JP2856984B2 - Metal coated film or sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal-coated film or sheet having good reflection efficiency and excellent heat resistance, weather (light) resistance and dimensional stability due to moisture absorption.

[0002]

2. Description of the Related Art From the viewpoint of energy saving, in recent years, the efficiency of lighting equipment has been improved by installing a metal-coated film or sheet called a reflector on the back side of lighting and reflecting light emitted to the back side. ing. In addition, a more natural indoor lighting is demanded, and natural light is guided from indoors to indoors using reflection of a metal-coated film or sheet. Conventionally, as such a metal-coated film or sheet, a metal-coated film or sheet of polyethylene terephthalate resin (hereinafter abbreviated as PET) has been used, but since the light transmittance of the PET film or sheet is low, it is used as a reflecting mirror. However, there is a problem in that the reflectance of light, which is an important characteristic of (1), is low, and furthermore, the temperature rises when installed behind the lighting, but there is a problem that the film or sheet gradually discolors.

[0003] As a material having excellent transparency, there is a stretched film or sheet of an acrylic resin. The metal-coated film or sheet has a good reflectance, but the Tg of the acrylic resin is low. There is a problem of shrinkage, and there is a problem that dimensions change due to a change in environmental humidity, and deformation occurs.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems, that is, it has good reflection efficiency,
An object of the present invention is to provide a metal-coated film or sheet having excellent heat resistance, weather (light) resistance, and dimensional stability due to moisture absorption.

[0005]

The present inventors have made intensive studies on solving the above problems, and as a result, surprisingly, a metal-coated film or sheet of a certain alicyclic polycarbonate resin has a light reflection efficiency. The present invention was found to be excellent in heat resistance, weather (light) resistance and moisture absorption dimensional stability, and completed the present invention.

[0006] An object of the present invention is composed of repeating units represented by the following general formula [1] to [3], one
The repeating unit represented by the general formula [1] (hereinafter referred to as “general formula
The repeating unit represented by [m] is abbreviated as the unit [m].
Is sometimes substantially equal to the total mole fraction (y + z) of the mole fraction (y) of the unit [2] and the mole fraction (z) of the unit [3]. The mole fraction (y) of [2] is in the range of 20 mol% or more and 50 mol% or less, which is achieved by a metal-coated film or sheet in which a thin metal film is formed on a film or sheet of an alicyclic polycarbonate resin. You.

[0007]

Embedded image However, in the general formula [1], n is 0, 1 or 2, and in the general formula [3], A is a divalent saturated aliphatic hydrocarbon group having 20 or less carbon atoms, a saturated alicyclic hydrocarbon. Or an aromatic hydrocarbon group.

The content (x) of the structural unit of the general formula [1] in the alicyclic polycarbonate resin (hereinafter abbreviated as alicyclic polycarbonate resin) which is the base resin of the metal-coated film or sheet of the present invention is as follows: Substantially 50 mol%
It is. The content (y) of the structural unit of the general formula [2] is 20
５０50 mol%, preferably 30-50 mol%. If the content is less than 20 mol%, the dimensional stability due to moisture absorption tends to decrease, which is not preferable. The content (z) of the structural unit of the general formula [3] is basically 50-y mol%.

The structural unit represented by the general formula [1] is specifically as follows. Particularly, when the structural unit is a repeating unit in which n is 1 or 2, the heat distortion temperature of the film or sheet is high, and thus it is preferable.

When n = 0

[0011]

Embedded image When n = 1

[0012]

Embedded image When n = 2

[0013]

Embedded image Further, specific examples of the structural unit of the general formula [3] include the following.

When A is a saturated aliphatic hydrocarbon

[0015]

Embedded image When A is a saturated alicyclic hydrocarbon

[0016]

Embedded image When A is an aromatic hydrocarbon

[0017]

Embedded image When A is a saturated alicyclic hydrocarbon or an aromatic hydrocarbon, the heat deformation temperature is high, which is preferable.

The structural units represented by the general formulas [1] and [3] may be only one type or a mixture of two or more types. Further, other structural units may be included as long as the effects of the present invention are not impaired. The substitution amount is usually 10 mol% or less.

