JP2008248132A - Particles containing polyethylene terephthalate-based polymer compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide particles which are quickly dissolved and dispersed into water, and promptly released, into water, a polymer compound composed of an ethylene terephthalate unit and a polyoxyethylene terephthalate unit. <P>SOLUTION: This particles comprise a mixture formed by melt-mixing (A) a polymer compound composed of an ethylene terephthalate unit and a polyoxyethylene terephthalate unit and (B) a nonionic water-soluble polymer compound. The particles are formulated into a detergent composition. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to particles containing a polyethylene terephthalate polymer compound and a method for producing the same. The present invention also relates to a powder detergent composition containing the particles.

  A polymer compound (hereinafter sometimes referred to as POET) having an ethylene terephthalate unit and a polyoxyethylene terephthalate unit as a basic skeleton is used to prevent dirt from adhering to clothing. There is a known effect of making it difficult to adhere (SG performance) or easily removing dirt (SR performance) (for example, Patent Document 1).

It is known that POET generally has a higher antifouling effect as the degree of polymerization, that is, the viscosity increases. It is also known that it is preferable from the standpoint of adsorptivity to fibers and prevention of detachment during rinsing. Further, in order to improve the stability of POET in a detergent, a technique using a melt in which POET / sodium polyacrylate is 2/1 to 8/1 (weight ratio) is known (see, for example, Patent Document 2). .
JP 2004-115969 A JP-A-61-83298

  However, Patent Document 2 is a technique for stabilizing POET in a detergent, and does not mention any composition that can further improve the solubility of particles containing POET. An object of the present invention is to provide particles that can be rapidly dissolved and dispersed in water and can quickly release POET into water.

  The present invention provides a mixture obtained by melt-mixing (A) a polymer compound comprising an ethylene terephthalate unit and a polyoxyethylene terephthalate unit and (B) a nonionic water-soluble polymer compound. It is related with the particle | grains to contain, and the powder detergent composition containing this particle | grain.

  The present invention also includes a step of melt-mixing (A) a polymer compound comprising an ethylene terephthalate unit and a polyoxyethylene terephthalate unit and (B) a nonionic water-soluble polymer compound. Relates to a method for producing particles.

  According to the present invention, particles capable of rapidly dispersing and dissolving in water and releasing a polymer compound containing ethylene terephthalate units and polyoxyethylene terephthalate units into water can be obtained. In the powder detergent composition of the present invention containing such particles, it is sufficient to quickly release a polymer compound comprising an ethylene terephthalate unit and a polyoxyethylene terephthalate unit into the washing liquid. A dirt release effect (SR effect) is obtained.

<Particle>
The particles of the present invention comprise (A) a polymer compound comprising an ethylene terephthalate unit and a polyoxyethylene terephthalate unit [hereinafter referred to as component (A)], and (B) a nonionic water-soluble polymer compound. [Hereinafter referred to as component (B)] is a particle containing a mixture obtained by melt mixing.

[(A) component]
Although the weight average molecular weight of (A) component is not specifically limited, The thing of 500-100000 is preferable and the thing of 1000-30000 is more preferable. The weight average molecular weight of component (A) can be measured, for example, by gel permeation liquid chromatography (GPC) using a mixed solution of acetonitrile and water (phosphate buffer) as a developing solvent and polyethylene glycol as a standard substance. it can.

  The ethylene terephthalate unit and the polyoxyethylene terephthalate unit may be randomly copolymerized or block copolymerized. The molar ratio of the ethylene terephthalate unit (A1) to the polyoxyethylene terephthalate unit (A2) is preferably (A1) / (A2) = 90/10 to 10/90, more preferably 70/30 to 50/50. (A) 0.1-30 mass% is preferable in a particle | grain, and, as for the compounding quantity of a component, 0.1-10 mass% is more preferable.

  The component (A) may contain monomer units other than ethylene terephthalate units and polyoxyethylene terephthalate units. Among all monomer units constituting component (A), ethylene terephthalate units and polyoxyethylene terephthalate units. Is preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 100 mol%.

[Component (B)]
The nonionic water-soluble polymer compound is a polymer that dissolves 1% by mass or more in water at 25 ° C. excluding the component (A), and its weight average molecular weight is preferably 1000 to 100,000, and more preferably 2000 to 50000. Here, the weight average molecular weight of the component (B) was measured by gel permeation liquid chromatography (GPC), and the following conditions were used. Both eluents and added salts were prepared from grades for liquid chromatography.

