JP2021169602A - Compatibilizer - Google Patents

Abstract

To provide a compatibilizer that gives a molding of a resin composition excellent mechanical strength.SOLUTION: The present disclosure provides a compatibilizer (X) for a polyacetal resin containing a block polymer (A) including a block of a hydrophobic polymer (a) as a polyolefin (a2) and a block of a hydrophilic polymer (b) as constitutional units. The present disclosure provides a resin composition (Y) containing the compatibilizer (X), a polyolefin resin (D), and a polyacetal resin (E). The present disclosure provides a molding obtained by molding the resin composition (Y). The present disclosure provides a molded article obtained by applying a coat and/or print onto the molding.SELECTED DRAWING: None

Description

The present invention relates to compatibilizers.

Resins with different polarities cannot be simply blended. Therefore, an attempt has been made to develop a thermoplastic resin using a compatibilizer (for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2000-017120

However, even with the technique of Patent Document 1, the compatibility of the resin composition is insufficient, and the mechanical strength of the molded product of the resin composition is not satisfactory.
An object of the present invention is to provide a compatibilizer that imparts excellent mechanical strength to a molded product of a resin composition.

The present inventors have arrived at the present invention as a result of studies for achieving the above object. That is, the present invention is a phase for a polyacetal resin containing a block polymer (A) having a block of a hydrophobic polymer (a) as a polyolefin (a2) and a block of a hydrophilic polymer (b) as constituent units. It is a solubilizer (X).

The compatibilizer (X) for a polyacetal resin of the present invention has the following effects.
(1) An excellent mechanical strength (tensile strength, impact strength) is given to a molded product of a resin composition.
(2) It has excellent compatibility and gives a molded product an excellent appearance.

<Polyolefin (a2)>
The polyolefin (a2) in the present invention is a polyolefin which is a hydrophobic polymer (a).
The hydrophobic polymer means a polymer having a water absorption rate (24 hours) of less than 0.1% by weight. The water absorption rate (24 hours) in the present invention can be measured by a known measuring method. That is, the water absorption rate can be measured according to the method for determining the water absorption rate described in JIS K7209 (2000).

The polyolefin (a2) includes a polyolefin (a2-1) having a carboxyl group at both ends of the polymer, a polyolefin (a2-2) having a hydroxyl group at both ends of the polymer, and a polyolefin (a2) having an amino group at both ends of the polymer. -3) and polyolefin having an isocyanate group at both ends of the polymer (a2-4), polyolefin having a carboxyl group at one end of the polymer (a2-5), and polyolefin having a hydroxyl group at one end of the polymer (a2-6). , Polyolefin (a2-7) having an amino group at one end of the polymer, polyolefin (a2-8) having an isocyanate group at one end of the polymer, and the like. Of these, (a2-1) and (a2-5) having a carboxyl group at the terminal are preferable.
The terminal in the present invention means a terminal where the repeating structure of the monomer unit constituting the polymer is interrupted. Further, both ends mean both ends in the main chain of the polymer, and one end means one end in the main chain of the polymer.

As (a2-1), a polyolefin (a2) containing a polyolefin having both ends modifiable as a main component (preferably a content of 50% by weight or more, more preferably 75% by weight or more, particularly preferably 80 to 100% by weight). -01) with carboxyl groups introduced at both ends; (a2-2) with hydroxyl groups introduced at both ends of (a2-01); (a2-3) with (a2-01) Amino groups are introduced at both ends of (a2-4); and as (a2-4), those having isocyanate groups introduced at both ends of (a2-01) can be used.

As the (a2-5) to (a2-8), instead of the polyolefin (a2-01), a polyolefin having a modifiable one end as a main component (preferably a content of 50% by weight or more, more preferably 75% by weight) is used. As described above, those in which a carboxyl group, a hydroxyl group, an amino group or an isocyanate group are introduced into one end of the polyolefin (a2-02), which is particularly preferably 80 to 100% by weight) can be used.

The polyolefin (a2-01) whose main component is a polyolefin whose both ends can be modified includes one or more olefins having 2 to 30 carbon atoms (preferably 2 to 12, more preferably 2 to 10). (Co) polymerization of the mixture [(Co) polymerization means polymerization or copolymerization. The same applies below. ] And the modified polyolefin {high molecular weight [preferably number average molecular weight (hereinafter abbreviated as Mn) 50,000 to 150,000], mechanically, thermally or chemically. (Decomposition method)} is included.
Of these, a modified polyolefin is preferable from the viewpoint of easy modification and availability when introducing a carboxyl group, a hydroxyl group, an amino group or an isocyanate group, and more preferable is heat. It is a reduced polyolefin. According to the thermal reduction, a low molecular weight polyolefin having an average number of terminal double bonds of 1.5 to 2 per molecule can be easily obtained as described later, and the low molecular weight polyolefin has a carboxyl group, a hydroxyl group, and an amino group. Alternatively, it is easy to introduce an isocyanate group or the like to modify it.

Mn (number average molecular weight) and Mw (weight average molecular weight) in the present invention can be measured by gel permeation chromatography (GPC) under the following conditions.
Equipment (example): "HLC-8120" [manufactured by Tosoh Corporation]
Column (example): "TSKgelGMHXL" (2)
"TSKgel Multipore HXL-M" (1 bottle)
Sample solution: 0.3 wt% orthodichlorobenzene solution Injection amount: 100 μl
Flow rate: 1 ml / min Measurement temperature: 135 ° C
Detection device: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) 12 points (molecular weight: 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400 , 190,000, 355,000, 1,090,000, 2,890,000) [manufactured by Tosoh Corporation]

The heat-decomposed polyolefin is not particularly limited, but is obtained by heating a high-molecular-weight polyolefin in an inert gas (300 to 450 ° C. for 0.5 to 10 hours, for example, JP-A-3-62804). Examples thereof include those obtained by the method described in the publication) and those obtained by heating in air to reduce heat.

The high molecular weight polyolefin used in the heat reduction method is a (co) polymer of one or a mixture of two or more olefins having 2 to 30 carbon atoms (preferably 2 to 12, more preferably 2 to 10). [Mn is preferably 12,000 to 100,000, more preferably 15,000 to 70,000. The melt flow rate (hereinafter abbreviated as MFR; the unit is g / 10 min) is preferably 0.5 to 150, more preferably 1 to 100. ] Etc. can be mentioned. Here, MFR is a numerical value representing the melt viscosity of the resin, and the larger the value, the lower the melt viscosity. An extruded plastometer defined by JIS K6760 is used for the measurement of MFR, and the measuring method conforms to the method specified by JIS K7210 (1976). For example, in the case of polypropylene, it is measured under the conditions of 230 ° C. and a load of 2.16 kgf.
Examples of the olefin having 2 to 30 carbon atoms include an α-olefin having 2 to 30 carbon atoms and a diene 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-. Tetracosen and the like can be mentioned.
Examples of the diene having 4 to 30 carbon atoms include butadiene, isoprene, cyclopentadiene and 1,11-dodecadien.
Among the olefins having 2 to 30 carbon atoms, ethylene, propylene, α-olefin having 4 to 12 carbon atoms, butadiene, isoprene and a mixture thereof are preferable from the viewpoint of molecular weight control, and ethylene is more preferable. Propylene, α-olefins having 4 to 10 carbon atoms, butadiene and mixtures thereof, particularly preferred are ethylene, propylene, butadiene and mixtures thereof.

