JP7248500B2 - Cyclic polyetherester composition and antibacterial resin composition containing same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a cyclic polyetherester composition, a method for producing the same, and an antibacterial resin composition.

Conventionally, antibacterial properties have been imparted to resins by adding antibacterial components to meet hygienic needs. When a low-molecular-weight compound is used as an active ingredient that makes the resin exhibit an antibacterial function, the active ingredient is easily eluted to the outside by washing or immersing the resin material, and the above function is accompanied by this. There are problems such as a decrease in Therefore, a method has been reported in which a quaternary ammonium structure, which is an antibacterial component, is incorporated into a specific resin and mixed in the resin to maintain antibacterial properties (for example, Patent Document 1).
However, since a cationic site is incorporated at the end of the resin, synthesis of the antibacterial component is complicated. Furthermore, since the structure of the antibacterial component is also limited, it cannot be applied to commercially available antibacterial agents, and there is also a problem of versatility.

Japanese Patent No. 3086186

An object of the present invention is to provide an antibacterial resin composition excellent in antibacterial persistence, and a cyclic polyether ester used in the antibacterial resin composition.

The present inventor has arrived at the present invention as a result of intensive studies in order to solve the above problems. That is, the present invention provides a cyclic polyetherester composition (Q) containing a cyclic polyetherester (P) formed by bonding groups represented by the following general formula (1), and a method for producing the same. It is also an antibacterial resin composition (F) containing a cyclic polyetherester composition (Q) containing the cyclic polyetherester (P), a polymer compound (E) and an antibacterial component (G).

［一般式（１）において、Ｒ^１は、炭素数２～２１の２価の炭化水素基である。Ｒ^１の水素原子は、それぞれ独立に、ハロゲン基、アセチル基、アルコキシ基又はフェノキシ基で置換されていても良い。；Ａは、炭素数２～８の２価の炭化水素基である。Ａの水素原子は、それぞれ独立に、ハロゲン原子で置換されていても良い。；ｍは４以上５００以下の整数であり、それぞれの基に含まれるｎは０以上、５００以下の整数であり、少なくともｎが１以上の基を１つ以上含む。；ｍ個あるＲ^１は同じであっても異なっていてもよく、ｍ×ｎ個あるＡは同じであっても異なっていてもよい。］

[In general formula (1), R ¹ is a divalent hydrocarbon group having 2 to 21 carbon atoms. Each hydrogen atom of R ¹ may be independently substituted with a halogen group, an acetyl group, an alkoxy group or a phenoxy group. ; A is a divalent hydrocarbon group having 2 to 8 carbon atoms; Each hydrogen atom of A may be independently substituted with a halogen atom. m is an integer of 4 or more and 500 or less, n contained in each group is an integer of 0 or more and 500 or less, and at least one group in which n is 1 or more is included. m R ¹ 's may be the same or different, and m×n A's may be the same or different. ]

The cyclic polyetherester of the present invention imparts excellent antibacterial persistence to the resin by blending it with the antibacterial component into the resin.

The cyclic polyetherester of the present invention is a cyclic polyetherester formed by bonding 4 or more units of groups represented by the general formula (1) as structural units.

In general formula (1), R ¹ is a divalent hydrocarbon group having 2 to 21 carbon atoms. Each hydrogen atom of R ¹ may be independently substituted with a halogen group (fluoro group, chloro group, bromo group and iodo group), acetyl group, alkoxy group or phenoxy group.

Examples of the divalent hydrocarbon group having 2 to 21 carbon atoms include an alkylene group having 2 to 21 carbon atoms, an alkenylene group having 2 to 21 carbon atoms, a cycloalkylene group having 4 to 21 carbon atoms, and an arylene group having 6 to 21 carbon atoms. and an aralkylene group having 7 to 21 carbon atoms.

Examples of alkylene groups having 2 to 21 carbon atoms include linear alkylene groups having 2 to 21 carbon atoms (ethylene group, trimethylene group, tetramethylene group, pentamethylene group and n-henicosanylene group), and alkylene groups having 3 to 21 carbon atoms. Branched alkylene groups (1-methylethylene group, 2-methylethylene group, 1-ethylethylene group, 2-ethylethylene group, 1-methylpropylene group, 2-methylpropylene group, 1,1-dimethylpropylene group, 1- hexylpropylene group, 1-hexylbutylene group, 1-octylethylene group, 1-undecylpropylene group, 1-undecylbutylene group, etc.).

Linear alkenylene groups having 2 to 21 carbon atoms (ethenylene group, propenylene group, tridecenylene group, pentadecenylene group, henicosenylene group, etc.) and branched alkenylene groups having 3 to 21 carbon atoms (1-ethylethenylene group, 1,2-dimethylethenylene group) group, 1-butylethenylene group, 1-hexylethenylene group and 1-octylethenylene group) and the like.

The cycloalkylene group having 4 to 21 carbon atoms includes a cyclobutylene group, a cyclopentylene group, a 2-methylcyclopentylene group, a cyclohexylene group, a 1,3-dimethylcyclohexylene group, a cycloheptylene group, and 1-ethylcyclopentylene. rene group, cyclooctylene group, cyclononylene group, cyclodecylene group, cycloundecylene group, cyclododecylene group, cyclotridelene group, cyclotetradecylene group, cyclopentadecylene group, cyclohexadecylene group, cycloheptadecylene group, cyclo Octadecylene group, cyclononadecylene group, cycloeicosilene group, norbornylene group, dicyclopentylene group, isopropylidenedicyclohexylene group, cyclohexanedimethylene group and the like.
Examples of alkenylene groups having 2 to 21 carbon atoms include linear alkenylene groups having 2 to 21 carbon atoms (ethenylene group, propenylene group, tridecenylene group, pentadecenylene group, henicosenylene group, etc.) and branched alkenylene groups having 3 to 21 carbon atoms (1 -ethylethenylene group, 1,2-dimethylethenylene group, 1-butylethenylene group, 1-hexylethenylene group and 1-octylethenylene group, etc.).

Examples of the arylene group having 6 to 21 carbon atoms include o-, p- or m-phenylene group, 2,4-naphthylene group, biphenylene group, terphenylene group, anthrylene group, phenanthrylene group, fluorenylene group and pyrenylene group. be done.

The aralkylene group having 7 to 21 carbon atoms includes a phenylmethylene group, a diphenylmethine group, a 1-phenylethylene group, an o-phenyleneethyl group and a naphthylmethylene group.

Groups in which at least one of the hydrogen atoms of these groups is substituted with a halogen group, an acetyl group, an alkoxy group or a phenoxy group include a 1-bromo-trimethylene group, a 1-acetyl-trimethylene group and a 1-methoxy-trimethylene group. and 1-phenoxy-trimethylene groups.

From the viewpoint of reaction efficiency, R ¹ is preferably a straight chain alkylene group having 3 to 16 carbon atoms or a branched alkylene group having 3 to 16 carbon atoms, and more preferably a trimethylene group, a tetramethylene group, a pentamethylene group, or tridecenylene. group, pentadecenylene group, 1-hexylpropylene group, 1-hexylbutylene group, 1-undecylpropylene group and 1-undecylbutylene group.

In general formula (1), A is a divalent hydrocarbon group having 2 to 8 carbon atoms. Each hydrogen atom of A may be independently substituted with a halogen group.

Among the divalent hydrocarbon groups having 2 to 8 carbon atoms, in the method for producing a cyclic polyetherester described later, from the viewpoint of keeping the reaction rate high and facilitating the production, preferred are a phenylethylene group and a carbon Examples thereof include alkylene groups having 2 to 4 carbon atoms, more preferably linear alkylene groups having 2 to 4 carbon atoms (ethylene group, propylene group, butylene group, etc.) and branched alkylene groups having 3 to 4 carbon atoms (methylethylene group, etc.). , ethylethylene group, methylpropylene group and 2-methylpropylene, etc.), particularly preferred are linear alkylene groups having 2 to 4 carbon atoms and branched alkylene groups having 3 to 4 carbon atoms, and most preferred is , an ethylene group and a propylene group.

