JP6675847B2 - Water repellent for thermoplastic resin - Google Patents

Description

  The present invention relates to a water repellent for a thermoplastic resin having continuous water repellency.

  Currently, various thermoplastic resins are used in automobiles, home appliances, and stationery. It is used in a wide range of fields such as food containers. However, various additives are blended because a function suitable for each use cannot be obtained with only a thermoplastic resin.

  Conventionally, as a method for improving the surface properties such as water repellency, lubricity, and releasability of a thermoplastic resin, a method in which a substance having a surface property improving effect such as a silicone compound is kneaded into the thermoplastic resin, the surface of the thermoplastic resin is used. And the like. Above all, the method of kneading is used industrially because it is simple without increasing the number of production steps and has a high effect of improving the surface characteristics of the thermoplastic resin. However, simply kneading a substance having a surface property improving effect such as a silicone compound into the thermoplastic resin as it is may be difficult to uniformly knead it, and furthermore, it may cause bleed out and cannot maintain continuous water repellency. There is a problem.

  As a conventional technology of a water repellent used by kneading into a thermoplastic resin, as a conventional technique, polypropylene, an organopolysiloxane having a vinyl group having a specific average molecular weight, a composition containing a specific amount of an organic peroxide is melt-kneaded, and then molded. For producing a polypropylene resin molded product (Patent Document 1), a radical-generating catalyst comprising a specific amount of a polypropylene resin and a polyorganosiloxane containing at least one silicon-bonded alkenyl group in one molecule. For producing a polypropylene-based resin composition characterized by heating and kneading and chemically bonding in the absence of a compound (Patent Document 2), a polypropylene-based resin, a polypropylene wax, and at least one silicon atom in one molecule. Polyorganosiloxane containing bonded radical polymerizable functional groups and organic peroxide Polypropylene resin composition characterized by obtained by thermally kneading, etc. (Patent Document 3) are disclosed. However, the prior art has advantages and disadvantages, and a better one is required.

JP-A-6-16824 JP-A-8-127660 JP 2013-241534 A

  An object of the present invention is to improve the surface properties by blending it with a thermoplastic resin to give continuous water repellency, and to prevent the appearance of appearance from deteriorating without surface peeling, and to provide a water repellent for thermoplastic resins. And a thermoplastic resin composition containing the water repellent and a molded article thereof.

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a urethane composition containing a polyorganosiloxane as a component solves the above-mentioned problems. The present inventors have further studied based on these findings, and have completed the present invention.
That is, the present invention has the following configuration.
[1] A water repellent for a thermoplastic resin, comprising a urethane composition to which the following (A) to (D) are bonded.
(A) polyisocyanate (B) polyorganosiloxane having two or more active hydrogen functional groups in one molecule (C) active hydrogen compound having one active hydrogen functional group in one molecule (D) in one molecule A thermoplastic resin composition comprising: an alcohol having three or more hydroxyl groups [2]; a thermoplastic resin; and the water repellent for a thermoplastic resin according to [1].
[3] A thermoplastic resin composition molded article obtained by molding the thermoplastic resin composition according to the above item 2.
[4] A method for producing a water-repellent agent for a thermoplastic resin, comprising a step of reacting and binding components including the following (A) to (D) to produce a urethane composition.
(A) polyisocyanate (B) polyorganosiloxane having two or more active hydrogen functional groups in one molecule (C) active hydrogen compound having one active hydrogen functional group in one molecule (D) in one molecule Having three or more hydroxyl groups

  The water-repellent agent for a thermoplastic resin of the present invention has a function as a surface modifier, and improves the surface properties of the thermoplastic resin composition by being added to the thermoplastic resin to provide continuous water repellency. In addition, it is possible to provide a thermoplastic resin composition which is excellent in compatibility with thermoplasticity, has no surface peeling, and has a beautiful appearance, and a molded product thereof.

[(A) polyisocyanate]
The (A) polyisocyanate (hereinafter also referred to as “component A”) used in the present invention is a compound containing two or more isocyanate groups in one molecule, and is, for example, an aliphatic polyisocyanate or an aromatic polyisocyanate. And isocyanate.

