JP2015157799A - Antimicrobial agent for resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antimicrobial agent for a resin, which exhibits excellent antimicrobial activity to a thermoplastic resin by addition of a small amount, while maintaining mechanical strength of a molded article, and which can maintain its effect.SOLUTION: The antimicrobial agent for a resin comprises a quaternary ammonium salt with a counterion, which is a super strong acid, and a block polymer having a structure where a polyolefin block and a hydrophilic polymer block, having a volume resistivity value of 1×10to 1×10Ω cm, are bonded via at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond, an imide bond, and a urethane bond.

Description

  The present invention relates to an antibacterial agent for resin. More specifically, the present invention relates to an antibacterial agent for resin comprising a quaternary ammonium salt and a block polymer.

  Conventionally, antibacterial properties have been imparted by adding an antibacterial agent to a resin for hygienic needs and the like. Antibacterial agents to be added include inorganic antibacterial agents such as silver, copper and zinc zeolite (see Patent Document 1), organic antibacterial agents such as imidazole antibacterial agents (see Patent Document 2), and thiazoline antibacterial agents. (Refer to Patent Documents 3 and 4), a salt of an anionic polymer and a quaternary ammonium salt (refer to Patent Document 5), and a complex of a polyether ester amide and a quaternary ammonium salt (refer to Patent Document 6). ing.

JP-A-6-116458 Japanese Patent Laid-Open No. 52-7435 JP-A-8-310903 Japanese Patent Laid-Open No. 11-207880 JP 2000-154105 A JP 2004-285157 A

However, the antibacterial agents described in Patent Documents 1 to 4 cannot exhibit the effect unless a large amount is added to the resin, coloring of the resin due to the addition of a large amount, a decrease in the mechanical strength of the molded product, There was a problem that the effect was lost by washing with water. On the other hand, the polyether ester amide and quaternary ammonium salt complex described in Patent Document 5 is insufficient in dispersibility and compatibility with thermoplastic resins such as polyolefin resins, although the antibacterial properties of the molded article are improved. There was a problem in lowering the mechanical strength of the molded product.
An object of the present invention is to provide an antibacterial agent for resin that exhibits excellent antibacterial properties while maintaining the mechanical strength of a molded product with a small amount of addition to a thermoplastic resin and can maintain the antibacterial properties. It is.

The inventor of the present invention has arrived at the present invention as a result of intensive investigations to achieve the above object. That is, the present invention relates to a quaternary ammonium salt (A) whose counter ion is a super strong acid, and a hydrophilic polymer having a block of polyolefin (a) and a volume resistivity of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm. The block (b) contains a block polymer (B) having a structure in which the block is bonded via at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond, an imide bond and a urethane bond. An antibacterial resin composition comprising the antibacterial agent for resin (X); the (X) and the thermoplastic resin (D).

The antibacterial agent for resin of the present invention has the following effects.
(1) It imparts excellent antibacterial properties and durability to thermoplastic resins.
(2) A molded article of the antibacterial resin composition comprising the antibacterial agent and the thermoplastic resin is excellent in mechanical strength.

[Quaternary ammonium salt (A)]
In the present invention, the quaternary ammonium salt (A) whose counter ion is a super strong acid includes a quaternary ammonium salt (A1) represented by the following general formula (1); an amide group [alkyl (10 to 10 carbon atoms). 24) a quaternary ammonium salt (A2) having an amidoalkyl (2 to 6 carbon atoms) group and / or a hydroxyalkyl group having 2 to 4 carbon atoms; and a cyclic amine (pyridine, morpholine, etc.) type quaternary ammonium Salt (A3) is included, and (A1) is preferred.

R ¹ and R ² in the general formula (1) represent a linear or branched aliphatic hydrocarbon group having 1 to 22 (preferably 1 to 14) carbon atoms (such as an alkyl group and an alkenyl group).
As the linear aliphatic hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, Alkyl groups obtained by removing hydroxyl groups from alcohol derived from coconut oil (hereinafter abbreviated as coconut oil alkyl groups), oleyl groups, and the like can be mentioned. Examples of branched hydrocarbon groups include isopropyl groups and 2-ethylhexyl groups. . Of these, preferred are those having 1 to 14 carbon atoms, more preferred are 1 to 8 carbon atoms, particularly preferred are 1 or 2 carbon atoms, and most preferred is a methyl group. R ¹ and R ² may be the same or different, but are preferably the same.

R ³ represents a linear or branched aliphatic hydrocarbon group having 1 to 22 carbon atoms, an arylalkyl group having 7 to 22 carbon atoms, or an arylalkenyl group having 7 to 22 carbon atoms.
Examples of the linear or branched aliphatic hydrocarbon group include those exemplified above, examples of the arylalkyl group include benzyl group and phenethyl group, and examples of the arylalkenyl group include styryl group and cinnamyl group.
R ³ is preferably a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms, an arylalkyl group having 7 to 15 carbon atoms, an arylalkenyl group having 7 to 15 carbon atoms, and more preferably Is a linear or branched aliphatic hydrocarbon group having 6 to 14 carbon atoms.

R ⁴ represents a linear or branched aliphatic hydrocarbon group having 8 to 22 carbon atoms (such as an alkyl group or an alkenyl group).
Examples of the linear aliphatic hydrocarbon group include octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, coconut oil alkyl group and oleyl group, and branched aliphatic hydrocarbon groups. Examples of the group include a 2-ethylhexyl group. R ⁴ is preferably a linear or branched aliphatic hydrocarbon group having 8 to 18 carbon atoms, and more preferably a linear or branched aliphatic hydrocarbon group having 10 to 16 carbon atoms. X ⁻ represents an anion of a super strong acid.

As a specific example of the quaternary ammonium group constituting (A1), when R ³ is an aliphatic hydrocarbon group, for example, one having one long-chain alkyl group (trimethyldodecyl ammonium, trimethyl tetradecyl ammonium, Trimethyl hexadecyl ammonium, trimethyl octadecyl ammonium, trimethyl coconut oil alkyl ammonium, trimethyl-2-ethylhexyl ammonium, dimethyl ethyl dodecyl ammonium, dimethyl ethyl tetradecyl ammonium, dimethyl ethyl hexadecyl ammonium, dimethyl ethyl octadecyl ammonium, dimethyl ethyl coconut oil alkyl ammonium , Dimethylethyl-2-ethylhexylammonium, methyldiethyldodecylammonium, methyldiethyltetradecylan Ni, methyldiethylhexadecylammonium, methyldiethyloctadecylammonium, methyldiethyl palm oil alkylammonium and methyldiethyl-2-ethylhexylammonium), having two long-chain alkyl groups (6 to 22 carbon atoms) (dimethyldihexylammonium , Dimethyldioctylammonium, dimethyldidecylammonium and dimethyldidodecylammonium), those having one long-chain alkenyl group (8 to 22 carbon atoms) (trimethyloleylammonium, dimethylethyloleylammonium and methyldiethyloleylammonium) .
When R ³ is an arylalkyl group, for example, dimethyldecylbenzylammonium, dimethyldodecylbenzylammonium, dimethyltetradecylbenzylammonium, dimethylhexadecylbenzylammonium, dimethyl coconut oil alkylbenzylammonium, dimethyloleylbenzylammonium and dimethyl-2 -Ethylhexylbenzylammonium.
Of these, trimethylhexadecylammonium, dimethyldidecylammonium, dimethyldodecylbenzylammonium and dimethyltetradecylbenzylammonium are preferable from the viewpoint of antibacterial properties.

  Examples of the quaternary ammonium group constituting (A2) include oleamidoethyldiethylmethylammonium, stearamideethyldiethylbenzylammonium, and stearamidopropyldimethylhydroxyethylammonium groups.

  As the quaternary ammonium group constituting (A3), an alkyloxy (carbon number 8-24) methylpyridinium group (for example, stearyloxymethylpyridinium group), an alkyl (carbon number 8-24) oxymethylpyridinium group (for example, hexagonal group) Decyloxymethylpyridinium group) and alkyl (C10-24) pyridinium group (for example, tetradecylpyridinium group).

