Polyester resin-containing composition

Abstract

Provided is an aqueous polyester resin dispersion composition which, over a long period, has high rotproof properties and retains adhesive properties. More specifically, an aqueous polyester resin dispersion composition containing pyrithione or a salt thereof is provided.

Description

[Technical Field]

[0001] The present disclosure relates to a polyester resin-containing composition, etc. The contents of all documents described in this specification are incorporated herein by reference. [Background technology]

[0002] Aqueous polyester resin dispersion compositions are used in a variety of applications, such as binders and fiber treatment agents. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2001-310944 Summary of the Invention [Problem to be solved by the invention]

[0004] When the polyester resin aqueous dispersion composition is used as a binder, a fiber treatment agent, or the like, it is preferable that the composition maintains high antiseptic properties and adhesiveness for a long period of time.

[0005] The present inventors have conducted research to provide an aqueous polyester resin dispersion composition that has high antiseptic properties and maintains adhesiveness for a long period of time, and have found that high adhesiveness often results in poor antiseptic properties, and conversely, increased antiseptic properties often result in poor adhesion (i.e., there appears to be a trade-off between adhesion and antiseptic properties).

[0006] Even after obtaining this finding, the present inventors have conducted further investigations in order to obtain an aqueous polyester resin dispersion composition that has high antiseptic properties and maintains adhesiveness for a long period of time. [Means for solving the problem]

[0007] The present inventors then discovered that by incorporating a specific preservative into a polyester resin aqueous dispersion composition, it is possible to obtain a polyester resin aqueous dispersion composition that has high preservative properties and maintains adhesiveness for a long period of time, and have made further improvements.

[0008] The present disclosure includes, for example, the subject matter described in the following sections: Section 1. An aqueous polyester resin dispersion composition containing pyrithione or a salt thereof. Section 2. Item 2. The composition according to item 1, comprising 100 to 1000 ppm of pyrithione or a salt thereof. Section 3. Item 3. The composition according to item 1 or 2, further comprising polyvinyl alcohol. Section 4. Item 4. The composition according to any one of Items 1 to 3, wherein the polyester is a copolymer of a dicarboxylic acid and a glycol. Section 5. the dicarboxylic acid is at least one selected from the group consisting of terephthalic acid, isophthalic acid, and orthophthalic acid; The glycol is at least one selected from the group consisting of ethylene glycol, diethylene glycol, polyethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol. Item 5. The composition according to item 4. Section 6. Item 6. The composition according to any one of Items 1 to 5, wherein the polyester resin is a resin containing a polyester or a resin containing a polyester and polyvinyl alcohol. [Effects of the Invention]

[0009] The present invention provides an aqueous dispersion composition of a polyester resin that exhibits high antiseptic properties and maintains adhesiveness for a long period of time. The aqueous dispersion composition is useful for a variety of applications, such as binders and fiber treatment agents. DETAILED DESCRIPTION OF THE INVENTION

[0010]

[0032] Each embodiment included in the present disclosure will be described in more detail below. The present disclosure preferably includes, but is not limited to, an aqueous polyester resin dispersion composition and uses thereof, and the present disclosure includes all that is disclosed in the present specification and that can be recognized by a person skilled in the art.

[0011] The aqueous polyester resin dispersion composition of the present disclosure contains pyrithione or a salt thereof. In this specification, the aqueous polyester resin dispersion composition of the present disclosure may be referred to as the "composition of the present disclosure."

[0012] The composition of the present disclosure contains pyrithione or a salt thereof, which is known to be useful as a preservative.

[0013] Pyrithione is a compound represented by the following structural formula:

[0014] [ka]

[0015] Preferred examples of pyrithione salts include metal salts, and more specifically, preferred examples include sodium pyrithione, potassium pyrithione, magnesium pyrithione, barium pyrithione, bismuth pyrithione, strontium pyrithione, copper pyrithione, zinc pyrithione, cadmium pyrithione, and zirconium pyrithione. Of these, sodium pyrithione, potassium pyrithione, and zinc pyrithione are preferred. The structural formulas of sodium pyrithione and copper pyrithione are shown below. Sodium pyrithione is also known as 2-pyridinethiol 1-oxide sodium.