  Examples of the aliphatic polyisocyanate include 1,3-trimethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, 1,6-hexamethylene diisocyanate, and cyclohexylene 1,2-diisocyanate. , Cyclohexylene 1,3-diisocyanate, cyclohexylene 1,4-diisocyanate, isophorone diisocyanate, hydrogenated m-xylylene diisocyanate, hydrogenated p-xylylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, norbornane diisocyanate, lysine Triisocyanate and the like.

  Examples of the aromatic polyisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and 4,4'- Diphenylpropane diisocyanate, 4,4'-diphenylhexafluoropropane diisocyanate, 1,4-naphthalene diisocyanate, 3,3'-dimethoxybiphenyl diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, m-xylylene diisocyanate Examples include isocyanate, p-xylylene diisocyanate, 4-chloroxylylene-1,3-diisocyanate, 2-methylxylylene diisocyanate, and the like.

Among the above various polyisocyanates, preferably 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and more preferably 1,6-hexamethylene diisocyanate, Isophorone diisocyanate. These polyisocyanates are more economical than other polyisocyanates, have appropriate reactivity with the B component, C component, and D component described below, and stabilize the urethane composition obtained by bonding. Suitable for good performance.
In the present invention, the above-mentioned various polyisocyanates may be used alone or in combination of two or more.

[(B) Polyorganosiloxane having two or more active hydrogen functional groups in one molecule]
The (B) polyorganosiloxane having two or more active hydrogen functional groups in one molecule (hereinafter, also referred to as "component B") used in the present invention has two atoms per atom in the polyorganosiloxane. The above active hydrogen functional groups are bonded.

  Here, the polyorganosiloxane is a polymer substance in which an organic group is added to a structure in which a silicon atom is bonded to another silicon atom via an oxygen atom. The properties of the polyorganosiloxane vary depending on the molecular weight, and those having a high molecular weight are gum-like and those having a low molecular weight are oil-like. In the present invention, both the gum component and the oil component B can be used.

  The skeleton of the polyorganosiloxane constituting the component B may be linear, branched, or cyclic, or a mixture thereof.

The active hydrogen functional group is a functional group capable of releasing pronto (H ⁺ ), and includes, for example, a hydroxyl group, an amino group, a carboxyl group, and a mercapto group.

As the component B, for example, a side-chain modified polydimethylsiloxane having two or more active hydrogen functional groups and a double- or one-terminal modified polydimethylsiloxane having two or more active hydrogen functional groups can be mentioned. Specifically, examples of the side chain-modified polydimethylsiloxane include side-chain amino-modified polydimethylsiloxane, side-chain carbinol-modified polydimethylsiloxane, side-chain carboxyl-modified polydimethylsiloxane, and the like. Examples of the polydimethylsiloxane modified at one end include amino-modified polydimethylsiloxane at both ends, carbinol-modified polydimethylsiloxane at both ends, silanol-modified polydimethylsiloxane at both ends, carboxyl-modified polydimethylsiloxane at both ends, and mercapto-modified polydimethylsiloxane at both ends. Examples include phenol-modified polydimethylsiloxane at both ends, hydroxypolyether-modified polydimethylsiloxane at both ends, and diol-modified polydimethylsiloxane at one end. Above all, it is economical, has an appropriate reactivity with the component A, and improves the stability of the urethane composition obtained by bonding, so that the side chain carbinol-modified polydimethylsiloxane, both terminals Carbinol-modified polydimethylsiloxane is preferred.
The above-mentioned various B components may be used alone or in combination of two or more.

[(C) Active hydrogen compound having one active hydrogen functional group in one molecule]
The (C) active hydrogen compound having one active hydrogen functional group in one molecule (hereinafter also referred to as “C component”) used in the present invention has one active hydrogen functional group in one molecule. There is no particular limitation, and examples thereof include an alcohol having one active hydrogen functional group, a carboxylic acid having one active hydrogen functional group, and an amine having one active hydrogen functional group.

The active hydrogen functional group is a functional group capable of releasing pronto (H ⁺ ), and includes, for example, a hydroxyl group, an amino group, a carboxyl group, and a mercapto group.

