JPH06271747A - Polyester-based stretch label - Google Patents

Abstract

PURPOSE:To obtain a stretch label which has high surface tension, low haze, and low residual strain, and enables distinct printing by using a specific copolyester as the material. CONSTITUTION:This stretch label is produced by using, as the material, at least one copolyester selected from a copolyester (a) produced from a dicarboxylic acid component consisting mainly of an alicyclic dicarboxylic acid and a diol component consisting mainly of an alicyclic diol, a copolyester (b) produced from a dicarboxylic acid component consisting mainly of an arom. dicarboxylic acid and a diol component consisting mainly of a satd. aliph. diol, and a copolyester (c) produced from a satd. aliph polylactone and a copolyester produced from a diol component consisting mainyl of an arom. diol and a dicarboxylic acid component consisting mainly of a satd. aliph. dicarboxylic acid.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester stretch label.

[0002]

2. Description of the Related Art A polyethylene film is printed on its back side, and a label formed by sticking two end faces together and expanding the diameter into a column is used to insert an article into the label, and to utilize the elasticity of the label. Stretch labels attached to the outside of an article have been conventionally known. For example: 1) A stretch label obtained by melting and extruding low-density polyethylene with an extruder, and then rapidly cooling it so that the thickness accuracy is within ± 7% of the average wall thickness (JP-A-58-144883). 2) Stretch label composed of two kinds of linear polyethylenes having short chain branches having different densities (JP-A-61-1)
No. 15944) has been proposed.

However, the stretch labels 1) and 2) are
Due to the high crystallization rate of polyethylene, spherulites are formed during film formation. For this reason, there is a problem that the obtained film has a large haze, and the stretch label obtained by printing becomes unclear. Furthermore, since the surface tension of the polyethylene film is as small as 31 dyn / cm, the adhesion of the ink is poor, and in order to improve this, it was necessary to increase the surface tension by a method such as corona discharge treatment. However, the surface tension of the label subjected to corona discharge treatment decreases with time, and it is difficult to perform the corona discharge treatment uniformly, and the surface tension of the label varies.
There are drawbacks such as missing printing and ink transfer to the rolls of the printing machine, which stains the equipment and products.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems and to provide a polyester stretch label having high label surface tension, low fog and residual strain, and capable of clear printing. It is in.

[0005]

The dicarboxylic acid component of alicyclic hydrocarbon used in the present invention is a compound having an aromatic ring such as cycloparaolefin and two carboxylic acid groups, and is, for example, Examples of the dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cycloheptanedicarboxylic acid and 1,3-cycloheptanedicarboxylic acid. These may be used alone or in combination of two or more.

The diol component of the alicyclic hydrocarbon used in the present invention is a dicarboxylic acid of cycloparaolefin, such as 1,4-cyclohexanediol, 1,3-cyclohexanediol and 1,4-cycloheptane. Diol, 1,
Examples include 3-cycloheptanediol. These may be used alone or in combination of two or more.

The aromatic dicarboxylic acid component used in the present invention is a compound having an aromatic ring such as benzene and two carboxylic acid groups, and examples thereof include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, Examples thereof include anthracene dicarboxylic acid, diphenylene dicarboxylic acid, telephenylene dicarboxylic acid, diphenylyl ether dicarboxylic acid, and phenylene diacetic acid. These may be used alone or in combination of two or more.

The saturated aliphatic dicarboxylic acid component used in the present invention is a compound having two carboxylic acid groups at both molecular terminals of a saturated aliphatic hydrocarbon, such as oxalic acid, malonic acid and succinic acid. , Glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sepasic acid and the like. The carbon number (including the carbon of the carboxylic acid group) of the saturated aliphatic dicarboxylic acid component is preferably 2 to 8 because the moldability of the film deteriorates as the length increases. These may be used alone or in combination of two or more.

The aromatic diol component used in the present invention is a compound having an aromatic ring such as benzene and two hydroxyl groups, and examples thereof include hydroquinone, resorcin, xylene glycol, dihydroxydiphenyl and dihydroxy-p-terphenyl. , Bisphenol-A, alkylene oxide addition bisphenol-A, and the like.
These may be used alone or in combination of two or more.

The saturated aliphatic diol component used in the present invention is a saturated aliphatic hydrocarbon having two hydroxyl groups at both molecular terminals.
A compound having methylene glycol, ethylene glycol, propylene glycol, trimethylene glycol, neopentyl glycol, butanediol,
Examples include hexanediol. The carbon number of the saturated aliphatic diol component is preferably 1 to 8 because the moldability of the film deteriorates as the carbon number increases. These may be used alone or in combination of two or more.

The aliphatic polylactone used in the present invention is a compound obtained by ring-opening polymerization of an alicyclic ester containing an ester functional group in the ring.
Examples thereof include caprolactone, poly δ-valerolactone, poly β-propiolactone, and the like. When the degree of polymerization of the aliphatic polylactone component is low, the flexibility of the obtained film is low, and when it is high, the transparency of the obtained film is low. These may be used alone or in combination of two or more.

