JPH11246682A - Slipping sheet-like shaped article and holder for sliding member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sheet-like shaped article having improved slipperiness and improved abrasion resistance, and to provide the use of the sheet-like shaped article as a holder for a sliding member (for example, the window glass of an automobile). SOLUTION: This easily slipping sheet-like shaped article consists mainly of the resin mixture of 20-95 wt.% of high density polyethylene (density: about 0.945-0.970) having a weight-average mol.wt. of 10,000-300,000 with 80-5 wt.% of a crystalline polyester-based resin (for example, polybutylene terephthalate). The polyester-based resin component may be blended with an amorphous thermoplastic resin in an amount of 1-40 wt.% (based on the total weight of the polyester-based resin and the amorphous thermoplastic resin), thereby furthermore improving the slipperiness and the abrasion resistance. When the sheet-like shaped product is a filmy product 5, the sheet-like shaped article is effectively utilized for a molding or stabilizer for the window glass of an automobile.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a slip-shaped molded article having improved slipperiness. And the slippery sheet-shaped molded product is effectively used as a member of a holding tool such as a window glass of an automobile.

[0002]

2. Description of the Related Art There are various fields of application that require sliding properties. For example, in a mall used in contact with a windshield (opening / closing door) of an automobile, a fiber material made of nylon, tetron, fluororesin, or the like is used in a portion in contact with the glass. Among them, fluororesin fibers are most excellent in slipperiness, but they are weak and liable to fall, and their abrasion resistance is not sufficient. These drawbacks are that the water droplets and dust adhering to the glass surface are not sufficiently removed, or that the dust once wound is not removed out of the system, which may damage the glass surface.

[0003] In order to improve the abrasion resistance defect of the above-mentioned fluororesin fiber, the present inventors have previously made a specific resin composition (a high-density polyethylene and a crystalline polyester, and an amorphous (A composition in which a thermoplastic resin is mixed), which is made into a fibrous form, and a patent application has been filed for a technique which is stiff and has excellent abrasion resistance, as well as a sliding property equivalent to that of the fluororesin. (Japanese Patent Application No. 9-85228
issue)

[0004]

The above-mentioned patent application is for use in a fibrous state, but in consideration of various uses thereafter, in addition to the use in a fibrous form, a film form or the like is used.
Use in plate form has also proven to be effective. In the present invention, the special resin in the above-mentioned patent application is made into a slippery sheet-like molded body, and the use thereof is also provided, which is achieved by the following means.

[0005]

According to the present invention, as described in claim 1, 20 to 95% by weight of a high-density polyethylene having a weight average molecular weight of 100,000 to 300,000 and 80 to 5% by weight of a crystalline polyester resin. % Of the two-component slippery sheet-shaped molded product, and further, as described in claim 2, a part of the polyester-based resin is substituted with an amorphous thermoplastic resin, and the substituted resin is used. Is 1 to 40% by weight based on the total amount of the crystalline polyester resin and the amorphous thermoplastic resin.
The present invention is characterized by providing a slip-shaped molded article containing three components as main components. Claims 3 to 5 are also provided as inventions dependent on Claims 1 and 2.

Further, as a preferable use form of the slippery sheet-shaped molded article according to the first aspect, the slippery sheet-shaped molded article is provided on a sliding surface with a member which slides relatively in the seventh aspect. It is provided as a holding member for a sliding member provided, and as a member that slides relatively, it is specifically used in an opening / closing window glass for a vehicle, that is, a molding for an opening / closing window glass of an automobile. To provide.

Hereinafter, the present invention will be described in more detail.

[0008]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, the high-density polyethylene has a weight average molecular weight of 10,000 to 300,000, preferably 2,000 to 300,000.
200,000, a polyethylene having a density of 0.945 to 0.970. The polyethylene is significantly different from ultra-high molecular weight polyethylene having a molecular weight of 700,000 or more, and thereby has an appropriate property which affects slipperiness (for example, low dynamic friction and no sliding noise during friction) and abrasion resistance. rigidity,
Furthermore, the effect on the formability (such as smooth forming with a smooth surface) as a sheet-shaped formed body is exerted more greatly. When the weight-average molecular weight exceeds 300,000, the effect of such an action becomes small. Conversely, when the weight-average molecular weight is reduced, it is out of the range of high-density polyethylene, so that the improvement effect of the present invention is hardly seen. Therefore, the lower limit of the molecular weight of high-density polyethylene is 10,000. Preferred in this range is 20 to 200,000,
The density then is in the range of about 0.945 to 0.970.