  Examples of the alcohol having one active hydrogen functional group include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 1-hexanol, 1-heptanol, -Octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol Nol, 1-nonadecanol, 1-icosanol, 1-hemicosanol, 1-docosanol, 1-tricosanol, 1-tetracosanol, 1-pentacosanol, 1-hexacosanol, 1-heptacosanol, 1-octacosanol, 1- Nonacosanol, 1-triacon Nord and the like. Among them, 1-octadecanol and 1-docosanol are preferable from the viewpoint of exhibiting appropriate compatibility with the thermoplastic resin.

  Examples of the carboxylic acid having one active hydrogen functional group include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, berargonic acid, capric acid, 1-undecylic acid, and lauric acid Acid, 1-tridecylic acid, myristic acid, 1-pentadecylic acid, palmitic acid, margaric acid, stearic acid, oleic acid, 1-nonadecylic acid, arachidic acid, 1-hemicosanoic acid, behenic acid, erucic acid, 1-tricosylic acid Lignoceric acid, 1-pentacosanoic acid, cerotic acid, 1-heptacosanoic acid, montanic acid, 12-hydroxystearic acid, isostearic acid and the like. Above all, stearic acid, behenic acid, and montanic acid are preferable from the viewpoint of developing appropriate compatibility with the thermoplastic resin.

Examples of the amine having one active hydrogen functional group include, for example, methylamine, ethylamine, propylamine, isopropylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecyl Amine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, icosylamine, unicosylamine, docosylamine, benzylamine, aniline, 4-methoxyphenylamine, 4-methyl Phenylamine, 2-methylphenylamine, cyclopentylamine, cyclohexylamine, cyclooctylamine, dimethylamine, diethylamine, dipropyl Min, diisopropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, diundecylamine, didodecylamine, ditridecylamine, ditetradecylamine, dipentadecylamine, dihexadecyl Amine, diheptadecylamine, dioctadecylamine, dinonadecylamine, diicosylamine, diunicosylamine, didocosylamine, dibenzylamine, diphenylamine, N-methylaniline, bis (4-methoxyphenyl) amine, bis (4-methyl Phenyl) amine, bis (2-methylphenyl) amine, dicyclopentylamine, dicyclohexylamine, dicyclooctylamine and the like. Among them, dioctadecylamine and didocosylamine are preferred from the viewpoint of exhibiting appropriate compatibility with the thermoplastic resin.
Further, the above various C components may be used alone or in combination of two or more.

[(D) Alcohol having 3 or more hydroxyl groups in one molecule]
Examples of (D) an alcohol having three or more hydroxyl groups in one molecule (hereinafter, also referred to as “D component”) used in the present invention include glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, and hexaglycerol. Glycerin, heptaglycerin, octaglycerin, nonaglycerin, decaglycerin, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,6-hexanetriol, trimethylolpropane, hydroxyquinol, Phloroglucinol, pyrogallol and the like. Of these, glycerin, diglycerin, and triglycerin are preferred from the viewpoint of the physical properties of the polyurethane resin, particularly, the difficulty in gelation. The above-mentioned various D components may be used alone or in combination of two or more.

  The water repellent for a thermoplastic resin of the present invention contains a urethane composition to which components A to D are bonded. The urethane composition is a polymer in which the isocyanate group in the component A is chemically bonded to any one of the active hydrogen functional group in the component B, the active hydrogen functional group in the component C, and the hydroxyl group in the component D. Here, since the D component has three or more hydroxyl groups in one molecule, it is a branch point in the polymer. In addition, since the B component has one active hydrogen functional group in one molecule, it plays the role of a terminal cap in the polymer.

  As the compounding ratio (molar ratio) of the A component and the B component contained in the urethane composition, the A component: B component is preferably 75:25 to 55:45, and more preferably 70:30 to 60:40. is there. It is preferable that the content is within the above-mentioned range because the continuous water repellency and appearance, which are the effects of the present invention, are improved.

  As a compounding ratio (molar ratio) of the A component and the C component contained in the urethane composition, the A component: C component is preferably 90:10 to 60; 40, and more preferably 70:30 to 85:15. . It is preferable that the content is within the above-mentioned range because the continuous water repellency and appearance, which are the effects of the present invention, are improved.