The aliphatic polyether used in the present invention is a linear polymer containing an ether bond in the main chain,
For example, polyoxymethylene, polyoxyethylene,
Examples thereof include polyoxypropylene, polyoxy (trimethylene oxide), polyoxybutylene and polyoxy (tetratrimethylene oxide). When the degree of polymerization of the aliphatic polyether component is low, the flexibility of the obtained film is low, and when it is high, the transparency of the obtained film is low. These may be used alone or in combination of two or more.

The polyester stretch label of the present invention comprises: 1) Copolymerization of a dicarboxylic acid component mainly composed of an alicyclic hydrocarbon dicarboxylic acid component and a diol component mainly composed of an alicyclic hydrocarbon diol derivative. 2) Copolymer of 2) dicarboxylic acid component mainly composed of aromatic dicarboxylic acid component and saturated aliphatic dicarboxylic acid component and diol component mainly composed of saturated aliphatic diol, 3) saturated aromatic dicarboxylic acid component A copolymer of a dicarboxylic acid component mainly composed of an aliphatic dicarboxylic acid component and a diol component mainly composed of a saturated aliphatic diol, 4) a diol component mainly composed of an aromatic diol component,
A copolymer of a saturated aliphatic dicarboxylic acid-based dicarboxylic acid component and a saturated aliphatic polylactone;
And 5) one or more selected from the group consisting of a copolymer of a dicarboxylic acid component mainly containing an aromatic dicarboxylic acid component, a diol component mainly containing a saturated aliphatic diol, and a saturated aliphatic polyether. Of polyester copolymer.

When the amount of the aromatic dicarboxylic acid component in the dicarboxylic acid when the diol component is mainly a saturated aliphatic diol is small, the moldability of the film is poor, and when it is large, the flexibility of the obtained film is lowered. For 5
95 mol% is preferable, and 20-80 mol% is more preferable.

When the amount of the aromatic diol component in the diol when the dicarboxylic acid component is mainly a saturated aliphatic dicarboxylic acid is small, the moldability of the film is deteriorated, and when the amount is large, the flexibility of the obtained film is deteriorated. For 5
95 mol% is preferable, and 20-80 mol% is more preferable.

When a saturated aliphatic polylactone is copolymerized with a copolymer of a dicarboxylic acid component mainly containing an aromatic dicarboxylic acid component and a diol component mainly containing a saturated aliphatic diol, the amount of the saturated aliphatic polylactone is When the amount is small, the moldability of the film is deteriorated, and when the amount is large, the flexibility of the obtained film is decreased.
Mol% is preferable, more preferably 20-80 mol%
Is.

When the dicarboxylic acid component having the aromatic dicarboxylic acid component as the main component, the diol component having the saturated aliphatic diol as the main component and the saturated aliphatic polyether are copolymerized, the amount of the saturated aliphatic polyether is small. If so, the flexibility of the obtained film decreases, and if it increases, the moldability of the film deteriorates, so 0.5 to 10 mol% in the total copolymer is preferable.

In the stretch label of the present invention, a film obtained by melt-extruding the above polyester-based copolymer by a conventionally known method such as a T-die method or a tubular method may be subjected to printing such as gravure printing if necessary. After the application, when the obtained film is a flat film, the label formed by sticking two films and pasting them together is expanded by a cylinder and held,
By inserting the article into the inside and releasing the expansion of the label, the elasticity of the label is used to install the label on the outside of the article. The bonding method is not particularly limited, and any conventionally known method such as heat sealing, solvent bonding, bonding with an adhesive, or the like can be used.

[0019]

EXAMPLES The present invention will be described in more detail by way of examples.

Example 1 Cyclohexanedicarboxylic acid 1282 g, cyclohexanedimethanol 1862 g, tetrabutoxytitanium 5
g, 1,3,5-trimethyl-2,4,6-tris (3,5-3-t-butyl
40 g of -4 hydroxybenzyl) benzene was supplied to a reactor purged with nitrogen and mixed, and then reacted at 200 ° C. for 2 hours, then heated to 250 ° C., depressurized to 2 mmHg, and subjected to polycondensation reaction for 1 hour. A polyester copolymer having a dicarboxylic acid component of 100 mol% cyclohexanedicarboxylic acid component and a diol component of 100 mol% cyclohexanedimethanol component was obtained. The polyester-based copolymer thus obtained was used at a temperature of 250 ° C. and a thickness of 60 using a T-die extruder.
A film of μm was obtained. The obtained film was subjected to the following tests.