The Mn of the polyolefin (a2-01) is preferably 800 to 20,000, more preferably 1,000 to 10,000, from the viewpoint of compatibility and reactivity with the hydrophilic polymer (b) described later. Particularly preferably, it is 1,200 to 6,000.
The number of terminal double bonds in (a2-01) is preferably 1 to 40 per 1,000 carbon atoms, and more preferably 2 to 30 from the viewpoint of controlling the molecular weight of the block polymer (A). Particularly preferably, the number is 4 to 20.

(A2-01) The average number of terminal double bonds per molecule is preferably 1.1 to 5 from the viewpoint of ease of forming a repeating structure in the molecule and the thermoplasticity of the block polymer (A) described later. It is more preferably 1.3 to 3, particularly preferably 1.5 to 2.5, and most preferably 1.8 to 2.2.

When a method for obtaining a low molecular weight polyolefin by a heat reduction method is used, it is easy (a2-01) to have an average number of terminal double bonds of 1.5 to 2 per molecule in the range of Mn 800 to 6,000. [Katsuhide Murata, Tadahiko Makino, Journal of the Japanese Society of Chemistry, p. 192 (1975)].

The polyolefin (a2-02) containing a polyolefin having a modifiable one end as a main component can be obtained in the same manner as in (a2-01), and the Mn of (a2-02) has compatibility and mechanical strength (a2-02). From the viewpoint of mechanical properties), it is preferably 2,000 to 50,000, more preferably 2,500 to 30,000, and particularly preferably 3,000 to 20,000.
The number of double bonds per 1,000 carbon atoms of (a2-02) is preferably 0.3 to 20 and more preferably 0.5 to 20 from the viewpoint of controlling the molecular weight of the block polymer (A). The number is 15, particularly preferably 0.7 to 10.

(A2-02) The average number of double bonds per molecule is preferably 0.5 to 1.4 from the viewpoint of ease of forming a repeating structure in the molecule and the thermoplasticity of the block polymer (A) described later. It is more preferably 0.6 to 1.3, particularly preferably 0.7 to 1.2, and most preferably 0.8 to 1.1.
Of (a2-02), the low molecular weight polyolefin obtained by the heat denaturation method is preferable from the viewpoint of easiness of denaturation, and more preferably Mn obtained by the heat denaturation method is 3. Thousands to 20,000 polyethylenes and / or polypropylenes.
When a method for obtaining a low molecular weight polyolefin by the heat reduction method is used, the average number of terminal double bonds per molecule is 1 to 1.5 (a2-) in the range of Mn of 6,000 to 30,000. 02) is obtained.
Since the low molecular weight polyolefin obtained by the heat reduction method has an average number of the terminal double bonds, it can be easily modified by introducing a carboxyl group, a hydroxyl group, an amino group, an isocyanate group or the like.

Although (a2-01) and (a2-02) are obtained as, for example, a mixture thereof, the mixture may be used as it is, or may be used after purification and separation. Of these, a mixture is preferable from the viewpoint of manufacturing cost and the like.

Hereinafter, (a2-1) to (a2-4) having a carboxyl group, a hydroxyl group, an amino group or an isocyanate group at both ends of the polyolefin (a2-01) will be described, but one end of the polyolefin (a2-02) will be described. Regarding (a2-5) to (a2-8) having these groups, the one in which (a2-01) is replaced with (a2-02) is the same as (a2-1) to (a2-4). Can be obtained.

As the polyolefin (a2-1) having a carboxyl group at both ends of the polymer, the terminal of (a2-01) is α, β-unsaturated carboxylic acid (anhydride) (α, β-unsaturated carboxylic acid, its alkyl). (1 to 4 carbon atoms) means an ester or an anhydride thereof. The same shall apply hereinafter.) Polyethylene (a2-1-1) and (a2-1-1) having a modified structure are mixed with lactam or aminocarboxylic acid. The polyolefin (a2-1-2) having the next modified structure, the polyolefin (a2-1-3) having the structure modified by oxidizing or hydroformulating (a2-01), (a2-1-3) is lactam or A polyolefin (a2-1-4) having a structure secondarily modified with an aminocarboxylic acid, a mixture of two or more of these, and the like can be used.

(A2-1-1) can be obtained by modifying (a2-01) with α, β-unsaturated carboxylic acid (anhydride).
Examples of the α, β-unsaturated carboxylic acid (anhydride) used for the modification include monocarboxylic acid, dicarboxylic acid, alkyl (1 to 4 carbon atoms) ester of mono or dicarboxylic acid, and anhydride of mono or dicarboxylic acid. Specifically, (meth) acrylic acid [(meth) acrylic acid means acrylic acid or methacrylic acid. The same applies below. ], Methyl (meth) acrylate, butyl (meth) acrylate, maleic acid (anhydride), dimethyl maleate, fumaric acid, itaconic acid (anhydride), diethyl itaconic acid and citraconic acid (anhydride). Be done.
Of these, from the viewpoint of easiness of modification, dicarboxylic acid, an alkyl ester of mono or dicarboxylic acid and an anhydride of mono or dicarboxylic acid are preferable, and maleic acid (anhydride) and fumaric acid are more preferable. , Particularly preferred is maleic acid (anhydride).

The amount of α, β-unsaturated carboxylic acid (anhydride) used for denaturation is based on the weight of the polyolefin (a2-01), the ease of forming a repeating structure in the molecule, and the heat of the block polymer (A) described later. From the viewpoint of plasticity, it is preferably 0.5 to 40% by weight, more preferably 1 to 30% by weight, and particularly preferably 2 to 20% by weight.
Modification with α, β-unsaturated carboxylic acid (anhydride) is performed by, for example, the terminal double bond of (a2-01) by either a solution method or a melting method. It can be carried out by subjecting (anhydride) to an addition reaction (ene reaction), and the reaction temperature is preferably 170 to 230 ° C.

(A2-1-1) can be obtained by secondary modification of (a2-1) with lactam or aminocarboxylic acid.
Examples of the lactam used for the secondary denaturation include lactam having 6 to 12 carbon atoms (preferably 6 to 8, more preferably 6), and specifically, caprolactam, enantractam, laurolactam, undecanolactam and the like. Can be mentioned.
Examples of the aminocarboxylic acid include aminocarboxylic acids having 2 to 12 carbon atoms (preferably 4 to 12, more preferably 6 to 12), and specifically, amino acids (glycine, alanine, valine, leucine, isoleucine). And phenylalanine, etc.), ω-aminocaproic acid, ω-aminoenantic acid, ω-aminocapric acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like.
Of the lactams and aminocarboxylic acids, caprolactam, laurolactam, glycine, leucine, ω-aminocapricic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid are preferred, and 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 lactam or aminocarboxylic acid used for the secondary denaturation is based on the weight of the object to be modified (a2-1), from the viewpoint of the ease of forming a repeating structure in the molecule and the thermoplasticity of the block polymer (A). It is preferably 0.5 to 200% by weight, more preferably 1 to 150% by weight, and particularly preferably 2 to 100% by weight.

(A2-3) can be obtained by a method of oxidizing (a2-01) with oxygen and / or ozone (oxidation method), or by introducing a carboxyl group by hydroformylation by an oxo method.
The introduction of the carbonyl group by the oxidation method can be carried out by a known method, for example, the method described in US Pat. No. 3,692,877. Introduction of carbonyl groups by hydroformylation can be carried out by a variety of methods, including known methods, such as Macromolecules, VOL. This can be done by the method described on pages 31, 5943.
(A2-4) can be obtained by secondary modification of (a2-3) with lactam or aminocarboxylic acid.
Examples of the lactam and the aminocarboxylic acid include the same as those exemplified as the lactam and the aminocarboxylic acid used for the secondary modification of (a2-1), and the preferable range and the amount used are also the same.