The molecular weight of the alicyclic polycarbonate resin is preferably from 10,000 to 200,000 (in terms of polystyrene) in terms of number average molecular weight, more preferably from 20,000 to 200,000.
150,000 is preferred. If the molecular weight is low, the mechanical strength of the film or sheet of the present invention becomes insufficient, and if it is too high, film formation becomes difficult.

When the content of an alkali metal, an alkaline earth metal, titanium, zinc, lead, manganese, antimony, germanium or a compound of these metals in an alicyclic polycarbonate resin is 5 ppm or less in metal element concentration, It is less colored in a film forming process by extrusion molding and the like, and is particularly preferable for applications requiring low coloring. Conventionally, in the production of resins, these metals or metal compounds have been used as polymerization catalysts and used while being mixed in the resin, but the present inventors have found that these metals or metal compounds are alicyclic compounds used as substrates. cause coloration is a slightly film or sheet of the polycarbonate resin is present, found that these mixing can be improved coloration by substantially eliminated. This can be achieved by a novel method using a borate ester such as tetra-n-butylammonium tetraphenylboronate as a polymerization catalyst in the production of a resin, for example.

The alicyclic polycarbonate resin is prepared from a raw material such as an acid, an ester thereof, an acid chloride (the structural unit represented by the general formula [2] is phosgene), an acid anhydride, a diol, an ester thereof, or an alkoxide. Can be produced by a known method (Japanese Patent Laid-Open No. 2-6951).
No. 9). Examples of the catalyst include tetraalkyl orthotitanate, zinc acetate, antimony oxide, germanium oxide, various alkoxides such as potassium-t-butoxide and sodium methoxide, alkali metals such as lithium and sodium, and lithium hydride and sodium hydride. Known catalysts such as alkali metal hydrides can be used. Further, it can be produced by a novel method using a borate ester such as tetra-n-butylammonium tetraphenylboronate as a catalyst.

A resin modifier such as a plasticizer, a dye / pigment, an ultraviolet absorber, an antioxidant, and a lubricant is added to the alicyclic polycarbonate resin as long as the effects of the present invention are not impaired.
Alternatively, other resins can be blended.

As a method for forming the film or sheet, a known method can be adopted, but an extrusion method is preferred. As the melting temperature in the extrusion molding, a temperature in the range of usually 180 to 350 ° C is used, and particularly preferably 200 to 300 ° C is used.

The film or sheet may be stretched. In this case, there is an advantage that mechanical strength such as bending strength is improved and handleability is improved. In particular, those having an orientation release stress (ASTM D1504, hereinafter abbreviated as ORS) in the stretching direction of 3 to 30 kg / cm ² are preferable because the mechanical strength is improved. ORS is the internal stress caused by stretching, frozen in a stretched film or sheet.

For the stretching, a known method can be used. For example, from a temperature higher by 10 ° C. than the glass transition temperature (Tg) of the resin,
At a temperature between 50 ° C. and higher, stretching can be performed by a roll uniaxial stretching method, a tenter uniaxial stretching method, a simultaneous biaxial stretching method, a sequential biaxial stretching method, or an inflation method. Stretch ratio is 1.1
~ 3.5 times is preferably used.

Various methods can be applied as a method for forming a metal film on a film or a sheet of an alicyclic polycarbonate resin, but a dry process for forming a dry thin film, that is, vacuum deposition, sputtering, ion plating, ion assisted deposition , CVD and the like are preferred, and vacuum deposition and sputtering are particularly preferred.

As the metal, silver, aluminum, gold, platinum, chromium, and the like can be used, and silver and aluminum are preferable because of particularly high reflection efficiency. Usually, the thickness of the metal film is preferably from 500 to 1500 angstroms. For example, two or more kinds of metals may be laminated such that an indium metal film is laminated on the silver metal film for protection in order to improve the durability of the silver metal film.

Further, a thin film of a metal oxide or the like is vacuum-deposited on the metal thin film to protect the metal, or a synthetic resin paint or a scratch-resistant film is used to protect the metal thin film or the alicyclic polycarbonate resin film or sheet. The protective film may be formed with a paint or the like.