Next, the crystalline polyester resin will be described. This is generally a polyester resin obtained by polycondensation of a dicarboxylic acid component and a diol component and has crystallinity (melting point). Here, in the case of an amorphous polyester, a sheet-like molded article obtained by mixing with the high-density polyethylene cannot obtain improved slipperiness and abrasion resistance as required by the present invention. That is, the polyethylene alone does not act synergistically on the above, especially on the wear resistance and slipperiness. This is probably because the polyethylene was mixed in such a state that it was simply dispersed in the polyethylene.

[0010] The crystalline polyester is melted and plasticized at the time of molding into a sheet-like molded article, but it is not preferable if the difference in melting point from the high-density polyethylene is too large. In this sense, a polycondensation with a semi-aromatic polyester rather than a wholly aromatic polyester, that is, a dicarboxylic acid component or a diol component, wherein one of the dicarboxylic acid component and the diol component has an aromatic group, and the other has an aliphatic group. Is preferred.

For example, specific examples include resins such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Of these, the former three are preferable, and polybutylene terephthalate is more preferable.

The mixing ratio of the former two is as described above, but preferably 30 to 80% by weight of high-density polyethylene having a weight average molecular weight of 10,000 to 300,000, and 70 to 20% by weight of a crystalline polyester resin. . This is specified because it is affected by the mixture ratio of the two in order to express the above-mentioned characteristics to the maximum.

That is, the high-density polyethylene is 95% by weight.
On the other hand, if the content of the crystalline polyester resin is less than 5% by weight, it is difficult to obtain appropriate rigidity evaluated as one of abrasion resistance. On the other hand, if the polyethylene content is less than 20% by weight, that is, if the polyester resin content is more than 80% by weight, the slipperiness is insufficient and it is used as a holding device for windshields of automobiles. This is because sliding noise is likely to occur.

The high-density polyethylene and the crystalline polyester resin are basically mixed with a single component, but each is composed of two or more components, that is, two or more types of polyethylene having different densities are mixed. The polyester resin may be used as the polyethylene resin. On the other hand, in the polyester resin, for example, a mixture of polybutylene terephthalate and polyethylene terephthalate may be used as the polyester resin.

Further, an amorphous thermoplastic resin may be further mixed as the third component with the above two components. This is because the mixing of the resin further contributes to the improvement of wear resistance and heat resistance as a whole. However, the mixing ratio of the resin does not exceed that of the crystalline polyester resin. This is because when the amorphous thermoplastic resin is mixed in a larger amount than the crystalline polyester resin, it acts in the direction of deteriorating the wear resistance. The mixing amount is preferably 1 to 4 with respect to the total amount of the polyester resin and the amorphous thermoplastic resin.
0% by weight, more preferably 5 to 35% by weight.

As the amorphous thermoplastic resin, the above-mentioned 2
Those which are compatible with the components are preferable, and examples thereof include polymethyl methacrylate, polycarbonate, and polystyrene, and polycarbonate is more preferable.

In the method of mixing the above components in a predetermined amount, the respective powders or pellets are simply mixed with a high mixer or the like,
In order to form a mixed powder for molding or to make the mixing more uniform, the mixed powder is further kneaded with a twin-screw kneading extruder and pelletized, and this is used as a mixed resin for molding. But the latter is more desirable.

Incidentally, a small amount of various additives generally used in the mixing is acceptable. In addition, a small amount of other crystalline thermoplastic resin or the like may be added as the third component or the fourth component within a range that does not significantly impair the characteristics of the present invention.

The sheet-like molded article of the above-mentioned mixed composition is
Its form ranges from a film to a thick plate, and is numerically about 10 μm to 10 mm. Therefore, the state (thickness, length, width, etc.) differs depending on the purpose of use, and may be used after processing to a specification corresponding to the purpose.

The sheet-like molded body can be easily molded by a molding apparatus which can be generally melt-extruded into a film or plate, but it can be molded by other compression molding or the like. Absent. In the case of melt extrusion molding, it is common to extrude continuously and take it out after cooling, or stretch it in one or two directions simultaneously with or after the extrusion. In particular, it is desirable to stretch in one direction. This is because the form of use as the sliding material is often one-way, and when the stretching direction and the sliding direction match, a molded article having more slipperiness and more abrasion resistance can be obtained. The stretching ratio may be appropriately determined by a preliminary test from the relation with the effect, but in the case of a film, it is preferable to use a maximum of 3 times as a guideline in unidirectional stretching.

Since the sheet-shaped molded article has a function of slipperiness as well as excellent abrasion resistance, the sheet-shaped molded article can effectively exhibit these properties, especially between members which slide relatively. Effective for intervening fields. Here, there are at least two members opposed to each other with respect to the relatively slidable member. If one of the members is fixed and the other slides while abutting on the other, the speed is further reduced. Differently, at least two members in at least a sliding relationship when they are in a sliding relationship in the same direction.

