JPH06255058A - Polyester laminated film - Google Patents

Abstract

PURPOSE:To provide excellent processability and to extremely reduce change of an external appearance due to a sunlight after processing by setting yellowing after irradiating by the use of a mercury lamp for a specific time to a specific value in a laminated film laminated with polyester containing specific ingredient and heat sealable polyester and having substantially no orientation. CONSTITUTION:A polyester A containing 5-30mol% of long chain aliphatic dicarboxylic acid group having 15C or less alkylene group as acid ingredient and 80mol% of diol ingredient as constituent containing mainly 1,4-butanediol residue, and a heat sealable polyester B containing 5-30mol% of long chain aliphatic dicarboxylate residue having 16C or more alkylene group as acid ingredient, 80mol% of diol ingredient as constituent containing mainly 1,4- butanediol residue are laminated. The polyester laminated film is substantially a film having no orientation, and not particularly oriented. Thickness ratio, laminated structure of the polyesters A, B are so set that yellowing after it is irradiated by the use of a mercury lamp for 100 hours is set to 3.0 or less.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester laminated film having flexibility, excellent transparency, heat sealability and weather resistance.

[0002]

2. Description of the Related Art As a flexible polyester base material, a hard segment such as polyethylene terephthalate is copolymerized with a long chain aliphatic dicarboxylic acid such as dodecane dicarboxylic acid or dimer acid or a long chain branched aliphatic dicarboxylic acid ( JP-B-42-8709), or terpolymerization of terephthalic acid and dimer acid as an acid component and 1,4 butanediol and ethylene glycol as an alcohol component (JP-A-3-231930). Has been done.

[0003]

However, in the method of simply copolymerizing a long-chain aliphatic dicarboxylic acid or a long-chain branched aliphatic dicarboxylic acid with polyethylene terephthalate, the obtained sheet changes with time or is bent during processing. There is a problem that the appearance changes due to whitening caused by the above. Further, the sheet obtained from a terephthalic acid and dimer acid as an acid component and a quaternary copolymer of 1,4 butanediol and ethylene glycol as an alcohol component has poor weather resistance,
In particular, there has been a problem that the color change such as yellow is large and the appearance of the processed product is impaired.

An object of the present invention is to solve the above problems and to obtain a film excellent in heat sealability and appearance after processing.

[0005]

A polyester laminated film of the present invention which meets this object has 15 carbon atoms as an acid component.
Polyester A having 5 to 30 mol% of the following long-chain aliphatic dicarboxylic acid residue having an alkylene group and 80 mol% or more of the diol component having 1,4-butanediol residue as a main constituent component, and heat-sealing property A substantially non-oriented laminated film formed by laminating polyester B,
The yellowing Δb 100 hours after irradiation with a mercury lamp is 3.0 or less.

The polyester A in the polyester laminated film of the present invention contains 5 to 5 long chain aliphatic dicarboxylic acid residues having an alkylene group having 15 or less carbon atoms as an acid component.
30 mol%, 80 mol% or more of the diol component is 1,
The main component is a 4-butanediol residue. As the acid component constituting the polyester A, terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, benzophenone dicarboxylic acid, and ester formation thereof as aromatic dicarboxylic acid components Examples thereof include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and ester-forming derivatives thereof. These aromatic dicarboxylic acid components may be used alone or in combination of two or more.

Further, the polyester A contains 5 to 30 mol% of a long-chain aliphatic dicarboxylic acid residue having an alkylene group having 15 or less carbon atoms as an acidic component in order to improve weather resistance and bending whitening property. Contains. In particular, 5 to 20 mol% is preferable for improving weather resistance and bending whitening property.

The long-chain aliphatic dicarboxylic acid components used include oxalic acid, malonic acid, succinic acid, glutaric acid,
Adipic acid, pimelic acid, suberic acid, azelaic acid,
Examples include straight-chain aliphatic dicarboxylic acids such as sebacic acid, undecadioic acid, dodecadioic acid, brassic acid, tetradecadioic acid, pentadecadioic acid, hexadecadioic acid, and heptadecadioic acid, and their ester-forming derivatives. . In particular, adipic acid, sebacic acid, dodecadioic acid and the like can be preferably used in order to improve the reactivity of the polymer, the weather resistance, the bending whitening property and the like.

Polyester A has a glycol component of 80 mol% or more as a 1,4-butanediol component, and when it is 85 mol% or more, it changes with time.
It is preferable in that it does not cause thermal whitening during processing. As the other diol component, one or more glycol components selected from aliphatic, alicyclic and aromatic diols having 10 or less carbon atoms may be contained.

Further, the polyester A may contain a long-chain aliphatic dicarboxylic acid residue having an alkylene group having 16 or more carbon atoms within a range that does not impair the characteristics due to recovery of raw materials.