Although the thickness of the metal-coated film or sheet of the present invention is not essentially limited, it is generally 10 μm.
Those having a thickness of 5 to 5 mm, especially 20 μm to 1 mm, are usually used. If the thickness is too small or too large, it is generally not preferred in terms of productivity, handling, and the like.

The metal-coated film or sheet according to the present invention has high reflection efficiency, excellent durability and dimensional stability due to moisture absorption, and is a reflector used for improving the efficiency of lighting, and a reflector for guiding natural light into a room. In addition, it is also preferable for other uses, for example, as a decorative metal-coated film or sheet obtained by coloring a film or sheet.

The metal-coated film or sheet of the present invention may be used alone as a sheet, but in the case of a film, it is usually used after being adhered to another substrate, and an adhesive is applied to the metal thin film side. It is conveniently used in the form of a coating.

In the present invention, films having a thickness of less than 254 μm are distinguished from films and those having a thickness of 254 μm or more are distinguished from sheets.

The method for measuring characteristic values will be described below. Transparency: Evaluated by total light transmittance (ASTM D1003). -Colorimetry: Measured according to JIS K7105 (C light source,
10 ° field of view, transmission method). -Metal analysis: Analyzed by atomic absorption method. -Moisture absorption dimensional stability: After drying in an oven at 80 ° C for 48 hours, it was evaluated by dimensional change after leaving it in an environment of 23 ° C and 95% humidity for 7 days. -Number average molecular weight: Determined by GPC measurement in comparison with a standard polystyrene molecular weight (polystyrene conversion). Glass transition temperature (Tg): Measured by differential thermal analysis (in nitrogen, heating temperature 10 ° C./min). ORS: Measured according to ASTM D1504. -Folding strength: The object to be measured is made into a strip having a width of 15 mm.
The number of times of bending without breaking was determined by using a T-type folding fatigue tester {Bending speed 30 times / minute, manufactured by Toyo Seiki Seisaku-sho, Ltd.}. Reflection efficiency: Comparison was made based on the total reflectance of light having a wavelength of 400 nm. Heat and light resistance tests: A film or sheet surface was irradiated with a fluorescent lamp at a temperature of 75 ° C. for 30 days, and changes were observed.

[0034]

EXAMPLES The present invention will be specifically described with reference to examples.

Example 1 13.4 kg of trans-2,3-di (hydroxymethyl) -perhydro-1, 4: 5,8-dimethanonaphthalene
Using 12.9 kg of diphenyl carbonate and 0.7 g of tetra-n-butylammonium tetraphenylboronate as a catalyst, an alicyclic polycarbonate resin comprising a repeating structural unit represented by the general formula [4] was obtained by a melt condensation reaction. Obtained. The number average molecular weight of the obtained resin was 38,000, and Tg was 125 ° C.

This was extruded at an extrusion temperature of 250 ° C. to produce a 100 μm film.

[0037]

Embedded image Metal analysis of this film by atomic absorption spectrometry revealed that the content of each of the alkali metals, alkaline earth metals, titanium, zinc, lead, manganese, antimony, and germanium was 1 ppm or less.

Total light transmittance 93%, haze 0.3%
The colorimetric values of L * are 96.39 and a * is-
It was a colorless film excellent in transparency, with little coloration, 0.01 and b * of 0.19.

Using a vacuum evaporation apparatus (manufactured by Japan Vacuum Engineering Co., Ltd., SRC-10-D) on the produced film,
Silver was vacuum deposited at 4.5 × 10 ^-5 Torr and a deposition rate of 2 to 10 Å. The thickness of the deposited silver was 760 angstroms.

It is a beautiful silver vapor-deposited film and has a reflectance of 9
3%. The dried film was left in an environment of 23 ° C. and 90% humidity for 7 days, but the dimensional change was only about 0.01%.

The film was irradiated with a fluorescent lamp at a temperature of 75 ° C. for 30 days, and an endurance test was conducted. As a result, no change in the reflectance or the like was found in the film. Further, although the sample was heated to 120 ° C., no deformation was observed.