As such a relatively sliding member, for example, in the field of OA equipment, a cleaning member opposed to a photosensitive drum, a transfer belt, and various rollers in a copying machine, or a mouse input device in a personal computer. In the field of vehicles such as mats and automobiles, wipers facing the front glass, malls and stabilizers facing the open / close window glass, white boards facing the eraser in the teaching materials field, doors and sills in the architectural field, slides and luggage in the transportation field Can be mentioned.

The sheet-like molded body has various forms of use, such as a film form, a plate form, use for one of the members, or use for both, depending on the opposing members. In the case of (1), a film-shaped molded body is used, which is fixed to only one of them, and is physically or adhesively fixed to the base fabric of the member. In particular, fixing with an adhesive is complete and easy. This is because the sheet-shaped molded body has an excellent adhesive property that can be easily adhered to a general adhesive, unlike a molded body made of a fluorine-based resin or a single ethylene resin. . As the adhesive, generally known thermosetting type urethane type, epoxy type, ester type and the like can be preferably used.

The form of use of the above-mentioned sheet-like molded body is generally affixed to a member serving as a substrate and is often used linearly by surface contact. Further, there is a case where the sheet is cut into strips and used in a state of line contact.

There is also a case where fine protrusions are formed on the surface of the sheet-like molded body and used. The effect of this projection (this projection is also raised) is that it is easier to remove as well as water or dust adhering to the sliding surface as well as being more slippery. is there. In other words, this effect is due to the effect that the adhered substance is caught every time sliding occurs and is sequentially discharged out of the system.

A preferred example of the above-mentioned sheet-like molded body having a protrusion is a film-like molded body between a sliding member for opening and closing a window glass of a vehicle and a molding, and is used in such a manner as to be adhered to a molding base. . This is specifically described below with reference to FIG.

FIG. 1 is a sectional view of a front door body of an automobile. That is, there is an opening / closing window glass 1, and a molding M is provided at an entrance portion thereof and abuts from both sides. The molding M is pressing the glass at two upper and lower portions as contact surfaces. The molding M comprises a rubber base 4 and a film-shaped molded body 5 according to the present invention. The film-shaped molded body 5 is extended to the surface of the pressing rubber base 4 from the contact surface with the glass 1 to the non-contact surface by using an adhesive (here, a urethane-based thermosetting resin is used). ). In addition, the film-shaped molded body 5 has not only a simple protrusion on its surface but also a raised protrusion (not shown).
Is shaped. The thickness of the molded body 5 is generally about 10 to 500 μm, but this depends on the type of automobile and the shape of the molding. Further, the shape (shape, size, number, etc.) of the protrusions also depends on various conditions, but the shape and shape are circular and have a height of about 1 to 200 μm. Good to decide. In addition, the method of buffing with emery paper,
There is a sanding method using a belt sander or a drum sander. The molding M is supported by a door outer panel 2 having reinforcing panels 3 and 3a and a door inner panel 2a.

The structure of the molding M in FIG. 1 also has a function as a window glass stabilizer. That is, the upper entrance contact surface has a molding function, and the lower (pseudo-square shape having a lip) contact surface has a stabilizer (vibration-proof) function. Therefore, there is also a front door having a structure in which a mall is connected separately from the stabilizer. Regardless of the front door having any structure, the sheet-like molded body in the present invention can be used not only for moldings but also for the stabilizer.

It is presumed that the effects of the present invention are exhibited by the following effects. When the cross section and the surface of the sheet-like molded body are observed with an electron microscope photograph, the high-density polyethylene becomes an extremely fine streak in a crystalline polyester resin (for example, in the case of polybutylene terephthalate) and is in a densely packed state. It can be seen that the particles are oriented in the extrusion direction. It is presumed that such a state is attributable to a moderate compatibility between the polyethylene and the polyester resin. Therefore, the polyethylene, which particularly affects the slipperiness, is more slippery, and even when it slides while being in contact with various sliding members, the wear is extremely small, which leads to a great improvement in wear resistance as a whole. It is thought that there is.

Further, the addition of an amorphous thermoplastic resin (for example, polycarbonate) as the third component further improves the adhesiveness and heat resistance because the compatibility between the high-density polyethylene and the crystalline polyester resin is further increased. it is conceivable that.

[0031]

The present invention will be further described by way of examples together with comparative examples.

The dynamic friction coefficient (μ) measured in each example
d), sliding noise (abnormal noise) and wear resistance are values measured under the following conditions.

