JP2000308601A - Parts for toilet seat - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide parts for a toilet seat high in practicability, comprising a propylene polymer which is excellent in abrasion-resistance and free from degradation of the surface appearance by repeated rubbing with a cloth or a paper in cleaning works, and excellent in antifouling property in which firmly attached dirt such as line deposit can be easily removed with light wiping. SOLUTION: These parts of the toilet seat comprise a formed body of a propylene polymer composition having 0.05-3 pts.wt. of a crystal core agent blended in 100 pts.wt. of propylene polymer or 100 pts.wt., of propylene polymer containing 0.1-10 wt.% poly-siloxane, and its degree of crystallization of a surface layer measured by a reflection X-ray diffraction method is not less than 60%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toilet seat component made of a polypropylene resin. More specifically, the present invention relates to a toilet seat component having a high practical value and excellent in scratch resistance and stain resistance of a surface made of a specific propylene polymer composition.

[0002]

2. Description of the Related Art A molded article made of a propylene polymer has been widely used as a constituent member of a toilet seat part, taking advantage of its features of excellent heat resistance and chemical resistance and easy molding and recycling. However, in use in a toilet, there are problems in use, such as damage to a toilet seat sheet, a toilet lid, and the like during cleaning, and strong adhesion of dirt such as water scale.

Attempts have been made to improve the abrasion resistance and antifouling properties of toilet seat sheets and toilet lids by reducing the frictional force by adding a lubricant. However, such a method has been proposed to reduce the relative stress applied to the surface. However, the above-mentioned problem has not been essentially solved.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide excellent abrasion resistance so that the surface appearance does not deteriorate due to repeated friction with a cloth or paper in a cleaning operation, and furthermore, a strong adhesion. It is an object of the present invention to provide a toilet seat component made of a propylene polymer having an antifouling property, which can easily remove stains such as water stains with a light wiping degree.

[0005]

Means for Solving the Problems The present inventors have further studied the impact resistance, abrasion resistance and antifouling properties of toilet seat components. As a result, the present inventors have found that the crystallinity of the surface layer of the molded body measured by reflection X-ray diffraction has a high correlation with the scratch resistance and the antifouling property, and the crystallinity in a specific range. It has been found that excellent scratch resistance and antifouling properties can be obtained in the polypropylene molded article of the present invention, and the present invention has been completed.

According to the present invention, the present invention is directed to a toilet seat component such as a toilet seat sheet, a toilet lid, a main body case, and a washing nozzle for washing a human body, wherein at least one of the components comprises a crystal nucleating agent. A propylene polymer composition containing 0.05 to 5 parts by weight and a surface layer having a crystallinity of 60% or more as measured by reflection X-ray diffraction. The present invention relates to a toilet seat component excellent in abrasion resistance and stain resistance.

[0007] Further, the present invention provides a propylene polymer of 99.9 to 99.9 in order to further improve the scratch resistance and stain resistance.
A propylene polymer composition obtained by mixing 0.05 to 3 parts by weight of a nucleating agent with respect to 100 parts by weight of a composition consisting of 0% by weight and 0.1 to 10% by weight of polysiloxane; Crystallinity of the surface layer measured by X-ray diffraction method is 60
% For toilet seats.

Hereinafter, the technical structure of the present invention will be described in detail. When the present invention is described with reference to the drawings, it goes without saying that the present invention is not limited to the illustrated one.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, the propylene polymer used is not particularly limited, but the most preferably used is a propylene homopolymer.
In the present invention, needless to say, a copolymer obtained by copolymerizing an α-olefin other than propylene with propylene to such an extent that the properties of the propylene homopolymer are not significantly changed can also be used. In this case, a propylene α-olefin copolymer in which the content of α-olefins other than propylene is less than 3.0 mol% in monomer units is preferable. Examples of the α-olefin other than propylene include ethylene, 1-butene, 1-pentene,
Examples thereof include 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, and the like, and two or more of these may be contained. Further, as the propylene-α-olefin copolymer described above,
Either a random copolymer or a block copolymer may be used, and a block copolymer is particularly preferable.

