JP6559524B2 - Hydrophilizing agent - Google Patents

Description

  The present invention relates to a hydrophilizing agent.

  In general, when the surface of the substrate is hydrophilized, water droplets attached to the substrate are spread uniformly. As a result, adhesion of hydrophobic pollutants such as combustion products, oils and fats and sealant elution components contained in exhaust gas from urban dust, automobiles, etc., and even when the hydrophobic pollutants adhere, rain, washing or water Removal by a simple operation such as wiping becomes possible. In addition, it is expected to improve adhesion to a substrate, adhesion, plating characteristics, antistatic properties and the like.

  In the medical field, it is expected that the cultured cells can be easily collected by making the culture vessel for transplanted cells hydrophilic. It is also expected to prevent blood coagulation by hydrophilizing the components of the blood purification apparatus.

  As one method for making the substrate surface hydrophilic, a method of forming a mixture of a resin and a hydrophilizing agent (hereinafter referred to as a kneading method) is known. The kneading method has an advantage that the production of a molded product is simpler than the method of applying a hydrophilizing agent to the substrate surface. As such a hydrophilizing agent, for example, there is a method using a sulfonate and an amine compound (Patent Document 1).

JP-A-9-272758

  However, the hydrophilizing agent of Patent Document 1 has a problem that the hydrophilicity decreases with time. Then, an object of this invention is to provide the hydrophilic agent which can maintain hydrophilicity over a long period of time.

  In order to solve the above-mentioned problems, the hydrophilizing agent according to the present invention is a hydrophilizing agent containing an adduct (A) of a saccharide, and the saccharide residue in the adduct (A) of the saccharide. The total of the content of the group and the content of the oxyethylene group is 20 to 100% by mass.

  In the hydrophilizing agent according to the present invention, the number average molecular weight of the alkylene oxide adduct (A) of the saccharide is preferably 400 to 10,000.

  In the hydrophilizing agent according to the present invention, the saccharide in the alkylene oxide adduct (A) of the saccharide is preferably at least one selected from disaccharides and sugar alcohols.

  The resin molded article according to the present invention is a resin molded article containing an alkylene oxide adduct (A) and a resin (B) of a saccharide, and contains a saccharide residue in the alkylene oxide adduct (A) of the saccharide. The sum of the amount and the content of oxyethylene groups is 20 to 100% by mass.

  According to the present invention, a hydrophilizing agent that can maintain hydrophilicity over a long period of time is obtained.

  Hereinafter, preferred embodiments of the present invention will be described.

  The hydrophilizing agent of this embodiment contains the saccharide alkylene oxide adduct (A).

  In the saccharide alkylene oxide adduct (A) used in the present invention, the sum of the saccharide residue content and the oxyethylene group content is 20 to 100% by mass. By setting it within the above range, hydrophilicity can be maintained over a long period of time. The sum of the content of saccharide residues and the content of oxyethylene groups is preferably 30 to 90% by mass, and more preferably 40 to 80% by mass. In the present specification, the saccharide residue is a group obtained by removing a hydrogen atom of a hydroxyl group to which an alkylene oxide is added from a saccharide.

  The saccharide alkylene oxide adduct (A) used in the present invention preferably contains 0 to 80% by mass of an oxyethylene group. By setting it within the above range, hydrophilicity can be maintained over a long period of time. The content of oxyethylene groups is preferably 10 to 70% by mass, and more preferably 30 to 60% by mass.

  Examples of the saccharide in the alkylene oxide adduct (A) of saccharide used in the present invention include sugar and sugar alcohol. Examples of the sugar include monosaccharides such as glucose, fructose, galactose and mannose, disaccharides such as sucrose, lactose, maltose and trehalose, polysaccharides such as cellulose, amylose and chitin. Examples of the sugar alcohol include sorbitol, mannitol, maltitol, and erythritol. Of these, disaccharides and sugar alcohols are preferred, and sucrose is more preferred because of its relatively low viscosity and ease of handling and the ability to maintain hydrophilicity for a longer period.

  Examples of the alkylene oxide added to the saccharide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, glycidol, and tetrahydrofuran. Among these, since hydrophilicity can be maintained over a longer period, propylene oxide alone or a combination of ethylene oxide and propylene oxide is preferable, and a combination of ethylene oxide and propylene oxide is more preferable. In addition, when using combining ethylene oxide and propylene oxide, these mixtures may be added and you may add separately.

  Examples of the method for adding the alkylene oxide include known methods such as introducing alkylene oxide into a reaction vessel at 70 to 120 ° C. and 0 to 0.3 MPa in the presence of a saccharide and a catalyst and reacting with the saccharide. The method can be used.