The coefficient of kinetic friction (μd) indicates lubricity. The smaller the numerical value is, the better the lubricity is. The measurement is performed according to the test method described in ASTM D1897 under the following measurement conditions. Was. Measuring restraint: A film test of a predetermined thickness obtained in each example was cut into a width of 20 mm and a length of 100 mm, and this was cut into a plastic holding jig, a rubber sheet having a thickness of 3 mm and a thermosetting urethane. It was fixed to the adhesive via a mold adhesive. Opposite sliding members: tempered glass having a width of 200 mm and a length of 500 mm. Load applied to the measurement holder: 3 kg Measurement environment: Dry (D) with a relative humidity of 25% (temperature of 25 ° C)
ry), 100% relative humidity (temperature 25 ° C.) wet (Wet), and a transitional wet-dry semi-wet (SWet) when changing from wet to dry.
Environmental measurements.

The sliding noise (abnormal noise) is determined by the dynamic friction coefficient (μ
d) A hearing test was conducted in which the sound generated at the time of the measurement was heard and judged by ear. Those that were received as unpleasant sounds due to sound generation were evaluated on a three-point scale of x.

The abrasion resistance was measured by using a restraining tool prepared under the same conditions as the restraining tool for measuring the coefficient of dynamic friction, fixing the same, and sliding the sliding part on the tempered glass plate from side to side. However, the conditions at that time are as follows. Load applied to the tempered glass plate: 2 kg Wear amount (mg): One-way sliding distance is 400 mm, the time required for this reciprocating motion is 5.3 seconds, and 1 hour under dry conditions (relative humidity 25%, temperature 25 ° C.). Abrasion amount of the film (for test) when rubbed 10,000 times (one reciprocation). The smaller the amount, the better the abrasion.

Example 1 High-density polyethylene powder (HIZEX, type 2100JP, manufactured by Mitsui Chemicals, Inc.)
With a density of 0.957 and a weight average molecular weight of 60,000 (hereinafter referred to as “HDPE”) and polybutylene terephthalate powder (Duranex, 2
000P) (hereinafter referred to as "PBT") was sufficiently mixed at a ratio of 50% by weight, and kneaded in a twin-screw extruder (with a barrel temperature of 100 to 230 ° C) to be pelletized.

Next, the obtained pellets were weighed 500 mm,
Feed to an extruder having a T die with a lip opening of 0.35 mm, barrel temperature 100 to 270 ° C, T die temperature 265 ° C
And subsequently stretched twice in the machine direction to form a film. The thickness of the obtained film is 50 ± 3μ
At m, the surface was very smooth.

Using the obtained film, two restrainers for measurement were prepared, and the dynamic friction coefficient, sliding noise and wear resistance were measured. The results are shown in Table 1.

(Example 2) HDPE powder of Example 1 and P
BT powder and polycarbonate powder (manufactured by Teijin Chemicals Limited, Panlite, L-1225WP) (hereinafter “PC”)
50% by weight, 35% by weight and 15% by weight, respectively.
After sufficient mixing at a ratio of weight%, the mixture was kneaded with a twin-screw extruder and pelletized as in Example 1. The obtained pellet was extruded into a film by a T-die extruder. The thickness of the obtained film was 50 ± 3 μm, and the surface was extremely smooth. Then, three items were measured for the film in the same manner as in Example 1, and these were summarized in Table 1.

Example 3 50% by weight of the HDPE powder
And 50% by weight of polyethylene terephthalate powder (manufactured by Mitsubishi Rayon Co., Ltd., Dianite, MA-580), and these were mixed in a twin-screw extruder (barrel temperature 100
(To 270 ° C.) and kneaded while pelletizing.
Next, the pellets were extruded from a T-die into a film in the same manner as in Example 1. However, the molding temperature in this case was a barrel temperature of 100 to 275 ° C. The thickness of the obtained film was 50 ± 3 μm, and the surface was extremely smooth as in Example 1. Then, with respect to this film, three items were measured in the same manner as in Example 1, and these were summarized in Table 1.

(Comparative Example 1) Instead of HDPE in Example 1, a low density polyethylene powder (Ultzex, type 4570, manufactured by Mitsui Chemicals, Inc., having a density of 0.94)
Example 1 except that the weight average molecular weight is 88,000)
A film was formed under exactly the same conditions as in the above. The thickness of the obtained film was 50 ± 3 μm. In this case, three items were measured in the same manner as in Example 1, and the results are summarized in Table 1.