The Mn of (a2-1) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly preferably 1,000 to 20,000, from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b) described later. It is preferably 2,500 to 10,000.
The acid value of (a2-1) is preferably 4 to 280 mgKOH / g, more preferably 4 to 100 mgKOH / g, particularly from the viewpoint of reactivity with (b) and thermoplasticity of the block polymer (A). It is preferably 5 to 50 mgKOH / g.

Examples of the polyolefin (a2-2) having a hydroxyl group at both ends of the polymer include a polyolefin having a hydroxyl group obtained by modifying the polyolefin (a2-1) having a carboxyl group at both ends of the polymer with an amine having a hydroxyl group, and two of these. Mixtures of seeds and above can be used.
Examples of the amine having a hydroxyl group that can be used for modification include an amine having a hydroxyl group having 2 to 10 carbon atoms, and specifically, 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, and 4-amino. Butanol, 5-aminopentanol, 6-aminohexanol and 3-aminomethyl-3,5,5-trimethylcyclohexanol can be mentioned.
Of these, amines having hydroxyl groups having 2 to 6 carbon atoms (2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol and 6-amino) are preferable from the viewpoint of ease of modification. Hexanol, etc.), more preferred are 2-aminoethanol and 4-aminobutanol, and particularly preferred are 2-aminoethanol.

The amount of the amine having a hydroxyl group used for the modification is preferable from the viewpoint of the ease of forming a repeating structure in the molecule and the thermoplasticity of the block polymer (A) described later, based on the weight of the object to be modified (a2-1). Is 0.5 to 50% by weight, more preferably 1 to 40% by weight, and particularly preferably 2 to 30% by weight.
The Mn of (a2-2) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly preferably 1,000 to 20,000, from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b) described later. It is preferably 2,500 to 10,000.
The hydroxyl value of (a2-2) is preferably 4 to 280 mgKOH / g, more preferably 4 to 100 mgKOH / g, particularly from the viewpoint of reactivity with (b) and thermoplasticity of the block polymer (A). It is preferably 5 to 50 mgKOH / g.

Examples of the polyolefin (a2-3) having an amino group at both ends of the polymer include a polyolefin having an amino group obtained by modifying the polyolefin (a2-1) having a carboxyl group at both ends of the polymer with a diamine (Q1). Two or more mixtures of the above can be used.
As the diamine (Q1), a diamine having 2 to 12 carbon atoms can be used, and specific examples thereof include ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine and decamethylenediamine.
Of these, diamines having 2 to 8 carbon atoms (ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, etc.) are preferable from the viewpoint of ease of modification, and ethylenediamine and hexamethylenediamine are more preferable. Particularly preferred is ethylenediamine.

The amount of (Q1) used for the modification of (a2-1) is based on the weight of (a2-1) from the viewpoint of the ease of forming a repeating structure in the molecule and the thermoplasticity of the block polymer (A) described later. It is preferably 0.5 to 50% by weight, more preferably 1 to 40% by weight, and particularly preferably 2 to 30% by weight. The modification of (a2-1) by (Q1) is preferably 0.5 to 1,000% by weight, more preferably 0.5 to 1,000% by weight, based on the weight of (a2-1) from the viewpoint of preventing polyamide (imide) formation. A method is preferably used in which 1 to 500% by weight, particularly preferably 2 to 300% by weight of (Q1) is used, and then the unreacted (Q1) is removed at 120 to 230 ° C. under reduced pressure.

The Mn of (a2-3) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly preferably 1,000 to 20,000, from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b) described later. It is preferably 2,500 to 10,000.
The amine value of (a2-3) is preferably 4 to 280 mgKOH / g, more preferably 4 to 100 mgKOH / g, particularly from the viewpoint of reactivity with (b) and thermoplasticity of the block polymer (A). It is preferably 5 to 50 mgKOH / g.

As the polyolefin (a2-4) having an isocyanate group at both ends, a polyolefin having an isocyanate group in which (a2-2) is modified with poly (2 to 3 or more) isocyanate (hereinafter abbreviated as PI) and these. A mixture of two or more of the above can be mentioned.
The PIs include an aromatic PI having 6 to 20 carbon atoms (excluding carbon atoms in the NCO group, the same applies hereinafter), an aliphatic PI having 2 to 18 carbon atoms, an alicyclic PI having 4 to 15 carbon atoms, and carbon. Includes numbers 8 to 15 aromatic aliphatic PIs, variants of these PIs and mixtures of two or more of these.

Aromatic PIs include 1,3- or 1,4-phenylenediocyanate, 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, Examples thereof include 5-naphthylene diisocyanate.

The aliphatic PI includes ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, and bis. Examples thereof include (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

Examples of the alicyclic PI include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexene diisocyanate, methylcyclohexene diisocyanate (hydrogenated TDI), and bis (2-isocyanatoethyl). Examples thereof include -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornene diisocyanate.

Examples of the aromatic aliphatic PI include m- or p-xylylene diisocyanate (XDI) and α, α, α', α'-tetramethylxylylene diisocyanate (TMXDI).

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

The reaction between PI and (a2-2) can be carried out in the same manner as, for example, the urethanization reaction.
The molar equivalent ratio (NCO / OH) of PI and (a2-2) is preferably 1.8 / 1-3 / 1, and more preferably 2/1.
If necessary, a known catalyst used in the urethanization reaction may be used to promote the urethanization reaction. Examples of the catalyst include metal catalysts {tin catalysts [dibutyltin dilaurate and stanas octoate, etc.], lead catalysts [lead 2-ethylhexanoate, lead octenoate, etc.], and other metal catalysts [metal salts of naphthenate (cobalt naphthenate, etc.). Etc.) and phenylmercury propionate, etc.]}; amine catalysts {triethylenediamine, diazabicycloalkene [1,8-diazabicyclo [5,4,0] undecene-7, etc.], dialkylaminoalkylamines (dimethylaminoethylamine and Dimethylaminooctylamine, etc.), heterocyclic aminoalkylamine [2- (1-aziridinyl) ethylamine, 4- (1-piperidinyl) -2-hexylamine, etc.] carbonate or organic acid (gilic acid, etc.) salt, N -Methyl or ethylmorpholine, triethylamine and diethyl- or dimethylethanolamine, etc.}; and a combination system of two or more of these.
The amount of the catalyst used is preferably 3% by weight or less, preferably 0.001 to 2% by weight, based on the total weight of PI and (a2-2).

The Mn of (a2-4) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly preferably 1,000 to 20,000, from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b) described later. It is preferably 2,500 to 10,000.

The Mn of the polyolefin (a2) is preferably 200 to 25,000, more preferably 500 to 20,000, and particularly preferably 1,000 to 15,000 from the viewpoint of compatibility and mechanical strength.

<Hydrophilic polymer (b)>
The hydrophilic polymer (b) in the present invention means a polymer having a water absorption rate (24 hours) of 0.1% by weight or more.

Examples of the hydrophilic polymer (b) include the hydrophilic polymer described in Patent No. 3488163, specifically, a polyether (b1), a polyether-containing hydrophilic polymer (b2), and a cationic polymer (b3). And anionic polymer (b4) and the like.
Among the hydrophilic polymers (b), (b1) and (b2) are preferable from the viewpoint of mechanical strength (mechanical characteristics) and compatibility.