Column: Two pieces of G4000PWXL + G2500PWXL manufactured by Tosoh Corporation
Eluent: 0.2M phosphate buffer (pH 6.9) / acetonitrile = 9/1 (volume ratio),
Detector: differential refractometer,
Temperature: 40 ° C
Standard: Polyethylene glycol measurement concentration: 5 mg / ml,
Injection volume: 100 μl

  Examples of the component (B) include polyethylene glycol (PEG), polyacrylic acid amide, polyglycerin, polyether-modified silicone, and an alkylene oxide adduct of alcohol. Among them, PEG, particularly PEG having a weight average molecular weight of 3000 to 10,000. Is preferred. (B) 0.1-40 mass% is preferable in a particle | grain, and, as for the compounding quantity of a component, 15-35 mass% is more preferable.

  The particles of the present invention preferably contain a mixture obtained by melt mixing at a mass ratio of (A) / (B) = 99/1 to 1/99, and the mass ratio is 50 / 50-5. / 95 is more preferable, and 40/60 to 10/90 is still more preferable. The term “melting” includes the case where the component (A) and / or the component (B) is partially melted.

[Component (C)]
From the viewpoint of solubility, it is preferable to contain a powder having a particle diameter of 3 mm or less as the component (C), and more preferably 1 to 2000 μm.

Examples of the component (C) include amorphous silicate, silicon dioxide, silicate, aluminosilicate, sugar, polysaccharide, salt, bentonite and the like. Of these, silicon dioxide, amorphous silicate, and calcium silicate are more preferable. Specific examples of sugars and polysaccharides include cellulose, starch, and derivatives thereof. Of these, dextrin is preferable, and a specific volume of 5 to 10 m ² / g is more preferable from the viewpoint of oil absorption, and a glass transition temperature of 200 ° C. or higher is particularly preferable from the viewpoint of stability at high temperatures. preferable. (C) As for the compounding quantity of a component, 10-40 mass% is preferable in particle | grains, and 15-35 mass% is more preferable. These components may be used alone or in combination.

[Other ingredients]
In addition to the components (A), (B), and (C) described above, dimethyl silicone, a water-insoluble polyether-modified silicone that reduces the viscosity, and an emulsifier include an anionic surfactant and a non-ionic interface. Activators, cationic surfactants, and amphoteric surfactants can be blended. Among these, for example, those that meet the definition of the component (B) such as a high molecular weight nonionic surfactant are handled as the component (B).

[Production method of particles]
The manufacturing method of the particle | grains of this invention has the process of melt-mixing (A) component and (B) component.

  In the present invention, melt mixing refers to performing mechanical mixing at a temperature at which either component (A) or component (B) melts. The molten state includes a state where either the component (A) or the component (B) is partially melted to a state where both of them are completely melted. Preferably, a part or both of them are melted, and it is more preferable that all of them are melted. The mixing conditions are not particularly limited. For example, it is preferable to mix more uniformly, but the component (A) or the component (B) may have a sea-island structure. Further, components other than the component (A) and the component (B) are not concerned with the presence or absence of melting or the presence or absence of dispersion. In addition, it is preferable to perform melt mixing at a temperature of about 20 ° C. higher than the higher melting point of the component (A) or the component (B).

  The melt kneading of the component (A) and the component (B) is preferably performed together with the component (C). Moreover, the mixture obtained by melt-mixing (A) component and (B) component can also be granulated with other components, such as (C) component, as needed. In any case, it is preferable that the final particle is obtained through a granulated product. Examples of the granulation method include extrusion granulation, rolling granulation, and compaction granulation.

  The particles of the present invention containing the component (A) and the component (B) are preferably produced by compacting by extrusion granulation. By using the production method of extruding granulation and compacting, the component (A) in the particles is subdivided, so that there is an advantage that performance is exhibited by quickly dispersing in washing and coating on clothes.

  In the case of extrusion granulation, each component is sufficiently premixed in advance using a mixer such as a Henschel mixer, a high speed mixer, or a nauter mixer, and then the resulting mixture is made into a “Petter” manufactured by Fuji Powder Corporation. It can be obtained by extrusion granulation and compaction by a known extruder such as “Double” or “Twin Dome Gran” manufactured by Fuji Paudal. Further, a kneading and extruding apparatus such as “Extrude Ohmic” manufactured by Hosokawa Micron Corporation can be used, and in this case, the above-mentioned premixing can be omitted.