Comparative Example 2 15% by weight of the HDPE powder
And a PBT powder at a component ratio of 85% by weight, and a film was formed from the mixed powder under the same conditions as in Example 1 below. The thickness of the obtained film is 50 ±
At 3 μm, the surface condition was the same as in Example 1. This film was measured for three items in the same manner as in Example 1, and the results are summarized in Table 1.

Comparative Example 3 In Comparative Example 2, the HDPE
A film was formed under the same conditions except that the component ratio was changed to 98% of powder and 2% by weight of PBT powder. The thickness of the obtained film was 50 ± 3 μm, and the surface condition was the same as in Comparative Example 2. However, the film was peeled off during the test.

Example 4 50% by weight of the HDPE powder, 40% by weight of the PBT powder and polymethyl methacrylate powder (Acrypet, manufactured by Mitsubishi Rayon Co., Ltd.)
VH type, # 001) was mixed at a component ratio of 10% by weight, and the mixed powder was kneaded and pelletized in the same manner as in Example 1 and extruded into a film from a T-die. The thickness of the obtained film was 50 ± 3 μm and the surface was smooth. The above three items were measured for this film and are summarized in Table 1.

Example 5 A mounting test was performed using an automobile having a front door having the structure shown in FIG. First, in Example 1, the surface of the film was buffed for 3 minutes using a 500 mesh emery paper, and the surface was subjected to a projection process. This was cut into a width of 15 mm and a length of 850 mm. This was bonded and fixed with a thermosetting urethane-based adhesive as shown in FIG. The width of the film in contact with the window glass 1 is about 10 mm in total length in cross section.
It is. The pressing of the molding M against the window glass 1 was about 87 g / cm ² . The above three items were measured for this film and are summarized in Table 1.

Practical installation of the above molding M (semi-wet)
, And a dust test. This dust
The test was conducted by spraying a dust designated as JIS Class 1 at the time of wetness and examining the scratched state of the window glass 1. No damage was confirmed in the test 200 times.

【The invention's effect】

The easily-slidable sheet-like molded article of the present invention has high slidability even when used under strong pressure, and has very little sliding wear. These properties are brought about by a specific combination of high-density polyethylene and a crystalline polyester resin part (including a case where one part thereof is replaced with an amorphous thermoplastic resin), and the orientation state of the polyester resin. Have been.

Also, since the adhesiveness is excellent, it is easy to adhere to the opposing sliding portion base. Having slidability and adhesiveness are characteristics that are not found in fluorine-based resin molded articles, and also mean that they are easy to process and can be used in a wider variety of applications. .

The unpleasant noise that often occurs when sliding between the opposing sliding members is not affected by the type of the member or the environment (dry, wet, semi-wet).
Does not occur.

The easily molded sheet-like molded article of the present invention is effectively used for various uses. Specifically, for example, when the molded body is a film, it is effective to use it as it is or to form a protrusion to form a molding or a stabilizer portion of a window glass (open / close) of a vehicle.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an example of a front door body of an automobile.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Window glass 2 Door inner panel 2a Door outer panel 3 Reinforcement panel 3a Reinforcement panel 4 Suppression rubber base 5 Film molded body

[Table 1]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 67/02 B60J 1/16 D 69/00 5/00 501L

Claims (8)

[Claims] An easy-to-use mixed resin comprising as a main component a mixed resin of 20 to 95% by weight of high density polyethylene having a weight average molecular weight of 100,000 to 300,000 and 80 to 5% by weight of a crystalline polyester resin. A lubricated sheet-like molded body. 2. A part of the crystalline polyester resin is replaced by an amorphous thermoplastic resin, and the amorphous thermoplastic resin is reduced to a total amount of the crystalline polyester resin and the amorphous thermoplastic resin. A lubricated sheet-like molded product characterized by comprising three components as main components in an amount of 1 to 40% by weight. 3. A high-density polyethylene having a weight average molecular weight of 2 to 3.
The slippery sheet-shaped molded product according to claim 1 or 2, wherein the molded product has a density of 200,000 and a density of 0.945 to 0.970. 4. The slippery sheet according to claim 1, wherein the thermoplastic polyester resin is at least one selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate. Molded body. 5. The amorphous thermoplastic resin is polycarbonate,
The slip-like sheet-shaped molded product according to any one of claims 2 to 4, which is at least one selected from the group consisting of polymethyl methacrylate and polystyrene. 6. The slippery sheet-like molded product according to claim 1, wherein a minute protrusion is provided on at least one surface of the slippery sheet-like molded product. 7. A holding member for a sliding member, characterized in that the slippery sheet-shaped molded body according to claim 6 is provided on a sliding contact surface with a member that slides relatively. 8. A holding member for a sliding member according to claim 7, wherein said relatively sliding member is a window glass for opening and closing a vehicle.