The super strong acid which is the counter ion of (A) is an acid having a stronger acid strength than 100% sulfuric acid ("super strong acid / super strong base" by Kozo Tabe, Ryoji Noyori, published by Kodansha Scientific, p1). Hammett's acidity function (H ₀ ) is less than -11.93 of 100% sulfuric acid, and examples include proton acids and acids composed of proton acids / Lewis acids.
Specific examples of the protonic acid, trifluoromethanesulfonic acid (H ₀ = -14.10), pentafluoroethane sulfonic acid (H ₀ = -14.00), and the like.
Examples of the protonic acid used in the protonic acid / Lewis acid combination include hydrogen halides (hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, etc.), and examples of the Lewis acid include boron trifluoride and pentafluoride. Phosphorous fluoride, antimony pentafluoride, arsenic pentafluoride, taurine pentafluoride and the like. The combination of the protonic acid / Lewis acid is arbitrary, but specific examples of the super strong acid obtained by combining them include boron tetrafluoride acid, hexafluorophosphoric acid, chlorofluoroboric acid, hexafluoroantimonic acid, hexa Examples thereof include fluorinated arsenic acid and taurine hexafluoride.
Among the above super strong acids, from the viewpoint of heat resistance of the quaternary ammonium salt (A) represented by the general formula (1) of the present invention, Hammett's acidity function (H ₀ ) is preferably −12. 00 or less, such as trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, boron tetrafluoride, phosphorus hexafluoride, chlorofluoroboric acid, antimony hexafluoride, arsenic hexafluoride, taurine hexafluoride, etc. Further preferred are trifluoromethanesulfonic acid, tetrafluoroboric acid and hexafluorophosphoric acid, and particularly preferred are trifluoromethanesulfonic acid and boron tetrafluoroboric acid.

  Among (A), (A1) is preferable from the viewpoint of antibacterial properties, its durability, and heat resistance, and dimethyldidecylammonium tetrafluoroborate and didecyldimethylammonium trifluoromethanesulfonic acid are particularly preferable. Salts, trimethyl hexadecyl ammonium tetrafluoroborate, dimethyl coconut oil alkylbenzyl ammonium tetrafluoroborate and dimethyl coconut oil alkyl benzyl ammonium trifluoromethanesulfonic acid.

  The production method of (A) is not limited and may be a known method, for example, the following methods [I] and [II]. The method [II] is preferred.

  [I] An alkali metal salt (sodium salt or potassium salt) of the super strong acid is added to an aqueous solution (20 to 70% by weight) of a quaternary ammonium salt [for example, a salt comprising a chloroanion] (a quaternary ammonium salt). / Equivalent ratio of super strong acid salt is usually 1/1 to 1 / 1.5, preferably 1 / 1.05 to 1 / 1.3), and an aqueous solution obtained by stirring and mixing at room temperature for about 2 hours is 70 to 80 After stirring for about 1 hour at 0 ° C., the lower layer (water layer) which has been allowed to stand and separate is removed, and the water in the upper layer is distilled off under reduced pressure to obtain the desired quaternary ammonium salt.

  [II] Carbonic acid dialkyl ester (alkyl group having 1 to 5 carbon atoms) of the same amount or more (preferably 1.1 to 5.0 equivalents) as the tertiary amine in the presence of a solvent (for example, methanol) (third 10 to 1000% based on the weight of the quaternary amine) or in the absence, the reaction temperature is 80 to 200 ° C., preferably 100 to 150 ° C. to form a quaternary ammonium salt, and the super strong acid is added ( 1.0-1.2 equivalents based on the equivalent of quaternary ammonium) and salt exchange by stirring at 10-50 ° C. for 1 hour. The solvent is distilled off under reduced pressure at 80 to 120 ° C. to obtain the desired quaternary ammonium salt. Examples of the carbonic acid dialkyl ester include dimethyl carbonate and diethyl carbonate, and the content of the carbonic acid diester (measurement method: gas chromatography method) is preferably 200 ppm or less, more preferably 0 to 100 ppm based on the weight of (A). Particularly preferably, it is 0 to 50 ppm. If the dialkyl carbonate is 200 ppm or less, it is preferable from the viewpoint of the mechanical strength of a molded product obtained by molding the antibacterial resin composition described later of the present invention.

  (A) in the present invention is usually solid at normal temperature (25 ° C.), and its melting point is usually 30 to 100 ° C., preferably 40 to 80 ° C.

[Polyolefin (a)]
The polyolefin (a) in the present invention includes a polyolefin (a1) having carbonyl groups (preferably carboxyl groups, the same shall apply hereinafter) at both ends of the polymer, a polyolefin (a2) having hydroxyl groups at both ends of the polymer, and amino groups. Polyolefin (a3) having both ends of the polymer and polyolefin (a4) having isocyanate groups at both ends of the polymer can be used. Further, a polyolefin (a5) having a carbonyl group at one end of the polymer, a polyolefin (a6) having a hydroxyl group at one end of the polymer, a polyolefin (a7) having an amino group at one end of the polymer, and an isocyanate group at one end of the polymer The polyolefin (a8) and the like possessed by can be used.
Of these, polyolefins (a1) and (a5) having a carbonyl group are preferable because of easy modification.

  (A1) to (a4) are polyolefins (a0) whose main component is a polyolefin that can be modified at both ends (preferably 50% or more, more preferably 75% or more, particularly preferably 80 to 100%). Those having a carbonyl group, a hydroxyl group, an amino group or an isocyanate group introduced at both ends are used. (A0) has 1 to 40, preferably 1 to 30, and particularly preferably 4 to 20 double bonds per 1,000 carbon atoms. Low molecular weight polyolefins [particularly number average molecular weight [hereinafter abbreviated as Mn] by thermal degradation method in terms of ease of modification. The measurement is based on a gel permeation chromatography (GPC) method. ] Of 1,200 to 6,000 polyethylene and / or polypropylene] is preferred.

In the low molecular weight polyolefin by the thermal degradation method, Mn is in the range of 800 to 6,000 and the average terminal double bond amount per molecule is 1.5 to 2 [Katsuhide Murata, Tadahiko Makino, The Chemical Society of Japan, p. 192 (1975)].
The low molecular weight polyolefin by the thermal degradation method can be obtained, for example, by the method described in JP-A-3-62804.

  (A5) to (a8) are polyolefins whose main component (preferably 50% or more, more preferably 75% or more, particularly preferably 80 to 100%) is a polyolefin (a00) that can be modified at least at one end. A compound in which a carbonyl group, a hydroxyl group, an amino group, or an isocyanate group is introduced into one end of (a00) is used.

(A00) can be obtained in the same manner as (a0), and Mn of (a00) is usually 2,000 to 50,000, preferably 2,500 to 30,000, particularly preferably 3,000 to 20,000.
(A00) has a double bond of 0.3 to 20, preferably 0.5 to 15, particularly preferably 0.7 to 10 carbon atoms per 1,000 carbon atoms.
From the viewpoint of easy modification, low molecular weight polyolefins (particularly polyethylene and / or polypropylene having Mn of 2,000 to 20,000) by thermal degradation are preferred.
In the low molecular weight polyolefin by the thermal degradation method, those having an average terminal double bond amount of 1 to 1.5 per molecule are obtained with Mn in the range of 5,000 to 30,000.
In addition, (a0) and (a00) are usually obtained as a mixture thereof, but these mixtures may be used as they are, or may be used after purification and separation. From the viewpoint of production cost and the like, it is preferably used as a mixture.

  Hereinafter, (a1) to (a4) having a carbonyl group, a hydroxyl group, an amino group or an isocyanate group at both ends of the polyolefin (a0) will be described, but these groups are present at one end of the polyolefin (a00) (a5) -(A8) can be obtained in the same manner as (a1)-(a4) by replacing (a0) with (a00).

  Hereinafter, (a1) to (a4) having a carbonyl group, a hydroxyl group, an amino group or an isocyanate group at both ends of the polyolefin (a0) will be described, but these groups are present at one end of the polyolefin (a00) (a5) -(A8) can be obtained in the same manner as (a1)-(a4) by replacing (a0) with (a00).

(A11) can be obtained by modifying (a0) with an α, β-unsaturated carboxylic acid (anhydride).
Examples of the α, β-unsaturated carboxylic acid (anhydride) used for modification include mono- and dicarboxylic acids having 3 to 10 carbon atoms (hereinafter sometimes abbreviated as C), and anhydrides thereof, for example, Examples include (meth) acrylic acid, maleic acid (anhydride), fumaric acid, itaconic acid (anhydride), and citraconic acid (anhydride). Of these, maleic acid (anhydride) and fumaric acid are preferred, and maleic acid (anhydride) is particularly preferred.
The amount of α, β-unsaturated carboxylic acid (anhydride) used for modification is usually 0.5 to 40%, preferably 1 to 30% based on the weight of the polyolefin (a0) (in the above and below). ,% Represents weight%).
The modification with α, β-unsaturated carboxylic acid (anhydride) can be performed by adding either a solution method or a melt method to the terminal double bond of (a0), α, β-unsaturated carboxylic acid (anhydride). Can be carried out by thermally adding (ene reaction). The temperature at which (a0) is reacted with the α, β-unsaturated carboxylic acid (anhydride) is usually 170 to 230 ° C.