The polyester A of the present invention has a difference (Tc) between the cold crystallization temperature (Tcc) and the glass transition temperature (Tg).
ΔTcg defined by c-Tg) is preferably 50 ° C. or lower, more preferably 30 ° C. or lower, particularly preferably 2
It is 5 ° C or lower. If ΔTcg is too large, problems such as the tensile Young's modulus increase with time occur. Also, T
When g is 10 ° C. or less, flexibility is excellent, which is preferable.

The heat-sealable polyester B of the present invention preferably has a melting point of 120 to 240 ° C. in terms of heat sealability, and particularly at 140 to 220 ° C., not only self-heat adhesiveness but also polyvinyl chloride and polyethylene. It is preferable because the thermal adhesion to other materials is improved.

As the polyester B, as an acid component,
Terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl ether dicarboxylic acid,
Examples thereof include aromatic dicarboxylic acid components such as benzophenone dicarboxylic acid, aliphatic dicarboxylic acid components such as sebacic acid and dimer acid, and ester-forming derivatives thereof. The glycol component is at least one glycol component selected from aliphatic, alicyclic and aromatic diols having 10 or less carbon atoms, preferably 1,4-butanediol and ethylene glycol. For example, isophthalic acid-copolymerized polybutylene terephthalate and dimer acid-copolymerized polybutylene terephthalate can be preferably used.

Particularly, in order to improve aging and heat sealability, the polyester B contains 5 to 30 long-chain aliphatic dicarboxylic acid residues having an alkylene group having 16 or more carbon atoms.
Mol%, diol component 80 mol% or more 1,4-
A polyester having a butanediol residue as a main constituent is preferable.

The long-chain aliphatic dicarboxylic acid having an alkylene group having 16 or more carbon atoms includes, for example, octadecadionic acid, nonadecadionic acid, ecosandioic acid, heneicosanedionic acid, docosandionic acid, tricosandionic acid,
Tetracosandionate, pentacosandionate, hexacosandionate, heptacosandionate, octacosandionate, nonacosandionate, triacontandionate and their ester-forming derivatives, having 10 to 10 carbon atoms
The dimer acid obtained by dimerizing 25 unsaturated fatty acids, its hydrogenated body, its ester forming derivative, etc. can be mentioned. Particularly, those containing a dimer acid component are preferable because they are excellent in transparency and heat sealability.

Here, the intrinsic viscosity of the polyester A or B preferably used is 0.5 to 2.0 dl /
g is preferable, and more preferably 0.7 to 1.8 dl /
When it is g, both the film forming property and the mechanical properties are good, which is desirable.

The polyester laminated film of the present invention needs to have a yellowing Δb of 3.0 or less after 100 hours of irradiation with a mercury lamp, and preferably 2.0 or less causes a change in color tone after processing. It is desirable because it has little appearance and is stable.

In order to impart such weather resistance, it is preferable that the thickness composition ratio of the polyester A and the polyester B of the laminated film is 1/500 to 1/2, and the heat-sealing property, folding whitening property, and weather resistance. 1/3 from the sex balance
It is desirable that it is 00 to 1/3. The laminated structure of the laminated film is polyester A / polyester B, polyester B / polyester A / polyester B.
Etc., and may be a laminate of three or more layers.

The polyester laminated film of the present invention having such a laminated constitution is a substantially non-oriented film and is not particularly stretched.

The total thickness of the film is 1-1000 μm.
m, preferably 10 to 500 μm, particularly preferably 1
It is 5 to 300 μm.

The polyester laminated film of the present invention has a tensile Young's modulus of 10 to 200 kg / in terms of processability.
The range of mm ² is desirable, and preferably 30 to
It is in the range of 120 kg / mm ² .

The haze of 100 μm equivalent of the polyester laminated film of the present invention is preferably 0.1 to 20% in order to improve the transparency and the appearance after processing, and more preferably 0.2 to It is preferably set to 10%.

Furthermore, in each layer of the polyester laminated film of the present invention, a crystal nucleating agent, an antioxidant, a coloring preventing agent, a pigment, a dye, an ultraviolet absorber, a release agent, and
Lubricants, flame retardants, antistatic agents, inorganic and / or organic particles and the like can be added. In particular, in order to provide slipperiness, it is preferable that the polyester A and / or B contain 0.01 to 5% by weight of inorganic particles such as silicon oxide having an average particle diameter of about 0.01 to 10 μm with respect to each polyester.

Next, the method for producing the flexible laminated polyester film of the present invention will be explained, but it is not limited to this. After drying the polyesters A and B, the polyester A layer resin and the B layer resin are melt-extruded by using different extruders, respectively, and then A / B or B / A /
Stack so as to be B.

The laminated body composed of the laminated polyesters A and B as a basic constitution is melt extruded into a sheet or a cylinder, and is rapidly cast by application of static electricity to obtain a laminated polyester film. The film thus obtained may be subjected to corona discharge treatment, coating, etc., if necessary.

[0026]

EXAMPLES The present invention will now be described in more detail with reference to examples. The characteristics in the examples were measured as follows. (1) Intrinsic viscosity (IV) It measures at 25 degreeC using o-chlorophenol as a solvent. The unit is dl / g.