Examples of the polyether (b1) include a polyether diol (b1-1), a polyether diamine (b1-2) and a modified product thereof (b1-3).
Examples of the polyether diol (b1-1) include those obtained by subjecting the diol (b0) to an addition reaction of an alkylene oxide (hereinafter abbreviated as AO), and specific examples thereof are represented by the general formula (1). There are things that are done.

H- (OR ¹ ) _m- O-E ^1- O- (R ² O) _n- H (1)

^{E 1} in the general formula (1) is a residue obtained by removing all hydroxyl groups from the diol (b0).
Examples of the diol (b0) include an aliphatic dihydric alcohol having 2 to 12 carbon atoms, an alicyclic dihydric alcohol having 5 to 12 carbon atoms, an aromatic dihydric alcohol having 6 to 18 carbon atoms, and a tertiary amino group-containing diol. And so on.
Examples of the aliphatic dihydric alcohol having 2 to 12 carbon atoms include ethylene glycol (hereinafter abbreviated as EG), 1,2-propylene glycol (hereinafter abbreviated as PG), and 1,4-butanediol (hereinafter 1,1). Examples thereof include 4-BD (abbreviated as 4-BD), 1,6-hexanediol (hereinafter abbreviated as 1,6-HD), neopentyl glycol (hereinafter abbreviated as NPG) and 1,12-dodecanediol.

Examples of the alicyclic dihydric alcohol having 5 to 12 carbon atoms include 1,4-di (hydroxymethyl) cyclohexane and 1,5-di (hydroxymethyl) cycloheptane.
Examples of the aromatic dihydric alcohol having 6 to 18 carbon atoms include monocyclic aromatic dihydric alcohols (xylylenediol, hydroquinone, catechol, resorcin, ursiol, bisphenol A, bisphenol F, bisphenol S, 4,4'-dihydroxy. Diphenyl-2,2-butane and dihydroxybiphenyl, etc.) and polycyclic aromatic dihydric alcohols (dihydroxynaphthalene, binaphthol, etc.) and the like.
Examples of the tertiary amino group-containing diol include aliphatic or alicyclic primary amines having 1 to 12 carbon atoms (methylamine, ethylamine, cyclopropylamine, 1-propylamine, 2-propylamine, pentylamine, isopentylamine). , Cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, nonylamine, decylamine, undecylamine, dodecylamine, etc.) and aromatic primary amines (aniline, benzylamine, etc.) with 6 to 12 carbon atoms. Bishydroxyalkylated products can be mentioned.
Of these, from the viewpoint of reactivity with the bishydroxyalkylated product, an aliphatic dihydric alcohol having 2 to 12 carbon atoms and an aromatic dihydric alcohol having 6 to 18 carbon atoms are preferable, and EG is more preferable. And bisphenol A.

^{R 1} and R ² in the general formula (1) are independently alkylene groups having 2 to 4 carbon atoms. Examples of the alkylene group having 2 to 4 carbon atoms include an ethylene group, a 1,2- or 1,3-propylene group and a 1,2-, 1,3-, 1,4- or 2,3-butylene group. Be done.
M and n in the general formula (1) are independently numbers 1 to 300, preferably 2 to 250, and more preferably 10 to 100.
^{R 1} and R ² when m and n in the general formula (1) are 2 or more, respectively, may be the same or different, and the (OR ¹ ) m and (R ² O) n portions may be randomly combined or block connected. But it may be.

The polyether diol (b1-1) can be produced by subjecting the diol (b0) to an addition reaction with AO.
As AO, AO having 2 to 4 carbon atoms [ethylene oxide (hereinafter abbreviated as EO), 1,2- or 1,3-propylene oxide (hereinafter abbreviated as PO), 1,2-, 1, 3-, 1,4-, 2,3- or butylene oxide (hereinafter abbreviated as BO), and a combination system of two or more of these are used, but if necessary, other AOs [with 5 to 12 carbon atoms] are used. α-olefin oxide, styrene oxide, epichlorohydrin (epichlorohydrin, etc.), etc.] can also be used in combination in a small proportion (30% by weight or less based on the total weight of AO).
When two or more types of AO are used in combination, the binding form may be either random binding or block binding. Preferable AOs are EO alone and EO in combination with other AOs.

The addition reaction of AO can be carried out by a known method, for example, in the presence of an alkaline catalyst at a temperature of 100 to 200 ° C.
^{The content of (OR 1} ) m and (R ² O) n based on the weight of the polyether diol (b1-1) represented by the general formula (1) is preferably 5 to 99.8% by weight. More preferably, it is 8 to 99.6% by weight, and particularly preferably 10 to 98% by weight.
^{The content of the oxyethylene group based on the weights of (OR 1} ) m and (R ² O) n in the general formula (1) is preferably 5 to 100% by weight, more preferably 10 to 100% by weight, particularly. It is preferably 50 to 100% by weight, most preferably 60 to 100% by weight.

Examples of the polyether diamine (b1-2) include those represented by the general formula (2).

H ₂ N-R ^3- (OR ⁴ ) _p- O-E ^2- O- (R ⁵ O) _q- R ^6- NH ₂ (2)

^{E 2} in the general formula (2) is a residue obtained by removing all hydroxyl groups from the diol (b0). Examples of the diol (b0) include those similar to those described above, and the preferred range is also the same.
^{R 3} , R ⁴ , R ⁵ and R ⁶ in the general formula (2) are independently alkylene groups having 2 to 4 carbon atoms. Examples of the alkylene group having 2 to 4 carbon atoms include ^{those similar to those exemplified as R 1} and R ² in the general formula (1), and the preferable range is also the same.
P and q in the general formula (2) are independently numbers 1 to 300, preferably 2 to 250, and more preferably 10 to 100.
When p and q in the general formula (2) are 2 or more, R ⁴ and R ⁵ may be the same or different, and the (OR ⁴ ) p and (R ⁵ O) q portions may be randomly combined or block-combined. But it may be.

The polyether diamine (b1-2) can be obtained by converting all the hydroxyl groups of the polyether diol (b1-1) into amino groups. For example, it can be produced by reacting (b1-1) with acrylonitrile and hydrogenating the obtained cyanoethylated product.

The modified product (b1-3) includes an aminocarboxylic acid modified product (terminal amino group), an isocyanate modified product (terminal isocyanate group) and an epoxy modified product (terminal epoxy group) of (b1-1) or (b1-2). And so on.
The modified aminocarboxylic acid can be obtained by reacting (b1-1) or (b1-2) with an aminocarboxylic acid or lactam.
The isocyanate-modified product can be obtained by reacting (b1-1) or (b1-2) with polyisocyanate or reacting (b1-2) with phosgene.
The epoxy-modified product is prepared by reacting (b1-1) or (b1-2) with a diepoxyd (epoxy resin such as diglycidyl ether, diglycidyl ester and alicyclic diepoxy: epoxy equivalent 85-600). It can be obtained by reacting b1-1) with epihalohydrin (epichlorohydrin, etc.).

The Mn of the polyether (b1) is preferably 150 to 20,000, more preferably 300 to 18,000, and particularly preferably 1, from the viewpoint of heat resistance and reactivity with the hydrophobic polymer (a). It is 000 to 15,000, most preferably 1,200 to 8,000.