(A12) can be obtained by secondary modification of (a11) with lactam or aminocarboxylic acid.
Examples of the lactam used for the secondary modification include C6-12 lactams such as caprolactam, enantolactam, laurolactam, and undecanolactam.
Examples of the aminocarboxylic acid include C2-12 aminocarboxylic acids such as amino acids (such as glycine, alanine, valine, and phenylalanine), ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocapric acid, 11- Examples include aminoundecanoic acid and 12-aminododecanoic acid. Of these, caprolactam and 12-aminododecanoic acid are preferred.
The amount of lactam or aminocarboxylic acid used for the secondary modification is 0.1 to 50, preferably 0.3 to, per residue of α, β-unsaturated carboxylic acid (anhydride) in (a11). The number is 20, particularly preferably 0.5 to 10, and most preferably 1.

  (A13) can be obtained by oxidizing (a0) with oxygen and / or ozone or hydroformylating by the oxo method. The introduction of the carbonyl group by oxidation can be carried out, for example, by the method described in US Pat. No. 3,692,877.

  (A13) can be obtained by oxidizing (a0) with oxygen and / or ozone or hydroformylating by the oxo method. The introduction of the carbonyl group by oxidation can be carried out, for example, by the method described in US Pat. No. 3,692,877.

  (A14) can be obtained by secondary modification of (a13) with lactam or aminocarboxylic acid. The same lactam and aminocarboxylic acid as can be used in (a12) can be used.

Mn of (a1) is usually 800 to 25,000, preferably 1,000 to 20,000, particularly preferably 2,500 to 10,000. It is preferable that Mn is in the range of 800 to 25,000 in terms of heat resistance and reactivity with the hydrophilic polymer (b) described later.
The acid value of (a1) is usually 4 to 280 (mg KOH / g, hereinafter, only numerical values are described), preferably 4 to 100, particularly preferably 5 to 50. An acid value within this range is preferable in terms of reactivity with the hydrophilic polymer (b) described later.

As the polyolefin (a2) having a hydroxyl group at both ends of the polymer, a polyolefin having a hydroxyl group obtained by modifying (a1) with hydroxylamine, and a mixture of two or more of these can be used.
Examples of hydroxylamine that can be used for modification include C2-10 hydroxylamine, such as 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, 4-aminobutanol, and the like. Of these, 2-aminoethanol is preferred.

The modification with hydroxylamine can be carried out by directly reacting (a1) with hydroxylamine. The reaction temperature is usually 120 to 230 ° C.
The amount of hydroxyl group of hydroxylamine used for modification is 0.1 to 2, preferably 0.3 to 1. per one residue of α, β-unsaturated carboxylic acid (anhydride) in (a1). The number is 5, particularly preferably 0.5 to 1.2, and most preferably 1.

Mn of (a2) is usually 800 to 25,000, preferably 1,000 to 20,000, particularly preferably 2,500 to 10,000. It is preferable that Mn is in the range of 800 to 25,000 in terms of heat resistance and reactivity with the hydrophilic polymer (b) described later.
The hydroxyl value of (a2) is usually 4 to 280 (mg KOH / g, hereinafter, only numerical values are described), preferably 4 to 100, particularly preferably 5 to 50. A hydroxyl value within this range is preferable in terms of reactivity with the hydrophilic polymer (b) described later.

As the polyolefin (a3) having an amino group at both ends of the polymer, a polyolefin having an amino group obtained by modifying (a1) with a diamine (Q13) and a mixture of two or more of these can be used.
Examples of the diamine (Q13) used for this modification include C2-18 (preferably 2-12) diamines such as ethylenediamine, hexamethylenediamine, heptamethylenediamine, and octamethylenediamine. Of these, ethylenediamine is preferred.

The modification with diamine can be carried out by directly reacting (a1) and diamine (Q13). The reaction temperature is usually 120 to 230 ° C.
The amount of the amino group of the diamine used for modification is 0.1 to 2, preferably 0.3 to 1.5, per residue of α, β-unsaturated carboxylic acid (anhydride) in (a1). The number is preferably 0.5 to 1.2, and most preferably 1.

  Mn of (a3) is usually 800 to 25,000, preferably 1,000 to 20,000, particularly preferably 2,500 to 10,000. It is preferable that Mn is in the range of 800 to 25,000 in terms of heat resistance and reactivity with the hydrophilic polymer (b) described later. The amine value of (a3) is usually 4 to 280 (mg KOH / g, hereinafter, only numerical values are described), preferably 4 to 100, particularly preferably 5 to 50. An amine value within this range is preferable in terms of reactivity with the hydrophilic polymer (b) described later.

As the polyolefin (a4) having an isocyanate group at both ends, a polyolefin having an isocyanate group obtained by modifying (a2) with poly (2 to 3 or more) isocyanate (hereinafter abbreviated as PI) and a mixture of two or more of these Can be used.
As PI, C (excluding C in the NCO group, the same shall apply hereinafter) 6 to 20 aromatic PI, C2 to 18 aliphatic PI, C4 to 15 alicyclic PI, and C8 to 15 araliphatic PI , Modified products of these PIs, and mixtures of two or more thereof.

  Specific examples of the aromatic PI include 1,3- and / or 1,4-phenylene diisocyanate (diisocyanate is hereinafter abbreviated as DI), 2,4- and / or 2,6-tolylene DI (TDI), crude TDI, 2,4′- and / or 4,4′-diphenylmethane DI (MDI), 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3, 3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene DI and the like can be mentioned.

  Specific examples of the aliphatic PI include ethylene DI, tetramethylene DI, hexamethylene DI (HDI), dodecamethylene DI, 2,2,4-trimethylhexamethylene DI, lysine DI, 2,6-diisocyanatomethyl carbonate. Examples include proate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

  Specific examples of the alicyclic PI include isophorone DI (IPDI), dicyclohexylmethane-4,4′-DI (hydrogenated MDI), cyclohexylene DI, methylcyclohexylene DI (hydrogenated TDI), bis (2- And isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane DI.

  Specific examples of the araliphatic PI include m- and / or p-xylylene DI (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.

  Specific examples of the araliphatic PI include m- and / or p-xylylene DI (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.

The reaction between (a2) and PI can be carried out in the same manner as a normal urethanization reaction.
The equivalent ratio (NCO / OH ratio) between PI and (a2) in forming the isocyanate-modified polyolefin is usually 1.8 / 1 to 3/1, preferably 2/1.

  Mn of (a4) is preferably 800 to 25,000, more preferably 1,000 to 20,000, and particularly preferably 2,500 from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b). -10,000.

[Hydrophilic polymer (b)]
Examples of the hydrophilic polymer (b) in the present invention include those contained in the hydrophilic polymer (b) described in Japanese Patent No. 3488163. That is, as (b), polyether (b1), polyether-containing hydrophilic polymer (b2), cationic polymer (b3), and anionic polymer (b4) can be used.
The volume resistivity value (unit: Ω · cm) of the hydrophilic polymer (b) is 1 × 10 ⁵ to 1 × 10 ¹¹ , preferably 1 × 10 ⁶ to 1 × 10 ⁹ . There is no volume specific resistance value of less than 1 × 10 ⁵ , and when it exceeds 1 × 10 ¹¹ , the antibacterial properties of the molded product described later deteriorate.
The volume resistivity is determined by molding the hydrophilic polymer (b) by using an injection molding machine “PS40E5ASE” [manufactured by Nissei Plastic Industry Co., Ltd.] at a cylinder temperature of 190 ° C. and a mold temperature of 50 ° C. A molded product (100 × 100 × 2 mm) was prepared, and in accordance with ASTM D257 (2007), the injection molded product was used at 23 ° C. using a super insulation meter “DSM-8103” [manufactured by Toa DKK Corporation] It is a value measured in an atmosphere with a humidity of 50% RH.