(2) Melting point (Tm), glass transition temperature (T
g), cold crystallization temperature (Tcc), ΔTcg Determined using a differential scanning calorimeter DSC2 (manufactured by Perkin Elmer). It was kept melted at 280 ° C. for 5 minutes under a nitrogen stream, and then cooled using liquid nitrogen. When the sample thus obtained was heated at a temperature rising rate of 10 ° C./min, the change in specific heat due to the transition from the glass state to the rubber state was read, and this temperature was taken as the glass transition temperature (Tg). . The exothermic peak temperature associated with crystallization was defined as the cold crystallization temperature (Tcc), and the endothermic peak temperature associated with crystal melting was defined as the melting point (Tm). Further, ΔTcg is defined by the following formula. ΔTcg = Tcc-Tg

(3) Mechanical Properties Regarding Young's modulus, breaking strength and breaking elongation, ASTM
-Measure according to D-882-81 (method A).

(4) Haze (H ₁₀₀ ) converted to 100 μm Measured according to JIS-K-6714, and calculated by the following formula. H ₁₀₀ (%) = H × 100 / d where H is the measured value of haze (%), and d is the film thickness (μm) of the haze measurement part.

(5) Weather resistance (yellowing Δb) Difference in color change of film about 100 hours after irradiation with a mercury lamp, Δ
The b value is obtained from a color difference meter.

(6) Processing suitability and appearance change Vinyl chloride film with white and black colors and about 180 ° C.,
Heat seal at 3 kg / mm ² , heating time 5 seconds, heat seal strength and whitening property, and film after sealing is 90
The suitability for use was judged by visually measuring the bending whitening property after repeated bending and the appearance change after being left indoors for about 3 months.

Example 1 Polybutylene terephthalate / dodecanedicarboxylic acid (hereinafter abbreviated as D) copolymer (D component amount = 2) was used for the core layer (A layer).
0 mol%, ΔTcg = 11.3 ° C., melting point = 190 ° C., I
V = 0.80) resin and a polyethylene terephthalate / hydrogenated dimer acid (hereinafter abbreviated as DA) copolymer (hereinafter abbreviated as DA) containing 0.1% by weight of silicon oxide particles (average particle diameter 2 μm) in the surface layer (B layer). DA component amount = 17 mol%, melting point = 190
C., IV = 0.80) are melt-extruded using separate extruders, and B / A / B (lamination ratio 1:
It was laminated in 3 layers so as to be 8: 1) and extruded into a sheet.

As shown in Table 1, the thus obtained film had a Young's modulus of 52 kg / mm ² and a haze of 0.
9. The yellow change Δb after irradiation with the mercury lamp for 100 hours was 1.0. Regarding workability and appearance, the heat sealing force was 1.5 kg / cm, and the whitening of the seal part and
A film without folding whitening and having no change in appearance after 3 months was obtained.

Example 2 Polyester B in Example 1 was replaced with polyethylene terephthalate / isophthalic acid (hereinafter abbreviated as I) copolymer (I
Component amount = 35 mol%, melting point 160 ° C., IV = 0.78)
A film was obtained in the same manner as in Example 1 except that a resin was used. As shown in Table 1, Young's modulus was 50 kg / m.
m ² , haze 1.0, yellow change Δb after irradiation with a mercury lamp for 100 hours was 1.1, heat sealing force was 0.8 kg, whitening of the seal part and bending whitening did not occur, and appearance also changed after 3 months. There wasn't.

Comparative Examples 1 to 3 Each single film film shown in Table 2 was formed into a film in the same manner as in Example 1. The properties of the film thus obtained are summarized in Table 1, but either the processability or the appearance is poor,
No film satisfying all of them was obtained.

[0036]

[Table 1]

[0037]

[Table 2]

[0038]

According to the polyester laminated film of the present invention, since it is a non-oriented film of the specific polyesters A and B with low yellowing, it is not only excellent in processability but also excellent in processability.
The change in appearance due to sunlight after processing can be extremely reduced, and it can be suitably used, for example, as a sheet to be attached to a decorative plate, a wall, or the like.

Claims (2)

[Claims] 1. A long-chain aliphatic dicarboxylic acid residue having an alkylene group having 15 or less carbon atoms as an acid component is 5 to 30 mol% and 80 mol% or more as a diol component is mainly a 1,4-butanediol residue. A substantially non-oriented laminated film obtained by laminating polyester A as a constituent and heat-sealable polyester B, which is irradiated with a mercury lamp.
A polyester laminated film having a yellowing Δb of 3.0 or less after 0 hour. 2. The heat-sealable polyester B comprises:
5-30 mol% of a long-chain aliphatic dicarboxylic acid residue having an alkylene group having 16 or more carbon atoms as an acid component, and 80 mol% or more of a diol component have a 1,4-butanediol residue as a main constituent component. The polyester laminated film according to claim 1.