  As the saccharide used for the alkylene oxide addition reaction, saccharide alone can be used, but from the viewpoint of reducing the viscosity of the reaction solution, it is preferable to use saccharide dissolved in a compound capable of dissolving saccharide. Examples of such compounds that can dissolve saccharides include hydroxyl-containing compounds other than saccharides such as water, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerin, and trimethylolpropane. Of these, water is preferable because of its high solubility in sugars and easy distillation after the addition reaction. Moreover, it is preferable that the usage-amount of the compound which can melt | dissolve saccharides is 20 mass parts or less with respect to 100 mass parts of saccharides from a viewpoint of raising the ratio of the alkylene oxide added to saccharides.

  The catalyst used for the alkylene oxide addition reaction is not particularly limited. For example, alkali metals such as potassium hydroxide and sodium hydroxide, alkaline earth metals such as calcium hydroxide and magnesium hydroxide, diethanolamine, triethylamine and the like. Amines, cationic polymerization catalysts, double metal cyanide complex catalysts, and the like. The usage-amount of a catalyst is 0.01-5.0 mass parts with respect to 100 mass parts of saccharides, for example.

  The amount of alkylene oxide added in the saccharide alkylene oxide adduct (A) is preferably 3 to 200 mol per mol of saccharide. By setting it within the above range, the hydrophilicity can be maintained over a longer period. The addition amount of the alkylene oxide is more preferably 5 to 100 mol, and further preferably 7 to 50 mol.

  The saccharide alkylene oxide adduct (A) preferably has an average hydroxyl value of 30 to 1000 mgKOH / g. By setting it within the above range, the hydrophilicity can be maintained over a longer period. The average hydroxyl value is more preferably 70 to 800 mgKOH / g, and further preferably 120 to 700 mgKOH / g. The average hydroxyl value can be measured according to JIS K0070.

  The saccharide alkylene oxide adduct (A) preferably has a number average molecular weight of 400 to 10,000. By setting it within the above range, the hydrophilicity can be maintained over a longer period. The number average molecular weight is more preferably 500 to 6000, still more preferably 700 to 4000, and particularly preferably 700 to 3000.

  The alkylene oxide addition reaction product may be further purified. By performing the purification treatment, the hydrophilicity can be maintained for a longer period. Examples of such purification treatment include adsorbent treatment and distillation treatment. Among these, the adsorbent treatment is preferable because the production process is easy.

  The adsorbent treatment method is not particularly limited. For example, the alkylene oxide addition reaction product and the adsorbent are mixed using a stirrer or the like, the alkylene oxide addition reaction product is passed through an adsorbent packed column, and the like. Is mentioned. Among these, the method of mixing the alkylene oxide addition reaction product and activated carbon is preferable because the operation is simple. When a solvent such as water or an organic solvent is used, the adsorbent may be added after mixing with the alkylene oxide addition reaction product in advance, or the adsorbent is dispersed in the solvent and then mixed with the alkylene oxide addition reaction product. May be.

  The adsorbent is for adsorbing and removing impurities contained in the alkylene oxide addition reaction product. Such an adsorbent may be in the form of powder, granules, or pellets, and is preferably in the form of powder. Examples of such an adsorbent include activated carbon, zeolite, and the like. Particularly, since the heat resistance of the hydrophilizing agent is more excellent, activated carbon is preferable, and the pH in a 1% by mass aqueous suspension is 4 to 11. Activated carbon is more preferable, and activated carbon having a pH of 4.5 to 7.5 is more preferable.

  The amount of the adsorbent used is not particularly limited, but is preferably 0.1 to 20.0 parts by mass, and 1.0 to 10.0 parts by mass with respect to 100 parts by mass of the alkylene oxide addition reaction product. More preferably. By making the usage-amount of adsorption agent in the said range, a manufacturing process will become a simpler thing.

  Moreover, it is preferable to use a solvent in the adsorbent treatment. By using the solvent, the viscosity of the alkylene oxide addition reaction product is reduced, and the purification treatment can be easily performed.

  Moreover, in the said adsorption agent process, you may use various additives, such as antioxidant and a ultraviolet absorber other than the said solvent.

  The resin molded product according to the present invention contains the saccharide alkylene oxide adduct (A) and the resin (B). The alkylene oxide adduct (A) of the saccharide is the same as that usable with the hydrophilizing agent of the present invention. It is preferable that the resin molded article contains the saccharide alkylene oxide adduct (A) and the resin (B) in a mixed state.