As the polyether (b1), polyether diol (b11), polyether diamine (b12), and modified products (b13) thereof can be used.
Examples of the polyether-containing hydrophilic polymer (b2) include polyether ester amide (b21) having a segment of polyether diol (b11) as a polyether segment forming component, and polyether amide imide (b22) having a segment of (b11). ), Polyether ester (b23) having the segment (b11), polyether amide (b24) having the segment (b12), and polyether urethane (b25) having the segment (b11) or (b12) Can be used. As the cationic polymer (b3), a cationic polymer having 2 to 80, preferably 3 to 60, cationic groups (c2) separated by a nonionic molecular chain (c1) in the molecule can be used. .
As the anionic polymer (b4), dicarboxylic acid (e1) having a sulfonyl group and diol (b0) or polyether (b1) are essential structural units, and 2 to 80, preferably 3 to Anionic polymers having 60 sulfonyl groups can be used.

The polyether (b1) will be described.
Of (b1), the polyether diol (b11) has a structure obtained by addition-reacting alkylene oxide (hereinafter abbreviated as AO) to the diol (b0). The general formula: H- (OA ¹ ) those represented by ^{_{m -O-E 1 -O- (A}} 1 O) m '-H and the like.
In the above formula, E ¹ is a residue obtained by removing the hydroxyl group from the diol (b0), A ¹ is a C2-4 alkylene group, and m and m ′ represent the number of AO additions per hydroxyl group of the diol (b0). m (OA ¹ ) and m ′ (A ¹ O) may be the same or different, and the bond form in the case where they are composed of two or more oxyalkylene groups is a block or Either random or a combination thereof may be used. m and m ′ are usually integers of 1 to 300, preferably 2 to 250, particularly preferably 10 to 100. M and m ′ may be the same or different.

Examples of the diol (b0) include dihydric alcohols (for example, C2-12 aliphatic, alicyclic or aromatic ring-containing dihydric alcohols), C6-18 dihydric phenols, and tertiary amino group-containing diols.
Examples of the aliphatic dihydric alcohol include alkylene glycol [ethylene glycol, propylene glycol (hereinafter abbreviated as EG and PG, respectively)], 1,4-butanediol, 1,6-hexanediol, neopentyl glycol (hereinafter 1 each). , 4-BD, 1,6-HD, abbreviated as NPG), and 1,12-dodecanediol.
Examples of the alicyclic dihydric alcohol include cyclohexanedimethanol, and examples of the aromatic ring-containing dihydric alcohol include xylylene diol. Examples of the dihydric phenol include monocyclic dihydric phenol (hydroquinone, catechol, resorcin, urushiol, etc.), bisphenol (bisphenol A, -F and -S, 4,4'-dihydroxydiphenyl-2,2-butane, Dihydroxybiphenyl and the like) and condensed polycyclic dihydric phenols (dihydroxynaphthalene, binaphthol and the like).

Examples of the tertiary amino group-containing diol include C1-12 aliphatic or alicyclic primary monoamines (methylamine, ethylamine, cyclopropylamine, 1-propylamine, 2-propylamine, amylamine, isoamylamine, hexylamine. 1,3-dimethylbutylamine, 3,3-dimethylbutylamine, 2-aminoheptane, 3-aminoheptane, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, nonylamine, decylamine, undecylamine, dodecylamine, etc.) Examples thereof include bishydroxyalkylated products and bishydroxyalkylated products of C6-12 aromatic monocyclic monoamines (aniline, benzylamine, etc.).
Of these, aliphatic dihydric alcohols and bisphenols are preferred, and EG and bisphenol A are particularly preferred.

The polyether diol (b11) can be produced by adding AO to the diol (b0).
AO includes C2-4 AO [ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- and 1,3-butylene oxide (hereinafter abbreviated as EO, PO, BO, respectively), and Two or more of these combined systems are used, and if necessary, other AO or substituted AO (hereinafter collectively referred to as AO) such as C5-12 α-olefin, styrene oxide, epihalohydrin (epichlorohydrin). Etc.) can be used together in a small proportion (for example, 30% or less based on the weight of the total AO).
When two or more kinds of AO are used in combination, the coupling form may be random and / or block. Preferred as AO is EO alone or a combination of EO and another AO (random and / or block addition). The added number of AO is an integer of usually 1 to 300, preferably 2 to 250, particularly preferably 10 to 100 per hydroxyl group of the diol (b0).

AO can be added by a known method, for example, at a temperature of 100 to 200 ° C. in the presence of an alkali catalyst. The content of the C2-4 oxyalkylene unit in (b11) is usually from 5 to 99.8%, preferably from 8 to 99.6%, particularly preferably from 10 to 98%.
The content of oxyethylene units in the polyoxyalkylene chain is usually 5 to 100%, preferably 10 to 100%, more preferably 50 to 100%, and particularly preferably 60 to 100%.

The polyether diamine (b12) has the general formula: H ₂ N—A ² — (OA ¹ ) _m —O—E ¹ —O— (A ¹ O) _{m ′} —A ² —NH ₂ (symbol E in the formula ¹ , A ¹ , m and m ′ are the same as described above, and A ² is a C2-4 alkylene group. A ¹ and A ² may be the same or different. .
(B12) can be obtained by changing the hydroxyl group of (b11) to an amino group by a known method. For example, the terminal obtained by cyanoalkylating the hydroxyl group of (b11) is reduced to an amino group. Can be used.
For example, it can be produced by reacting (b11) with acrylonitrile and hydrogenating the resulting cyanoethylated product.

Examples of the modified product (b13) include the aminocarboxylic acid modified product (terminal amino group), the isocyanate modified product (terminal isocyanate group) and the epoxy modified product (terminal epoxy group) of (b11) or (b12). It is done.
The modified aminocarboxylic acid can be obtained by reacting (b11) or (b12) with aminocarboxylic acid or lactam.
The isocyanate-modified product can be obtained by reacting (b11) or (b12) with a polyisocyanate as described later or reacting (b12) with phosgene.
The epoxy modified product is obtained by reacting (b11) or (b12) with diepoxide (epoxy resin such as diglycidyl ether, diglycidyl ester, alicyclic diepoxide: epoxy equivalent 85 to 600), or (b11) and epihalohydrin. It can be obtained by reacting with (e.g. epichlorohydrin).

  Number average molecular weight of the polyether (b1) [hereinafter abbreviated as Mn. The measurement is performed by a gel permeation chromatography (GPC) method to be described later] is usually 150 to 20,000, from the viewpoint of antibacterial properties, its durability, heat resistance and reactivity with the polyolefin (a). , Preferably 300 to 18,000, more preferably 1,000 to 15,000, particularly preferably 1,200 to 8,000.

The measurement conditions for Mn are as follows. Hereinafter, Mn is measured under the same conditions.
Equipment: High temperature GPC
Solvent: Orthodichlorobenzene Reference substance: Polystyrene Sample concentration: 3 mg / ml
Column stationary phase: PLgel MIXED-B
Column temperature: 135 ° C

  Examples of the polyether-containing hydrophilic polymer (b2) include polyether ester amide (b21) having a segment of polyether diol (b11) as a polyether segment forming component, and polyether amide imide having a segment of (b11) ( b22), polyether ester (b23) having the same segment (b11), polyether amide (b24) having the same segment of polyether diamine (b12) and polyether having the same segment (b11) or (b12) A urethane (b25) is mentioned.

The polyether ester amide (b21) is composed of a polyamide (Q1) having a carboxyl group at the terminal and a polyether diol (b11).
(Q1) includes a ring-opening polymer of C4-20 lactam (Q11) (described above); a polycondensate of C2-20 aminocarboxylic acid (Q12) (described above); diamine (Q13) ( The above) (C2-20 aliphatic diamine, C6-15 alicyclic diamine, C8-15 araliphatic diamine, C6-15 aromatic diamine, etc.) and C2-20 dicarboxylic acid (Q14) (The foregoing) Polyamide (Q15) with [aliphatic dicarboxylic acid, aromatic dicarboxylic acid, alicyclic dicarboxylic acid and their ester-forming derivatives [lower alkyl (C1-6) ester, anhydride, etc.], etc.] And mixtures thereof.
(Q1) is preferably a ring-opening polymer of caprolactam, a polycondensate of 12-aminododecanoic acid and a polyamide of adipic acid and hexamethylenediamine, and more preferably caprolactam. It is a ring-opening polymer.