  The short axis particle diameter of the particles of the present invention obtained through extrusion granulation is preferably 0.3 to 2.5 mm, more preferably 0.5 to 2.0 mm, still more preferably 0.7 to 1.0 mm. Degree. Moreover, the shape can be extruded in shapes, such as a cylindrical shape or a noodle-shaped granulated material.

  In producing the particles of the present invention, the particles may be pulverized or sized by a known method and apparatus. The equipment used when pulverizing or sizing is not particularly limited, and a known pulverizer (or pulverizer) can be used. For example, a high speed mixer (Fukae Kogyo Co., Ltd.), Malmerizer, Fitzmill (Dalton Co., Ltd.), Power Mill (Paurec Co., Ltd.), Comil (Quadro Co.), etc. can be mentioned. From the viewpoint of the amount of fine powder generated that affects the properties and productivity, it is preferable to use a pulverizer such as a power mill using a knife cutter or a comil that pulverizes particles by pressing the impeller and screen.

  Examples of the power mill include an apparatus disclosed in Japanese Patent Laid-Open No. 5-96195. This device is a device with a cutter blade and a cylindrical screen. Particles thrown into the power mill inlet fall freely inside the power mill, and are crushed and adjusted by a pulverizing blade disposed on the cutter blade during this natural fall. Be grained.

  Examples of the comil include an apparatus disclosed in US Pat. No. 4,759,507. This device is an instrument having an impeller and a screen, and particles thrown into the comil inlet are pressed against the screen by the centrifugal force generated by the rotating impeller. The small particles are instantaneously and also lifted by the swirl generated due to the conical shape, and the particles that have risen are pulverized and sized by the impeller.

  The degree of pulverization is determined while evaluating the long axis particle diameter and short axis particle diameter of the obtained particles by, for example, an image analysis method as described in JP-A-2003-130785. If the pulverization conditions are determined, particles having a desired shape can be produced with good reproducibility for the same extruded granulated product.

[Powder detergent composition]
The particles of the present invention can be incorporated into common powder detergents, particularly powder detergent compositions for textile products. From the viewpoint of cleaning performance and SR performance, the blending amount of the particles in the powder detergent composition is preferably 1 to 30% by mass, and more preferably 1 to 10% by mass.

[Combination with finish containing silicone]
The combination of the detergent composition of the present invention and the silicone-containing finishing agent tends to improve the water absorption feeling of the clothes due to the effect of POET, compared to the case where a general detergent and a silicone-containing finishing agent are used in combination. It is done.

The components used in Examples and Comparative Examples are shown below.
A-1: POET polymer compound having a weight average molecular weight of 12,000 of ethylene terephthalate unit / polyoxyethylene terephthalate unit = 73/27 (molar ratio) A-2: ethylene terephthalate unit / polyoxyethylene terephthalate unit = 52 / 48 (molar ratio) POET polymer compound with a weight average molecular weight of 2700; A-3: ethylene terephthalate unit / polyoxyethylene terephthalate unit = 56/44 (molar ratio) POET polymer compound with a weight average molecular weight of 20000, “SRP-6” manufactured by Rhodia, average number of moles of ethylene oxide added per molecule 50
B-1: polyethylene glycol, weight average molecular weight 8000
B-2: polyethylene glycol, weight average molecular weight 4000
B-3: polyether-modified silicone (“Y-7006” manufactured by Toray Dow Corning Co., Ltd.)
B-4: Polyethylene glycol (“KPEG6000LA” manufactured by Kao Corporation)
C-1: Tokuseal NR (manufactured by Tokuyama Corporation), average aggregate particle size 130 μm

Moreover, the evaluation method of solubility and SR performance performed by the Example and the comparative example is shown below.
[1] Evaluation Method of Particle Solubility 0.2g of particles is prepared, 20 ° C. tap water is prepared in a 1 L beaker, stirred at 800 rpm for 5 minutes with a 35 mm stirrer piece, and filtered through SUS316 twill 400 mesh. It was dried at 105 ° C. for 30 minutes, the undissolved mass was measured, and the solubility (%) was calculated by the following formula.
Solubility (%) = 100− (mass after drying−mass before drying) /0.2×100

[2] Evaluation method of SR performance (2-1) Pretreatment of synthetic fiber The detergent obtained in the examples or comparative examples at a standard concentration (0.8% by mass), synthetic fiber (polyester taffeta, 5 pieces of 6 cm × 6 cm) Is pretreated and dried overnight. Pre-treatment uses a targotometer (manufactured by Uesima), tap water, water volume 500 ml, water temperature 20 ° C., rotation speed 80 rpm, washing 5 minutes, rinsing 3 minutes twice, dewatering 1 minute (washing machine dewatering tank), The cloth amount in the bath was 25 g (also using cotton cloth for mass adjustment), and the cloth ratio in the bath was cotton cloth / polyester taffeta = 8/2 (mass ratio).