Examples of the polyether-containing hydrophilic polymer (b2) include a polyether ester amide (b2-1) having a segment of a polyether diol (b1-1) and a polyether amidimide (b2-) having a segment of (b1-1). 2), a polyether ester (b2-3) having a segment of (b1-1), a polyether amide (b2-4) having a segment of a polyether diamine (b1-2) and (b1-1) or (b1). Examples thereof include polyether urethane (b2-5) having the segment of -2).

The content of the polyether (b1) segment in the polyether-containing hydrophilic polymer (b2) is preferably 30 to 80% by weight based on the weight of (b2) from the viewpoint of compatibility and mechanical strength, and further. It is preferably 40 to 70% by weight.
The content of the oxyethylene group in (b2) is preferably 30 to 80% by weight, more preferably 40 to 70% by weight, based on the weight of (b2) from the viewpoint of compatibility and mechanical strength. ..
The lower limit of Mn in (b2) is preferably 800, more preferably 1,000, from the viewpoint of heat resistance. The upper limit of Mn in (b2) is preferably 50,000, more preferably 30,000, from the viewpoint of reactivity with the hydrophobic polymer (a).

Examples of the cationic polymer (b3) include polymers having a cationic group separated by a nonionic molecular chain in the molecule.
The nonionic molecular chain is a group consisting of a divalent hydrocarbon group, an ether bond, a thioether bond, a carbonyl bond, an ester bond, an imino bond, an amide bond, an imide bond, a urethane bond, a urea bond, a carbonate bond and a syroxy bond. Examples thereof include a divalent hydrocarbon group having one or more groups selected from the above, and a hydrocarbon group having a heterocyclic structure having a nitrogen atom or an oxygen atom.
Of the nonionic molecular chains, a divalent hydrocarbon group and a divalent hydrocarbon group having an ether bond are preferable.
Examples of the cationic group include a group having a quaternary ammonium salt or a phosphonium salt. Examples of the counter anion forming the quaternary ammonium salt or the phosphonium salt include superacid anions and other anions.
Examples of the superacid anion include an anion of a superacid (boric acid tetrafluoride, phosphoric acid hexafluoride, etc.) derived from a combination of a protonic acid and a Lewis acid, and an anion such as trifluoromethanesulfonic acid.
Other anionic, halogen ions ^{(F -, Cl -, Br} - and I ^{-, _{etc.), OH -, PO 4 -}} , CH 3 OSO 4 -, C 2 H 5 OSO 4 -, and ClO ₄ ^- and the like Can be mentioned.
Examples of the protonic acid that induces a super strong acid include hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide and the like.
Examples of Lewis acid include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride and tantalum pentafluoride.
(B3) The number of cationic groups in one molecule is preferably 2 to 80, more preferably 3 to 60.

Specific examples of (b3) include cationic polymers described in JP-A-2001-278985.

The Mn of (b3) is preferably 500 to 20,000, more preferably 1,000 to 15,000, and particularly preferably 1, from the viewpoint of compatibility and reactivity with the hydrophobic polymer (a). It is 200 to 8,000.

The anionic polymer (b4) contains a dicarboxylic acid (γ') having a sulfonyl group and a diol (b0) or a polyether (b1) as essential constituent units, and 2 to 80 in the molecule, preferably 3 to 3. It is a polymer having 60 sulfonyl groups.
Examples of (γ') include those in which a sulfonyl group is introduced into the dicarboxylic acid (γ), and only an aromatic dicarboxylic acid having a sulfonyl group, an aliphatic dicarboxylic acid having a sulfonyl group, and a sulfonyl group serve as salts. Examples thereof include aromatic dicarboxylic acids and aliphatic dicarboxylic acids having a sulfonyl group.

Examples of the aromatic dicarboxylic acid having a sulfonyl group include 5-sulfoisophthalic acid, 2-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfo-2,6-naphthalenedicarboxylic acid, and ester-forming derivatives thereof [alkyl. (1 to 4 carbon atoms) esters (methyl esters, ethyl esters, etc.), acid anhydrides, etc.] can be mentioned.
Examples of the aliphatic dicarboxylic acid having a sulfonyl group include sulfosuccinic acid and its ester-forming derivative [alkyl (1 to 4 carbon atoms) ester (methyl ester, ethyl ester, etc.), acid anhydride, etc.].
Examples of the salt forming an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid having a sulfonyl group in which only the sulfonyl group is a salt include alkali metal (lithium, sodium and potassium, etc.) salts and alkaline earth metals (magnesium, calcium, etc.). Amine salts such as salts, ammonium salts, mono, di or triamines having hydroxyalkyl (2-4 carbon atoms) groups (mono, di or triethylamine, mono, di or triethanolamine, diethylethanolamine, etc.) and the amines. Examples include quaternary ammonium salts.
Of these, aromatic dicarboxylic acids having a sulfonyl group are preferred, more preferred are 5-sulfoisophthalic acid salts, and particularly preferred are 5-sulfoisophthalic acid sodium salts and 5-sulfoisophthalic acid potassium salts. ..

Of the (b0) or (b1) constituting (b4), alkanediols having 2 to 10 carbon atoms, EG, polyethylene glycol (hereinafter abbreviated as PEG) (degree of polymerization 2 to 20), bisphenol ( An EO adduct (number of moles added: 2 to 60 mols) of (bisphenol A, etc.) and a mixture of two or more thereof.
As the manufacturing method of (b4), a known polyester manufacturing method can be applied as it is. The polyesterification reaction is carried out under reduced pressure in a temperature range of 150 to 240 ° C., and the reaction time is preferably 0.5 to 20 hours. Further, if necessary, a known catalyst used for the esterification reaction may be used. Examples of the esterification catalyst include an antimony catalyst (antimony trioxide, etc.), a tin catalyst (monobutyltin oxide, dibutyltin oxide, etc.), a titanium catalyst (tetrabutyl titanate, etc.), a zirconium catalyst (tetrabutylzirconate, etc.), and a metal acetate. Examples include catalysts (zinc acetate, etc.).

The Mn of (b4) is preferably 500 to 20,000, more preferably 1,000 to 15,000, and particularly preferably 1, from the viewpoint of compatibility and reactivity with the hydrophobic polymer (a). It is 200 to 8,000.

<Block polymer (A)>
The block polymer (A) in the present invention comprises a block of the hydrophobic polymer (a) which is the polyolefin (a2) and a block of the hydrophilic polymer (b) as constituent units.
As a preferable form of the block polymer, at least the block of (a2) and the block of the hydrophilic polymer (b) are selected from the group consisting of an ester bond, an amide bond, an ether bond, an imide bond, a urethane bond and a urea bond. It is a block polymer having a structure bonded via one type of bond.
In the present invention, the polyolefin (a2) may be referred to as the hydrophobic polymer (a) for convenience.
The weight ratio of the block (a) constituting (A) to the block (b) is preferably 10/90 to 80/20, more preferably 20/20, from the viewpoint of compatibility and mechanical strength. It is 80 to 75/25.

The structure in which the block (a) constituting (A) and the block (b) are combined includes (a2)-(b) type, (a)-(b)-(a) type, and (b). )-(A)-(b) type and [(a)-(b)] n type (n represents the average number of repetitions).
As the structure of the block polymer (A), a [(a)-(b)] n-type structure in which (a) and (b) are repeatedly and alternately bonded is preferable from the viewpoint of compatibility and mechanical strength.
[(A)-(b)] n in the n-type structure is preferably 2 to 50, more preferably 2.3 to 30, particularly preferably 2.7, from the viewpoint of compatibility and mechanical strength. ~ 20, most preferably 3-10. ^{n can be determined by Mn and 1 1} H-NMR analysis of the block polymer (A).