The polyether amide imide (b22) is composed of a polyamide imide (Q2) having at least one imide ring and a polyether diol (b11).
(Q2) includes a polymer comprising a C4-20 lactam (Q11) and a trivalent or tetravalent aromatic polycarboxylic acid (Q21) capable of forming at least one imide ring; a C2-20 amino Examples thereof include a polymer composed of carboxylic acid (Q12) and (Q21); a polymer composed of polyamide (Q15) and (Q21); and a mixture thereof.

The polyether ester (b23) is composed of polyester (Q3) and polyether diol (b11).
(Q3) is a polyester of C2-20 dicarboxylic acid (Q14) and glycol [dihydric alcohol etc. in the diol (b0)]; C6-12 lactone (above) or C2-20 hydroxy And polyesters of carboxylic acids; and mixtures thereof.
The polyether amide (b24) is composed of polyamide (Q1) and polyether diamine (b12).
Polyether urethane (b25) includes diisocyanate among the polyisocyanates, polyether diol (b11) or polyether diamine (b12) and, if necessary, chain extender [dihydric alcohol, diamine in diol (b0) ( Q13) etc.].

The content of the polyether (b1) segment in the polyether-containing hydrophilic polymer (b2) is preferably 30 to 80%, more preferably 40 to 70% based on the weight of (b2), from the viewpoint of moldability. is there.
The content of oxyethylene groups in (b2) is 30 to 80%, more preferably 40 to 70%, based on the weight of (b2), from the viewpoint of moldability.
Mn in (b2) is preferably 800, more preferably 1,000 from the viewpoint of antibacterial properties, its durability, and heat resistance, more preferably 1,000, and a preferable upper limit from the viewpoint of reactivity with polyolefin (a) is 50,000, Preferably it is 30,000.

The cationic polymer (b3) is a hydrophilic polymer having 2 to 80, preferably 3 to 60, cationic groups (c2) separated in the molecule by a nonionic molecular chain (c1).
Examples of the cationic group (c2) include a group having a quaternary ammonium salt or a phosphonium salt. Examples of the counter anion of (c2) include a super strong acid anion and other anions.
The super strong acid anion includes an anion of a super strong acid (tetrafluoroboric acid, hexafluorophosphoric acid, etc.) derived from a combination of a protonic acid (d1) and a Lewis acid (d2), a super strong acid anion such as trifluoromethanesulfonic acid, etc. Examples include strong acid anions.
Examples of other anions include halogen ions (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ etc.), OH ⁻ , PO ₄ ⁻ , CH ₃ OSO ₄ ⁻ , C ₂ H ₅ OSO ₄ ⁻ , ClO ₄ ^{− and the} like. Can be mentioned.
Specific examples of the protonic acid (d1) that induces a super strong acid include hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, and the like.
Specific examples of the Lewis acid (d2) include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, and tantalum pentafluoride.

The nonionic molecular chain (c1) includes a divalent hydrocarbon group, or 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 / or Or a divalent organic group such as at least one divalent hydrocarbon group selected from the group consisting of a hydrocarbon group having a siloxy bond and a hydrocarbon group having a heterocyclic structure containing a nitrogen atom or an oxygen atom; and these These two or more types are used in combination.
Of these (c1), preferred are a divalent hydrocarbon group and a divalent hydrocarbon group having an ether bond.

  The Mn of the cationic polymer (b3) is preferably 500 to 20,000, more preferably 1,000 to 15,000, particularly from the viewpoint of antibacterial properties, its durability and reactivity with the polyolefin (a). Preferably, it is 1,200 to 8,000.

  Specific examples of the cationic polymer (b3) include cationic polymers described in JP-A No. 2001-278985.

The anionic polymer (b4) comprises a dicarboxylic acid (e1) having a sulfonyl group and a diol (b0) or a polyether (b1) as essential structural units, and 2 to 80, preferably 3 to 60 in the molecule. It is a hydrophilic polymer having one sulfonyl group.
As the dicarboxylic acid (e1), an aromatic dicarboxylic acid having a sulfonyl group, an aliphatic dicarboxylic acid having a sulfonyl group, or a salt of only these sulfonyl groups can be used.

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 [lower Alkyl (C1-4) ester (methyl ester, ethyl ester, etc.), acid anhydride, etc.].
Examples of the aliphatic dicarboxylic acid having a sulfonyl group include sulfosuccinic acid and ester-forming derivatives thereof [lower alkyl (C1-4) ester (methyl ester, ethyl ester, etc.), acid anhydride, etc.].
Examples of the salts in which only these sulfonyl groups are converted include salts of alkali metals (lithium, sodium, potassium, etc.), salts of alkaline earth metals (magnesium, calcium, etc.), ammonium salts, hydroxyalkyl (C2-4). ) Amine salts such as mono-, di- or tri-amines having organic groups (organic amine salts such as mono-, di- or tri-ethylamine, mono-, di- or tri-ethanolamine, diethylethanolamine), etc. Examples include quaternary ammonium salts of amines and combinations of two or more of these.
Of these, preferred are aromatic dicarboxylic acids having a sulfonyl group, more preferred are 5-sulfoisophthalic acid salts, and particularly preferred are 5-sulfoisophthalic acid sodium salt and 5-sulfoisophthalic acid potassium salt.

Among (b0) and (b1) constituting (b4), C2-10 alkanediol, EG, polyethylene glycol (hereinafter abbreviated as PEG) (degree of polymerization 2-20), bisphenol (bisphenol A, etc.) EO adduct (number of added moles 2 to 60) and a mixture of two or more thereof.
As a manufacturing method of (b4), the normal polyester manufacturing method can be applied as it is. The polyesterification reaction is usually performed in a temperature range of 150 to 240 ° C. under reduced pressure, and the reaction time is 0.5 to 20 hours. Moreover, in this esterification reaction, you may use the catalyst used for normal esterification reaction as needed.
Examples of esterification catalysts include antimony catalysts (such as antimony trioxide), tin catalysts (such as dibutyltin oxide), titanium catalysts (such as tetrabutyl titanate), zirconium catalysts (such as tetrabutylzirconate), and metal acetate catalysts (acetic acid). Zinc, etc.).

  Mn of (b4) is preferably 500 to 20,000, more preferably 1,000 to 15,000, particularly preferably 1 from the viewpoint of antibacterial properties, its durability and reactivity with the polyolefin (a). , 200-8,000.

[Block polymer (B)]
In the present invention, the block polymer (B) is selected from the group consisting of the polyolefin (a) block and the hydrophilic polymer (b) block consisting of an ester bond, an amide bond, an ether bond, an imide bond and a urethane bond. And having a structure bonded through at least one kind of bond.
Among these, the block polymer (B1) in which (b) is a polyether (b1) and (b) is a cationic polymer (b3) are preferable from the viewpoint of antibacterial properties, their durability, and the mechanical strength of the molded product. ) Is a block polymer (B3), and (b) is a block polymer (B4) which is an anionic polymer (b4).

  The weight ratio of the block (a) and the block (b) constituting (B) is preferably 10/90 to 80/20, more preferably 20/80 to 75 /, from the viewpoint of antibacterial properties and its durability. 25.

  Mn in (B) is preferably from 2,000 to 1,000,000, more preferably from 4,000 to 500,000, particularly preferably 6,000, from the viewpoint of mechanical strength and antibacterial properties of the molded product described later. ~ 100,000.

[Antimicrobial for resin (X)]
The antibacterial agent for resin (X) of the present invention comprises the quaternary ammonium salt (A) and the block polymer (B).
The weight ratio [(A) / (B)] of (A) and (B) in the antibacterial agent for resin of the present invention is preferably 3/97 to 30/70 from the viewpoint of antibacterial properties and mechanical strength of the molded product. More preferably, it is 5/95 to 20/80.

  The antibacterial agent for resin (X) of the present invention can be produced, for example, by melt-kneading (A) and (B) and then molding into a shape such as pellets or powder. As a specific example, it can be produced by mixing (A) and (B) with a mixer such as a Henschel mixer, then melt-kneading (150 to 260 ° C.) with a twin screw extruder and further pelletizing.

[Antimicrobial resin composition]
The antibacterial resin composition of the present invention comprises the antibacterial agent for resin (X) and a thermoplastic resin (D) described later.
The weight ratio [(X) / (D)] of the antibacterial agent for resin (X) and the thermoplastic resin (D) is preferably 3/97 to 30/70, from the viewpoint of antibacterial properties and mechanical strength. Preferably it is 5/95-20/80.

