JP2001348437A - Film for molding, reflector base material, and reflector for lighting unit using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reflector base material for a lighting unit which is lightweight and excellent in the surface smoothness, safety, moldability, heat resistance, and handleability, and to provide a reflector for a lighting unit which is unnecessary for the pretreatment at the time of forming a reflecting layer, suitable for a mass production, lightweight, highly specular, excellent in heat resistance, heat radiation, safety and handleability, and also inexpensive and has high quality. SOLUTION: The reflector base material for a lighting unit is characterized in that the base material is a molding made of the film which has a close proximity between the molding temperature and the releasable temperature after the cooling posterior to the molding; and the reflector or a lighting unit has on the base material a reflecting layer mounted with the vapor deposition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film for molding used as a lamp reflector of a headlamp or a fog lamp of an automobile, a reflector substrate using the film, and a lighting device formed from the substrate. It relates to a reflector.

[0002]

2. Description of the Related Art As a reflector (lamp reflector) of a headlamp (headlight) or a fog lamp of an automobile, a metal such as glass or aluminum and a plastic injection molding or compression molding such as polyphenylene sulfide or unsaturated polyester resin. BACKGROUND ART A material in which a metal reflecting layer formed of aluminum, a nickel-chromium alloy, titanium oxide, or the like as a reflective substance is formed on a reflector base body made of a body or the like is mainly used.

[0003] That is, light bulbs such as halogen bulbs and xenon bulbs are used as light sources for headlamps (headlights) and fog lamps of automobiles, and the temperature near the base of the bulb may be heated to 200 ° C or more. For this reason, as the reflector base material, an injection molded article or a compression molded article of glass, metal or plastic with improved heat resistance by mixing an inorganic reinforcing material such as glass fiber or calcium carbonate is used. is there.

[0004] However, those using glass as a reflector base material have problems such as heavy weight and easy breakage. In addition, in the case of using a metal and a reinforced resin molded body as a reflector base, in addition to a large weight, in order to improve a reflective mirror surface performance (smoothness), a resin coat or the like is used before a reflective substance is deposited. There was a problem that secondary processing was required and the number of manufacturing steps was large.

[0005] In addition, those using a reinforced resin molded body as a reflector base material are lighter in weight than those using a metal as a reflector base material, but from the viewpoint of base material strength and restrictions on molding technology. Since the base material itself has a low heat radiation property and the projector type has a structure that can easily store heat, there is a concern about heat retention in maintaining the shape, and a rise in the temperature inside the housing. To shorten the life of the bulb itself.

Further, when a reinforced resin molding is used as a reflector base material, a gas such as a chlorine compound may be generated when the lamp is turned on and heated, and this gas adheres and solidifies to a front lens such as a headlamp. It also included the problem of fogging the lens and degrading lamp performance.

On the other hand, Japanese Utility Model Publication No. Sho 62-10887 discloses a sheet-made reflector made of a film sheet which has been mirror-finished by aluminium vapor deposition. It is disclosed that the pre-treatment is unnecessary, but since the film sheet used here is polyethylene having poor heat resistance, the reflector made of this sheet is used as a headlamp using a high heat generation lamp such as a halogen bulb. It was not possible to apply it as a reflector such as in terms of heat-resistant shape retention force.

In Japanese Patent Publication No. 5-88481, there is described a reflector in which a visible light-reflecting infrared transmitting multilayer film is formed on a reflector substrate made of a film made of a polyimide resin and a polyetherketone resin. It is disclosed that the reflecting mirror can withstand heat such as halogen bulbs by using a polyimide resin or the like in addition to being difficult to be damaged, but this reflecting mirror is a visible light reflecting infrared transmitting multilayer film. Was formed on a base material and could not be practically used as a reflector for headlamps and fog lamps for automobiles. In addition, the feature that "it can withstand heat generated by halogen bulbs and the like by using a polyimide resin or the like as a reflector base material" is difficult to control the temperature conditions during molding, and is not suitable for vacuum molding. In the molding by the pressure method, a long time is required for heating and cooling the mold, so that the molding time becomes long, which means that it is not practical in terms of cost and mass production. Further, when a thermoplastic film having a low glass transition point is used, there is a problem that heat resistance is poor.