In general formula (1), R ¹ , A and n may be the same or different when there is more than one.

As the cyclic polyetherester (P) contained in the antibacterial resin composition of the present invention, if m is 4 or more, the number of moles of the oxyalkylene group represented by n in the general formula (1) is a specific value A cyclic polyetherester (P) may be used, or a plurality of cyclic polyetheresters (P) having different values of n may be used in combination. When a plurality of cyclic polyetheresters (P) having different addition mole numbers (n) of the oxyalkylene group represented by n in the general formula (1) are used in combination, the oxy The value and ratio of the added moles of the alkylene group can be adjusted according to the type of the resin and the antibacterial component.

The adjustment of the values of m and n in the general formula (1) and the adjustment of the content of the cyclic polyetherester (P) having n within a specific range can It can be carried out by adjusting the ratio of the lactone having 2 to 8 carbon atoms and the alkylene oxide having 2 to 8 carbon atoms and changing the addition method of the alkylene oxide. , the content of the cyclic polyetherester (P) having a specific value of n can be increased, and the total proportion of the cyclic polyetherester (P) having a value within a certain range of n can be increased. In addition, the adjustment of the content of the cyclic polyetherester (P) having m within a specific range is performed in the presence of a fired composite oxide and/or a fired hydrotalcite containing aluminum and magnesium, which will be described later. It can also be obtained by further reacting an intermediate obtained by subjecting the cyclic compound (B) to an alkoxylation reaction. The value of m and the value of n of the cyclic polyetherester (P) are described in Polym. Chem., 2014, 5, 6905. can be analyzed and confirmed by MALDI-TOF MS described in .

In general formula (1), m is an integer of 4 or more. The value of m is preferably an integer of 4 or more and 500 or less from the viewpoint of retaining the antibacterial component and maintaining the antibacterial function.
The m number of R ¹ and the n×m number of A may be the same or different, but are preferably the same. If m is 3 or less, the function of retaining the antibacterial component is lowered, making it easier to precipitate. On the other hand, if m is more than 500, the viscosity increases and the handleability deteriorates.

In the general formula (1), n means the number of added moles of the oxyalkylene group represented by (OA), and is an integer of 0 or more and 500 or less from the viewpoint of reactivity. In addition, from the viewpoint of suppressing the viscosity to improve handling and suppressing precipitation of the antibacterial component from the resin, it is preferably an integer of 5 to 250, more preferably 5 to 100. The total number of added moles of all oxyalkylene groups constituting 1 mol of the cyclic polyether ester (P) is an integer of 1 or more and 2000 or less, suppressing the viscosity to improve handling, and removing the antibacterial component from the resin. From the viewpoint of suppressing precipitation, it is preferably an integer of 20-1000, more preferably 20-500.
From the viewpoint of effectively capturing the antibacterial component, the number n of (OA) contained in the group represented by the general formula (1) is preferably 1 to 500, more preferably 1 to 100, particularly preferably 5. ~100.
The number of moles (m×n) and ratio of the oxyalkylene groups added to the cyclic polyetherester (P) can be adjusted according to the resin and antibacterial component used.

The composition of R ¹ when there are m and A when there are m×n is given by Polym. Chem. , 2014, 5, 6905. The structure of the cyclic polyetherester can be identified by measurement and analysis by time-of-flight mass spectrometry (also referred to as MALDI-TOF MS) by the matrix-assisted laser desorption ionization method described in .

In the case where the cyclic polyetherester (P) is a mixture of a plurality of cyclic compounds having different repeating numbers, etc. of the structural units of the cyclic polyetherester (P), the values of "m" and "n" are the repeating number _mi and the repeating number for each cyclic compound. It can be obtained by calculating the average added mole number (n _i ) for each unit and calculating the average value for all the cyclic compounds. Specifically, it can be confirmed by the following method.

1. First, let I _i be the intensity of the i-th peak in the MALDI-TOF MS spectrum, and J _i be the number of added moles of the peak. Also, let the number of repeating units at this time be K _i .
2. An average value is calculated based on the peak intensity of the cyclic polyetherester contained in the cyclic polyetherester composition (Q) in the MALDI-TOF MS spectrum.
The average value m (average) of the number of repeating units is represented by the relational expression (1).
<Relational expression (1)>
m (average) = [ΣK _i ×I _i ]/ΣI _i
In the present invention, the value of "m" is determined based on MALDI-TOF MS spectra unless otherwise specified.
The average value n (average) of the number of added moles per number of repeating units is represented by the relational expression (2).
<Relational expression (2)>
n (average) = [ΣJ _i /K _i ×I _i ]/ΣI _i
In the present invention, the value of "m" is determined based on MALDI-TOF MS spectra unless otherwise specified.

Also, the average value of “m×n” can be obtained from the product of the relational expressions (1) and (2) based on the relational expression (3).
<Relational expression (3)>
m×n (average)=[ΣK _i ×I _i ]/ΣI _i ×[ΣJ _i /K _i ×I _i ]/ΣI _i

Further, the value of "m×n (average)" can also be obtained by GPC analysis, which will be described later, based on the relational expression (4).
<Relational expression (4)>
m × n (average) = [Number average molecular weight of cyclic compound composition (GPC measurement value)] / [Number average molecular weight (GPC) of cyclic compound for molecular weight comparison] × [“m × n” value of comparative cyclic compound ]

The range of “m” for each cyclic compound constituting the cyclic polyetherester composition (Q) is the minimum to maximum number of repeating units specified in the MALDI-TOF MS spectrum.

In addition, the range of "m" of each cyclic compound constituting the cyclic polyetherester composition (Q) can also be determined by GPC analysis, which will be described later, based on the relational expressions (5) and (6).
First, the entire chromatogram of the cyclic compound composition is divided vertically and in order of elution time into three parts having area ratios of 2.5%, 95%, and 2.5%, respectively.
At this time, the number-average molecular weight calculation results of each chromatogram divided into three are designated as Mn(1), Mn(2), and Mn(3) in descending order of elution time.
<Relational expression (5)>
m (maximum value) = [Mn (1) of cyclic polyetherester composition (Q)]/[Mn (1) of cyclic compound for molecular weight comparison] x [maximum value of “m” of cyclic compound for comparison]
<Relational expression (6)>
m (minimum value) = [Mn (3) of cyclic polyetherester composition (Q)]/[Mn (3) of cyclic compound for molecular weight comparison] × [minimum value of “m” of cyclic compound for comparison]

The cyclic polyetherester of the present invention may be used alone or in combination of two or more.
Preferred as the cyclic polyetherester of the present invention, from the viewpoint of antibacterial persistence, in the general formula (1), A is an ethylene group, a propylene group, a methylethylene, a chloropropylene group or a phenylethylene group, and R ¹ is Cyclic compounds in which both ends of a divalent group such as a trimethylene group, a pentamethylene group, a tetradecamethylene group or a vinylene group are bound.

The number average molecular weight (hereinafter abbreviated as Mn) of the cyclic polyetherester (P) of the present invention can be adjusted according to the molecular weight of the polymer compound (E) used in combination, which will be described later. From the viewpoint of bleed-out resistance of the ester-containing resin composition, it is preferably 350 to 300,000, more preferably 1,000 to 300,000, and particularly preferably 2,000 to 30,000. . From the viewpoint of improving handling properties, the Mn of the cyclic polyetherester (P) is preferably 350 to 300,000, more preferably 350 to 170,000. The Mn of the cyclic polyetherester (P) can be set within the above preferable range by adjusting the number of moles of the alkylene compound to be added and the reaction conditions of the multimerization step described later.