(2-2) Method for Producing Contaminated Cloth A prefabricated synthetic sebum stain prepared in advance (composition is 45% by weight oleic acid, 40% by weight trioleic acid, 15% by weight squalene, colored with orange oil) 30 μl per sheet was applied and allowed to dry overnight while protected from light.

(2-3) Cleaning method Prepare 1L of tap water at 20 ° C in a tartometer, and put the detergent obtained in the example or comparative example to a concentration of 0.8% by mass, and 5 sheets of contaminated cloth. , Rotating at 80 rpm, washing for 10 minutes, rinsing for 3 minutes, dewatering for 1 minute (washing machine dewatering tank), and left to dry overnight in a dark place.

(2-4) Calculation method of SR performance The SR performance was evaluated by the cleaning rate based on the residual amount of dirt. Using a spectroscopic colorimeter (Nippon Denshoku Industries Co., Ltd. SE-2000), the reflectance before and after cleaning of the contaminated cloth is measured, applied to the following calculation formula, and calculated as a cleaning rate. The raw cloth is in a state before the model sebum stain is applied.
Washing rate (%) = [(reflectance of contaminated cloth after washing−reflectivity of contaminated cloth before washing) / (reflectance of raw cloth−reflectance of contaminated cloth before washing)] × 100

Example 1
20% by mass of A-1 previously melted at 80 ° C. (amount in particle composition, the same in the following examples) and 80% by mass of B-1 previously melted at 80 ° C. at 80 ° C. in a beaker After melting and mixing, the temperature was returned to room temperature, and the solidified molten mixture was pulverized to obtain particles. This particle was washed with detergent (detergent composition: 12 parts by weight of anionic surfactant, 10 parts by weight of nonionic surfactant, 1 part by weight of PEG, 1 part by weight of soap, 28 parts by weight of zeolite, 21 parts by weight of soda ash, 12 parts by weight of sodium nitrate, 12 parts by weight of sulfurous acid. (Na 0.5 part, NaCl 4 part, oligomer D 6 part, crystalline silicate 2 part, fluorescent whitening agent 0.2 part, enzyme 0.8 part, moisture 1.5 part) 1 mass part was mix | blended with respect to the mass part. The solubility of the particles is 95%, and the SR performance (cleaning rate) is 45% for the detergent only and 60% for the particle-containing detergent.

Example 2
Particles were obtained in the same manner as in Example 1 except that the ratio of A-1 was 80% by mass and the ratio of B-1 was 20% by mass. 1 part by mass of this particle was blended with respect to 100 parts by mass of the detergent used in Example 1. When the solubility of the particles and the SR performance of the detergent were evaluated in the same manner as in Example 1, the solubility was 75% and the SR performance (cleaning rate) was 50%.

Example 3
After 14% by mass of A-1 and 56% by mass of B-1 were melt mixed at 80 ° C., C-1 was flown together with 30% by mass to obtain particles. The particles were blended in an amount of 1.4 parts by mass with respect to 100 parts by mass of the detergent used in Example 1. When the solubility of the particles and the SR performance of the detergent were evaluated in the same manner as in Example 1, the solubility was 98% and the SR performance (cleaning rate) was 65%.

Comparative Example 1
80% by mass of A-1 and 20% by mass of sodium polyacrylate (average molecular weight 2000) were melt-mixed at about 82 ° C. and then returned to room temperature, and the solidified melt mixture was pulverized to obtain particles. 1 part by mass of this particle was blended with respect to 100 parts by mass of the detergent used in Example 1. When the solubility of the particles and the SR performance of the detergent were evaluated in the same manner as in Example 1, the solubility was 70% and the SR performance (cleaning rate) was 50%.