[0009]

SUMMARY OF THE INVENTION The present invention has been achieved as a result of studying to solve the problems in the prior art described above.

Accordingly, a first object of the present invention is to provide a molding film and a reflector base for lighting equipment which are lightweight and have excellent surface smoothness, safety, moldability, heat resistance and handleability. is there.

A second object of the present invention is to eliminate the need for a pretreatment at the time of forming the reflective layer, which is suitable for mass production, is lightweight, has high specularity, and is excellent in heat resistance, heat dissipation, safety and handleability. Another object of the present invention is to provide a low-cost and high-quality reflector for lighting equipment.

[0012]

Means for Solving the Problems To achieve the above object, the molding film of the present invention comprises: (1) a storage elastic modulus at 200 ° C. of 90%;
The difference between the temperature at which the storage elastic modulus is reduced to 200 ° C. and the temperature at which the storage elastic modulus is reduced to 10% with respect to the storage elastic modulus at 200 ° C. is 50 ° C. or less, and the molecular structure has an imide bond.

The following are preferred embodiments.

(2) The storage elastic modulus at 200 ° C. is 30 ° C.
The film for molding according to the above (1), wherein the film has a storage modulus of more than 50%.

(3) The film has the general formula (I) or (I)
The molding film according to the above (1), having the structural unit represented by I).

[0016]

Embedded image

[0017]

Embedded image [Where R ₁ is

[0018]

Embedded image R ₂ is

[0019]

Embedded image And any one of the groups represented by
The molar ratio of Y is from 100 to 20: 0 to 80. (4) The film according to the above (1), wherein the film has structural units represented by formulas (III) and (IV).

[0020]

Embedded image

[0021]

Embedded image [Where R ₃ is

[0022]

Embedded image Any one selected from the groups represented by
Is from 100 to 20: 0 to 80. Further, the reflector base material is characterized in that (1) using these films, they are formed by hot stamping or vacuum forming. Further, (2) the reflector substrate according to the above (1), further comprising a main body part, an outer flange part, and an inner flange part forming a reflection surface.

Further, the reflector for lighting equipment of the present invention comprises:
(1) A reflective layer is formed by depositing a reflective material on the reflector base material. Further, (2) the reflector for lighting equipment according to the above (1), wherein the reflecting material is aluminum or silver, and (3) the reflector (1), which is used as a lamp reflector of a vehicle.
Alternatively, the reflector for lighting equipment described in (2) is also preferable.

[0024]

The film of the present invention is characterized by the fact that the molding temperature and the temperature at which it can be cooled and taken out after molding are close to each other, and the time from molding to taking out is short, thereby reducing the cost. . In addition, since the reflector base for lighting equipment of the present invention is formed of a specific plastic film molded body having excellent heat resistance, the surface smoothness thereof is good and pretreatment at the time of forming the reflection layer is unnecessary. In addition, it can be obtained at low cost by a simple molding method such as vacuum molding, and is excellent in safety and handling because it is extremely lightweight and hard to break.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the storage elastic modulus refers to a value obtained by using DVE-V4 manufactured by Rheology Co., Ltd. at a driving frequency of 110 Hz, a heating rate of 2 ° C./min, and a vibration displacement of 16 μm.

The molding film of the present invention can be prepared by selecting appropriate diamines and acid dianhydrides as raw materials.
The difference between the temperature at which the storage elastic modulus is reduced to 90% with respect to the storage elastic modulus of ° C and the temperature at which the storage elastic modulus is reduced to 10% with respect to the storage elastic modulus at 200 ° C can be made 50 ° C or less.

Hereinafter, the reflector base for lighting equipment and the reflector for lighting equipment of the present invention will be described in further detail with reference to the drawings.

FIG. 1 is a partially cutaway perspective view showing an example of a reflector for lighting equipment of the present invention, and FIG. 2 is a partially cutaway side view showing one example of a reflector for lighting equipment of the present invention.

As shown in FIG. 1, the reflector substrate 1 for lighting equipment of the present invention comprises a molded body obtained by vacuum-molding a film having a glass transition temperature of 200 ° C. or higher. It has a main body part 2, an outer flange part 4 and an inner flange part 6 forming a part, and this example is configured as a lamp reflector base of an automobile headlamp.