The Mn of the cyclic polyetherester can be measured using gel permeation chromatography (hereinafter abbreviated as GPC) under the following conditions.

The Mn of the cyclic polyetherester (P) can be measured using gel permeation chromatography (hereinafter abbreviated as GPC) under the following conditions.
・ Apparatus: "TOSOH ECO HLC-8320 GPC" [manufactured by Tosoh Corporation]
・ Column: "Guardcolumn Super AW-H" (1 piece), "TSKgel Super AW2500, TSKgel Super AW3000, TSKgel Super AW4000 connected one each" [all manufactured by Tosoh Corporation]
・Sample solution: 0.125% by weight DMF (LiBr 0.01 mol/L) solution ・Solution injection amount: 20 μL
・Flow rate: 0.6 mL/min ・Measurement temperature: 40°C
・Detection device: Refractive index detector ・Reference substance: Standard polyethylene oxide

The cyclic polyetherester of the present invention can be produced by the production method of the present invention detailed below.

In the method for producing a cyclic polyetherester of the present invention, a cyclic compound (B) is reacted with a cyclic ether compound (C) having 2 to 8 carbon atoms in which hydrogen atoms may be substituted with halogen atoms to obtain an intermediate. It can be produced by a production method including a step of obtaining (P') (hereinafter abbreviated as an alkoxylation step) and a step of obtaining a cyclic polyetherester (P) by multimerizing the intermediate obtained by the alkoxylation reaction. Also, the alkoxylation step and the multimerization step can be carried out simultaneously.

The cyclic compound (B) is represented by general formula (2), and may be used alone or in combination of two or more.

In general formula (2), R ² is a divalent hydrocarbon group having 2 to 21 carbon atoms. Each hydrogen atom of R ² may be independently substituted with a halogen group, an acetyl group, an alkoxy group or a phenoxy group, and the same groups as those for R ¹ can be used.

Specific examples of the cyclic compound (B) include the following lactones having no active hydrogen-containing group. For example, β-lactone (β-propiolactone, β-butyrolactone, etc.), γ-lactone (γ-butyrolactone, etc.), δ-lactone (δ-valerolactone, etc.), ε-lactone (ε-caprolactone, etc.), Lactones with chain alkyl groups (γ-enantholactone, γ-undecanolactone, γ-dodecanolactone and δ-dodecanolactone, etc.), γ-crotonolactone, α-methylene-γ-butyrolactone, γ-methylene-γ -butyrolactone, α-bromo-γ-butyrolactone, α-chloro-γ-butyrolactone, α-iodo-γ-butyrolactone, tetronic acid, macrocyclic lactone (15-pentadecanolactone) and aromatic lactone (3,4- dihydrocoumarin) and the like.
As the lactone containing two or more carbonyl structures, D, L and D/L-lactide, poly-ε caprolactone and the like can also be suitably used. From the viewpoint of reactivity, β-lactone (β-propiolactone, β-butyrolactone, etc.), γ-lactone (γ-butyrolactone, etc.), δ-lactone (δ-valerolactone, etc.), ε-lactone (ε-caprolactone, etc.) etc.), tetronic acid, macrocyclic lactones (15-pentadecanolactone) and aromatic lactones (3,4-dihydrocoumarin), more preferably γ-lactones (γ-butyrolactone, γ-crotonolactone, etc.) , δ-lactone (δ-valerolactone, etc.), ε-lactone (ε-caprolactone, etc.).
These lactones may be used singly or in combination of two or more.

The cyclic compound (B) can be obtained not only by purchasing it as a reagent but also by producing it by the following intramolecular condensation reaction or the like.
For example, the compound represented by general formula (2) has a carboxy group bonded to one end of the group represented by R ² and a hydroxyl group bonded to the opposite end of the group represented by R ² . It can be obtained by intramolecular condensation of a monovalent group to which a carboxy group and a hydroxyl group are bonded, using the compound described above.
As a method for synthesizing lactone or the like by intramolecular dehydration, a known method of heat dehydration; S. Nimitz, R.; H. Wollemberg, Tetrahedron Lett. 1978, 19, 3523 and known synthesis methods using enzymes such as lipase can be used.

Preferred examples of the above-mentioned "compound in which a carboxyl group is bound to one end of the group represented by R ² and a hydroxyl group is bound to the opposite end of the group represented by R ² " include 4 to 22 monohydroxy monocarboxylic acids and the like.

Monohydroxymonocarboxylic acids having 4 to 22 carbon atoms include linear hydroxycarboxylic acids having 4 to 22 carbon atoms (3-hydroxypropanoic acid, 4-hydroxybutyric acid, 5-hydroxypentanoic acid, 6-hydroxyhexanoic acid, 15 -hydroxypentadecanic acid, 16-hydroxyhexadecanoic acid and 4-hydroxy-2-butenoic acid, etc.) and branched hydroxycarboxylic acids having 3 to 22 carbon atoms (3-hydroxybutanoic acid, 5-hydroxytridecanoic acid, 2-methylene- 4-hydroxybutyric acid, 4-phenyl-4-hydroxybutyric acid, 2,2-dimethyl-4-hydroxybutyric acid, 4-hexyl-4-hydroxybutyric acid and 4-hydroxy-2-methyl-2-butenoic acid, etc.) mentioned.

A hydroxycarboxylic acid molecule in which at least one hydrogen atom among the hydrogen atoms bonded to the carbon atoms of the monohydroxymonocarboxylic acid having 4 to 22 carbon atoms is substituted with a halogen group, an acetyl group, an alkoxy group or a phenoxy group Lactones with internal dehydrated structures can also be used. Among the monohydroxy monocarboxylic acids having 4 to 22 carbon atoms, examples of hydroxycarboxylic acids in which at least one hydrogen atom bonded to a carbon atom is substituted with a halogen group include 2-bromo-4-hydroxybutyric acid and the like. Examples of the hydroxycarboxylic acid substituted with an acetyl group include 2-acetyl-4-hydroxybutanoic acid, and examples of the hydroxycarboxylic acid substituted with an alkoxy group include 2-methoxy-4-hydroxybutyric acid. Examples of hydroxycarboxylic acids substituted with a phenoxy group include 2-phenyl-4-hydroxybutyric acid.

Cyclic ether compounds having 2 to 8 carbon atoms (C) include ethylene oxide, 1,2- or 1,3-propylene oxide, 1,2-, 1,3-, 1,4- or 2,3-butylene oxide, 1,2-dichlorooxetane, 1,2-pentylene oxide, 1,2-hexylene oxide, tetrahydrofuran, styrene oxide, cyclohexene oxide, epichlorohydrin and epibromohydrin. Of these, when used in an antibacterial resin to be described later, ethylene oxide, 1,2- or 1,3-propylene oxide, 1,2- , 1,3-, 1,4- or 2,3-butylene oxide are preferred. The cyclic ethers having 2 to 8 carbon atoms may be used singly or in combination of two or more.

When two or more of (C) are used in combination, the divalent group represented by A in the resulting cyclic polyetherester has different types corresponding to the types of cyclic ethers used.

In the alkoxylation reaction step included in the production method of the present invention, a reaction in which a cyclic ether having 2 to 8 carbon atoms is inserted between the carbonyl group and the ether-bonding oxygen atom of the cyclic compound (B) (carbonyl group In the case of a reaction that inserts an oxyalkylene group between and an oxygen atom, an alkoxylation reaction) occurs.
For example, when γ-butyrolactone is used as the cyclic compound (B) and ethylene oxide is used as the cyclic ether having 2 to 8 carbon atoms, the group represented by the (OA) group in the general formula (1) is oxyethylene _{and R} ¹ is _a trimethylene _{group .} A cyclic compound formed by combining is formed.