[0016] [ka]

[0017] [ka]

[0018] The pyrithione or salt thereof can be used alone or in combination of two or more kinds.

[0019] In the composition of the present disclosure, pyrithione or a salt thereof is preferably contained in an amount of, for example, 100 to 1000 ppm. The upper or lower limit of this range may be, for example, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, or 950 ppm. For example, the range may be 150 to 950 ppm.

[0020] The composition of the present disclosure preferably further contains polyvinyl alcohol. The polyvinyl alcohol preferably has a weight-average molecular weight of approximately 500 to 2500. The upper or lower limit of the weight-average molecular weight range may be, for example, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, or 2400. For example, the weight-average molecular weight may be 600 to 2400. Furthermore, polyvinyl alcohol having a saponification degree of 70 to 99 mol% is preferred. That is, polyvinyl alcohol is produced by saponifying polyvinyl acetate, and the saponification degree is preferably 70 to 99 mol%. The upper or lower limit of the degree of saponification may be, for example, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, or 98 mol%. For example, the degree of saponification may be 71 to 98 mol%.

[0021] When the composition of the present disclosure contains polyvinyl alcohol, the polyvinyl alcohol is preferably contained in an amount of, for example, 0.5 to 20 parts by mass relative to 100 parts by mass of the polyester resin. The upper or lower limit of this range may be, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19 parts by mass. For example, the range may be 1 to 19 parts by mass.

[0022] The polyester resin is not particularly limited as long as it is a resin containing polyester. It may also be a resin containing polyester and polyvinyl alcohol. Such a resin can be prepared, for example, by melt-kneading polyester and polyvinyl alcohol. The melt-kneading can be carried out, for example, using an extruder (particularly a twin-screw extruder). The polyvinyl alcohol contained in the polyester resin can preferably be the same as the polyvinyl alcohol preferably contained in the composition of the present disclosure described above. Note that when the melt-kneading is carried out at a temperature equal to or higher than the melting point of the polyester used and lower than the melting point of the polyvinyl alcohol used, the obtained polyester resin can be a resin consisting essentially of polyester alone.

[0023] When the polyester resin is a resin containing polyester and polyvinyl alcohol, the ratio of the polyester to polyvinyl alcohol content is preferably 0.1 to 5 parts by weight of polyvinyl alcohol per 100 parts by weight of polyester, and the upper or lower limit of this range may be 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, or 4.9 parts by weight. For example, the range may be 0.2 to 4 parts by mass.

[0024] The polyester resin preferably contains 90 to 100% by mass of polyester. The upper or lower limit of this range may be, for example, 91, 92, 93, 94, 95, 96, 97, 98, or 99% by mass. For example, the range may be 91 to 99% by mass. In addition to polyester and polyvinyl alcohol, the polyester resin may contain other resins as long as the effects of the composition of the present disclosure are not impaired. For example, it may contain a general thermoplastic resin other than polyester (such as polyolefin and its copolymer, polyamide, or polyurethane). It may also contain a polymeric emulsifier other than polyvinyl alcohol (such as ethylene oxide-propylene oxide copolymer, polyvinyl ether, polyacrylamide, or hydroxyethyl cellulose), a preservative, or the like. These components can be mixed into the polyester resin, for example, during the melt-kneading stage.

[0025] Although not particularly limited, the polyester resin is preferably a resin consisting essentially of polyester alone, or a resin consisting essentially of polyester and polyvinyl alcohol alone, and more preferably a resin consisting essentially of polyester alone.

[0026] The polyester is preferably a copolymer of a dicarboxylic acid and a glycol. The copolymer can be obtained by condensation polymerization of a dicarboxylic acid and a glycol. The condensation polymerization can be carried out by, for example, a known method or a method that can be easily derived from a known method.