In this reflector 1 for lighting equipment,
The surface smoothness of the main body 2 retains the smoothness of the film as it is, and has sufficient performance to obtain a reflecting surface for a floodlight without any pretreatment before the reflective layer is deposited. ing.

If the strength of the main body 2 becomes a problem, a frame made of plastic injection molding resin, metal pressed parts, FRP, or the like is easily reinforced by being attached to the outside of the main body 2. be able to.

In the embodiment shown in FIG. 1, the main body 2 has a simple reflecting surface shape.
Any shape can be selected as long as it is a shape that can be molded, such as a polyhedron.

The reflector 8 for lighting equipment shown in FIG.
A reflective material such as aluminum is deposited on the inner peripheral surface of the reflector base material 1 shown in FIG.
0 is formed. In the step of forming the reflective layer 10, the reflector substrate 1 maintains the smoothness of the film as it is, so that there is no need to perform any pretreatment such as resin coating or degreasing.

In the reflector 1 for lighting equipment shown in FIG. 2, an insertion opening 12 for a light bulb (not shown) is opened at the center of the inner flange portion 6 and the periphery of the insertion opening 12 is formed. A lamp reflector is formed by forming the inner flange 6a.

In the reflector substrate 1 shown in FIG. 1, the outer flange portion 4 is formed into the final shape of the reflector 8 shown in FIG. 2, but a plurality of reflectors are industrially formed on one film. It is also possible to form the base materials 1 side by side, perform a vapor deposition process, and then separate the outer flange parts 4 while adjusting the outer shape.

In the above structure, the film forming the reflector substrate 1 for lighting equipment has a glass transition point temperature.
A film having a temperature of 200 ° C. or higher is used, and the thickness of the film may be a thickness supplied as a normal film, for example, about several micrometers to several millimeters.

Both stretched and unstretched films can be used. Films containing an inorganic or organic additive for the purpose of improving workability, etc., generally have a surface smoothness of the reflector substrate 1. Is undesirably reduced.

Then, the reflector substrate 1 for lighting equipment of the present invention
Can be obtained by molding the film into a desired shape by means such as hot die molding, vacuum molding, and high pressure gas spray molding. Vacuum molding is the simplest, the mold cost is low, and a large number of Since simultaneous molding is possible, it is economically advantageous. The vacuum forming method includes a straight method, a drape method, an air slip method, a snapback method, a plug assist method, and the like, and any known method can be applied.

Aluminum or silver is most suitable as a metal deposited on the reflector substrate 1 for a lighting device as a reflector from the viewpoint of reflectivity, but a chemically stable metal compound may be appropriately used. Alternatively, chromium, nickel-chromium alloy, or the like can be used as a base material for improving the adhesion strength to a reflective material or a film.

As a vapor deposition means for forming the reflective layer 10, a vacuum vapor deposition method, a sputtering method, an electron beam method, an ion plating method and the like can be used, but the present invention is not particularly limited to these. . Further, a protective film may be further formed on the obtained reflective layer 10 by coating, vapor deposition, or the like before use.

The shape of the reflector 8 for lighting equipment of the present invention may be any shape used as a headlamp or a fog lamp, and the reflective layer 10 is formed only on the portion of the reflector substrate 1 that requires reflection. May be available.

In addition, the reflective layer 10 can be formed on the opposite side of the reflector substrate 1 from the light bulb, and in this case, by providing the reflective layer 10 on the outside of the light bulb, the primary color of the polyimide film can be obtained. Yellow can be obtained as reflected light.

[0043]

EXAMPLES The present invention will be described more specifically with reference to the following examples. Example 1 1,3 bis- (4aminophenoxy) benzene in a 500 ml separable flask equipped with a DC stirrer
43 g (101 mmol) and 223.85 g of N, N'-dimethylacetamide are added and stirred at room temperature under a nitrogen atmosphere.
From 30 minutes to 1 hour, 6.49 g of 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride (2
0 mmol) in several portions. After stirring for one hour,
24.05 g of 4,4'-oxydiphthalic dianhydride (7
(8 mmol) in several portions. After stirring for another 1 hour, 16.22 g of a solution of pyromellitic dianhydride N, N'-dimethylacetamide (6 wt%) is added dropwise over 30 minutes, and the mixture is further stirred for 1 hour. The polyamic acid obtained here was 3500 poise.