The cyclic polyetherester produced in the alkoxylation reaction step causes a reaction in which the bond directly connecting the carbonyl group and the etheric oxygen atom on the ring is once cleaved, and furthermore, the carbonyl group and the etheric oxygen atom are directly It reacts with another cyclic polyetherester in which the linking bond has been cleaved, and an insertion addition reaction occurs in which the ether-bonding oxygen atoms of one cyclic polyetherester and the carbonyl groups of the other cyclic polyetherester are linked.
For example, when γ-butyrolactone is used as the cyclic compound (B) and ethylene oxide is used as the cyclic ether compound having 2 to 8 carbon atoms, as described above, —[(OCH ₂ CH ₂ ) _n OC ₃ H ₆ CO ]—, a cyclic compound is produced by directly bonding both ends of the divalent group.
Then, the two molecules of the cyclic compound undergo the cleavage reaction and the insertion-addition reaction to form a cyclic compound that is a dimer having two divalent groups in one molecule, and 3 molecules of the cyclic compound. reacts to form a cyclic compound which is a trimer having three divalent groups in one molecule. Further, as the multimerization reaction proceeds, a tetrameric or higher cyclic polyether ester having 4 or more of the above divalent groups in one molecule is produced.

The multimerization reaction may proceed simultaneously with the alkoxylation reaction, or may proceed by aging the cyclic compound composition as described later. Moreover, after the multimerization reaction, an alkoxylation reaction may be further performed.

The alkoxylation and multimerization steps described above are preferably carried out in the presence of a catalyst. Catalysts used in the reaction process include halides of metals (tin, nickel, zinc, aluminum, etc.), inorganic acids (sulfuric acid, phosphoric acid, etc.), boron compounds (trispentafluorophenylborane, etc.), alkali metals (lithium, sodium , potassium and cesium, etc.), amine compounds (diethylamine and triethylamine, etc.), phosphazene, double metal cyanide complex catalyst (zinc described in JP-A-2005-53952 and JP-A-2016-6203, etc.) metal complex catalysts containing two kinds of metals such as hexacyanocobaltate in the molecule), oxide composites described in JP-A-2000-354763, composite oxides of Al and Mg (D1) and layered It can be carried out using a double hydroxide, a calcined product thereof, or the like.

The layered double hydroxide used in the production method of the present invention is water of divalent metals (magnesium, iron, zinc, calcium, nickel, cobalt, copper, etc.) and trivalent metals (Al, Fe, Mn, etc.) It means an inorganic layered compound in which oxides are combined to form a laminated structure, and the general formula is [M ²⁺ _1−h M ³⁺ _h (OH) ₂ ][(W ⁱ⁻ ) _h/i ·jH ₂ O ] [Here, M ²⁺ is a divalent metal, M ³⁺ is a trivalent metal, and W ⁱ⁻ is an ivalent anion (HCO ₃ ⁻ , CO ₃ ²⁻ , PO ₄ ³⁻ , SO ₄ ²⁻ , Cl ⁻ , NO ₂ ⁻ and NO ₃ ^−, etc.), h, i and j are each independent positive numbers. ], which includes hydrotalcite, motucoleite, manaseite, stichtite, pyroaurite, takovite, yeardolite and meikisenerite. These layered double hydroxides are known as clay minerals and may be contained in naturally occurring minerals or obtained synthetically.

A catalyst may be used individually by 1 type, or may use 2 or more types together. Among these, the fired product of Al and Mg composite oxide (D1) and the fired product of Al and Mg hydrotalcite (D2) are preferable from the viewpoint of reaction efficiency.

The composite oxide (D1) used in the present invention is not particularly limited as long as it is an oxide containing Al and Mg. Preferred composite oxides include compounds represented by the following compositional formula (1) or (2). is mentioned.
[ _{aMgO.Al2O3.bH2O} ] _{( 1} )
[MgsAltOu] (2)

In the compositional formula (1), a and b are independent positive numbers. In composition formula (2), s, t and u are each independent positive numbers. From the viewpoint of reactivity, t/s is preferably 0.1 or more and less than 0.9. Examples of the composite oxide (D1) include 2.5MgO.Al ₂ O _{3.bH 2} O and Mg _0.7 Al _0.3 O _1.15 . available from the market as Kyoward 2000 [manufactured by Kyowa Chemical Industry Co., Ltd.].

Examples of the hydrotalcite (D2) used in the present invention include compounds represented by the following compositional formula (3).
[Mg _1-c Al _c (OH) ₂ ] ^c+ [CO _3c/2 ·dH ₂ O] ^c- (3)

In general formula (3), c is a number that satisfies 0<c≦0.33, and d is a number that satisfies 0<d≦1.0.

Examples _of the hydrotalcite (D2) _{include Mg6Al2 (} OH _{) 16CO3.4H2O} and _Mg4.5Al2 (OH _{) 13CO3.3.5H2O .} 500 [manufactured by Kyowa Chemical Industry Co., Ltd.] and Kyoward 1000 [manufactured by Kyowa Chemical Industry Co., Ltd.], etc., are commercially available.

As the hydrotalcite (D2) used in the present invention, in addition to the above compounds, known minerals described in West German Patent Publication No. 1592126, European Patent Publication No. 0207811, etc. can also be used.

(D1) and (D2) may be used alone or in combination of two or more. Among these, the composite oxide (D1) is preferable from the viewpoint of reactivity, and more preferable are 2.5MgO·Al ₂ O ₃ ·bH ₂ O (b is a positive number) and Mg _0.7 Al _{0 .3} O _1.15 .

The fired product of the composite oxide (D1) of Al and Mg or the fired product of the hydrotalcite (D2) containing Al and Mg is obtained by subjecting (D1) or (D2) to an air atmosphere, preferably under a nitrogen stream. Preferably, it can be obtained by a method of heat treatment at 400 to 1500° C. (more preferably 600 to 1000° C.) for 1 to 48 hours.
The fired product of (D1) or (D2) is hereinafter referred to as catalyst (D').

In the alkoxylation and multimerization steps, the content of the catalyst is not particularly limited, but from the viewpoint of reaction rate and filtration efficiency, it is 0.0001 to 0.0001 with respect to the total weight of the cyclic compound (B) and the cyclic ether compound (C). 60% by weight is preferred, 0.001 to 20% by weight is more preferred, and 0.01 to 20.0% by weight is particularly preferred.

Moreover, in the alkoxylation and multimerization steps, a solvent may be added in addition to the cyclic compound (B), the cyclic ether compound (C) and the catalyst from the viewpoint of facilitating stirring.

Examples of the solvent include toluene, xylene, benzene, dimethylsulfoxide, diglyme, triglyme, 1,4-dioxane, cyclohexane, hexane, diethyl ether, dimethylformamide, carbon tetrachloride, N-methylpyrrolidone, 1,2-dimethoxyethane, 1,2-dichloroethane, o-dichlorobenzene, chloroform and the like.
The solvents may be used singly or in combination of two or more.
Of these, toluene and xylene are preferred from the viewpoints of miscibility with the cyclic compound (B) and the cyclic ether compound (C), etc., high boiling point, ease of handling, and the like.
The weight of the solvent used in the alkoxylation step is preferably 0 to 99% by weight, more preferably 0 to 99% by weight, based on the total weight of the cyclic compound (B), the cyclic ether compound (C) and the catalyst, from the viewpoint of reaction rate and the like. is 0 to 90% by weight.