  As a compounding ratio (molar ratio) of the A component and the D component contained in the urethane composition, the A component: the D component is preferably 95: 5 to 80; 20, and more preferably 92.5: 7.5 to 85. : 15. It is preferable that the content is in the above range because the continuous water repellency and appearance are improved.

  There is no particular limitation on the method of binding the A to D components. For example, a method of heating and kneading a mixture containing all the A to D components in the presence or absence of a catalyst, And a method of kneading with heat while mixing, thereby obtaining a urethane composition to which the components A to D are bonded.

  The catalyst used in the heating and kneading is not particularly limited as long as it promotes the binding of the components A to D. For example, tin dioctylate, dibutyltin mercaptide, dibutyltin dilaurate, lead octylate, 2-octylate, Examples thereof include bismuth ethylhexylate, bismuth neodecanoate, and bismuth oxycarbonate, and more preferably dibutyltin mercaptide, dibutyltin dilaurate, and lead octylate because of their ability as a catalyst and availability.

  Examples of a method of obtaining the urethane composition by combining the components A to D by the heat kneading include a batch method using a reaction vessel or the like and a continuous method using a kneader or the like.

  Among the batch methods, as a method of heating and kneading a mixture containing all of the components A to D to cause a reaction, for example, an ordinary reaction vessel equipped with a stirrer, a heating jacket, a nitrogen introduction pipe, an air cooling pipe, and the like is used. , B component, C component, and D component are charged, and the temperature is increased to 70 to 90 using a temperature controller. Thereafter, the component A and a catalyst (for example, dioctyltin dilaurate) are added, and the mixture is stirred and mixed. The mixture containing all the components A to D is heated and kneaded to react, and the components A to D are combined to obtain a urethane composition. . The reaction is preferably performed under a nitrogen gas atmosphere, for example, under reduced pressure or normal pressure at a reaction temperature of 70 to 90 ° C. and a reaction time of about 15 minutes to 1 hour.

  Among the batch methods, as a method of reacting by heating and kneading while adding any of the components A to D stepwise, for example, a stirrer, a heating jacket, a nitrogen introducing pipe, an air cooling pipe, and the like are provided. The B component and the D component are charged into a conventional reaction vessel, and the temperature is raised to 70 to 90 using a temperature controller. Thereafter, the component A and a catalyst (for example, dioctyltin dilaurate) are added, and the mixture is stirred and mixed. The mixture containing the components A, B, and D is heated and kneaded to cause a reaction. The mixture is heated and kneaded to react, and the components A to D are combined to obtain a urethane composition. The reaction is preferably performed, for example, in a nitrogen gas atmosphere, and at normal pressure, a reaction temperature of 70 to 90 ° C. and a reaction time of about 15 minutes to 1 hour.

  As a continuous method, for example, using a kneader equipped with two sets of liquid addition devices, the A component is supplied from one set of liquid addition devices, and the oily B component, C component is supplied from another set of liquid addition devices. A mixture of component, component D, and a catalyst (eg, dioctyltin dilaurate) is provided. The mixture is heated and kneaded while being supplied at a predetermined ratio inside a kneader cylinder heated to 80 to 100 ° C. from each liquid addition device, whereby the A to D components are combined to obtain a urethane composition. The kneader is not particularly limited, and a known kneader can be used. For example, a single screw extruder, a twin screw extruder, or the like can be used. Among them, a twin-screw extruder is preferable in consideration of productivity and kneading power. The twin-screw extruder includes a twin-screw different-direction rotating non-meshing extruder, a twin-screw different-direction meshing extruder, a twin-screw same-direction non-meshing extruder, a twin-screw same-direction meshing extruder, and the like. Any of them can be used.

  The water repellent for thermoplastic resin of the present invention may contain other components other than the urethane composition as long as the effects of the present invention are not impaired. Other components other than the urethane composition include surface modifiers other than the urethane composition (lubricants, release agents, water repellents, etc.), antistatic agents, antifogging agents, heat stabilizers, antioxidants, weather resistance Agents, ultraviolet absorbers, fillers, flame retardants, coloring agents, neutralizing agents, anti-blocking agents and the like.