A part of the obtained polyamic acid is taken on a polyester film, and a uniform film is formed using a spin coater. This is a β-picoline / acetic anhydride mixed solution
(50:50) for 5 minutes for imidization. The obtained polyimide gel film was heated at 200 ° C. for 30 minutes and at 300 ° C. for 20 minutes.
Heat treatment at 400 ° C. for 5 minutes to obtain a polyimide film. The obtained polyimide (thickness: 50 μm, TG: 2
(15 ° C.) and attempted vacuum forming. A reflector substrate (lamp reflector substrate) for a vehicle headlamp having the shape shown in FIG. 1 was obtained. The storage elastic modulus of the obtained film was measured using DVE-V4 manufactured by Rheology Co., Ltd.
Hz, the temperature rising rate was 2 ° C./min, and the vibration displacement was 16 μm. The molding temperature was 237 ° C, the removal temperature was 214 ° C, and the temperature difference was 23 ° C. The measurement results are summarized in FIGS. 3 and 4 and Table 1. Example 2 In a 500 ml separable flask equipped with a DC stirrer, 34.12 g (83 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 226.51 g of N, N'-dimethylacetamide were placed. Under nitrogen atmosphere,
Stir at room temperature. 30 minutes to 1 hour later,
25.98 g (242 mmol) of 4,3 ′, 4′-benzophenonetetracarboxylic dianhydride are added in several portions. After stirring for 1 hour, pyromellitic dianhydride N,
N'-dimethylacetamide solution (6 wt%) 13.39
g was added dropwise over 30 minutes and stirred for an additional hour. The polyamic acid obtained here was 3500 poise.

A part of the obtained polyamic acid is taken on a polyester film, and a uniform film is formed using a spin coater. This is a β-picoline / acetic anhydride mixed solution
(50:50) for 5 minutes for imidization. The obtained polyimide gel film was heated at 200 ° C. for 30 minutes and at 300 ° C. for 20 minutes.
Heat treatment at 400 ° C. for 5 minutes to obtain a polyimide film. The obtained polyimide has a thickness of 125 μm, a Young's modulus of 3.2 GPa, a CTE of 60 ppm / ° C., and a TG of 230 ° C.
Met. Using the obtained film, a reflector base material (lamp reflector base material) for an automobile headlamp having the shape shown in FIG. 1 was obtained by vacuum forming. The storage elastic modulus of the obtained film was measured using DVE-V4 manufactured by Rheology at a driving frequency of 110 Hz, a temperature rising rate of 2 ° C./min, and a vibration displacement of 16 μm. Molding temperature 255 ° C, removal temperature 228 ° C, temperature difference 27
° C. The measurement results are summarized in FIGS. 3 and 4 and Table 1. Example 3 In a 500-ml separable flask equipped with a DC stirrer, 34.12 g (83 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 226.51 g of N, N'-dimethylacetamide were placed. Under nitrogen atmosphere,
Stir at room temperature. 30 minutes to 1 hour later,
25.98 g (242 mmol) of 4,3 ′, 4′-benzophenonetetracarboxylic dianhydride are added in several portions. After stirring for 1 hour, pyromellitic dianhydride N,
N'-dimethylacetamide solution (6 wt%) 13.39
g was added dropwise over 30 minutes and stirred for an additional hour. The polyamic acid obtained here was 3500 poise.

A part of the obtained polyamic acid is taken on a polyester film, and a uniform film is formed using a spin coater. This was dried at 100 ° C. for 60 minutes to obtain a self-supporting film. . The obtained film was heated at 200 ° C.3
Heat treatment was performed for 0 minute, 300 ° C. for 20 minutes, and 400 ° C. for 5 minutes to obtain a polyimide film. The resulting polyimide has a thickness:
50 μm. The storage elastic modulus of the obtained film was measured using DVE-V4 manufactured by Rheology Co., Ltd. at a driving frequency of 110 Hz and a heating rate of 2 ° C.
Per minute, at a vibration displacement of 16 μm. The molding temperature was 255 ° C, the removal temperature was 228 ° C, and the temperature difference was 27 ° C. The measurement results are summarized in FIGS. Example 4 36.73 g (89 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 227.95 g of N, N'-dimethylacetamide were placed in a 500 ml separable flask equipped with a DC stirrer. Under nitrogen atmosphere,
Stir at room temperature. 30 minutes to 1 hour later,
14.41 g (44 mmol) of 4,3 ′, 4′-benzophenonetetracarboxylic dianhydride are added in several portions.
After stirring for 1 hour, 9.17 g of pyromellitic dianhydride
(42 mmol) are added in several portions. After further stirring for 1 hour, 14.13 g of a pyromellitic dianhydride N, N'-dimethylacetamide solution (6 wt%) is added dropwise over 30 minutes, and the mixture is further stirred for 1 hour. The polyamic acid obtained here was 4000 poise.