  Examples of resins that can be used in the present invention include polystyrene resins, polyester resins, polyolefin resins, polycarbonate resins, polylactic acid resins, polyvinyl chloride resins, polysulfone resins, and other thermoplastic resins, phenol resins, urea resins, melamine resins, A thermosetting resin such as an epoxy resin can be used. Of these, thermoplastic resins are preferred.

  The content of the alkylene oxide adduct (A) of the saccharide in the resin molded product of the present invention is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin. By setting it within the above range, higher hydrophilicity can be maintained over a long period of time. The content is more preferably 0.5 to 5.0 parts by mass.

  The method for producing the resin molded article of the present invention is not particularly limited as long as it can be mixed with the saccharide alkylene oxide adduct (A). Examples of such a method include a method of mixing using a kneading machine such as an open type twin-screw kneader or a kneader.

  In the said manufacturing method, it is preferable that the mixing temperature of the alkylene oxide adduct (A) of saccharides and resin (B) is 140-240 degreeC. By setting it within the above range, the saccharide alkylene oxide adduct (A) and the resin (B) can be more uniformly mixed, so that higher hydrophilicity can be maintained over a long period of time.

  The resin molded article of the present invention can contain known additives in addition to the resin (B) and the saccharide alkylene oxide adduct (A). Examples of such additives include antioxidants, ultraviolet absorbers, flame retardants, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

  In this example, the saccharide alkylene oxide adducts (a-1) to (a-5) obtained in the following Production Examples 1 to 5 were used as the saccharide alkylene oxide adduct (A).

(Production Example 1)
A stainless steel autoclave was charged with 342 g (1 mol) of sucrose, 70 g of water, and 3 g of potassium hydroxide, and the inside of the reactor was purged with nitrogen. The temperature was raised to 80 ° C. to dissolve sucrose, then the temperature was raised to 100 ° C., and 352 g (8 mol) of ethylene oxide was introduced while maintaining the internal pressure at 0.3 MPa or less. After the introduction, the reaction was further carried out at 100 ° C. for 2 hours. Subsequently, 464 g (8 mol) of propylene oxide was introduced while maintaining the internal pressure at 0.3 MPa or less. After completion of the introduction of propylene oxide, an alkylene oxide adduct was obtained by reacting at 100 ° C. for 2 hours.
100 g of the obtained alkylene oxide adduct and 30 g of water were mixed and adjusted to 50 ° C., and acetic acid was further added to adjust the pH to 6. Subsequently, 10 g of powdered activated carbon (trade name: Strong Shirasagi A (manufactured by Nippon Enviro Chemicals, 1% aqueous solution pH: 4.9) was added and stirred for 2 hours at 50 ° C. Thereafter, the activated carbon was removed by filtration. By removing water at 90 ° C. under reduced pressure, a sucrose-ethylene oxide (8 mol) -propylene oxide (8 mol) block adduct (a-1) was obtained (average hydroxyl value: 445 mgKOH / g, Oxyethylene group content: 34% by weight, saccharide residue content and oxyethylene group content: 66% by weight, number average molecular weight: 1015)

(Production Example 2)
A stainless steel autoclave was charged with sucrose 342 (1 mol), water 70 g, and potassium hydroxide 3 g, and the inside of the reactor was purged with nitrogen. The temperature was raised to 80 ° C. to dissolve sucrose, then the temperature was raised to 100 ° C., and 928 g (16 mol) of propylene oxide was introduced while keeping the internal pressure at 0.3 MPa or less. After completion of the introduction, an alkylene oxide adduct was obtained by further reacting at 100 ° C. for 2 hours. The resulting alkylene oxide adduct was purified by the same method as in Production Example 1 to obtain a sucrose-propylene oxide (16 mol) block adduct (a-2). (Average hydroxyl value: 367 mg KOH / g, oxyethylene group content: 0% by weight, sum of saccharide residue content and oxyethylene group content: 27% by weight, number average molecular weight: 1241)

(Production Example 3)
The same operation as in Production Example 1 was carried out except that the amount of ethylene oxide used was 1320 g (30 mol) and the amount of propylene oxide used was 1160 g (20 mol), and sucrose-ethylene oxide (30 mol) -propylene oxide (20 Mol) Block adduct (a-3) was obtained. (Average hydroxyl value: 167 mgKOH / g, oxyethylene group content: 47% by weight, sum of saccharide residue content and oxyethylene group content: 59% by weight, number average molecular weight: 2753)

(Production Example 4)
Instead of propylene oxide, the same operation as in Production Example 2 was performed except that a mixture of 440 g (10 mol) of ethylene oxide and 580 g (10 mol) of propylene oxide was used, and sucrose- (ethylene oxide (10 mol) / propylene oxide ( 10 mol)) Random adduct (a-4) was obtained. (Average hydroxyl value: 341 mg KOH / g, oxyethylene group content: 32 wt%, sum of saccharide residue content and oxyethylene group content: 47 wt%, number average molecular weight: 1320)