  The thermoplastic resin composition containing the water repellent for a thermoplastic resin of the present invention and a molded product thereof are also one aspect of the present invention. By blending the thermoplastic resin water-repellent agent of the present invention with the thermoplastic resin, it is possible to improve the surface characteristics without largely changing the physical properties of the thermoplastic resin and to provide continuous water repellency. In addition, since the water repellent for thermoplastic resin has excellent compatibility with the thermoplastic resin, it is possible to obtain a thermoplastic resin composition having a clean appearance without surface peeling and a molded article thereof.

  As the thermoplastic resin used in the present invention, for example, polyethylene, chlorinated polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl brillal, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polystyrene, polymethyl methacrylate, polyamide , Polyurethane, acrylonitrile-styrene copolymer, acrylonitrile-ethylene-styrene, acrylonitrile-butadiene-styrene copolymer, ethylene-vinyl acetate copolymer, and the like.

  As the blending amount of the thermoplastic resin water repellent to the thermoplastic resin, the thermoplastic resin water repellent is 1 to 15 parts by mass, preferably 2 to 10 parts by mass, more preferably 100 parts by mass of the thermoplastic resin. Is 3 to 6 parts by mass.

  As a method of blending the thermoplastic resin water repellent with the thermoplastic resin, for example, heating and kneading in an extruder can be mentioned, and the thermoplastic resin having continuous water repellency by kneading at the melting temperature of the thermoplastic resin. A resin composition is obtained. The thermoplastic resin composition thus obtained can be subjected to molding means such as extrusion molding, injection molding, compression molding, sheet molding and the like, and used as a molded article of any shape. These molded articles are widely used as construction materials such as home appliances, automobiles, wallpapers, daily necessities such as toys, stationery and clothing, medical supplies such as nonwoven fabrics, electric wire covering materials, agricultural materials such as houses and tunnels, and the like.

  Hereinafter, the present invention will be described with reference to Examples, which merely illustrate the present invention and do not limit the present invention.

<< Production of water repellent for thermoplastic resin (urethane composition) >>
(1) Raw material A component: The following was used as the polyisocyanate.
A1: 1,6-hexamethylene diisocyanate (trade name; manufactured by Wako Pure Chemical Industries, Ltd.)
A2: Isophorone diisocyanate (trade name; manufactured by Wako Pure Chemical Industries, Ltd.)
Component B: The following was used as a polyorganosiloxane having two or more active hydrogen functional groups in one molecule.
B1: Carbinol-modified silicone oil at both ends (trade name: KF-6003; manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight: about 5000)
B2: Carbinol-modified silicone oil at both ends (trade name: KF-6002; manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight: about 3000)
Component C: The following was used as an active hydrogen compound having one active hydrogen functional group in one molecule.
C1: Behenyl alcohol (trade name: GINOL-22; manufactured by Godrig)
C2: Stearyl alcohol (trade name: Calcol 8688; manufactured by Kao Corporation)
D component: The following was used as an alcohol having three or more hydroxyl groups in one molecule.
D1: Glycerin (trade name: purified glycerin; manufactured by Sakamoto Pharmaceutical Co., Ltd.)
D2: Triglycerin (trade name: Triglycerin S; manufactured by Sakamoto Pharmaceutical Co., Ltd.)
The following was used as a catalyst.
Catalyst: dibutyltin dilaurate (trade name; manufactured by Wako Pure Chemical Industries, Ltd.)

(2) Mixing of Water Repellent for Thermoplastic Resin Table 1 shows the compounding amount of the water repellent for thermoplastic resin produced using the above-mentioned raw materials.

[Production of Water Repellent for Thermoplastic Resin (Example Products 1 to 6)]
It was produced by the following method using the same amount of raw materials shown in Table 1.
Components B and D were added to a three-necked flask equipped with a temperature controller, a nitrogen inlet tube and a stirrer, and heated to 80 ° C. in a nitrogen stream to raise the temperature. Thereafter, the component A and the catalyst were added and reacted at 80 ° C. for 30 minutes under normal pressure under a nitrogen stream. Next, the C component was added thereto, and reacted at 80 ° C. for 30 minutes under normal pressure under a nitrogen stream to obtain about 100 g of each of the water repellents for thermoplastic resins (Example products 1 to 6).