In the alkoxylation step, the temperature of the mixture of the cyclic compound (B) and the cyclic ether compound (C) and, if necessary, the catalyst and solvent is preferably 90 to 250°C, more preferably 100 to 190°C. is. Moreover, the time for the above temperature is preferably 1 to 200 hours.

In the multimerization step of the present invention, a solvent may be added in addition to the intermediate (P') and the catalyst from the viewpoint of facilitating stirring.
Solvents include toluene, xylene, benzene, dimethylsulfoxide, diglyme, triglyme, 1,4-dioxane, cyclohexane, hexane, diethyl ether, dimethylformamide, carbon tetrachloride, N-methylpyrrolidone, 1,2-dimethoxyethane, 1 , 2-dichloroethane, o-dichlorobenzene and chloroform.
A solvent may be used individually by 1 type, or may use 2 or more types together. Of these, toluene and xylene are preferred from the viewpoints of miscibility, high boiling point, ease of handling, and the like.
The weight of the solvent used in the multimerization step is preferably 0 to 99% by weight, more preferably 0 to 99% by weight, based on the total weight of the cyclic compound (B), the cyclic ether compound (C) and the catalyst, from the viewpoint of reaction rate and the like. 0 to 90% by weight.

In the multimerization step, the temperature of the reaction mixture is preferably 90-250°C, more preferably 100-190°C.

In the alkoxylation and polymerization step, various reaction raw materials [cyclic compound (B) and cyclic ether compound (C) or intermediate (P′) and, if necessary, catalyst and solvent] are put into a reactor and an inert gas ( The inside of the system is replaced with nitrogen, argon, etc.) and sealed, and the mixture is stirred and mixed at the above-mentioned reaction temperature and reaction time.
As the reaction apparatus, a known reaction apparatus such as a mixing vessel equipped with a stirring device and a heating device (flask with stirrer, autoclave, etc.) can be used.

The multimerization step can also be carried out by preparing the intermediate (P′) through the alkoxylation step and then aging the reaction mixture at a temperature of 90 to 250° C. (more preferably 100 to 190° C.).

In the production method of the present invention, the product obtained in the multimerization step [that is, the mixture containing the cyclic polyether ester] is further subjected to filtration operation (such as the method described in JP-A-2011-213864), gel permeation method and A step of purifying by a known method such as silica gel column chromatography (hereinafter abbreviated as purification step) may be included.
Only the cyclic polyetherester having a specific structure can be extracted by the above purification process.

The process for producing the cyclic polyetherester composition of the present invention may include a catalyst removal operation. A known method can be used as a method for removing the catalyst. Specifically, in addition to the method described in JP-A-2010-6964, diatomaceous earth (Dicalite 6000, Radiolite #700, etc.), which is a filtering agent, can be used. ), silica gel (Wakogel etc.), magnesium silicate (Kyoward 600, Kyoward 700) and the like. In the filtration operation, the above-mentioned filtering chemicals may be used singly or in combination of multiple types, but it is preferable to use multiple types from the viewpoint of filtration efficiency.
Moreover, from the viewpoint of improving the filtration rate, it is preferable to use diatomaceous earth, and in order to improve the removal efficiency of the catalyst, it is preferable to use magnesium silicate.
Filtration can be performed by a known method, and examples include a method of passing the cyclic polyester composition or its solution through a filter layer in which diatomaceous earth and magnesium silicate are laminated in layers. The solvent used for filtration is not limited as long as it dissolves the cyclic polyester, but from the viewpoint of dissolution efficiency, THF, DMF, ethyl acetate, toluene, and the like are preferable.

The cyclic polyetherester of the present invention imparts plasticity to the resin by being contained in the antibacterial resin composition (F) and the like described later, and is resistant to bleeding out from the antibacterial resin composition (F) described later. excellent in nature.

The antibacterial resin composition (F) of the present invention contains a cyclic polyetherester (P) and a polymer compound (E).

The antibacterial resin composition (F) of the present invention is excellent in dispersing resin additives and functioning as a binder. Therefore, the resin additive is excellent in the resistance to bleeding from the resin and in the resistance to falling off.
Examples of resin additives include various fillers (carbon, etc.), surfactants, and metal ions (silver ions, etc.). Among these, surfactants (cationic, anionic, those having amphoteric cation sites) and metal ions are efficiently dispersed by coordinating with the cyclic polyetherester (P), and A cyclic polyetherester (P) is preferable because it easily functions as a binder.

Examples of the polymer compound (E) having an SP value of 4 to 22 (cal/cm ³ ) ^1/2 contained in the antibacterial resin composition (F) include cellulose (tri)acetate, polyethylene glycol, polypropylene glycol, and polystyrene. , polyisoprene, polypropylene, poly(meth)acrylate, polyvinyl alcohol, poly N-isopropylamide, polysulfone, polyvinylpyrrolidone, polyethylene, polyisoprene, polybutadiene, polycarbonate, polyoxymethylene, polyoxypropylene, polyamide, modified polyphenylene ether, poly Butylene terephthalate, polyvinyl chloride, polyacrylonitrile, polyethylene terephthalate, polyethersulfone, polyphenylene sulfide, polyarylate, polyamideimide, polyetherimide, polyetheretherketone, polytetrafluoroethylene, polyvinylidene fluoride, ethylene vinyl alcohol, polyhexane Adipamide, polyurethane, acrylonitrile-butadiene-styrene copolymer (ABS), and the like.

Among these, from the viewpoint of compatibility, polystyrene, polyisoprene, polypropylene, poly(meth)acrylate, polyvinyl alcohol, polyN-isopropylamide, polyvinylpyrrolidone, polyethylene, polybutadiene, polycarbonate, polyoxymethylene, polyoxypropylene, polyamide , modified polyphenylene ether, polybutylene terephthalate, polyvinyl chloride, polyacrytonitrile, polyethylene terephthalate, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, polyamideimide, polyetherimide, polyetheretherketone, ethylene vinyl alcohol, polyhexane Adipamide, polyurethane, acrylonitrile-butadiene-styrene copolymer (ABS) are preferred.

These polymers may be used alone or in combination of two or more.

From the viewpoint of the compatibility of the cyclic polyetherester (P) with the polymer compound (E), the SP value of the polymer compound (E) is 4 to 22 (cal/cm ³ ) ^1/2 , more preferably. is 4 to 12 (cal/cm ³ ) ^1/2 , particularly preferably 6 to 10 (cal/cm ³ ) ^1/2 .

Here, the SP value means an amount defined by the following formula, where ΔE (unit: cal/mol) is cohesive energy density and V (unit: cm ³ /mol) is molecular volume. .
SP value = (ΔE/V) ^1/2 [Unit is (cal/cm ³ ) ^1/2 ]
For example, the method of Fedors is known as a specific method of obtaining the SP value, and this method includes the SP value obtained by the method and "A Method for Estimating both the Solubility PPmeters and Molar Volumes of Liquids, POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, vol.14, Issue 2, p.147-154", which was followed.

Further, the polymer compound (E) may be a polymer into which a reactive functional group has been introduced. Examples of the reactive functional group to be introduced include isocyanate group, alkenyl group, alkynyl group, (meth)acrylate group, and hydroxyl , carboxy group, ester group, aldehyde group, carbonyl group, halogen group, sulfo group, phospho group, disulfide group, triazide group, cyano group, imine substituent, amidine group, oxime group, silyl group, siloxy group, amino group, thio group, hydroxyl group, maleimide group and the like.