Comparative Example 1 A 100 μm thick PET film (Lumirror, manufactured by Toray Industries, Inc.) was vacuum-deposited in the same manner as in Example 1 to obtain a silver film having a thickness of 7 μm.
A 60 Å silver deposited film was prepared. The reflectivity was inferior to 86%, and irradiation with a fluorescent lamp at a temperature of 75 ° C. for 30 days reduced the reflectivity to 81%. The dried film was left in an environment of 23 ° C. and 90% humidity for 7 days, but the dimensional change was about 0.1%.

Example 2 In Example 1, trans-2,3-di (hydroxymethyl) -perhydro-1, 4: 5,8-dimethanonaphthalene was replaced by 13.4 kg of trans-2,3-di ( (Hydroxymethyl) -perhydro-1, 4: 5, 10:
6,9 One bird methanolate anthracene number average molecular weight by the same method except for using 17.4Kg is 62000
To produce an alicyclic polycarbonate resin comprising a repeating structure represented by the general formula [5], and extruded at an extrusion temperature of 260 ° C., to produce a film of 80 [mu].

[0044]

Embedded image Metal analysis of this film by atomic absorption spectrometry revealed that the content of each of the alkali metals, alkaline earth metals, titanium, zinc, lead, manganese, antimony, and germanium was 1 ppm or less.

The total light transmittance was 93%, and the colorimetric values were 96.31 for L *, -0.02 for a *, and 0.28 for b *. It was a colorless film having excellent properties.

A silver-coated film having a silver thickness of 780 angstroms was produced in the same manner as in Example 1. It was a beautiful silver vapor-deposited film, and the reflectance was 93%. 75 ℃
The film was irradiated with a fluorescent lamp at a temperature of 30 days for 30 days, and a durability test was carried out, but no change in reflectance or the like was found on the film. The dried film was left in an environment of 23 ° C. and 90% humidity for 7 days, but the dimensional change was only about 0.01%. Also, 1
Although heated to 50 ° C., no deformation was observed.

Example 3 In Example 1, trans-2,3-di (hydroxymethyl) -perhydro-1,4: 5,8-dimethanonaphthalene was replaced with 13.4 kg of trans-2,3-di ( (Hydroxymethyl) -perhydro-1, 4: 5,8-dimethanonaphthalene 6.7 kg and trans-2,3-di (hydroxymethyl) bicyclo [2.2.1] heptane 4.7 kg According to the method, the number average molecular weight of the structural unit represented by the general formula [6] is 48.
2,000 alicyclic polycarbonate resins, and 250
Extrusion molding was performed at an extrusion temperature of ° C to produce a 300 µ sheet.

[0048]

Embedded image Metal analysis of this sheet by atomic absorption spectroscopy revealed that alkali metals, alkaline earth metals, titanium, zinc, lead, manganese,
The content of antimony and germanium elements is 1p
pm or less.

The total light transmittance was 93%, and the colorimetric values were 96.36 for L *, -0.02 for a *, and 0.22 for b *. The colorless sheet was excellent in color.

In the same manner as in Example 1, a silver-coated sheet having a silver film thickness of 700 Å was produced. There was a beautiful silver vapor-deposited sheet, and the reflectance was 92%. A durability test was performed by irradiating a fluorescent lamp at a temperature of 75 ° C. for 30 days, but no change in reflectance or the like was found on the sheet. 2 dry sheets
After being left in an environment of 3 ° C. and 90% humidity for 7 days, the dimensional change was only about 0.02%. Further, although the sample was heated to 105 ° C., no deformation was observed.

Example 4 trans-2,3-di (hydroxymethyl) -perhydro-1, 4: 5,8-dimethanonaphthalene 13.4K
g, 9.0 kg of diphenyl carbonate, 3.5 kg of diphenyl terephthalate and 0.5 g of lithium hydride
Was used as a raw material, and the number average molecular weight of the structural unit represented by the general formula [7] was 35 in the same manner as in Example 1.
000 alicyclic-carbonate resins were produced.

[0052]

Embedded image An 80 μm film was prepared by extrusion. A silver-coated film having a thickness of 730 angstroms was produced in the same manner as in Example 1 as a film having excellent transparency.