Further, in the present invention, other resins may be mixed with the propylene polymer as long as the effects of the present invention are not impaired. Such other resins include ethylene, 1-butene, 1-pentyne, 1-hexene,
-Heptene, 1-octene, 1-nonene, 1-decene,
Preferred are α-olefin homopolymers such as 4-methyl-1-pentene, and block copolymers or random copolymers of these α-olefins and propylene.

Some propylene polymers suitably used in the present invention contain a boiling heptane-insoluble portion in an amount of 90% by weight or more, preferably 95% by weight or more. Furthermore, in the present invention, the isotactic pentad fraction by ¹³ C-NMR of the boiling heptane-insoluble portion used as an index of the crystallinity of polypropylene is 0.970 or more, particularly 0.97
A propylene polymer of 5 or more is preferable because the crystallization degree of the surface layer of the injection molded article can be effectively increased as shown in the production method described later.

The above-mentioned isotactic pentad fraction of the boiling heptane-insoluble portion means that the boiling heptane-insoluble portion of polypropylene is determined by A.I. The method published by Zambelli et al. (Macromolecules, 13, 26)
7 (1980)) means a value obtained by measuring the fraction of propylene monomer units at the center of a chain in which five propylene monomer units are consecutively meso-bonded in pentad units in a polypropylene molecule.

In the present invention, the fluidity of the propylene polymer is not particularly limited, but the moldability, rigidity,
Considering impact resistance, melt flow rate (hereinafter MF)
R) is 1 to 100 g / 10 min, preferably 10 to 70 g / 10 min, and more preferably 10 g / min.
３０30 g / 10 min. Here, MFR is JIS
According to K7210, the cylinder temperature is a value at 230 ° C.

In the present invention, the propylene polymer may be obtained by any method. Generally, a Ziegler-Natta type stereospecific catalyst is used, which comprises a magnesium chloride-supported titanium compound or a titanium trichloride compound and an organoaluminum compound, or a catalyst obtained by adding various electron-donating substances thereto.

As the above-mentioned titanium compound, a known compound used for polymerization of olefin is employed without any limitation. In particular, a titanium compound containing titanium, magnesium and halogen as components and having a high catalytic activity and capable of obtaining a highly crystalline polymer is preferable. Examples of such a titanium compound include titanium halides, particularly titanium tetrachloride supported on various magnesium compounds. As a method for producing this catalyst, a known method is employed without any limitation. For example, a method of co-milling titanium tetrachloride with a magnesium compound such as magnesium chloride, a method of co-milling titanium halide and a magnesium compound in the presence of an electron donor such as alcohol, ether, ester, ketone or aldehyde, or a solvent. And a method in which a titanium halide, a magnesium compound and an electron donor are brought into contact with each other.

Next, as the organoaluminum compound,
Known compounds used for olefin polymerization can be used without any limitation. For example, alkyl aluminums such as trimethyl aluminum, triethyl aluminum and tri-n-propyl aluminum; and halogen-containing alkyl aluminums such as ethyl aluminum sex chloride and diethyl aluminum chloride can be used.

In the present invention, in order to enhance the crystallinity of the obtained injection-molded article, it is preferable to use an electron donor in addition to the above-mentioned titanium compound and organoaluminum compound. Examples of the electron donor include ether, amine, amide, sulfur-containing compound, nitrile, carboxylic acid, acid amide, acid anhydride, acid ester, and organosilicon compound. Of these, organosilicon compounds are most preferred.

In the present invention, the propylene polymer may be polymerized in a gas phase or a liquid phase. The polymerization may be carried out in an inert liquid or an inert solvent with respect to the catalyst.The polymerization may be carried out by introducing hydrogen during polymerization, or the obtained polymer may be prepared by a molecular weight regulator such as an organic peroxide. Degraded ones may be used. Further, the polymerization can be carried out by any of batch, semi-batch and continuous methods. The polymerization conditions are not particularly limited as long as the effects of the present invention are recognized, and known conditions can be employed. For example, the polymerization temperature is 20-200 ° C., preferably 5
The range is 0 to 150 ° C. Further, the polymerization can be carried out in two or more stages under different conditions.