The Mn of (A) is preferably 2,000 to 1,000,000, more preferably 4,000 to 500,000, and particularly preferably 6,000 to 100,000 from the viewpoint of mechanical strength. be.

When (A) has a structure in which the block of (a) and the block of (b) are bonded via an ester bond, an amide bond, an ether bond or an imide bond, it is produced by the following method. Can be done.
Water (a) and (b) produced by amidation reaction, esterification reaction or imidization reaction at a reaction temperature of 100 to 250 ° C. and a pressure of 0.003 to 0.1 MPa under stirring. Hereinafter, a method of reacting for 1 to 50 hours while removing the generated water) from the reaction system can be mentioned. The weight ratio of (a) and (b) is 10/90 to 80/20, more preferably 20/80 to 75/25, from the viewpoint of compatibility and mechanical strength.

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

When (A) has a structure in which the block (a) and the block (b) are bonded via a urethane bond or a urea bond, it can be produced by the following method.
Examples thereof include a method in which (a) is charged into a reaction vessel, heated to 30 to 100 ° C. with stirring, and then (b) is charged and reacted at the same temperature for 1 to 20 hours. The weight ratio of (a) and (b) is 10/90 to 80/20, more preferably 20/80 to 75/25, from the viewpoint of compatibility and mechanical strength.
In order to accelerate the reaction, it is preferable to use 0.001 to 5% by weight of the catalyst based on the weights of (a) and (b). Examples of the catalyst include organic metal compounds (dibutyltin dilaurate, dioctyltin dilaurate, lead octanate and bismuth octanate, 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 a combination of two or more of these.

<Solution agent for polyacetal resin (X)>
The compatibilizer (X) for a polyacetal resin of the present invention contains the block polymer (A). The resin compatibilizer (X) is suitable as a compatibilizer for compatibilizing a polyacetal resin and a resin having different polarities, and in particular, a polyacetal resin (E) and a polyolefin resin (D), which will be described later, are used. Suitable for compatibility.

<Polyolefin resin (D)>
The polyolefin resin (D) in the present invention includes one or more (co) polymers of olefins, and one or more of olefins and one or more of other monomers. Contains copolymers.
The olefins include alkenes having 2 to 30 carbon atoms (hereinafter sometimes abbreviated as C), such as ethylene, propylene, 1- and 2-butene, and isobutene, and α-olefins having C5 to 30 (1-). Hexene, 1-decene, 1-dodecene, etc.); Other monomers include C4-30 unsaturated monomers having copolymerizability with olefins, such as vinyl acetate.

Specific examples of (D) include ethylene unit-containing (propylene unit-free) (co) polymers such as high-, medium- and low-density polyethylene, and ethylene and C4-30 unsaturated monomers [butene (1-). Butene, etc.), C5-30 α-olefin (1-hexene, 1-dodecene, etc.), vinyl acetate, etc.] and polymer (weight ratio is preferably 30/70 to 99/1, more preferably 50 / 50 to 95/5), etc .; propylene unit-containing (ethylene unit-free) (co) polymer, for example, a polymer (weight ratio) of polypropylene, propylene and a C4 to 30 unsaturated monomer (same as above). Is the same as above); ethylene / propylene copolymer (weight ratio is preferably 0.5 / 99.5 to 30/70, more preferably 2/98 to 20/80); ) Polymers, such as polybutene, are included.
Of these, from the viewpoint of mechanical strength and compatibility, polyethylene, polypropylene, ethylene / propylene copolymer, propylene / C4 to 30 unsaturated monomer copolymer, and more preferably ethylene / It is a propylene copolymer and an unsaturated monomer copolymer of propylene / C4 to 30.
The Mn (number average molecular weight) of (D) is preferably 10,000 to 500,000, more preferably 20,000 to 400,000, from the viewpoint of mechanical strength and compatibility.

<Polyacetal resin (E)>
Examples of the polyacetal resin (E) in the present invention include known polymers containing oxymethylene and, if necessary, oxyethylene as a unit structure.
Examples of the commercially available product of (E) include Delrin [registered trademark, manufactured by DuPont] and Duracon [registered trademark, manufactured by Polyplastics Co., Ltd.].
The polyacetal resin (E) may be used alone or in combination of two or more.

<Resin composition (Y)>
The resin composition (Y) of the present invention contains the phase solvent (X) for a polyacetal resin, a polyolefin resin (D), and a polyacetal resin (E).
The weight ratio [(D) / (E)] of (D) to (E) is preferably 10/90 to 90/10, more preferably 15/85 to 50, from the viewpoint of mechanical strength and compatibility. There are / 50 and 20/80 to 40/60.
Further, the weight ratio of the total weight of (D) and (E) to (X) {[(D) + (E)] / (X)} is preferably from the viewpoint of mechanical strength and compatibility. It is 80/20 to 99/1, more preferably 90/10 to 97/3.

If necessary, the composition contains a colorant, a mold release agent, an antioxidant, a flame retardant, and ultraviolet absorption other than the above (A), (D), and (E), as long as the effects of the present invention are not impaired. It can contain at least one of the following other additives (F) selected from the group consisting of agents, antibacterial agents, fillers, and transesterification inhibitors. Each of the (F) may be either one kind or a combination of two or more kinds.

Coloring agents (F1) include inorganic pigments [white pigments, cobalt compounds, iron compounds, sulfides, etc.], organic pigments [azo pigments, polycyclic pigments, etc.], dyes [azo-based, indigoid-based, sulfide-based, alizarin. System, aclysine system, thiazole system, nitro system, aniline system, etc.], etc.;

As the release agent (F2), lower (C1 to 4) alcohol esters of higher fatty acids (the above) (butyl stearate, etc.) and polyvalent (divalent to tetravalent or higher) fatty acids (C2 to 18) are used. ) Alcohol esters (hardened castor oil, etc.), glycols (C2-8) esters of fatty acids (C2-18) (ethylene glycol monostearate, etc.), liquid paraffins, etc.;

Examples of the antioxidant (F3) include phenol compounds [monocyclic phenol (2,6-di-t-butyl-p-cresol, etc.)) and bisphenol [2,2'-methylenebis (4-methyl-6-t-butylphenol). ) Etc.], Polycyclic phenol [1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, etc.], etc.], Sulfur compound (dilauryl 3) , 3'-thiodipropionate, etc.), phosphorus compounds (triphenylphosphite, etc.), amine compounds (octylated diphenylamine, etc.), etc.;

Examples of the flame retardant (F4) include halogen-containing flame retardants, nitrogen-containing flame retardants, sulfur-containing flame retardants, silicon-containing flame retardants, and phosphorus-containing flame retardants;

Examples of the ultraviolet absorber (F5) include benzotriazole [2- (2'-hydroxy-5'-methylphenyl) benzotriazole, etc.], benzophenone [2-hydroxy-4-methoxybenzophenone, etc.], salicylate [phenylsalicylate, etc.] Etc.], acrylate [2-ethylhexyl-2-cyano-3,3'1-diphenylacrylate, etc.], etc .;

Examples of the antibacterial agent (F6) include benzoic acid, sorbic acid, phenol halide, organic iodine, nitrile (2,4,5,6-tetrachloroisophthalonitrile, etc.), thiocyano (methylenebisthianosianate), and N-halo. Alkylthioimide, copper agent (8-oxyquinoline copper, etc.), benzimidazole, benzothiazole, trihaloallyl, triazole, organic nitrogen sulfur compound (Suraoff 39, etc.), quaternary ammonium compound, pyridine compound, etc.;

Examples of the filler (F8) include inorganic fillers (calcium carbide, talc, clay, etc.) and organic fillers (urea, calcium stearate, etc.);

Examples of the ester exchange inhibitor (F9) include phosphate esters [bisphenol A bis (diphenyl phosphate), monooctadecyl phosphate, dioctadecyl phosphate, etc.] and phosphite esters [Tris (2,4-di-t-butylphenyl). ) Phosphite, etc.] and the like.