Although the number average molecular weight of the polymer compound (E) is not particularly limited, it is preferably from 1,000 to 1,000,000 from the viewpoint of ease of synthesis.
The number average molecular weight of the polymer compound (E) can be measured under the following conditions using the following GPC.
・ Apparatus: "Waters Alliance 2695" [manufactured by Waters]
・ Column: "Guardcolumn Super HL" (1), "TSKgel
One each of SuperH2000, TSKgel SuperH3000, and TSKgel SuperH4000 connected" [all manufactured by Tosoh Corporation]
・Sample solution: 0.25 wt% tetrahydrofuran solution ・Solution injection amount: 10 μL
・Flow rate: 0.6 mL/min ・Measurement temperature: 40°C
・Detection device: refractive index detector ・Reference material: standard polystyrene

The polymer compound (E) can be produced by a known polymerization method.
Polycondensation reaction between polyisocyanate (toluene diisocyanate and 4,4'-diphenylmethane diisocyanate, etc.) and polyol (polypropylene glycol, etc.) in the case of polyurethane; polycondensation reaction between polycarboxylic acid and polyol in the case of polyester; In the case of acrylic acid, radical polymerization reaction of acrylic acid and/or acrylic acid ester; in the case of polysiloxane, hydrolysis polycondensation reaction of alkoxysilane; acid, amine, etc.) can be produced using a known method such as an alkylene oxide addition reaction.

In the synthesis of the polymer compound (E), from the viewpoint of facilitating the formation of a composite structure of the cyclic polyetherester (P) and the polymer compound (E), as described later, the cyclic polyetherester (P ) is preferably carried out in the presence of

The antibacterial resin composition (F) of the present invention may contain a solvent in addition to the cyclic polyetherester (P) and the polymer compound (E).
When using a solvent, it is preferable to appropriately select a solvent in which the cyclic polyetherester (P) is highly soluble. Preferred solvents include toluene, xylene, benzene, dimethylsulfoxide, diglyme, triglyme, 1,4-dioxane, cyclohexane, hexane, diethyl ether, tetrahydrofuran, dimethylformamide, water, carbon tetrachloride, N-methylpyrrolidone, 1,2- dimethoxyethane, 1,2-dichloroethane, chloroform and the like.

The antibacterial resin composition (F) of the present invention has a structure in which the ring component of the cyclic polyether ester (P) is penetrated by the polymer compound (E), which is the axial component. and NMR spectrum measurement, observation with an atomic force microscope, and the like.
In the measurement of powder X-ray diffraction, the presence or absence of rotaxane formation, that is, the polymer compound (E ) has penetrated, and the number of cyclic polyetheresters (P) that penetrate one molecule of the polymer compound (E) can be calculated from the NMR spectrum.

The antibacterial resin composition (F) of the present invention preferably forms a composite structure by having one or more molecules of the polymer compound (E) penetrate the cyclic polyetherester (P).

The antibacterial resin composition (F) of the present invention is obtained by mixing the cyclic polyetherester (P), the polymer compound (E) and, if necessary, other additives (solvents, etc.) and the presence of the cyclic polyetherester. It can be produced, for example, by polymerizing the polymer compound (E) by the method described above.

As the cyclic polyetherester (P) used in the production of the antibacterial resin composition (F) of the present invention, in the method for producing the cyclic polyetherester (P) of the present invention, without the purification step, The obtained reaction product may be used as it is, or a cyclic polyetherester (P) having a specific structure obtained by fractionating and purifying the reaction product through a purification step may be used.

Examples of the method for mixing the cyclic polyetherester (P) and the polymer compound (E) include a method of stirring and mixing the cyclic polyetherester (P) and the polymer compound (E) in the absence of solvent or in a solvent. The temperature during stirring and mixing is 0 to 250° C., preferably 10 to 200° C., and the mixing time is 1 second to 1 week, preferably 10 seconds to 3 days. The antibacterial resin composition (F) in which the polymer compound (E) penetrates the cyclic polyether ester (P) can be obtained by subjecting the solution after stirring and mixing to reprecipitation, filtration, centrifugation, membrane separation, column chromatography, and the like. can be isolated by the separation method of

The weight % of the cyclic polyetherester composition (Q) in the antibacterial resin composition (F) is 0.00% with respect to the total weight of the antibacterial resin composition (F) from the viewpoint of maintaining the strength of the resin. 001 to 50% by weight, more preferably 1 to 20% by weight, particularly preferably 1 to 10% by weight.

The antibacterial ingredient (G) contained in the antibacterial composition of the present invention includes natural antibacterial ingredients extracted from animals and plants or secreted by fungi, etc. Hookah tin, sodium monofluorophosphate, thymol, menthol, eugenol, tannin, polyphenol, ratania, chamomile, myrrh, sage, tea extract, cypress extract, oil-soluble licorice extract, mulberry bark extract, aloe extract, protamine , propolis, lysozyme and antibiotics (such as minocycline and tetracycline)] and synthetic antimicrobial ingredients can be used.

Antimicrobial components (G) preferably include biguanide compound-containing antimicrobial components, water-soluble silver salts, oxygen-containing antimicrobial components, paraoxybenzoic acid esters, phenolic antimicrobial components, cationic surfactants, amphoteric surfactants, and the like.

Biguanide compound-containing antibacterial ingredients include polyhexamethylene biguanide and chlorhexidine gluconate.

Water-soluble silver salts include silver sulfate, silver nitrate and silver acetate.

Hydrogen peroxide, sodium percarbonate, sodium perborate and the like can be mentioned as the oxygen-based antibacterial component.

Examples of paraoxybenzoic acid esters include methylparaben, ethylparaben, propylparaben, isopropylparaben, butylparaben, isobutylparaben and benzylparaben.

Phenolic antimicrobial ingredients include triclosan, chlorthymol, carvacrol, chlorophen, dichlorophen, hexachlorophen, chloroxylenol, chlorocresol, o-phenylphenol and isopropylmethylphenol.

Cationic surfactants include primary amine salt-type cationic surfactants, secondary amine salt-type cationic surfactants, tertiary amine salt-type cationic surfactants, and quaternary ammonium salt-type cationic surfactants. Cationic surfactants can be mentioned.

The primary amine salt-type cationic surfactants include primary amines, inorganic acids (hydrochloric acid, nitric acid, sulfuric acid, hydroiodic acid, etc.) or organic acids (acetic acid, formic acid, oxalic acid, lactic acid, gluconic acid, Adipic acid, alkylphosphoric acid, etc.) can be used, and the primary amines include monoalkylamines having 2 to 21 carbon atoms (ethylamine, laurylamine, stearylamine, cetylamine, and phenylamine). icosylamine, etc.).

Secondary amine salt-type cationic surfactants include inorganic acids (hydrochloric acid, nitric acid, sulfuric acid, hydroiodic acid, etc.) or organic acids (acetic acid, formic acid, oxalic acid, lactic acid, gluconic acid, gluconic acid, etc.). Adipic acid, alkylphosphoric acid, etc.) can be used, and secondary amines include aliphatic secondary amines having 2 to 20 carbon atoms (dimethylamine, diethylamine, ethylpropylamine, methyl pentylamine and ethyloctadecylamine) and amines obtained by adding an alkylene oxide to one hydrogen atom bonded to the nitrogen atom of the above-mentioned monoalkylamine.

Tertiary amine salt-type cationic surfactants include inorganic acids (hydrochloric acid, nitric acid, sulfuric acid, hydroiodic acid, etc.) or organic acids (acetic acid, formic acid, oxalic acid, lactic acid, gluconic acid, Adipic acid, alkylphosphoric acid, etc.) can be used, and the tertiary amines include aliphatic tertiary amines having 6 to 20 carbon atoms (triethylamine, ethyldimethylamine and N, N, N′,N′-tetramethylethylenediamine, etc.), alicyclic amines [N-methylpyrrolidine, N-methylpiperidine, N-methylhexamethyleneimine, N-methylmorpholine and 1,8-diazabicyclo (5,4,0 )-7-undecene, etc.], nitrogen-containing heterocyclic aromatic amines (4-dimethylaminopyridine, N-methylimidazole and 4,4′-dipyridyl, etc.), hydroxyl group-containing tertiary amines (triethanolamine monostearate, etc. ) and amines obtained by adding an alkylene oxide to one hydrogen atom bonded to the nitrogen atom of the secondary amine.