In the toilet seat component of the present invention, the crystallinity of the surface layer portion of the toilet seat component measured by the reflection X-ray diffraction method, generally, the crystallinity within 100 μm from the surface is 60% or more. It is a feature point. That is, by setting the crystallinity to 60% or more, it is possible to obtain a toilet seat component having excellent scratch resistance that has not been achieved conventionally. Conversely, toilet seat parts having a crystallinity of less than 60% do not provide satisfactory abrasion resistance.

Conventionally, a method of adding a crystal nucleating agent to a propylene polymer has been generally used as a means for increasing the crystallinity of an injection molded article. However, although the molded product obtained by simply injection-molding such a composition has improved internal crystallinity, the crystallinity of the surface layer does not unexpectedly increase as much as the internal crystal. It was insufficient to improve the scratch resistance of the surface. On the other hand, the toilet seat component of the present invention has an extremely high degree of crystallinity in the surface layer as described above, and exhibits excellent scratch resistance as will be apparent from the examples described later.

In the present invention, the crystallinity of the surface layer of the toilet seat component is an index indicating the amount of the propylene polymer crystal component in the surface layer of the toilet seat component, and is a value obtained by reflection X-ray diffraction measurement. is there. That is, the crystallinity of the surface layer of the toilet seat component is set such that the angle between the surface of the toilet seat component and the incident X-ray becomes 1.0 ° using an X-ray diffractometer equipped with a thin film sample device. Diffraction intensity is measured with the toilet seat component installed, and the obtained X-ray diffraction intensity curve is subjected to waveform separation into an amorphous halo and each crystalline peak, and the area of the amorphous halo (the amorphous halo It is a value obtained by the following equation (1) from the integrated intensity) and the area of all crystalline peaks (sum of the integrated intensity of each crystalline peak).

Crystallinity of surface layer = Sc / (Sc + Sa) × 100 (%) (1) where Sc: area of all crystalline peaks Sa: area of amorphous halo

In the present invention, the upper limit of the crystallinity of the surface layer of the toilet seat component is not particularly limited, but is preferably 80% or less in consideration of impact resistance and dimensional stability. .

In the propylene polymer used in the present invention, a nucleating agent is used in an amount of 0.0
It is necessary to add 5-5 parts by weight, of which 0.1-3
Part by weight is particularly preferred. If the amount is less than 0.05 parts by weight, the desired scratch resistance cannot be obtained. Also,
If the amount exceeds 5 parts by weight, the effect of addition will be saturated and there is no point in increasing the amount of addition, and it is disadvantageous in terms of cost.

As the above-mentioned nucleating agent, known ones can be used without any limitation, and two or more nucleating agents may be used in combination. Specifically, Al-p-
Carboxylic acid metal salt compounds such as t-butylbenzoate, sodium β-naphthoate, sodium cyclohexanecarboxylate and sodium cyclopentanecarboxylate; lithium bis (4-t-butylphenyl) phosphate, bis (4-t- Butylphenyl) aluminum phosphate, calcium bis (4-tert-butylphenyl) phosphate, magnesium bis (4-tert-butylphenyl) phosphate,
Sodium 2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate, lithium 2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate, Aluminum 2,2′-methylene-bis (4,6-di-tert-butylphenyl) phosphate, calcium 2,2′-methylidene-bis (4,6-di-tert-butylphenyl) phosphate, 2, 2'-methylidene-bis (4,6-
Magnesium di-t-butylphenyl) phosphate, 2,
Sodium 2'-ethylidene-bis (4,6-di-tert-butylphenyl) phosphate, lithium 2,2'-ethylidene-bis (4,6-di-tert-butylphenyl) phosphate, 2, 2'-ethylidene-bis (4,6-di-tert-butylphenyl) aluminum phosphate, bis- (4-t
-Butylphenyl) phosphate calcium salt, bis- (4-
aromatic metal phosphate compounds such as t-butylphenyl) magnesium phosphate; dibenzylidene sorbitol;
1.3,2.4-di (methylbenzylidene) sorbitol, 1.3,2.4-di (ethylbenzylidene) sorbitol, 1.3,2.4-di (butylbenzylidene) sorbitol, 1.3,2 Di- (methoxybenzylidene) sorbitol, 1.3, 2.4-di (ethoxybenzylidene) sorbitol, 1.3-chlorobenzylidene, 2.4-methylbenzylidene sorbitol, di (mono (methyl) dibenzylidene sorbitol, etc.) Benzylidene sorbitol compounds; inorganic compounds such as silica, titanium dioxide, carbon black, fine powder talc, mica, alum, pigments and the like. Of these,
The use of Al-pt-butyl benzoate, 2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate metal salt, or the like is most preferable for improving scratch resistance. is there.