A part of the obtained polyamic acid is taken on a polyester film, and a uniform film is formed using a spin coater. This is a β-picoline / acetic anhydride mixed solution
(50:50) for 5 minutes for imidization. The obtained polyimide gel film was heated at 200 ° C. for 30 minutes and at 300 ° C. for 20 minutes.
Heat treatment at 400 ° C. for 5 minutes to obtain a polyimide film. The storage modulus of the resulting film is
Using E-V4, drive frequency 110Hz, heating rate 2 ℃ /
And the vibration displacement was 16 μm. The molding temperature was 275 ° C, the removal temperature was 236 ° C, and the temperature difference was 39 ° C. The measurement results are summarized in FIGS. Example 5 In a 500 ml separable flask equipped with a DC stirrer, 37.29 g (91 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 227.74 g of N, N'-dimethylacetamide were placed. Under nitrogen atmosphere,
Stir at room temperature. 30 minutes to 1 hour later,
11.71 g (36 mmol) of 4,3 ′, 4′-benzophenonetetracarboxylic dianhydride are added in several portions.
After stirring for 1 hour, pyromellitic dianhydride 11.30
g (51 mmol) are charged in several portions. After further stirring for 1 hour, 14.35 g of a solution of pyromellitic dianhydride N, N'-dimethylacetamide (6 wt%) is added dropwise over 30 minutes, and the mixture is further stirred for 1 hour. The polyamic acid obtained here was 4,500 poise.

A part of the obtained polyamic acid is taken on a polyester film, and a uniform film is formed using a spin coater. This is a β-picoline / acetic anhydride mixed solution
(50:50) for 5 minutes for imidization. The obtained polyimide gel film was heated at 200 ° C. for 30 minutes and at 300 ° C. for 20 minutes.
Heat treatment at 400 ° C. for 5 minutes to obtain a polyimide film. The obtained polyimide has a thickness of 50 μm. Using the obtained film, a reflector base material (lamp reflector base material) for an automobile headlamp having the shape shown in FIG. 1 was obtained by vacuum forming. The storage elastic modulus of the obtained film was measured using DVE-V4 manufactured by Rheology at a driving frequency of 110 Hz, a temperature rising rate of 2 ° C./min, and a vibration displacement of 16 μm. Molding temperature 282
° C, the removal temperature was 238 ° C, and the temperature difference was 44 ° C. The measurement results are summarized in FIGS. 3 and 4 and Table 1. Example 6 19.92 g (48 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 9.72 g (48 mmol) of 4,4'diaminodiphenyl ether in a 500 ml separable flask equipped with a DC stirrer. , N, N '
-Add 226.80 g of dimethylacetamide and stir at room temperature under a nitrogen atmosphere. 30.33 g (92 mmol) of 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride are added in several portions over 30 minutes to 1 hour. After stirring for 1 hour, pyromellitic dianhydride N,
N'-dimethylacetamide solution (6 wt%) 15.33
g was added dropwise over 30 minutes and stirred for an additional hour. The polyamic acid obtained here was 4000 poise.