It is a beautiful silver vapor-deposited film and has a reflectance of 9
1%. A durability test was performed by irradiating a fluorescent lamp at a temperature of 75 ° C. for 30 days, but no change in reflectance or the like was observed in the film.

Example 5 From the alicyclic polycarbonate resin used in Example 1, a sheet of about 400 μm was prepared by extrusion molding. This was subjected to simultaneous biaxial stretching using a pantograph-type stretching tester manufactured by Toyo Seiki Seisaku-Sho, Ltd. at 160 ° C. and a stretching ratio of 2 times each in the longitudinal and transverse directions to produce a stretched film having a thickness of 100 μ.

The metal of this film was analyzed by atomic absorption spectroscopy. Alkali metal, alkaline earth metal, titanium, zinc,
The contents of all elements of lead, manganese, antimony and germanium were 1 ppm or less.

The total light transmittance was 93%, and the colorimetric values were 96.37 for L *, -0.01 for a *, and 0.18 for b *. It was a colorless film having excellent properties. The ORS of this film was 8 kg / cm ² in both directions.

In the same manner as in Example 1, a silver-coated film having a silver film thickness of 700 Å was produced. It was a beautiful silver vapor-deposited film, and the reflectance was 93%. The folding strength was as strong as 50 times, and the handling strength was excellent. 75
A durability test was performed by irradiating a fluorescent lamp at 30 ° C. for 30 days, but no change in reflectance or the like was found in the film.

Example 6 The film produced in Example 1 was subjected to aluminum vacuum evaporation in the same manner as in Example 1. The thickness of the deposited film was 810 angstroms.

A beautiful aluminum vapor-deposited film,
The reflectance was 81%. In addition, no warpage due to a change in humidity was observed. Dry film at 23 ° C, 90%
It was left for 7 days in a humid environment, but the dimensional change was about 0.0
Only 1%.

Comparative Example 2 A 100 μm thick PET film (Lumirror manufactured by Toray Industries, Inc.) was subjected to aluminum vacuum evaporation in the same manner as in Example 1. The thickness of the deposited film was 800 angstroms. The reflectivity was inferior to 71%. 2 dry films
After being left in an environment of 3 ° C. and 90% humidity for 7 days, the dimensional change was about 0.1%.

[0061]

According to the present invention, a reflector having excellent reflectance, heat resistance, weather (light) resistance and dimensional stability due to moisture absorption can be obtained by using a polycarbonate resin metal-coated film or sheet having an alicyclic structural unit. This reflector is suitable for use in improving lighting efficiency by being installed behind lighting equipment, for guiding natural light, and for decoration.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) B32B 1/00-35/00 G08G 63/64 C08G 64/02

Claims (5)

(57) [Claims] 1. A repeating unit represented by the following general formula [1] , comprising repeating units represented by the following general formulas [1] to [3] :
The unit molar fraction (x) is a repeating unit represented by the general formula [2].
Unit mole fraction (y) and repetition represented by general formula [3]
Total mole fraction of the mole fraction of units (z) (y + z) is substantially equal, the formula the molar fraction of the repeating unit represented by [2] (y) is 50 mol% or less than 20 mol% A metal-coated film or sheet in which a thin metal film is formed on a film or sheet made of an alicyclic polycarbonate resin within the above range. Embedded image However, in the general formula [1], n is 0, 1 or 2, and in the general formula [3], A is a divalent saturated aliphatic hydrocarbon group having 20 or less carbon atoms, a saturated alicyclic hydrocarbon. Or an aromatic hydrocarbon group. 2. The metal-coated film or sheet according to claim 1, wherein the alicyclic polycarbonate resin has a number average molecular weight of 10,000 to 200,000. 3. The content of an alkali metal, an alkaline earth metal, titanium, zinc, lead, manganese, antimony, germanium or a compound of these metals in an alicyclic polycarbonate resin is 5 ppm or less in metal element concentration. 3. The metal-coated film or sheet according to claim 1. 4. The metal-coated film or sheet according to claim 1, wherein the alicyclic polycarbonate resin film or sheet is stretched. 5. A thin metal film made of silver or aluminum .
The metal-coated film or sheet according to claim 1, which is a membrane .