The total content of (F) based on the total weight of (D) and (E) is, for example, 45% or less, preferably 0 from the viewpoint of the effect of each additive and the mechanical strength (mechanical properties) of the molded product. .001 to 40%, more preferably 0.01 to 35%; the content of each (E) is preferably 0.1 to 3%, more preferably 0.2 to 2 from the same viewpoint. %; (F2) is preferably 0.01 to 3%, more preferably 0.05 to 1%; (F3) is preferably 0.01 to 3%, still more preferably 0.05 to 1%; (F4). ) Is preferably 0.5 to 20%, more preferably 1 to 10%; (F5) is preferably 0.01 to 3%, further preferably 0.05 to 1%; (F6) is preferably 0. 5 to 20%, more preferably 1 to 10%; (F8) is preferably 0.5 to 10%, further preferably 1 to 5%; (F9) is 0.01 to 3%, still more preferably 0. It is 05 to 1%.

The resin composition of the present invention can be obtained by melt-mixing the compatibilizer (X) for resin, the polyolefin resin (D), the resin (E) of the present invention, and other additives (F) if necessary.
As a method of melt-mixing, generally, a method of mixing pellet-shaped or powder-shaped components with an appropriate mixer (Henschel mixer, etc.) and then melting-mixing with an extruder to pelletize is applied. can.
The order of addition of each component during melt mixing is not particularly limited, but for example,
[1] A method in which (X), (D), (E), and (F) if necessary are collectively added and melt-mixed;
[2] A part of (X), (D) and / or (E) is melt-mixed in advance to prepare a high-concentration composition (masterbatch resin composition) of (X), and then the remaining (D). And / or (E) and, if necessary, a method of melting and mixing (F) (master batch method or master pellet method); and the like.
The concentration of (X) in the masterbatch resin composition in the method [2] is preferably 40 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 (X) can be easily dispersed in the resin composition.

<Molded product>
The molded product of the present invention is obtained by molding the resin composition (Y) of the present invention. Examples of the molding method include injection molding, compression molding, calender molding, slush molding, rotary molding, extrusion molding, blow molding, film molding (cast method, tenter method, inflation method, etc.), and a single layer depending on the purpose. It can be molded by any method incorporating means such as molding, multi-layer molding or foam molding.

The molded product of the present invention has excellent mechanical properties and excellent appearance, and also has good paintability and printability, and a molded product can be obtained by painting and / or printing the molded product.
Examples of the method for coating the molded product include, but are not limited to, air spray coating, airless spray coating, electrostatic spray coating, immersion coating, roller coating, and brush coating.
As the paint, a paint generally used for painting plastics can be used, and specific examples thereof include polyester melamine resin paint, epoxy melamine resin paint, acrylic melamine resin paint and acrylic urethane resin paint.
The coating film thickness (dry film thickness) can be appropriately selected depending on the intended purpose, and is, for example, 10 to 50 μm.

As a method of printing on a molded product or a coated surface of the molded product, any printing method generally used for printing plastic can be used, and gravure printing, flexographic printing, screen printing, pad printing can be used. , Dry offset printing, offset printing and the like.
As the printing ink, known inks used for printing plastics can be used, and examples thereof include gravure ink, flexographic ink, screen ink, pad ink, dry offset ink, and offset ink.

Since the compatibilizer (X) for polyacetal resin has excellent compatibility, it gives a molded product of the resin composition excellent mechanical strength and excellent appearance. Therefore, the housing formed by various molding methods [injection molding, compression molding, calender molding, slush molding, rotary molding, extrusion molding, blow molding, foam molding and film molding (cast method, tenter method and inflation method), etc.] Products (for home appliances / OA equipment, game equipment, office equipment, etc.), plastic container materials [tray (IC tray, etc.) and other containers used in clean rooms], various cushioning materials, covering materials (packaging film and protection) It is suitable as a material for films, etc.), flooring sheets, artificial turf, mats, tape base materials (for semiconductor manufacturing processes, etc.) and various molded products (automobile parts, etc.).

Examples of the present invention will be described below, but the present invention is not limited thereto. In the following, parts indicate parts by weight.

<Manufacturing example 1>
[Manufacture of polyolefin (a2-1-1α) having carboxyl groups at both ends]
In a stainless steel pressure resistant reaction vessel equipped with a stirrer, a thermometer, a heating / cooling device, a nitrogen introduction tube and a depressurizing device, in a pressure resistant reaction vessel, a low molecular weight polypropylene [polypropylene (MFR: 10 g / MFR: 10 g /) obtained by a heat reduction method. 10 min) was heat-decomposed at 410 ± 0.1 ° C. under nitrogen aeration (80 mL / min) for 16 minutes. Mn: 3,400, number of double bonds per 1,000 carbon atoms: 7.0, average number of double bonds per molecule: 1.8, content of polyolefins that can be modified at both ends: 90 weight %] 90 parts, 10 parts of maleic anhydride and 30 parts of xylene were added, mixed uniformly, replaced with nitrogen, heated to 200 ° C. with stirring under sealing, melted, and reacted at the same temperature for 10 hours. I let you. Next, excess maleic anhydride and xylene were distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. for 3 hours to form a polyolefin (a2-1-1α) 95 having carboxyl groups at both ends of the polymer. I got a part. The acid value of (a2-1-1α) was 27.5, and Mn was 3,600.

<Manufacturing example 2>
[Production of polyolefin (a2-1-2) obtained by secondary modification of (a2-1-1α)]
88 parts of (a2-1-1α) and 12 parts of 12-aminododecanoic acid were put into the same pressure-resistant reaction vessel as in Production Example 1, mixed uniformly, and then heated to 200 ° C. with stirring under a nitrogen gas atmosphere. Then, the reaction was carried out at the same temperature under reduced pressure (0.013 MPa or less) for 3 hours to obtain 96 parts of polyolefin (a2-1-2) obtained by secondary modification of (a2-1-1α). The acid value of (a2-1-2) was 24.8, and Mn was 4,000.

<Manufacturing example 3>
[Manufacturing of polyether ester (b2α)]
79 parts of polyetherdiol [PEG (Mn: 600], 21 parts of dodecanedioic acid, and 0.1 part of zirconyl acetate were put into a reaction vessel equipped with a stirrer, a thermometer and a heating / cooling device, and while stirring. The temperature is raised to 240 ° C. and polymerized under reduced pressure (0.13 kPa or less) at the same temperature for 6 hours to obtain a viscous polyether ester (b2α) (hydroxyl value: 36.2, acid value: 0.4). rice field.