[Thermoplastic resin (D)]
Examples of the thermoplastic resin (D) in the present invention include polyolefin resins [eg, polyprolene (PP), polyethylene, ethylene-vinyl acetate copolymer resin (EVA), ethylene-ethyl acrylate copolymer resin, etc.]; Methyl methacrylate, etc.]; polystyrene resin [eg polystyrene, styrene / acrylonitrile copolymer (AN resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / butadiene / styrene copolymer (MBS resin) , Styrene / methyl methacrylate copolymer (MS resin), etc.]; polyester resin [for example, polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polybutylene adipate Polyamide resin [for example, nylon 66, nylon 69, nylon 612, nylon 6, nylon 11, nylon 12, nylon 46, nylon 6/66, nylon 6/12, etc.]; Polycarbonate resin [for example, polycarbonate, polycarbonate / ABS resin alloy and the like]; polyvinyl chloride resin; polyacetal resin; thermoplastic polyurethane resin and the like.
Of the above thermoplastic resins (D), preferred are polyolefin resins, polystyrene resins, polyacetal resins, polyvinyl chloride resins, polyester resins, polycarbonate resins, thermoplastic polyurethane resins, and more preferred are polyolefin resins, polystyrene resins, polyacetal resins. Polyvinyl chloride resin and thermoplastic polyurethane resin, particularly preferred are polyolefin resin, polystyrene resin and polyvinyl chloride resin.

  The antibacterial resin composition of the present invention is further selected from pigments, nucleating agents, plasticizers, stabilizers, fillers, flame retardants, antioxidants and ultraviolet absorbers as necessary, as long as the effects of the present invention are not impaired. Other additives may be included.

   Examples of pigments include titanium oxide, bengara, yellow lead, cadmium, ultramarine, azo series, phthalocyanine series, vat dye series, quinacridone series, dioxazine series, dyed lake, etc .; nucleating agents such as dibenzylidene sorbitol; plasticizers Phthalates (dioctyl phthalate, etc.), phosphates, adipic acid, sebates, glycolates, polyesters, epoxies, etc .; stabilizers include lead white, basic sulfite Lead, tribasic lead sulfate, dibasic lead phosphite, silica gel co-precipitated lead silicate, liquid metal, laurate organotin, maleate organotin, mercaptide organotin, antimony, poxy, phosphorous Acid ester, etc .; Fillers include calcium carbonate, talc, clay, silicic acid, silicate, asbestos , Mica, glass fiber, glass balloon, carbon fiber, metal fiber, ceramic whisker, titanium whisker, etc .; as a flame retardant, phosphate ester type [tricresyl phosphate, tris (2,3 dibromopropyl) phosphate, etc.], Bromine (such as decabromobiphenyl ether), antimony trioxide, magnesium hydroxide, borate (such as zinc borate and barium metaborate), aluminum hydroxide, red phosphorus, magnesium hydroxide, ammonium polyphosphate, het acid And tetrabromobisphenol A.

  Moreover, as antioxidant, phenolic antioxidant [2,6-di-t-butyl-p-cresol (BHT), 2,2′-methylenebis (4-methyl-6-t-butylphenol), etc.] Sulfur-based antioxidants [dilauryl 3,3′-thiodipropionate (DLTDP), distearyl 3,3′-thiodipropionate (DSTDP), etc.]; phosphorus antioxidants [triphenyl phosphite (TPP ), Triisodecyl phosphite (TDP), etc.]; amine antioxidants [octylated diphenylamine, Nn-butyl-p-aminophenol, N, N-diisopropyl-p-phenylenediamine, etc.], etc .; UV absorption Examples of the agent include benzophenone (2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2 ′, , 4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, etc.), salicylates (phenyl salicylate, 2,4-di-t-butylphenyl- 3,5-di-t-butyl-4-hydroxybenzoate, etc.), benzotriazole series [(2'-hydroxyphenyl) benzotriazole, (2'-hydroxy-5'-methylphenyl) benzotriazole, (2'- Hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, (2′-hydroxy-5′-methacryloyloxyethylphenyl) benzotriazole and its (co) polymer, etc.], acrylic [Ethyl-2-cyano-3,3-diphenyl acrylate , Methyl 2-carbomethoxy-3- (p-methoxybenzyl) acrylate], and the like; and the like.

  The amount of the other additives used is usually 80% or less, preferably 10 to 50% for the plasticizer and filler, and usually 40% or less, preferably 10 to 30% for the flame retardant, based on the weight of (D). %, Pigments are usually 40% or less, preferably 1 to 10%, nucleating agents and stabilizers are usually 10% or less, preferably 1 to 5%, antioxidants and UV inhibitors are usually 5% or less, preferably 0 .1 to 2%.

[Molded articles and molded articles]
The molded product of the present invention is formed by molding the antibacterial resin composition.
Examples of molding methods include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.), etc., depending on the purpose. Molding, multilayer molding, foam molding and the like can be performed by any method that incorporates means. Examples of the form of the molded product include a plate shape, a sheet shape, a film, a woven fabric, and a fiber (including a nonwoven fabric).

The molded article of the present invention has excellent antibacterial properties and mechanical strength, and also has good paintability and printability, and a molded article can be obtained by painting and / or printing the molded article.
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.
Examples of the paint include paints generally used for plastic coating such as polyester melamine resin paint, epoxy melamine resin paint, acrylic melamine resin paint, acrylic urethane resin paint, and these so-called relatively high-polarity paints, Further, paints with low polarity (such as olefins) can also be used.
The coating film thickness (dry film thickness) can be appropriately selected according to the purpose, but is usually 10 to 50 μm.

Further, as a method for further printing after coating the molded product or the molded product, any printing method generally used for plastic printing can be used. For example, gravure printing, flexographic printing, Examples include printing, screen printing, pad printing, dry offset printing, and offset printing.
As the printing ink, those usually used for printing plastics, for example, gravure ink, flexographic ink, screen ink, pad ink, dry offset ink and offset ink can be used.

  Hereinafter, the present invention will be further described with reference to Examples and Production Examples, but the present invention is not limited thereto. The part in an Example shows a weight part.

[Production of quaternary ammonium salt (A)]
<Production Example 1>
A glass reaction vessel equipped with a heating / cooling device, a stirrer, and a dropping funnel was charged with 56 parts of methanol, 163 parts of methyldi-n-decylamine (0.88 mol), and 144 parts of dimethyl carbonate (1.6 mol) at 120 ° C. Then, methanol and a part of dimethyl carbonate were distilled off to obtain 250 parts (0.52 mol) of 83% methanol solution of dimethyldi-n-decylammonium methyl carbonate. Further, after raising the temperature to 30 to 60 ° C., 114 parts (0.55 mol) of 42% aqueous solution of boron tetrafluoride was gradually added over 2 hours while maintaining the temperature. Thereafter, the mixture was further stirred at the same temperature for 1 hour, and then the upper layer which was allowed to stand and separated was collected, methanol and water were distilled off under reduced pressure at 80 to 100 ° C., and further dried under reduced pressure (decompression degree 950 hpa, 105 ℃ × 3 hours), then melted at 80 ℃, the precipitated salt was removed by filtration through a 200 mesh wire mesh, and dimethyldi-n-decylammonium tetrafluoroborate (A-1) 206 solid at room temperature Got a part.

<Production Example 2>
To 250 parts (0.52 mol) of an 83% methanol solution of dimethyldi n-decylammonium methyl carbonate obtained in the same manner as in Production Example 1, 79.5 parts (0.53 mol) of trifluoromethanesulfonic acid was added at room temperature. Stir for 2 hours. The reaction solution is neutralized by adding granular caustic potash (ph: 6-8), and the precipitated salt is filtered, then methanol in the filtrate is distilled off, dried under reduced pressure (same conditions as above), and melted at 120 ° C. It was taken out in a state, and 250 parts of dimethyldi n-decylammonium trifluoromethanesulfonate (A-2) solid at room temperature was obtained.

<Production Example 3>
293 parts (2.67 mole) of sodium tetrafluoroborate and 65 parts (0.49 mole) of 30% sodium hydroxide aqueous solution are blended at room temperature with 1,100 parts of water, and dimethyl coconut oil alkylbenzylammonium chloride 80% methanol solution 1058 parts (2.39 mol) was added and stirred for 2 hours. The reaction solution was further stirred at 50 to 60 ° C. and then allowed to stand at the same temperature for 1 hour. The lower layer (aqueous layer) was separated and removed, and the upper layer methanol and water were distilled off to obtain dimethyl coconut oil alkylbenzylammonium tetrafluoroborate (A-3) solid at room temperature.