A part of the obtained polyamic acid is taken on a polyester film, and a uniform film is formed using a spin coater. This is a β-picoline / acetic anhydride mixed solution
(50:50) for 5 minutes for imidization. The obtained polyimide gel film was heated at 200 ° C. for 30 minutes and at 300 ° C. for 20 minutes.
Heat treatment at 400 ° C. for 5 minutes to obtain a polyimide film. The obtained polyimide has a thickness of 50 μm. The storage elastic modulus of the obtained film was measured using DVE-V4 manufactured by Rheology Co., Ltd. at a driving frequency of 110 Hz, a heating rate of 2 ° C./min, and a vibration displacement of 16
It was measured in μm. Molding temperature 275 ℃, take-out temperature 236 ℃,
The temperature difference was 39 ° C. The measurement results are summarized in FIGS. Example 7 1,3 bis (4-aminophenoxy) benzene 6.5 in a 500 ml separable flask equipped with a DC stirrer.
8 g (23 mmol), 18.04 g (90 mmol) of 4,4 ′ diaminodiphenyl ether and 224.45 g of N, N′-dimethylacetamide are added, and the mixture is stirred at room temperature under a nitrogen atmosphere. 3,4,3 ', 4' from 30 minutes to 1 hour
-Benzophenonetetracarboxylic dianhydride 42.23
g (109 mmol) are charged in several portions. After stirring for 1 hour, 17.79 g of a pyromellitic dianhydride N, N'-dimethylacetamide solution (6 wt%) is added dropwise over 30 minutes, and the mixture is further stirred for 1 hour. The polyamic acid obtained here was 4000 poise.

A part of the obtained polyamic acid is taken on a polyester film, and a uniform film is formed using a spin coater. This is a β-picoline / acetic anhydride mixed solution
(50:50) for 5 minutes for imidization. The obtained polyimide gel film was heated at 200 ° C. for 30 minutes and at 300 ° C. for 20 minutes.
Heat treatment at 400 ° C. for 5 minutes to obtain a polyimide film. The obtained polyimide has a thickness of 50 μm. Using the obtained film, a reflector base material (lamp reflector base material) for an automobile headlamp having the shape shown in FIG. 1 was obtained by vacuum forming. The storage elastic modulus of the obtained film was measured using DVE-V4 manufactured by Rheology at a driving frequency of 110 Hz, a temperature rising rate of 2 ° C./min, and a vibration displacement of 16 μm. Molding temperature 282
° C, the removal temperature was 238 ° C, and the temperature difference was 44 ° C. The measurement results are summarized in FIGS. 3 and 4 and Table 1. Comparative Example 1 29.15 g of 4,4 'diaminodiphenyl ether in a 500 ml separable flask equipped with a DC stirrer
(140 mmol), N, N'-dimethylacetamide 22
Add 4.18 g and stir at room temperature under a nitrogen atmosphere. 30
After one minute to one hour, pyromellitic dianhydride 3
0.80 g (140 mmol) is charged in several portions. After stirring for 1 hour, 15.87 g of pyromellitic dianhydride N, N'-dimethylacetamide solution (6 wt%) was added to 30
Add dropwise over a minute and stir for an additional hour. The polyamic acid obtained here was 4000 poise.

A part of the obtained polyamic acid is taken on a polyester film, and a uniform film is formed using a spin coater. This is a β-picoline / acetic anhydride mixed solution
(50:50) for 5 minutes for imidization. The obtained polyimide gel film was heated at 200 ° C. for 30 minutes and at 300 ° C. for 20 minutes.
Heat treatment at 400 ° C. for 5 minutes to obtain a polyimide film. The obtained polyimide has a thickness of 50 μm. Next, vacuum forming was attempted using the obtained film. A reflector base material (lamp reflector base material) for an automobile headlamp having the shape shown in FIG. 1 could not be obtained. The storage elastic modulus of the film was measured using DVE-V4 manufactured by Rheology Co., Ltd.
Hz, the temperature rising rate was 2 ° C./min, and the vibration displacement was 16 μm. Molding temperature 350 ° C or higher, Discharge temperature 258 ° C, Temperature difference 50
° C or higher. The results of the measurement are summarized in FIG. Comparative Example 2 3.97 g (36.7 mmol) of parapenylenediamine in a 500 ml separable flask equipped with a DC stirrer,
22,07 g of 4,4 'diaminodiphenyl ether (1
10 mmol), N, N'-dimethylacetamide 224.
Add 03 g and stir at room temperature under a nitrogen atmosphere. From 30 minutes to 1 hour, 10.81 g (37 mmol) of 4,4 ′ biphenyltetracarboxylic dianhydride and 15.31 g (70 mmol) of pyromellitic dianhydride are added in several portions. After stirring for 1 hour, pyromellitic dianhydride N,
16.3 g of N'-dimethylacetamide solution (6 wt%)
Is added dropwise over 30 minutes, and the mixture is further stirred for 1 hour. The polyamic acid obtained here was 4000 poise.