As the quaternary ammonium salt-type cationic surfactant, the aforementioned tertiary amine can be used as a known quaternizing agent [halogenated alkyl (methyl chloride, methyl bromide, ethyl chloride, benzyl chloride, etc.), dimethyl sulfate, dimethyl Carbonate, alkylene oxide, etc.], lauryltrimethylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium bromide, stearyltrimethylammonium bromide, lauryldimethylbenzylammonium chloride (benzochloride ruconium), cetylpyridinium chloride and polyoxyethylenetrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium chloride and lanolin fatty acid aminopropylethyldimethylammonium ethylsulfate.

In addition to the above, as the primary to tertiary amine salt type cationic surfactants, "New Surfactant Introduction" [written by Takehiko Fujimoto, published by Sanyo Chemical Industries Co., Ltd. (1992), p.71 -74] can also be used solomin A type cationic surfactants, sapamine A type surfactants, Arcovel A type surfactants, imidazoline type surfactants, etc. described in Section 4.1. In addition to the above agents, solomine A-type quaternary ammonium salts and pyridinium salts described in "Shin Surfactant Guide" [written by Takehiko Fujimoto, published by Sanyo Chemical Industry Co., Ltd. (1992), pp. 76-78]. etc. can also be used.

As amphoteric surfactants, amino acid-type amphoteric surfactants, betaine-type surfactants, and amine oxide-type surfactants can be used in combination with various cationic surfactants. Among these amphoteric surfactants, amino acid type amphoteric surfactants are preferred from the viewpoint of antibacterial properties.

Amino acid type amphoteric surfactants include alkyldiaminoethylglycine or its salts, myristyldiaminoethylglycine or its salts, lauryldiaminoethylglycine, higher alkyl (C 12-18) aminopropionic acid or its salts. Among these, alkyldiaminoethylglycine or a salt thereof is preferable from the viewpoint of antibacterial properties, and Levon LAG-40 [manufactured by Sanyo Chemical Industries, Ltd.] 40% dodecylaminoethylaminoethylglycine hydrochloride can be used.

Examples of betaine-type amphoteric surfactants include alkyl betaine-type surfactants (lauryldimethylaminoacetate betaine, etc.), amidopropyl betaine-type surfactants (coconut oil fatty acid amidopropyl betaine), imidazolinium betaine-type surfactants (2- alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, etc.), sulfobetaine surfactants (laurylhydroxysulfobetaine, etc.), phosphobetaine surfactants (lauroylamide-ethylhydroxyethylcarboxymethyl-betainehydroxy sodium propyl phosphate, etc.).

Amine oxide surfactants include trialkyl N-oxides (lauryldimethylamine N-oxide, oleyldimethylamine N-oxide).

As the antibacterial component (G), quaternary ammonium salt-type cationic surfactants and amphoteric surfactants are preferred among others, such as dimethyldi-n-decylammonium chloride, benzalkonium chloride (alkyldimethylbenzylammonium chloride), de Tesylaminoethylaminoethylglycine hydrochloride is more preferred.

As the antibacterial component (G), a commercially available one may be used, or one synthesized by a known method may be used. For example, cationic surfactants can be obtained by known methods described in JP-A-2003-306698, JP-A-2002-53893, JP-A-2001-316209, etc., and are commercially available as antibacterial ingredients. and available as reagents may be used.

EXAMPLES The present invention will be further described with reference to examples below, but the present invention is not limited thereto. In addition, the part in an Example shows a weight part.

(Production example 1)
"Kyoward 300" [chemical formula: _{2.5MgO.Al2O3.bH2O} (b is a positive number), manufactured by Kyowa Chemical Industry Co., Ltd.] was heat-treated in an electric furnace at 900° _C for 24 hours _under a nitrogen stream. Then, a calcined product (hereinafter referred to as catalyst (D'-1) was prepared.
(Production example 2)
A catalyst was prepared in the same _manner as in Production Example 1, except that Kyoward 300 was changed to Kyoward 500 [ _Mg6Al2 (OH) _16CO3.4H2O , manufactured by Kyowa Chemical _Industry Co. _, Ltd.]. (D'-2) was obtained.
(Production example 3)
Same as Production Example 1 except that Kyoward 300 _was changed to Kyoward 1000 [ _Mg4.5Al2 (OH) _13CO3.3.5H2O , manufactured by Kyowa Chemical Industry Co. _, Ltd. _] A catalyst (D'-3) was obtained by the method of
(Production example 4)
_{A catalyst} ( _D ′-4) was obtained.

(Production example 5)
20.0 parts of ε-caprolactone dehydrated using molecular sieves [manufactured by Tokyo Chemical Industry Co., Ltd.] and the catalyst obtained in Production Example 1 (D' -1) 10 parts were added. After passing nitrogen for 1 hour, the pressure was reduced (gauge pressure - 0.1 MPa), the temperature was raised to 150 ° C., 67.4 parts of propylene oxide was injected over 1 hour, and aged for 0.5 hours. A compound (X'-1) was obtained by addition reaction of propylene oxide to ε-caprolactone as a starting material. A part of the obtained compound (X'-1) was sampled and analyzed by MALDI-TOF MS [MALDI mass spectrometer AXIMA-Performance, manufactured by Shimadzu Corporation, hereinafter the same]. As a result, the compound ( X'-1) is represented by chemical formulas (3) and ( ⁴ ) is a cyclic polyetherester represented by

(Production example 6)
20.0 parts of ε-caprolactone dehydrated using molecular sieves [manufactured by Tokyo Chemical Industry Co., Ltd.] and the catalyst obtained in Production Example 1 (D' -1) 10 parts were added. After nitrogen ventilation for 1 hour, the pressure was reduced (gauge pressure - 0.1 MPa), the temperature was raised to 150 ° C., 51.1 parts of ethylene oxide was pressurized over 1 hour, and aged for 0.5 hours, A compound (X'-2) was obtained by addition reaction of ethylene oxide to ε-caprolactone as a starting material. A part of the obtained compound (X'-2) was sampled and analyzed by MALDI-TOF MS [MALDI mass spectrometer AXIMA-Performance, manufactured by Shimadzu Corporation, hereinafter the same]. As a result, the compound ( X'-2) is represented by the chemical formula (5) in which R ¹ in the general formula (1) is a trimethylene group, A is an ethylene group, the average number of added moles (n) = 5 and m is 1 to 3. It is a cyclic polyetherester.

(Examples 1 to 11)
Into a stainless steel autoclave equipped with a stirrer and temperature control function, according to Table 1, the raw material and catalyst were charged, the pressure was reduced (gauge pressure - 0.1 MPa), the temperature was raised to 90 ° C., and nitrogen gas was introduced for 1 time. After 1 hour, the mixture was heated and stirred according to the conditions shown in Table 1.
200 parts of xylene was added to 20 parts of the resulting composition (PP-1 to PP-10) and the temperature was adjusted to 50°C. 50 parts of Kyoward 600 [manufactured by Kyowa Chemical Industry Co., Ltd.] and 50 parts of Kyoward 600 [manufactured by Kyowa Kagaku Kogyo Co., Ltd.] were filtered through a suction funnel packed in layers to separate the catalyst. Then, xylene was distilled off under reduced pressure and concentrated to obtain compositions containing cyclic compounds (P-1 to P-11).