<Example 1>
In a reaction vessel equipped with a stirrer, a thermometer and a heating / cooling device, 67.1 parts of (a2-1-1α), polyetherdiamine (b1-2) [α, ω-diaminoPEG (Mn: 2,000)) ] 32.9 parts, 0.3 part of the antioxidant "Irganox 1010" and 0.5 part of zirconyl acetate are added, the temperature is raised to 220 ° C. with stirring, and the temperature is the same under reduced pressure (0.013 MPa or less). The mixture was polymerized for 6 hours to obtain a polyacetal resin compatibilizer (X-1) containing a block polymer (A2-1).
The Mn of (A2-1) was 50,000.

<Example 2>
In Example 1, 67.1 parts of (a2-1-1α) and 32.9 parts of (b1-2), 60.1 parts of (a2-1-2) and polyetherdiol (b1-1α) [PEG. (Mn: 3,000)] A compatibilizer (X-2) containing a block polymer (A2-2) was obtained in the same manner as in Example 1 except that the amount was changed to 39.9 parts. The Mn of (A2-2) was 30,000.

<Example 3>
In Example 1, 67.1 parts of (a2-1-1α) and 32.9 parts of (b1-2), 71.5 parts of (a2-1-2) and polyetherdiol (b1-1β) [poly A compatibilizer (X-3) containing a block polymer (A2-3) was obtained in the same manner as in Example 1 except that the amount was changed to 28.5 parts of tetramethylene glycol (Mn: 1,800). ..
The Mn of (A2-3) was 40,000.

<Example 4>
In Example 1, 67.1 parts of (a2-1-1α) and 32.9 parts of (b1-2), 62.5 parts of (a2-2), 34.5 parts of polyether ester (b2α) and dodecane. A compatibilizer (X-4) containing a block polymer (A2-4) was obtained in the same manner as in Example 1 except that the diacid was changed to 3 parts.
The Mn of (A2-4) was 24,000.

<Example 5>
In a reaction vessel equipped with a stirrer, a thermometer and a heating / cooling device, 60.1 parts of (a2-1-1α) and 39.8 parts of polyether diol (b1-1α) [PEG (Mn: 3,000)] , 0.3 part of antioxidant "Irganox 1010" and 0.8 part of zirconyl acetate were added, the temperature was raised to 220 ° C. with stirring, and the mixture was polymerized under reduced pressure (0.013 MPa or less) at the same temperature for 10 hours. , A compatibilizer (X-5) containing a block polymer (A2-5) was obtained.
The Mn of (A2-5) was 85,000.

<Comparative example 1>
The polyolefin (a2-1-1α) obtained in Production Example 1 was used as it was as a compatibilizer for resin (ratio X-1) for comparison.

<Examples 11 to 27, Comparative Example 11>
According to the compounding composition (parts by weight) shown in Tables 1 and 2, the compounding components are mixed with a Henschel mixer for 3 minutes, and then melt-kneaded by a twin-screw extruder with a vent under the conditions of 100 rpm, a residence time of 5 minutes, and a cylinder temperature of 190 ° C. Each resin composition (Y) was obtained.

The contents of the symbols in Tables 1 and 2 are as follows.
(D-1): Propylene-ethylene copolymer ["PM771M", manufactured by SunAllomer Ltd.]
(D-2): Polypropylene resin ["PM600A", manufactured by SunAllomer Ltd.]
(D-3): Ethylene-α-olefin copolymer ["Toughmer DF640", manufactured by Mitsui Chemicals, Inc.]

(E-1): Polyacetal resin,
[Duracon M90S, manufactured by Polyplastics Co., Ltd.]
(E-2): Polyacetal resin,
[Delrin 500, manufactured by DuPont Co., Ltd.]
(G3-1): Antioxidant ["Irganox 1010", Tetrakis [Methylene-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl))
Propionate] Methane, made by BASF]

A test piece was prepared from the obtained resin composition using an injection molding machine "PS40E5ASE" [manufactured by Nissei Resin Industry Co., Ltd.] at a cylinder temperature of 190 ° C. and a mold temperature of 80 ° C., and evaluated by the following performance test. .. The results are shown in Tables 1-2.

<Performance test>
(1) Number average particle size (unit: μm) of dispersed phases in the resin composition (Y)
Using a scanning electron microscope [model number "S4800", manufactured by Hitachi, Ltd.], a test piece whose surface was vapor-deposited with platinum was observed in a range of 25 μm × 35 μm, and the number average particle diameter (unit: μm) of the dispersed phase was observed. Was measured to evaluate compatibility. The number average particle size is a number average value in the range of 25 μm × 35 μm. The smaller the number average particle size, the better the compatibility of the resin composition.

(2) Tensile strength (unit: MPa), tensile elongation (%)
The center of the tensile test piece Type I of ASTM D638 was marked with 50 mm intervals. This was attached to an autograph and pulled at a speed of 50 mm / min to determine the maximum strength and the maximum elongation rate until the test piece broke.

(3) Izod impact strength (unit: kJ / m ² )
Measurements were made according to ASTM D256 Methods A (notched, 3.2 mm thick).

(4) Appearance The appearance of the surface of the test piece (100 × 100 × 2 mm) was visually observed and evaluated according to the following criteria.
<Evaluation criteria>
⊚: Good appearance with no abnormalities (striped pattern of color, flow mark, etc.) ○: Almost no abnormality in appearance △: There are some abnormalities in appearance ×: There is abnormality in appearance

From the results in Tables 1 and 2, the compatibilizer (X) for a polyacetal resin of the present invention imparts excellent mechanical strength to the molded product of the resin composition as compared with the comparative one. In addition, it has excellent compatibility and gives a molded product an excellent appearance.

The compatibilizer (X) for a polyacetal resin of the present invention imparts excellent mechanical strength and excellent appearance to a molded product of a resin composition. Therefore, the housing formed by various molding methods [injection molding, compression molding, calender molding, slush molding, rotary molding, extrusion molding, blow molding, foam molding and film molding (cast method, tenter method and inflation method), etc.] Products (for home appliances / OA equipment, game equipment, office equipment, etc.), plastic container materials [tray (IC tray, etc.) and other containers used in clean rooms], various cushioning materials, covering materials (packaging film and protection) It is suitable as a material for films, etc.), flooring sheets, artificial turf, mats, tape base materials (for semiconductor manufacturing processes, etc.) and various molded products (automobile parts, etc.).

Claims (8)

A compatibilizer (X) for a polyacetal resin containing a block polymer (A) having a block of a hydrophobic polymer (a) which is a polyolefin (a2) and a block of a hydrophilic polymer (b) as a constituent unit. The compatibilizer according to claim 1, wherein the hydrophilic polymer (b) is a polyether (b1) and / or a polyether-containing hydrophilic polymer (b2). The first or second claim, wherein the block polymer (A) has a [(a)-(b)] n-type (n = 2 to 50) structure in which (a) and (b) are alternately bonded. Compatibility agent. A resin composition (Y) containing the compatibilizer (X) according to any one of claims 1 to 3, a polyolefin resin (D), and a polyacetal resin (E). 4. The resin composition according to claim 4, wherein the weight ratio [(D) / (E)] of (D) to (E) is 10/90 to 90/10. Claim 4 or 5 in which the weight ratio {[(D) + (E)] / (X)} of the total weight of (D) and (E) to (X) is 80/20 to 99/1. The resin composition described. A molded product obtained by molding the resin composition (Y) according to any one of claims 4 to 6. A molded article obtained by painting and / or printing the molded article according to claim 7.