A part of the obtained polyamic acid is taken on a polyester film, and a uniform film is formed using a spin coater. This is a β-picoline / acetic anhydride mixed solution
(50:50) for 5 minutes for imidization. The obtained polyimide gel film was heated at 200 ° C. for 30 minutes and at 300 ° C. for 20 minutes.
Heat treatment at 400 ° C. for 5 minutes to obtain a polyimide film. The obtained polyimide has a thickness of 50 μm. Next, vacuum forming was attempted using the obtained film. A reflector base material (lamp reflector base material) for an automobile headlamp having the shape shown in FIG. 1 could not be obtained. The storage elastic modulus of the film was measured using DVE-V4 manufactured by Rheology Co., Ltd.
Hz, the temperature rising rate was 2 ° C./min, and the vibration displacement was 16 μm. Molding temperature 350 ° C or higher, take-out temperature 247 ° C, temperature difference 50
° C or higher. The results of the measurement are summarized in FIG. Example 8 Aluminum was deposited on the lamp reflector base materials obtained in Examples 1, 2, 5, and 7 by a known vacuum deposition method to form a reflective layer having a thickness of 0.3 μm. In this reflective layer forming step, no pretreatment such as resin coating or degreasing was performed, but an extremely smooth vapor deposition surface could be formed. Then, an insertion opening for the electric bulb was opened at the center of the inner flange portion, and an inner flange was formed around the insertion opening.

The resulting reflective layer has extremely high smoothness.
When used as a lamp reflector for a headlamp, sufficient reflected light could be obtained.

The following can be understood from the results shown in FIGS. 3 and 4 and Table 1.

[0055]

[Table 1] In Table 1, ◎ indicates very excellent, ○ indicates possible, Δ indicates partially possible, and × indicates impossible.

From the results in Table 1, it is found that the storage elastic modulus at 200 ° C. obtained in Examples 1, 2, 5, and 7 was reduced to 90% with respect to the storage elastic modulus at 200 ° C. It shows that a film having a difference in temperature at which the storage modulus is reduced to 10% and a temperature difference of 50 ° C. or less has very good vacuum formability.

FIG. 3 shows the decrease in storage elastic modulus in% when the storage elastic modulus at 200 ° C. is set to 100 in Examples 1 to 7 and Comparative Examples 1 and 2. From the table, it was found that the films obtained in Examples 1 to 7 had a storage elastic modulus of 200 ° C., a temperature at which the storage elastic modulus was reduced to 90%, and a temperature of 20%.
It can be seen that the difference between the temperature at which the storage elastic modulus was reduced to 10% with respect to the storage elastic modulus at 0 ° C. was 50 ° C. or less.

FIG. 4 shows the decrease in storage elastic modulus in% when the storage elastic modulus at 30 ° C. is set to 100 in Examples 1 to 7. From this table, it can be seen that the films obtained in Examples 1 to 7 have a storage modulus at 200 ° C. which is larger than 50% of the storage modulus at 30 ° C.

That is, it can be seen from FIGS. 3 and 4 that the films obtained in Examples 1 to 7 satisfy Claims 1 and 2.
Furthermore, it can be seen from Table 1 that the film satisfying claim 1 is excellent in vacuum moldability and has excellent performance as a film for molding.

[0060]

As described above, since the reflector base material for lighting equipment of the present invention is formed of a specific plastic film molded body having excellent heat resistance, it has good surface smoothness and good reflection. Pre-treatment at the time of layer formation is unnecessary, and the molding temperature and the temperature at which it can be taken out after molding can be obtained at low cost by vacuum molding by using the proximity film. Because it is difficult, it is excellent in safety and handling. Here, the “film forming temperature” refers to a temperature at which the storage elastic modulus decreases to 10% with respect to the storage elastic modulus of 200 ° C. Further, “the temperature at which the resin can be taken out after cooling after molding” refers to a storage elastic modulus of 200 ° C. and a storage elastic modulus of 90 ° C.
% Refers to the temperature that has decreased.