According to the present invention, as a means for further improving the crystallinity of the surface layer of the toilet seat component, for example, a method of imparting a specific heat history to the surface layer in addition to the addition of the nucleating agent. Can also be applied. The method of giving the heat history is not particularly limited, but a preferable method is to add a crystal nucleating agent to 100 parts by weight of a propylene polymer containing 0.1 to 10% by weight of a polysiloxane.
After the injection molding of the propylene polymer containing 5 to 3 parts by weight, a method in which the surface temperature of the obtained injection molded body is maintained in a temperature range from 80 ° C. to lower than the melting temperature of the resin for 20 seconds to 5 hours, and the like. Specifically, by adjusting the inner surface temperature of the mold,
A method is employed in which the surface temperature of the molded body is maintained at a predetermined temperature for a predetermined time.

Another effect of blending a polysiloxane in the propylene polymer constituting the toilet seat component of the present invention is improvement in antifouling properties. In this case, the compounding amount of the polysiloxane is 0.1 to 10% by weight, preferably 0.5 to 10% by weight.
5% by weight. When the blending amount of the polysiloxane is less than 0.1% by weight, no improvement in the abrasion resistance is observed, and the effect of lowering the adhesion of the dirt component adhered to the surface is small. If the amount of the polysiloxane exceeds 10% by weight, not only the effect of the antifouling property is saturated, but also the abrasion resistance is remarkably reduced.

In the present invention, known polysiloxanes can be used without any limitation. Of these, organosiloxanes are preferable, and specific examples thereof include polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. A mixture of two or more of these may be used.

The propylene polymer of the present invention may contain optional components according to various purposes in addition to the components described above. Specifically, antioxidants, heat stabilizers,
Light stabilizers, ultraviolet absorbers, lubricants, anti-fog agents, anti-blocking agents, slip agents, crosslinking agents, flame retardants, dispersants, antistatic agents, coloring agents, inorganic fillers, antibacterial agents, fragrances, etc. Additives can be blended.

As the injection molding method of the toilet bowl component of the present invention, a known method can be used without any limitation. Examples include single-axis injection molding, multi-axis injection molding, injection compression molding, gas assist injection molding, gas compression injection molding, melt core injection molding, insert injection molding, core back injection molding, two-color injection molding, and the like.

The toilet seat parts of the present invention include toilet seat sheets, toilet lids, parts of a human body washing apparatus (wash nozzles, body cases, etc.) to which dirt components are relatively easy to adhere. In the present invention, as the shape of the toilet seat component, a known shape can be applied without any limitation. For example, FIG. 1 is a perspective view of a typical shape of a toilet lid when the toilet seat component of the present invention is a toilet lid, and FIG. 2 is a cross-sectional view thereof. Although the size of the toilet lid is not particularly limited, the thickness (E) is preferably 2 mm to 5 mm in consideration of appropriate strength and weight as the toilet lid.

[0032]

EXAMPLES Next, the present invention will be described in detail with reference to Examples, but it goes without saying that the present invention is not limited to these Examples.

The tests and evaluations in the examples were performed by the following methods.