(Production Example 5)
Maltitol was replaced with 344 g (1 mol), ethylene oxide was used in an amount of 440 g (10 mol), and propylene oxide was used in an amount of 580 g (10 mol). Maltitol-ethylene oxide (10 mol) -propylene oxide (10 mol) block adduct (a-5) was obtained. (Average hydroxyl value: 342 mgKOH / g, oxyethylene group content: 32 wt%, sum of saccharide residue content and oxyethylene group content: 58 wt%, number average molecular weight: 1315)

(Measurement method of average hydroxyl value)
It measured according to JIS K0070.

(Measurement method of number average molecular weight)
The number average molecular weight in terms of polyethylene was calculated by GPC method under the following conditions.
[Measurement condition]
Measurement sample: 1 wt% tetrahydrofuran solution
Apparatus: LC-10AD (trade name, manufactured by Shimadzu Corporation)
Column: GPC KF-801, GPC KF-801 and GPC KF-803 (
Product name, all manufactured by Showa Denko KK) connected in series Mobile phase: Tetrahydrofuran (flow rate: 0.8 mL / min)
Column temperature: 25 ° C

Moreover, the following were used as raw materials other than the saccharide alkylene oxide adduct (A).
・ Resin (B)
(B-1) Low density polyethylene (trade name: Novatec LL UF442, manufactured by Nippon Polyethylene)
・ Other ingredients (C)
(C-1) A mixture obtained by dissolving 60 g of sodium lauryl sulfate (trade name: EMAL 0, manufactured by Kao Corporation) and 40 g of lauryl monoethanolamide in 30 g of methanol and distilling off the methanol (c-2) Sodium alkylbenzenesulfonate ( (Product name: Raipon PS-230, manufactured by Lion Corporation) 80 g and lauryldiethanolamine 20 g were dissolved in 50 g of methanol, and the methanol was distilled off.

(Examples 1-7)
The saccharide alkylene oxide adduct (A) and the resin (B) were kneaded at 150 ° C. for 10 minutes using an open biaxial kneader at the ratio shown in Table 1. The obtained kneaded product was press-molded at 150 ° C. in a mold (diameter 10 cm, thickness 1 mm) to prepare a test piece. Using this test piece, the hydrophilicity was evaluated by the following method. The results are shown in Table 1.

(Hydrophilic)
The obtained test piece was left still for a predetermined period (1 day, 14 days, or 30 days) in a constant temperature and humidity chamber (set temperature: 60 ° C., set humidity: 70% RH). Using this test piece, the contact angle (degree) by the tangent method was measured according to JIS R3257.

(Comparative Examples 1 and 2)
The same operation as in Example 1 was carried out except that the other component (c-1) or (C-2) shown in Table 1 was used without using the saccharide alkylene oxide adduct (A). The results are shown in Table 1.

  As is apparent from Table 1, the hydrophilizing agent of the present invention can maintain hydrophilicity over a long period of time. On the other hand, in the case where the saccharide alkylene oxide adduct (A) is not used as in Comparative Examples 1 and 2, it can be seen that the hydrophilicity greatly decreases in a short period.

Since the hydrophilic agent of the present invention can maintain excellent hydrophilicity for a long period of time, it can be used as a hydrophilic agent used for resins and the like.

Claims (5)

A hydrophilizing agent containing an alkylene oxide adduct (A) of a saccharide,
The saccharides of the alkylene oxide adduct in (A), Ri sum 20-90% by mass of the content and the content of oxyethylene groups in saccharide residues,
A hydrophilizing agent , wherein propylene oxide is added to the saccharide alkylene oxide adduct (A) .   The hydrophilizing agent according to claim 1, wherein the saccharide alkylene oxide adduct (A) has a number average molecular weight of 400 to 10,000.   The hydrophilizing agent according to claim 1 or 2, wherein the saccharide in the alkylene oxide adduct (A) of the saccharide is at least one selected from disaccharides and sugar alcohols. A resin molded article containing an alkylene oxide adduct (A) of a saccharide and a resin (B),
The saccharides of the alkylene oxide adduct in (A), Ri sum 20-90% by mass of the content and the content of oxyethylene groups in saccharide residues,
A resin molded product in which propylene oxide is added to the alkylene oxide adduct (A) of the saccharide .   The resin molded product according to claim 4, wherein the resin (B) is a thermoplastic resin (B1).