Example 4
C-1 was charged into a 50 mass% Nauter mixer, the jacket temperature was set to 75 ° C, and the mixture was heated up. Next, 10% by mass of A-2 and 40% by mass of B-2, which were previously melt-mixed when the temperature of the powder reached 60 ° C., were added to obtain particles. 2 parts by mass of these particles were blended with respect to 100 parts by mass of the detergent used in Example 1. When the solubility of the particles and the SR performance of the detergent were evaluated in the same manner as in Example 1, the solubility was 98% and the SR performance (cleaning rate) was 58%.

Example 5
Dimethyl silicone (“KF 96-30,000 cs” manufactured by Shin-Etsu Chemical Co., Ltd., viscosity (25 ° C.) 30000 mm ² / s) 30.8% by mass, B-3 0.5% by mass, nonionic surfactant ( 8.7% by mass of “Emulgen 106” manufactured by Kao Co., Ltd., a silicone mixed solution obtained by mixing these in advance, and 27% by mass of C-1 were added to a Nauter mixer (manufactured by Hosokawa Micron Co., Ltd.). The temperature was raised to 75 ° C. and the mixture was heated. Next, when the temperature of the mixture reached 60 ° C., 6.2% by mass of A-3 previously melted and 26.8% by mass of B-4 were added, and after further mixing, the mixture was extracted. . Next, the obtained mixture was extruded through a screen having a pore diameter of 0.7 mm by an extrusion granulator (“Peletter Double EDX-60 type”, manufactured by Fuji Powder Co., Ltd.) and consolidated. Further, after the extruded granulated product was cooled, it was pulverized by a granulator (pulverized once by a power mill), and passed through a sieve to remove particles having a particle size of 355 μm or less to obtain particles. 3 parts by mass of these particles were blended with respect to 100 parts by mass of the detergent used in Example 1. When the solubility of the particles and the SR performance of the detergent were evaluated in the same manner as in Example 1, the solubility was 95% and the SR performance (cleaning rate) was 60%.

Example 6
The following evaluation was performed about the detergent obtained in Example 5.
(Preprocessing)
2. To remove oil adhering to a new commercially available cotton towel (100% cotton), a mini washing machine (Matsushita Electric Industrial Co., Ltd., product number: N-BK2) was used, and Kao Corporation Attack 3. After washing at 5 g for 5 minutes with water temperature of 20 ° C. and 5 L of water, centrifugal dehydration, rinsing with 5 L of water for 3 minutes, centrifugal dehydration, rinsing for 3 minutes, and centrifugal dehydration were performed. This process was repeated 5 times.

(Cleaning conditions and evaluation method)
To 5 L of water at 20 ° C., 5.0 g of the detergent obtained in Example 5 (referred to as detergent A) and 0.3 kg of treated cotton towel (4 sheets of 70 cm × 30 cm) were added and washed for 7 minutes. After centrifugal dehydration, rinse with 5 L of water for 3 minutes, centrifugal dehydration, and fiber treatment agent composition containing silicone with 5 L of water (composition of Example 1 of JP-A 2006-161188) for 3 minutes. Rinse and spin dry. This process was repeated 20 times and air-dried. The same operation was performed using a detergent in which particles obtained by using sodium sulfate instead of A-3 in the particles added in the detergent in Example 5 were mixed.

  When the water absorption feeling of the cotton towel treated under these washing conditions was compared, a better water absorption feeling was obtained when the detergent A and the fiber treatment composition containing silicone were combined.

Claims (7)

  (A) Particles containing a mixture obtained by melt-mixing a polymer compound comprising an ethylene terephthalate unit and a polyoxyethylene terephthalate unit and (B) a nonionic water-soluble polymer compound.   The particle according to claim 1, further comprising (C) 1 to 80% by mass of a powder having a particle diameter of 3 mm or less.   A powder detergent composition containing the particles according to claim 1.   (A) A method for producing particles, comprising a step of melt-mixing a polymer compound comprising an ethylene terephthalate unit and a polyoxyethylene terephthalate unit and (B) a nonionic water-soluble polymer compound.   The method for producing particles according to claim 4, comprising a step of granulating the mixture obtained by melt mixing together with (C) 1 to 80% by mass of a powder having an average particle diameter of 3 mm or less (ratio in the final particle composition).   Melting and kneading the (A) polymer compound and the (B) nonionic water-soluble polymer compound, (C) 1 to 80% by mass of the powder having an average particle diameter of 3 mm or less (ratio in the final particle composition) The method for producing particles according to claim 4, wherein   The method for producing particles according to claim 4 or 6, comprising a step of granulating a mixture obtained by melt mixing.