Further, the reflector for lighting equipment of the present invention is obtained by forming a reflective layer by vapor deposition on a reflector base made of a specific plastic film molded article having excellent heat resistance and surface smoothness. It is not necessary to perform pretreatment such as resin coating before depositing the reflective layer,
It can be obtained at low cost by mass production, and is extremely lightweight and hard to break, and it does not generate degassing which is a practical obstacle when lighting the lamp, so it has excellent heat dissipation, safety and handling properties, as well as heat resistance It has high performance and high specularity and exhibits high quality performance, and can be advantageously used as a lamp reflector for a headlamp, a fog lamp or a large floodlight of an automobile.

[Brief description of the drawings]

FIG. 1 is a partially cutaway perspective view showing an example of a reflector base for lighting equipment of the present invention.

FIG. 2 is a partially cutaway side view showing an example of a reflector for lighting equipment of the present invention.

FIG. 3 is a graph showing dynamic viscoelasticity at 200 to 350 ° C. of an example.

FIG. 4 is a graph showing dynamic viscoelasticity at 25 to 350 ° C. of an example.

[Description of Signs] 1 Reflector base material for lighting equipment 2 Main body part 4 Outer flange part 6 Inner flange part 6a Inner flange 8 Reflector for lighting equipment 10 Reflective layer 12 Light bulb insertion port

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) F21S 8/10 F21V 7/22 Z 4J043 F21V 15/01 G02B 5/10 C 7/22 B29C 51/08 G02B 5/10 B29K 79:00 // B29C 51/08 B29L 31:30 B29K 79:00 C08L 79:08 B29L 31:30 F21M 3/02 A C08L 79:08 (72) Inventor Hideaki Machida Nihonbashi, Chuo-ku, Tokyo 1-5-6 Hommachi F-term in Toray DuPont Co., Ltd. (Reference) 2H042 DA02 DA04 DA11 DA21 DB06 DB08 DC02 DC08 DD05 DE04 3K042 AA08 AB02 AC02 BB01 4F071 AA60 AH07 BB02 BB03 BC01 BC07 4F100 AB10B AB24B AK49ABA02A GB32 GB48 JJ03 JK07A JK15 JL03 JL05 JN06B YY00A 4F208 AA40 AC03 AH17 MA01 MA05 MB01 MC01 MW02 4J043 QB26 QB31 SA06 SB02 TA14 TA22 TB02 UA121 UA122 UA131 UA132 UA141 UA142 UA151 UB021 UB121 UB122 UB131 UB152 UB172 UB402 VA011 VA021 VA022 VA031 VA032 VA051 VA062 XA16 YA06 YA08 ZA32 ZB11 ZB21 ZB52

Claims (9)

[Claims] 1. The difference between the temperature at which the storage modulus is reduced to 90% for the storage modulus at 200 ° C. and the temperature at which the storage modulus is reduced to 10% for the storage modulus at 200 ° C. is 5%.
A molding film having a temperature of 0 ° C. or lower and an imide bond in the molecular structure. 2. The molding film according to claim 1, wherein the storage elastic modulus at 200 ° C. is larger than 50% of the storage elastic modulus at 30 ° C. 3. The molding film according to claim 1, wherein the film has structural units represented by formulas (I) and (II). Embedded image Embedded image Wherein R ₁ is R ₂ is And any one of the groups represented by
The molar ratio of Y is from 100 to 20: 0 to 80. ] 4. The film according to claim 1, wherein the film has structural units represented by general formulas (III) and (IV). Embedded image Embedded image Wherein R ₃ is Any one selected from the groups represented by
Is from 100 to 20: 0 to 80. ] 5. A reflector substrate formed by using the film according to any one of claims 1 to 4 and subjecting the film to hot pressing or vacuum forming. 6. The reflector substrate according to claim 5, further comprising a main body, an outer flange, and an inner flange forming a reflection surface. 7. A reflector for lighting equipment, wherein a reflector is formed on the reflector substrate according to claim 5 by vapor deposition of a reflector. 8. The reflector for lighting equipment according to claim 7, wherein the reflector is aluminum or silver. 9. The reflector for lighting equipment according to claim 7, wherein the reflector is used as a lamp reflector of a vehicle.