(1). Using the measured ¹³ C-NMR isotactic pentad fraction of boiling heptane insoluble portion, A. A method published by Zambelli et al. (Macromolecules, 1).
3, 267 (1980)), the fraction of propylene monomer units at the center of a chain of five meso-bonded propylene monomer units in pentad units in a polypropylene molecule was determined. The measurement conditions are as follows. Measurement mode: ¹ H complete decoupling Pulse width: 7.0 microseconds (C45 degrees) Pulse repetition time: 3 seconds Number of integrations: 10000 times Solvent: mixed solvent of ortho-dichlorobenzene / deuterated benzene (90/10% by volume) Sample Concentration: 120mg / 2.5ml solvent Measurement temperature: 120 ° C

(2). Measurement of Surface Crystallinity The diffraction intensity was measured using an X-ray diffractometer (JED-3500 manufactured by JEOL Ltd.) equipped with a thin film sample device (DX-GOT1 manufactured by JEOL Ltd.). The measurement conditions are as follows. Target: Copper (Cu-Kα ray) Tube voltage-tube current: 40 kV-400 mA X-ray incidence method: reflection method (thin film method) Irradiation slit width: 0.2 mm Light receiving slit width: 0.1 mm Detector: Scintillation counter X-ray Incident angle: The angle formed with the test piece surface is set to 1.0 degree Measurement angle range: 8 to 32 degrees Step angle: 0.1 degree Count time: 2.0 seconds X-ray diffraction intensity obtained under the above measurement conditions The curve is subjected to waveform separation into an amorphous halo and each crystalline peak, and the area of the amorphous halo (integrated intensity of the amorphous halo) and the area of all crystalline peaks (sum of the integrated intensity of each crystalline peak) The crystallinity of the surface layer of the injection-molded article was determined from the following equation (1). The peak separation is performed by using a general peak separation program to remove background caused by air scattering or the like in a diffraction angle (2θ) range of 9 to 31 degrees, and then use a general peak separation method using a Gaussian function and a Lorentz function. An amorphous halo and each crystalline peak were separated by a separation method. Crystallinity of surface layer = Sc / (Sc + Sa) × 100 (%) (1) where Sc: area of all crystalline peaks Sa: area of amorphous halo

(3). Scratch test-a The test piece was fixed to a fully automatic cross-cut peeling tester manufactured by Yasuda Seiki Seisaku-sho, and a load of 100 g was applied while a diamond needle (R = 250 μm) was set upright on the test piece surface.
The test piece was slid at a speed of 10 mm / sec. After the test was completed, the difference between the highest point and the lowest point of the scar was measured with a laser microscope (1LM21) manufactured by Lasertec Co., Ltd. to determine the maximum scar depth (μm).

(4). Scratch test-b A test piece was fixed to a fully automatic cross-cut peeling tester manufactured by Yasuda Seiki Seisakusho, a toilet paper was attached to a 2 cm square pad, the test piece was brought into contact with the test piece surface, and the test piece was pressed at a pressure of 100 g / cm ^2. Was reciprocated 100 times at a speed of 10 mm / s to perform a test. After the test was completed, the surface condition of the test piece was visually evaluated in the following three stages. ：: Scratches on the surface of the test piece were hardly noticeable ○: Scratches on the surface of the test piece were somewhat noticeable ×: Scratches on the surface of the test piece were noticeable

(5). Stain resistance test-a A dye gel for oral cavity was applied to one surface of the test, and dried and solidified by standing naturally. Further, the test piece was fixed to a fully automatic cross-cut peeling tester manufactured by Yasuda Seiki Seisaku-sho, Ltd.
Attached to a m-square pad, and brought into contact with the test piece surface, 100g
The test piece was slid at a speed of 10 mm / s at a pressure of / cm ² . After the test was completed, the surface condition of the test piece was visually evaluated in the following three stages. ◎: The residue of the dried solid on the test piece is hardly noticeable. ○: The residue of the dried solid on the test piece is somewhat noticeable. X: The residue of the dry solid on the test piece is noticeable.

(6). Stain resistance test-b The same test as in (5) was performed except that the oral dyeing gel was changed to black ink in (5).