[0027] The polyester preferably has a melting point of about 50 to 200° C. The upper or lower limit of the melting point may be, for example, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, or 190° C. For example, the melting point may be 60 to 190° C. The polyester preferably has a weight average molecular weight of about 5,000 to 60,000. The upper or lower limit of the range is, for example, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000, 20000, 21000, 22000, 23000, 24000, 25000, 26000, 27000, 28000, 29000, 30000, 31000, 3200 It may be 0, 33000, 34000, 35000, 36000, 37000, 38000, 39000, 40000, 41000, 42000, 43000, 44000, 45000, 46000, 47000, 48000, 49000, 50000, 51000, 52000, 53000, 54000, 55000, 56000, 57000, 58000, or 59000. The range may be, for example, 6000 to 59000.

[0028] Preferred examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, and orthophthalic acid. The dicarboxylic acid may be used alone or in combination of two or more.

[0029] Preferred examples of the glycol include ethylene glycol, diethylene glycol, polyethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, etc. The glycols may be used alone or in combination of two or more.

[0030] In the composition of the present disclosure, the polyester resin is preferably contained in an amount of, for example, about 20 to 80% by mass. The upper or lower limit of this range may be, for example, about 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, or 79% by mass. For example, the range may be 30 to 70% by mass or 40 to 60% by mass.

[0031] The aqueous medium of the composition of the present disclosure is preferably water, and various types of water can be used, such as tap water, industrial water, ion-exchanged water, deionized water, pure water, etc. Deionized water or pure water is particularly preferred.

[0032] The composition of the present disclosure can be prepared, for example, by adding a polyester resin to an aqueous medium, mixing, and dispersing. A surfactant (emulsifier) ​​may be used during mixing to aid dispersion, provided that the effects of the composition of the present disclosure are not impaired. A preferred example of the emulsifier is polyvinyl alcohol. Alternatively, emulsifiers known in the art may also be used.

[0033] As described above, the composition of the present disclosure preferably further contains polyvinyl alcohol. By adding and mixing polyvinyl alcohol as an emulsifier during the mixing step in the preparation, a composition further containing polyvinyl alcohol can be preferably prepared.

[0034] In this specification, the term "comprising" includes "consisting essentially of" and "consisting of." Furthermore, the present disclosure encompasses all arbitrary combinations of the constituent elements described in this specification.

[0035] Furthermore, the various characteristics (properties, structures, functions, etc.) described in each embodiment of the present disclosure above may be combined in any way to specify the subject matter encompassed by the present disclosure, i.e., the present disclosure encompasses all subject matter consisting of any combination of the combinable characteristics described herein. [Example]

[0036] Hereinafter, the embodiments of the present disclosure will be described more specifically with reference to examples, but the embodiments of the present disclosure are not limited to the following examples.

[0037] In the following studies, the polyvinyl alcohol used was "Poval 40-80E" (saponification degree 79 to 81 mol%), a product name of Kuraray Co., Ltd.

[0038] Example 1 Two hoppers were installed at the first feed port located 80 mm from the upstream tip of a twin-screw extruder (PCM-30, manufactured by Ikegai Corporation, L / D = 4 1.5, cylinder length 1260 mm), and polyester (melting point 95°C) and polyvinyl alcohol were fed into each hoppers at a rate of 40 kg / h and 0.48 kg / h, respectively.

[0039] The mixture was melt-kneaded at a cylinder temperature of 140°C and a rotation speed of 450 rpm up to a second supply port located 480 mm from the upstream tip of the twin-screw extruder, and then an 8% by mass aqueous polyvinyl alcohol solution was supplied from the second supply port at a rate of 9.2 kg / hour using a plunger pump.

[0040] The extruder was then kneaded and emulsified from the second feed port to the third feed port, located 1000 mm from the upstream end, at a cylinder temperature of 120°C and a rotation speed of 450 rpm. Then, 29.5 kg / h of pure water was fed into the third feed port using a plunger pump. The extruder was then kneaded from the third feed port to the extruder outlet at a cylinder temperature of 90°C and a rotation speed of 450 rpm. The mixture was then discharged from the extruder. This operation was continued for 10 minutes until operation stabilized. The switch valve was then opened, and the aqueous polyester resin dispersion was placed in a 5-L stirring vessel equipped with a propeller-type stirring rod (propeller diameter 58 mm, three blades) and stirred at 500 rpm.