[Production of block polymer (B)]
<Production Example 4> [Production of polyolefin (a11α) having carboxyl groups at both ends]
In a stainless pressure-resistant reaction vessel equipped with a stirrer, a thermometer, a heating / cooling device, a nitrogen introduction tube, and a decompression device, low molecular weight polypropylene obtained by a thermal degradation method [polypropylene (MFR: 10 g / 10 min) is 410 ± 0. Obtained by heat degradation for 16 minutes at 1 ° C. under nitrogen flow (80 mL / min). 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 polyolefin 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, purged with nitrogen, melted by heating to 200 ° C. with stirring and sealed, and reacted at the same temperature for 10 hours. I let you. Subsequently, excess maleic anhydride and xylene were distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to obtain 95 parts of polyolefin (a11α) having carboxyl groups at both ends of the polymer. . The acid value of (a11α) was 27.5, and Mn was 3,600.

<Production Example 5>
[Production of polyolefin (a12α) obtained by secondary modification of (a11α)]
In a pressure resistant reactor similar to Production Example 4, 88 parts of (a11α) and 12 parts of 12-aminododecanoic acid were added and mixed uniformly, and then heated to 200 ° C. with stirring in a nitrogen gas atmosphere. For 3 hours under reduced pressure (0.013 MPa or less) to obtain 96 parts of polyolefin (a12α) obtained by secondary modification of (a11α). The acid value of (a12α) was 24.8, and Mn was 4,000.

<Production Example 6>
[Production of polyolefin having hydroxyl groups at both ends (a21)]
In Production Example 4, 90 parts of low molecular weight polypropylene and 10 parts of maleic anhydride obtained by the thermal degradation method were replaced with 94 parts of low molecular weight ethylene / propylene random copolymer obtained by the thermal degradation method and 6 parts of maleic anhydride. Except having changed into the part, it carried out similarly to manufacture example 4, and obtained 98 parts of polyolefin (a11 (beta)) which has a carboxyl group at the both ends of a polymer. The acid value of (a11β) was 9.9, and Mn was 10,200.
The low molecular weight ethylene / propylene random copolymer obtained by the above thermal degradation method (Mn: 10,000, number of double bonds per 1,000 carbon atoms: 2.5, two per molecule) The average number of heavy bonds: 1.8, the content of polyolefin that can be modified at both ends: 90% by weight) is 410 ethylene / propylene random copolymer (ethylene content: 2% by weight, MFR: 10 g / 10 min). It was obtained by thermal degradation for 14 minutes at ± 0.1 ° C. under nitrogen aeration (80 mL / min).
Next, 97 parts of (a11β) and 5 parts of ethanolamine were charged into the same pressure resistant reactor as in Production Example 4, heated to 180 ° C. with stirring in a nitrogen gas atmosphere, and reacted at the same temperature for 2 hours. . Excess ethanolamine was distilled off under reduced pressure (0.013 MPa or less) at 180 ° C. over 2 hours to obtain a polyolefin (a21) having hydroxyl groups at both ends of the polymer. The hydroxyl value of (a21) was 9.9, the amine value was 0.01, and Mn was 10,200.

<Production Example 7>
[Production of modified polyolefin (a31) having amino groups at both ends]
In Production Example 4, 90 parts of low molecular weight polypropylene and 10 parts of maleic anhydride obtained by thermal degradation were changed to 80 parts of low molecular weight polypropylene and 20 parts of maleic anhydride obtained by thermal degradation. In the same manner as in Production Example 4, 92 parts of polyolefin (a11γ) having carboxyl groups at both ends of the polymer was obtained. The acid value of (a11γ) was 64.0, and Mn was 1,700. The low molecular weight polypropylene obtained by the above thermal degradation method (Mn: 1,500, the number of double bonds per 1,000 carbon atoms: 17.8, the average number of double bonds per molecule: 1.94, the content of polyolefin that can be modified at both ends: 98% by weight) is an ethylene / propylene random copolymer (ethylene content: 3% by weight, MFR: 7 g / 10 min) of 410 ± 0.1 ° C., It was obtained by heat degradation for 18 minutes.
Next, 90 parts of (a11γ) and 10 parts of bis (2-aminoethyl) ether are put into a pressure resistant reaction vessel similar to Production Example 4, and the temperature is raised to 200 ° C. with stirring in a nitrogen gas atmosphere. For 2 hours. Excess bis (2-aminoethyl) ether was distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 2 hours to obtain a modified polyolefin (a31) having amino groups at both ends. The amine value of (a31) was 64.0, and Mn was 1,700.

<Production Example 8>
[Production of Cationic Polymer (b3α)]
In a pressure-resistant reaction vessel similar to Production Example 4, 41 parts of N-methyldiethanolamine, 49 parts of adipic acid and 0.3 part of zirconyl acetate were added, and the temperature was raised to 220 ° C. over 2 hours, followed by 1 hour. The pressure was reduced to 0.013 MPa over a polyester reaction. After completion of the reaction, the reaction mixture was cooled to 50 ° C. and dissolved by adding 100 parts of methanol. While stirring, the temperature in the reaction vessel was kept at 120 ° C., 31 parts of dimethyl carbonate was added dropwise over 3 hours, and the mixture was aged at the same temperature for 6 hours. After cooling to room temperature, 100 parts of a 60 wt% hexafluorophosphoric acid aqueous solution was added and stirred at room temperature for 1 hour. Subsequently, methanol was distilled off under reduced pressure, and a cationic polymer (b3α) having an average of 12 quaternary ammonium groups (hydroxyl value: 30.1, acid value: 0.5, volume resistivity: 1 × 10 ⁵ Ω · cm )

<Production Example 9>
[Production of anionic polymer (b4α)]
In a pressure-resistant reaction vessel similar to Production Example 4, 67 parts of PEG (Mn: 300), 49 parts of sodium salt of 5-sulfoisophthalic acid dimethyl ester and 0.2 part of dibutyltin oxide were charged under a reduced pressure of 0.067 MPa. The temperature was raised to 190 ° C., and the ester exchange reaction was carried out at the same temperature for 6 hours while distilling off methanol. An anionic polymer (b4α) having an average of 5 sodium sulfonate groups in one molecule (hydroxyl value: 29.6, Acid value: 0.4, volume resistivity: 2 × 10 ⁶ Ω · cm).

<Production Example 10>
[Production of block polymer (B-1)]
In a reaction vessel equipped with a stirrer, a thermometer and a heating / cooling device, 67.1 parts of (a11α), polyetherdiamine (b12α) [α, ω-diaminoPEG (Mn: 2,000, volume resistivity: 1 × 10 ⁷ Ω · cm)] 32.9 parts, 0.3 parts of the antioxidant “Irganox 1010” and 0.5 parts of zirconyl acetate were added, the temperature was raised to 220 ° C. with stirring, and the pressure was reduced (0 Polymerization was carried out at the same temperature for 3 hours to obtain a viscous block polymer (B-1). Mn of (B-1) was 50,000.

<Production Example 11>
[Production of block polymer (B-2)]
In Production Example 10, (a11α) 67.1 parts and (b12α) 32.9 parts, (a12α) 60.1 parts and polyether diol (b11α) [PEG (Mn: 3,000, volume resistivity: 1 × 10 ⁷ Ω · cm)] A block polymer (B-2) was obtained in the same manner as in Production Example 10, except that the content was changed to 39.9 parts. Mn of (B-2) was 30,000.

<Production Example 12>
[Production of block polymer (B-3)]
In Production Example 10, (a11α) 67.1 parts and (b12α) 32.9 parts were changed to (a21) 48.0 parts, (b3α) 48.0 parts and dodecanedioic acid 4 parts. In the same manner as in Example 10, a block polymer (B-3) was obtained. The Mn of (B-3) was 100,000.

<Production Example 13>
[Production of block polymer (B-4)]
In Production Example 10, (a11α) 67.1 parts and (b12α) 32.9 parts were changed to (a31) 31.6 parts, (b4α) 68.4 parts and dodecanedioic acid 8 parts. In the same manner as in Example 10, a block polymer (B-4) was obtained. The Mn of (B-4) was 10,000.

<Production Example 14>
[Production of block polymer (B-5)]
In Production Example 10, (a11α) 67.1 parts and (b12α) 32.9 parts, (a12α) 71.5 parts and polyether diol (b11β) [polytetramethylene glycol (Mn: 1,800, inherent volume) (Resistance value: 1 × 10 ¹¹ Ω · cm) A block polymer (B-5) was obtained in the same manner as in Production Example 10, except that the value was changed to 28.5 parts. The Mn of (B-5) was 40,000.