(Examples 12-15)
The cyclic compound of the present invention (P -1 to 9) can be obtained. Details are given in Table 2 below. In the description in the table, [PP-_-1 to 4] indicate intermediates, and the cyclic compound after purification is described as [P-_]. The underlined portion contains the number of each example.
In each of Examples 11 to 14, the intermediate obtained through step 1 is described as [PP-_-1], the intermediate obtained through step 2 is described as [P-_-2], The intermediate obtained through step 3 is described as [PP-_-3].
The cyclic compound [P-_] of the present invention was obtained by purification according to the purification step 1 or 2 below.

(Step 1): The raw materials listed in Table 2 and the catalyst obtained in Production Example 1 were introduced into a stainless steel autoclave equipped with a stirrer and a temperature control function, the pressure was reduced (gauge pressure - 0.1 MPa), and nitrogen was added. After aeration for 1 hour, the temperature was raised to 150 ° C., the alkylene oxide shown in Table 1 was introduced over the reaction time shown in Table 2, and the intermediate (PP -__-1) was obtained.

Example 13 includes (step 2) and (step 3) in addition to the above (step 1).
(Step 2): The raw materials and catalysts shown in Table 2 were introduced into a stainless steel autoclave equipped with a stirrer and a temperature control function, the pressure was reduced (gauge pressure - 0.1 MPa), and nitrogen was blown for 1 hour. After that, the temperature was raised to 150 ° C., the alkylene oxide shown in Table 2 was introduced over the reaction time shown in Table 2, and the intermediate (PP-13-2) was obtained by aging for the time shown in Table 2. Obtained.

(Step 3): The raw materials and catalysts shown in Table 2 were introduced into a stainless steel autoclave equipped with a stirrer and a temperature control function, the pressure was reduced (gauge pressure - 0.1 MPa), and nitrogen was bubbled for 1 hour. After that, the temperature was raised to 150 ° C., the alkylene oxide shown in Table 1 was introduced over the reaction time shown in Table 1, and the intermediate (PP-13-3) was obtained by aging for the time shown in Table 2. Obtained.

(Purification of reaction mixture)
Add 100 parts of xylene to 20 parts of each intermediate (PP-_-1-3) obtained in Examples 12-15, adjust the temperature to 50 ° C., stir uniformly, and then add radiolite as a filter aid. #700 [manufactured by Showa Chemical Industry Co., Ltd.] and 50 parts of Kyoward 600 [manufactured by Kyowa Chemical Industry Co., Ltd.] were filtered through a suction funnel filled in layers to separate the catalyst. The xylene was then removed under reduced pressure and concentrated. Add 20 parts of methanol to the concentrate and stir, add 100 parts of water to reprecipitate, separate the precipitate by decantation, and dry the precipitate under reduced pressure to obtain a cyclic compound (P-11 to 15). A composition containing

As described below, it was confirmed by MALDI-TOF MS [MALDI mass spectrometer AXIMA- Performance was confirmed by analysis by Shimadzu Corporation. In addition, GPC measurement was performed as necessary. Table 3 shows the results.

<Number average molecular weight measurement>
GPC measurement of the cyclic polyetherester composition (Q) was performed under the following conditions.
・ Apparatus: "TOSOH ECO HLC-8320 GPC" [manufactured by Tosoh Corporation]
・ Column: "Guardcolumn Super AW-H" (1 piece), "TSKgel Super AW2500, TSKgel Super AW3000, TSKgel Super AW4000 connected one each" [all manufactured by Tosoh Corporation]
・Sample solution: 0.125% by weight DMF (LiBr 0.01 mol/L) solution ・Solution injection amount: 20 μL
・Flow rate: 0.6 mL/min ・Measurement temperature: 40°C
・Detection device: Refractive index detector ・Reference substance: Standard polyethylene oxide

Examples 16-36
<Antibacterial resin preparation method>
After mixing the parts of the antibacterial component shown in Table 4 and the parts of the resin shown in Table 1 with a Henschel mixer, they were melt-kneaded at 200°C in a vented twin-screw extruder to obtain an antibacterial resin composition in the form of pellets. . Further, these pellets were injection-molded to obtain moldings (50 mm×50 mm×2 mm) of Examples and Comparative Examples. As resins, transparent ABS resin "TE-10" (hereinafter abbreviated as ABS) manufactured by Denki Kagaku Kogyo Co., Ltd. and polypropylene resin "E-105GM" (hereinafter abbreviated as PP) manufactured by Prime Polymer Co., Ltd. are used. Used.

<Antibacterial test method>
The antibacterial properties of molded articles (Examples 16 to 36) and comparative molded articles (Comparative Examples 1 to 5) made of the antibacterial component for resin of the present invention before and after washing were measured according to JIS Z 2801 (Antibacterial processed products-Antibacterial test method/ antibacterial effect).
That is, a test bacterial solution prepared by diluting a normal bouillon medium 500 times with sterilized purified water so that the number of bacteria is 2.5 × 10 to 10 × 10 / ml, is applied to a test piece (molded test piece; 0.4 ml was dropped onto a surface (50 mm x 50 mm x 2 mm), and a film was placed on the top 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 hours. Thereafter, the test piece and film were washed out with 10 ml of SCDLP medium, and the liquid was immediately subjected to viable cell count measurement to determine the viable cell count. Table 4 shows the results. This evaluation indicates that the antibacterial durability is excellent when the number of viable bacteria after washing is low.

The cyclic compound of the present invention is used for various plasticizers, cross-linking agents, resin modifiers, antistatic agents, urethane elastomers, hard coats, films, urethane foams, paints, rubbers, medical materials, electronic materials, lubricating oil additives, and other industrial applications. It is useful as a functional material used for

Claims (5)

A cyclic polyetherester composition (Q) containing a cyclic polyetherester (P) formed by bonding groups represented by the general formula (1).

[In general formula (1), R ¹ is a divalent hydrocarbon group having 2 to 21 carbon atoms. Each hydrogen atom of R ¹ may be independently substituted with a halogen group, an acetyl group, an alkoxy group or a phenoxy group. ; A is a divalent hydrocarbon group having 2 to 8 carbon atoms; Each hydrogen atom of A may be independently substituted with a halogen atom. m is an integer of 4 or more and 500 or less, n contained in each group is an integer of 0 or more and 500 or less, and at least one group in which n is 1 or more is included. m R ¹ 's may be the same or different, and m×n A's may be the same or different. ] In general formula (1), R ¹ is a linear alkylene group having 3 to 16 carbon atoms or a branched alkylene group having 3 to 16 carbon atoms, A is a phenylethylene group, a linear alkylene group having 2 to 4 carbon atoms, and The cyclic polyetherester composition according to claim 1, which is at least one selected from the group consisting of branched alkylene groups having 3 to 4 carbon atoms. A cyclic compound (B) represented by the general formula (2) and a cyclic ether compound having 2 to 8 carbon atoms, a burned product of a composite oxide (D1) of aluminum and magnesium and / or aluminum and magnesium 3. A method for producing a cyclic polyetherester composition containing the cyclic polyetherester (P) according to claim 1 or 2, comprising a step of reacting in the presence of a calcined product of hydrotalcite (D2).

[In general formula (2), R ² is a divalent hydrocarbon group having 2 to 21 carbon atoms. Each hydrogen atom of ^R2 may be independently substituted with a halogen group, an acetyl group, an alkoxy group or a phenoxy group. ] A cyclic polyetherester composition (Q) containing the cyclic polyetherester (P) according to claim 1 or 2, a polymer compound having an SP value of 4.0 to 22 (cal/cm ³ ) ^1/2 ( E) and an antibacterial resin composition (F) containing an antibacterial component (G). 5. The antibacterial resin composition according to claim 4, wherein the antibacterial component (G) is a quaternary ammonium salt cationic surfactant and/or an amphoteric surfactant.