[0041] The dispersion stirred in the stirring tank was poured into the inlet of a cooling tube, cooled at a cooling temperature of 40°C, and then discharged from the outlet of the cooling tube located 10,800 mm from the inlet.

[0042] Sodium pyrithione (trade name "Slaoff 28" manufactured by Osaka Gas Chemicals Co., Ltd.) was added to the dispersion discharged from the outlet of the cooling tube in an amount of 300 ppm relative to the dispersion, to obtain an aqueous polyester resin dispersion.

[0043] Example 2 An aqueous polyester resin dispersion was obtained in the same manner as in Example 1, except that the sodium pyrithione was used at 500 ppm.

[0044] Comparative Example 1 An aqueous polyester resin dispersion was obtained in the same manner as in Example 1, except that sodium pyrithione was not added.

[0045] Comparative Example 2 An aqueous polyester resin dispersion was obtained in the same manner as in Example 1, except that 300 ppm of an isothiazolone preservative (trade name "Topside 240" manufactured by Permakem Asia Co., Ltd.) was added instead of sodium pyrithione.

[0046] Comparative Example 3 In Comparative Example 2, an aqueous polyester resin dispersion was obtained in the same manner as in Comparative Example 2, except that 1000 ppm of an isothiazolone-based preservative was added.

[0047] The polyester resin aqueous dispersions obtained in each of the Examples and Comparative Examples were evaluated for adhesiveness and storage stability (antiseptic performance) by the following methods. The results are shown in Table 1.

[0048] (Adhesiveness) The polyester resin aqueous dispersion obtained in each Example and Comparative Example was applied to an aluminum foil (width: 25 mm, thickness: 30 μm) using a coating machine (Bar Coater No. 4, manufactured by Nippon Cedars Service Co., Ltd.) so that the thickness of the film after drying would be approximately 4 μm. The aluminum foil to which the dispersion had been applied was heated and dried in an oven at 100°C for 1 minute to form a film.

[0049] Next, a PVC (polyvinyl chloride) (width: 25 mm) adherend was bonded to the obtained film using a heat sealing machine (product name "TP-701" manufactured by Tester Sangyo Co., Ltd.). The heat sealing conditions were a sealing temperature of 140°C and a sealing pressure of 2 kg / cm. 2 The sealing time was 3 seconds, and the resulting heat-sealable substrate (PVC / dispersion coating / aluminum foil) (width: 25 mm) was used as a test piece. After cooling the test piece, a T-peel test was performed using a tensile tester (Shimadzu Corporation, trade name "Autograph AGS-J") at a tension speed of 50 mm / min. This allowed the peel strength of the coating to be measured and the adhesiveness to be evaluated. The evaluation criteria were as follows:

[0050] Adhesiveness ○: Peel strength 15N / 25mm or more ×: Peel strength less than 15N / 25mm

[0051] (Storage stability (preservative performance)) The polyester resin aqueous dispersions obtained in each Example and Comparative Example were left to stand at 25°C for 3 months, and then evaluated for decay state by visual observation or by checking for odor. The evaluation criteria are as follows: ○: No mold or putrid odor ×: Mold growth or putrid odor

[0052] [Table 1]

Claims

1. A composition comprising a polyester resin, Contains pyrithione or a salt thereof and polyvinyl alcohol, The content of pyrithione or a salt thereof is 100 to 1000 ppm, The polyester resin aqueous dispersion composition has a polyvinyl alcohol content of 0.5 to 20 parts by mass per 100 parts by mass of the polyester resin.

2. The composition of claim 1 wherein the polyester resin is a copolymer of a dicarboxylic acid and a glycol.

3. the dicarboxylic acid is at least one selected from the group consisting of terephthalic acid, isophthalic acid, and orthophthalic acid; The glycol is at least one selected from the group consisting of ethylene glycol, diethylene glycol, polyethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol. The composition of claim 2.

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