaluation criteria>. A low gloss change rate indicates that the material has good scratch resistance.
Gloss change rate (%) = 100 x (gloss before abrasion - gloss after abrasion) / (gloss before abrasion)

<Evaluation Criteria>
◎: 0 ≤ [gloss change rate] ≤ 20
○: 20 < [gloss change rate] ≤ 25
○ ^- : 25 < [gloss change rate] ≤ 30
△: 30 < [gloss change rate] ≤ 40
×: 40 < [gloss change rate] ≤ 100

(4) Sustainability of scratch resistance A test piece with a thickness of 1.0 mm was immersed in toluene at 25°C for 10 minutes and washed with a cotton cloth. After controlling the temperature in a humidifier for 24 hours, the wear test was performed in the same manner as above, and the durability of the scratch resistance was evaluated according to the following <evaluation criteria>.

<Evaluation Criteria>
A: The increment of the gloss change rate is less than 5 compared to the gloss change rate before the wiping treatment with toluene.
◯: The gloss change rate increased by 5 or more and less than 10 compared to the gloss change rate before the wiping treatment with toluene.
Δ: Increase in gloss change rate of 10 or more and less than 15 compared to the gloss change rate before wiping treatment with toluene.
x: Increase in gloss change rate of 15 or more compared to the gloss change rate before wiping treatment with toluene.
-: In the above (3), Δ and × were not evaluated for durability of scratch resistance.

From Tables 4 and 5, it can be seen that the resin modifiers of the present invention can impart excellent scratch resistance and durability to thermoplastic resins without impairing their mechanical properties, compared to the comparative ones.

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, so that the scratch resistance can be improved. It is particularly useful as an agent, and is suitable for improving the scratch resistance of other polyolefin-based resin molded products used for interior and exterior parts of automobiles, industrial products such as precision equipment and home appliances, and water-related areas (toiletries, bathrooms, kitchens, etc.). be.
Since the resin composition (Z) using the resin modifier (Y) of the present invention has good scratch resistance, it can be used by various molding methods [injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding]. Molding, blow molding, foam molding and film molding (cast method, tenter method and inflation method), etc.] housing products (for home appliances, OA equipment, game equipment and office equipment, etc.), plastic container materials [used in clean rooms trays (IC trays, etc.) and other containers, etc.], various cushioning materials, covering materials (packaging films and protective films, etc.), flooring sheets, artificial turf, mats, tape substrates (for semiconductor manufacturing processes, etc.) ) and various molded products (automobile parts, etc.).
INDUSTRIAL APPLICABILITY According to the present invention, molded articles having excellent mechanical properties and excellent scratch resistance can be obtained.

Claims (9)

A block of polyolefin (a) having 30 mol% or more of structural units derived from propylene and a block of polysiloxane (b) as structural units, and having a molecular structure of any of the following (1) to (3): The polyolefin (a) has a number average molecular weight (Mn) of 2,000 to 7,000, and the polysiloxane (b) has a number average molecular weight (Mn) of is 1,000 to 6,000, the number average molecular weight (Mn) of the block polymer is 3,000 to 14,000, and the block polymer (X) is a block of the polyolefin (a) and the A resin modifier (Y) for a polyolefin resin (C1), in which blocks of polysiloxane (b) are bonded via an ester bond, an amide bond, an imide bond, a urethane bond or a urea bond .
(1) a linear (a)-(b) diblock structure;
(2) a 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). 2. The resin modifier according to claim 1, wherein the isotacticity of the propylene portion in said polyolefin (a) is 90-100%. 3. The resin modifier according to claim 1 , wherein the weight ratio [(b)/(X)] of the block of the polysiloxane (b) to the block polymer (X) is 10 to 60% by weight. The resin modifier according to any one of claims 1 to 3, wherein the block polymer (X) is a (a)-(b) diblock type polymer. The resin modifier according to any one of claims 1 to 4, wherein the block of the polysiloxane (b) is a block represented by general formula (1) or general formula (2).

[In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms; R ² to R ⁵ each independently represent a hydrocarbon group having 1 to ⁶ carbon atoms; represents a hydrocarbon group; R ⁷ represents an alkylene group having 2 to 4 carbon atoms; when there are multiple (OR ⁷ ), each may be the same or different, and the bonding form may be a block form or a random form. n is an integer of 1-500; a is 0 or 1; b represents an integer of 0-30. ]

[ ^In the formula, Q represents a hydroxyl group or an amino group; R ⁸ and R ¹⁵ each independently represent an alkylene group having 2 to ⁴ carbon atoms; may be different, and the bond 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; R ¹⁰ to R ¹³ each independently represents a hydrocarbon group having 1 to 6 carbon atoms; c and f are each independently an integer of 0 to 30; d and e are each independently 0 or 1; m is an integer of 1 to 500 . ] The resin modifier according to any one of claims 1 to 5, which is used as a scratch resistance improver. A resin composition containing the resin modifier (Y) according to any one of claims 1 to 6 and a thermoplastic resin (C) , wherein the thermoplastic resin (C) is a polyolefin resin (C1) ( Z). 8. The resin composition according to claim 7, wherein the resin modifier (Y) and the thermoplastic resin (C) have a weight ratio [(Y):(C)] of 0.5:99.5 to 50:50. thing. A molded article obtained by molding the resin composition (Z) according to claim 7 or 8 .