[Production of Water Repellent for Thermoplastic Resin (Example Product 7, Comparative Examples 1 to 4)]
It was produced by the following method using the same amount of raw materials shown in Table 1.
To a three-necked flask equipped with a temperature controller, a nitrogen inlet tube, and a stirrer, the components described among the components B, C, and D were added, and heated to 80 ° C. under a nitrogen stream to raise the temperature. Thereafter, the component A and a component described among the catalysts are added, and the mixture is reacted at 80 ° C. for 30 minutes under normal pressure under a nitrogen stream to obtain a water repellent for a thermoplastic resin (Example product 7, Comparative examples 1-4). Was obtained in an amount of about 100 g.

[Production of water repellent for thermoplastic resin (Example product 8)]
A twin-screw co-rotating intermeshing type extruder (model: model: MFU15TW-45MG-NH; manufactured by Technobell, screw diameter = 15 mm, L / D = 45) by the following method.
Barrel (C1 to C8, H / D) temperature 50 to 100 ° C (C1 = 50 ° C, C2, C3 = 70 ° C, C4 to C6 = 80 ° C, C7 = 90 ° C, C8 = 100 ° C, H / D = 110 ° C.), the temperature of the liquid addition devices 1 and 2 was set to 80 ° C., the screw rotation speed was set to 150 rpm, and the B component, C component, D component and the catalyst which had been mixed in advance were converted into C2 using the liquid addition device 1. Addition from the barrel, A component is added from the C2 barrel using the liquid addition device 2 and mixed, the first about 300 g discharged from the outlet of the twin-screw co-rotating meshing extruder is discarded, and about 500 g thereafter are discarded. The sample was collected to obtain a water repellent for thermoplastic resin (Example product 8).

<< Preparation of thermoplastic resin composition >>
In order to evaluate the effect of the obtained water repellent for thermoplastic resin, a molded article of a polypropylene resin composition was prepared by the following method.
12.0 g of a polypropylene-based resin (trade name: Prime Polypro F-327; manufactured by Prime Polymer Co., Ltd.) and a water repellent for thermoplastic resin (Examples 1 to 8 and Comparative Examples 1 to 4). 6 g was put into a small twin-screw co-rotating meshing extruder (model: Xplore MC15; manufactured by DSM), and kneaded for 2 minutes under the conditions of a barrel temperature of 190 ° C. and a screw rotation speed of 100 rpm for 2 minutes. After taking out in the form of a strand, it was cut into pellets. The above steps were performed three times to obtain about 30 g of a propylene-based resin composition in the form of pellets. The obtained pellet-shaped propylene-based resin composition is injection-molded using a small injection molding machine (model: C, Mobile-0813; manufactured by Shinko Selvic Co., Ltd.) at a barrel temperature of 210 ° C. and a mold temperature of 20 ° C., A flat plate (40 mm × 40 mm × 1.5 mm) propylene-based resin composition molded product (prototypes 1 to 12) was obtained. A propylene-based resin composition molded product (prototype 13) was obtained in the same manner except that the water-repellent agent for thermoplastic resin was not blended.

≫Evaluation of water repellent for thermoplastic resin 樹脂
(1) Continuous evaluation of water repellency The contact angle of the surface of the obtained propylene-based resin composition molded product (prototypes 1 to 13) was measured using a contact angle meter (model: CA-X; manufactured by Kyowa Interface Science Co., Ltd.). It measured using. The contact angle on the surface of the propylene-based resin composition molded article (prototype 13) in which the thermoplastic resin water-repellent is not used is an indicator that the water repellency is not improved.
Regarding the continuous water repellency, the contact angles before and after the washing operation were measured, and the values were compared and evaluated. Here, the continuous water repellency means that there is no difference between the contact angles before and after the cleaning operation.
The washing operation was performed by wiping the surface of the molded article of the propylene-based resin composition 10 times with absorbent cotton soaked with methyl ethyl ketone. Table 2 shows the results.
In the case of a propylene-based resin composition molded article, if the contact angle is 103 ° or more, it can be said that water repellency is excellent.