<Example 1> The isotactic pentad fraction of the boiling heptane-insoluble portion was 0.975, and the MFR was 15
g / 10min propylene homopolymer, Al-
0.15 parts by weight of pt-butylbenzoate and 0.3% by weight of polydimethylsiloxane were added, and pellets were obtained using an extruder. Using this, cylinder temperature 220
After injection molding at 70 ° C. and a mold temperature of 70 ° C., the surface temperature of the molded body obtained in the mold was kept at 80 ° C. or higher and lower than the melting temperature for 30 seconds, and the width (A) in FIGS. 405m
m, a length (B) of 400, a rear height (C) of 55 mm, a front height (D) of 12 mm, and a plate thickness (E) of 3 mm were prepared. The surface crystallization degree, scratch resistance, and antifouling property were evaluated using the obtained toilet lid. The results are shown in Table 1 below.

<Examples 2 to 5, Comparative Example 3> In Example 1, the amount of polydimethylsiloxane added was 0 to 15% by weight.
The same test as in Example 1 was performed, except that the temperature was changed between. The results are shown in Table 1 below.

Comparative Example 1 In Example 1, the amount of polydimethylsiloxane added was set to 0% by weight, and the cylinder temperature was set to 2%.
After injection molding at 00 ° C and a mold temperature of 70 ° C, the mold temperature was set to 4
0 ° C., and the surface temperature of the molded body obtained in the mold was 80 ° C.
As described above, the same test as in Example 1 was performed except that the temperature was maintained at a temperature lower than the melting temperature for 6 seconds. The results are shown in Table 1 below.

<Comparative Example 2> In Example 1, the isotactic pentad fraction of the boiling heptane-insoluble portion was 0.9.
Except that the propylene homopolymer of No. 63 was used, the amount of polydimethylsiloxane added was 1.0% by weight, and the surface temperature of the injection molded product obtained in the mold was kept at 80 ° C. or higher and lower than the melting temperature for 7 seconds. The same test as in Example 1 was performed. Table 1 shows the results.

Comparative Example 4 In Example 1, Al-p
The same test as in Example 1 was performed except that the addition amount of -t-butylbenzoate was 0 parts by weight and the addition amount of polydimethylsiloxane was 1.0% by weight. Table 1 shows the results.

[0045]

[Table 1]

[0046]

EFFECTS OF THE INVENTION A toilet seat sheet, a toilet lid, and an injection molded article of a propylene polymer obtained from the specific propylene polymer composition of the present invention and having a specific surface layer crystallinity,
Toilet seat components such as a hot water washing device component can be easily removed with a light wiping degree without diminishing the surface appearance due to repeated friction. Therefore, the toilet seat composed of these parts
This is very useful as a toilet seat part because the workability of cleaning is improved and the appearance is not deteriorated due to the cleaning work.

[Brief description of the drawings]

FIG. 1 is a perspective view of a toilet lid which is one of the toilet seat components of the present invention.

FIG. 2 is a cross-sectional view of the toilet lid of FIG.

[Explanation of symbols]

 A ………… Width B …………… Length C ……………… Front height D …………… Rear height E ………………

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Seiichiro Inoue 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka Tochiki Kiki Co., Ltd. 1-1-1 Toto Kiki Co., Ltd. (72) Inventor Hiroki Fujimura 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka Prefecture Toko Kiki Co., Ltd. (72) Inventor Teruhiko Nawata Mikage, Tokuyama-shi, Yamaguchi No. 1-1 Tokuyama-cho (72) Inventor Norihei Mitsumura No. 1-1 Mikage-cho, Tokuyama-shi, Yamaguchi F-term (reference) 2D037 AA13

Claims (2)

[Claims] 1. A toilet seat component such as a toilet seat sheet, a toilet lid, a main body case, and a washing nozzle for washing a human body, wherein at least one of the components has a nucleating agent of 0.05 to 0.05%.
It is composed of a propylene polymer composition containing 5 parts by weight, and has a surface layer crystallinity of 60 measured by a reflection X-ray diffraction method.
% For toilet seats having excellent scratch resistance and antifouling properties. 2. A propylene polymer composition comprising 99.9 to 90% by weight of a propylene polymer and 0.1 to 0.1% of a polysiloxane.
2. A toilet seat having excellent scratch resistance and antifouling properties according to claim 1, wherein 0.05 to 3 parts by weight of a nucleating agent is mixed with 100 parts by weight of a composition comprising 10% by weight. parts.