<Production Example 15>
[Production of block polymer (B-6)]
In Production Example 10, (a11α) 67.1 parts and (b12α) 32.9 parts were changed to (a21) 48.0 parts, (b3α) 48.0 parts and hexamethylene diisocyanate (HDI) 3 parts. Produced a block polymer (B-6) in the same manner as in Production Example 10. Mn of (B-6) was 100,000.

<Comparative Production Example 1>
[Production of block polymer (ratio B-1)]
A pressure-resistant reaction vessel was charged with 83.5 parts of ε-caprolactam, 16.5 parts of terephthalic acid, 0.3 part of “Irganox 1010” (manufactured by BASF) as an antioxidant and 6 parts of water. The mixture was heated and stirred at 220 ° C. under pressure and sealing for 4 hours to obtain 96 parts of a polyamide oligomer having an acid value of 112 having carboxyl groups at both ends. Next, 192 parts of bisphenol A ethylene oxide adduct of 2,000 Mn and 0.5 part of zirconyl acetate were added and polymerized at 245 ° C. under reduced pressure of 0.2 kPa or less for 5 hours to form a viscous block polymer (ratio B -1) was obtained. It was 80,000 of (ratio B-1).

<Examples 1-8, Comparative Examples 1-3>
According to the blending composition (parts by weight) shown in Table 1, the blending components are mixed for 3 minutes with a Henschel mixer, then melt kneaded with a twin screw extruder at 100 rpm, 220 ° C. and a residence time of 5 minutes, and further pelletized. Thus, the antibacterial agents for resins (X-1) to (X-8) and (X′-1) to (X′-3) of Examples 1 to 9 and Comparative Examples 1 to 3 were obtained. The results are shown in Table 1.

The contents of the symbols in Table 1 are as follows.
(Ratio A-1): Dimethyldi-n-decylammonium chloride

<Examples 9 to 23 and Comparative Examples 4 to 13>
According to the compounding composition (parts by weight) shown in Table 2, the compounding components were mixed with a Henschel mixer for 3 minutes, and then used at 100 rpm, 220 ° C. [(D-1, 2, 4) using a vented twin screw extruder. Case] or 190 ° C. [in the case of using (D-3)], the mixture was melt-kneaded under the condition of a residence time of 5 minutes to obtain an antibacterial resin composition.
Next, the obtained antibacterial resin composition is used with an injection molding machine “PS40E5ASE” [manufactured by Nissei Plastic Industry Co., Ltd.] and a cylinder temperature of 220 ° C. (when (D-1, 2, 4) is used) or 190 [In the case of using (D-3)], molding is performed at a mold temperature of 50 ° C. to produce an injection molded product (100 × 100 × 2 mm) and an injection molded product (127 × 10 × 4 mm), and the following performance test It was evaluated by. The results are shown in Table 2.

<Evaluation of antibacterial properties>
The antibacterial properties of the obtained injection molded products were evaluated according to JIS Z 2801 (antibacterial processed product-antibacterial test method / antibacterial effect).
A test bacterial solution prepared by diluting ordinary bouillon medium 500 times with sterilized purified water so that the number of bacteria becomes 2.5 × 10 ⁵ to 10 × 10 ⁵ cells / ml, was prepared by injection molding (100 × 100 × 2 mm) was dropped on a test piece cut out to 50 mm × 50 mm × 2 mm, and the film was covered from above so as not to dry, and cultured at a temperature of 35 ± 1 ° C. and a relative humidity of 90% or more for 24 ± 1 hour. Thereafter, the test piece and the film were washed out with 10 ml of SCDLP medium, and the solution was immediately subjected to viable cell count to determine the viable cell count (number of units forming a colony / ml).
<Evaluation of antimicrobial durability>
The obtained injection-molded product was washed with water and dried at 80 ° C. for 3 hours with a circulating dryer. After repeating this operation 10 times in total, the antibacterial property of the injection-molded product was evaluated in the same manner as the above method.

<Evaluation of mechanical strength>
(1) Izod impact value Measured by Method A according to ASTM D256 (1984). The test piece was cut from an injection molded product (127 × 10 × 4 mm) to 63.5 mm × 10 mm × 4 mm and provided with a notch (3.2 mm thickness).
(2) Compatibility The injection molded product (100 × 100 × 2 mm 2) was bent and broken at 25 ° C., and the fracture surface was observed, and the evaluation was made according to the following criteria.
Evaluation criteria A: The surface layer part does not peel at all.
○: The surface layer peels off very slightly.
(Triangle | delta): A surface layer part peels partially.
X: A surface layer part peels largely.

The contents of the symbols in Table 2 are as follows.
(Y-1): 2- (4′-thiazolyl) -benzimidazole
[Tokyo Chemical Industry Co., Ltd.]
(D-1): PP resin “PM771M” [manufactured by Sun Allomer Co., Ltd.]
(D-2): ABS resin “Cebian V 320F” [manufactured by Daicel Polymer Ltd.]
(D-3): Vinyl chloride resin “Vinica CB55EB” [Mitsubishi Chemical Corporation]
(D-4): HDPE resin (high density polyethylene resin)
"Novatec HJ580N" [Nippon Polyethylene Corporation]

  From the results of Table 2, the antibacterial agent for resins of the present invention imparts superior antibacterial properties and durability to thermoplastic resins compared to comparative ones. Furthermore, it turns out that the molded article of an antibacterial resin composition is excellent in mechanical strength.

  The antibacterial agent for resin of the present invention imparts excellent antibacterial property and durability to thermoplastic resins, and further provides excellent mechanical strength. Therefore, the antibacterial agent for resin and antibacterial resin composition of the present invention are Sanitary materials molded by various molding methods [injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, foam molding and film molding (for example, casting method, tenter method and inflation method), etc.] (Medical / hygiene materials, etc.), daily life materials (bottles, cups, trays, etc.), housing products [for home appliances / OA equipment, game machines, office equipment, etc.], plastic container materials [trays used in clean rooms (IC trays) Etc.), other containers, etc.], various cushioning materials, coating materials (wrapping film, protective film, etc.), flooring sheet, artificial grass, mat, tape Material (for the production process, etc.), as well as various molded articles can be widely used as (automobile parts, etc.) for material, it is extremely useful.

Claims (11)

The quaternary ammonium salt (A) whose counter ion is a super strong acid, and the block of the polyolefin (a) and the block of the hydrophilic polymer (b) having a volume resistivity value of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm And an antibacterial agent for resin comprising a block polymer (B) having a structure in which at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond, an imide bond and a urethane bond (X). The antibacterial agent for resin according to claim 1, wherein (A) is a quaternary ammonium salt represented by the general formula (1).

[Wherein, R ¹ and R ² are the same or different, a linear or branched aliphatic hydrocarbon group having 1 to 22 carbon atoms, and R ³ is a linear or branched aliphatic hydrocarbon group having 1 to 22 carbon atoms. A hydrocarbon group, an arylalkyl group having 7 to 22 carbon atoms or an arylalkenyl group having 7 to 22 carbon atoms, R ⁴ is a linear or branched aliphatic hydrocarbon group having 8 to 22 carbon atoms, and X ⁻ is Represents an anion of super strong acid. ] The antibacterial agent for resin according to claim 1 or 2, wherein the super strong acid has a Hammett acidity function (H ₀ ) of -12.00 or less.   The antibacterial agent for resin according to any one of claims 1 to 3, wherein the super strong acid is a super strong acid comprising a combination of a protonic acid and a Lewis acid.   The number average molecular weight of (B) is 6,000-100,000, The antibacterial agent for resin in any one of Claims 1-4.   The antibacterial agent for resin according to any one of claims 1 to 5, wherein (a) is a polyolefin by a thermal degradation method.   The antibacterial agent for resin according to any one of claims 1 to 6, wherein the weight ratio [(A) / (B)] of (A) to (B) is 3/97 to 30/70.   An antibacterial resin composition comprising the antibacterial agent for resin (X) according to any one of claims 1 to 7 and a thermoplastic resin (D).   The antibacterial resin composition according to claim 8, wherein the weight ratio [(X) / (D)] of (X) to (D) is 3/97 to 30/70.   A molded article formed by molding the antibacterial resin composition according to claim 8 or 9.   A molded article obtained by coating and / or printing the molded article according to claim 10.