(2) Evaluation of external appearance The external appearance was evaluated by visually observing the surface of the obtained propylene-based resin composition molded article (prototypes 1 to 13) and determining the degree of surface roughness (presence or absence of surface peeling) as follows. The evaluation was based on the evaluation criteria. Table 2 shows the results.
Here, the presence or absence of surface peeling is whether or not the thermoplastic resin and the thermoplastic resin water repellent in the thermoplastic resin composition are uniformly mixed, that is, the thermoplastic resin water repellent is a thermoplastic resin and It is an index of whether or not it has excellent compatibility.
[Evaluation criteria for surface roughness (presence or absence of surface peeling)]
：: No surface peeling occurred, no surface roughness, and very clean appearance.
Δ: Surface peeling occurred slightly, the surface was slightly roughened, and the appearance was slightly dirty.
×: Surface peeling occurred, surface roughness was observed, and the appearance was very dirty.

結果より、熱可塑性樹脂としてポリプロピレン系樹脂を用い、熱可塑性樹脂用撥水剤として実施例品を配合した熱可塑性樹脂組成物成形品は、継続的な撥水性を有し、また、表面剥離による表面の荒れによる表面の汚れがなく、外観はきれいな状態であった。すなわち熱可塑性樹脂用撥水剤の実施例品は、熱可塑性樹脂に対して相溶性に優れていた。
一方、熱可塑性樹脂用撥水剤として比較例品を配合した熱可塑性樹脂組成物成形品は、試作品１２は継続的撥水性がなく、試作品９〜１１は外観汚い状態であった。すなわち熱可塑性樹脂用撥水剤の比較例品１〜３は、ポリプロピレン系樹脂に対して相溶性に優れていなかった。

From the results, using a polypropylene resin as the thermoplastic resin, the thermoplastic resin composition molded article blended with the example product as a water repellent for the thermoplastic resin, has a continuous water repellency, and also due to surface peeling There was no dirt on the surface due to surface roughness, and the appearance was in a clean state. That is, the example product of the water repellent for thermoplastic resin had excellent compatibility with the thermoplastic resin.
On the other hand, in the molded article of the thermoplastic resin composition in which the comparative example was blended as the water repellent for the thermoplastic resin, the prototype 12 had no continuous water repellency, and the prototypes 9 to 11 were in a dirty appearance. That is, Comparative Examples 1 to 3 of the thermoplastic resin water repellent did not have excellent compatibility with the polypropylene resin.

Claims (4)

A water-repellent agent for kneading a thermoplastic resin containing a urethane composition to which the following (A) to (D) are bound , wherein the mixing ratio (mol) of (A) to (D) contained in the urethane composition is (A) :( B) = 77: 23-58: 42, (A) :( C) = 84: 16-46: 54, (A) :( D) = 96: 4-88: 12. A water repellent for kneading a thermoplastic resin, which is 12 .
(A) polyisocyanate (B) polyorganosiloxane having two or more active hydrogen functional groups in one molecule (C) active hydrogen compound having one active hydrogen functional group in one molecule (D) in one molecule Having three or more hydroxyl groups A thermoplastic resin composition comprising a thermoplastic resin and the water repellent for kneading the thermoplastic resin according to claim 1.   A thermoplastic resin composition molded article obtained by molding the thermoplastic resin composition according to claim 2. (A): (B) = 77:23 to 58:42, (A): (C) = 84:16 to 46:54, (A): (D) = 96 : A step of preparing a urethane composition by reacting and combining components contained in a blending ratio (molar ratio) of 4 to 88:12 , and kneading the urethane composition into a thermoplastic resin. A method for producing a thermoplastic resin composition .
(A) polyisocyanate (B) polyorganosiloxane having two or more active hydrogen functional groups in one molecule (C) active hydrogen compound having one active hydrogen functional group in one molecule (D) in one molecule Having three or more hydroxyl groups