Surface tension of the evaluation film The obtained film was measured according to the method of JIS K 6768. Haze value of film The haze value of the obtained film is measured according to JIS K 7105.
The measurement was performed according to the method of. Residual strain The obtained film was cut into a strip shape with a width of 15 mm so that the distance between the marked lines was 100 mm, and the film was pulled at a pulling speed of 500 mm / min until the distance between the marked lines became 130 mm with a tensile tester, then immediately 500 mm / min. Unloading was performed at the speed of, and the elongation of the test piece when the load became 0 was measured, and the residual strain after 30% elongation was taken. Appearance of stretch label Gravure printing was applied to the back surface of the obtained film, the film was folded into a tube shape with a folding diameter of 105 mm, seams were joined with an adhesive, and cut to 130 mm to obtain a stretch label.
The stretch label obtained is expanded by 20% in a cylinder to a diameter of 7
It was attached to a 0 mm cylindrical polyethylene terephthalate copolymer bottle, loosened, and the sharpness of printing was visually determined.

Example 2 1183 g of dimethyl terephthalate, 921 g of dimethyl sepasate, 2544 g of 1,4-butanediol, 10 g of tetrabutoxytitanium, 1,3,5-trimethyl-2,4,6-tris (3,5-3 -t-Butyl-4hydroxybenzyl) benzene 40
g in the same manner as in Example 1, the dicarboxylic acid component being 60 mol% terephthalic acid and 40 mol% sebacic acid, and the diol component being 100 mol% 1,4-butanediol.
A polyester-based copolymer of A film was obtained from the obtained polyester-based copolymer in the same manner as in Example 1 and subjected to the above-mentioned tests. Further, a stretch label was obtained in the same manner as in Example 1 except that the folding diameter was 90 mm, and the stretch label was mounted on a polyethylene terephthalate copolymer bottle, and the looseness and the sharpness of printing were visually determined.

Example 3 Composition 1 comprising 65 mol% of polybutylene terephthalate copolymer (manufactured by Polyplastics Co., trade name: Duranex 700FP) and 35 mol% of ε-caprolactone
00 parts by weight and 0.01 parts by weight of tetrabutyl titanate were fed into a reaction vessel in which nitrogen gas was replaced and mixed,
The reaction was conducted at 240 ° C. for 2 hours to obtain a polyester copolymer having a polyethylene terephthalate component of 65 mol% and a poly ε-caprolactone component of 35 mol%. A film was obtained from the obtained polyester-based copolymer in the same manner as in Example 1 and subjected to the above-mentioned tests. Fold diameter of 90m
A stretch label was obtained in the same manner as in Example 1 except that m was set, and the stretch label was attached to a polyethylene terephthalate copolymer bottle, and looseness and the sharpness of printing were visually determined.

Example 4 1972 g of dimethyl terephthalate, 2544 g of 1,4-butanediol, 729 g of polyoxy (tetratrimethylene oxide) having an average degree of polymerization of 20, and tetrabutoxytitanium 1
0 g and 40 g of 1,3,5-trimethyl-2,4,6-tris (3,5-3-t-butyl-4hydroxybenzyl) benzene were reacted in the same manner as in Example 1, and the dicarboxylic acid component was terephthalic acid. A polyester-based copolymer comprising 100 mol% of acid, 95 mol% of 1,4-butanediol and 5 mol% of polyoxy (tetratrimethylene oxide) was obtained. A film was obtained from the obtained polyester-based copolymer in the same manner as in Example 1 and subjected to the above-mentioned tests. Further, a stretch label was obtained in the same manner as in Example 1 except that the folding diameter was 90 mm, and the stretch label was mounted on a polyethylene terephthalate copolymer bottle, and the looseness and the sharpness of printing were visually determined.

[0025]

[Table 1]

Comparative Example 1 A polybutylene terephthalate-based copolymer (manufactured by Polyplastics Co., trade name: Duranex 700FP) was extruded in the same manner as in Example 1 to obtain a film, which was subjected to the above-mentioned tests. Further, a stretch label was obtained in the same manner as in Example 1 except that the folding diameter was 90 mm, and the stretch label was mounted on a polyethylene terephthalate copolymer bottle, and the looseness and the sharpness of printing were visually determined.

Comparative Example 2 Ethylene / vinyl acetate copolymer having a vinyl acetate content of 6% by weight (trade name: Ultrasen UE51 manufactured by Tosoh Corporation)
0F) was extruded in the same manner as in Example 1 to obtain a film,
It was subjected to the above-mentioned tests. Examples 1-4, Comparative Examples 1-
The results of No. 2 are also shown in Table 1.

[0028]

EFFECTS OF THE INVENTION Since the stretch label of the present invention is composed of the above polyester-based copolymer, the stretch label of the polyester has high surface tension, little clouding and residual strain, and enables clear printing. Can be obtained.

Claims (1)

[Claims] 1. A copolymer of a dicarboxylic acid component mainly composed of an alicyclic hydrocarbon dicarboxylic acid component and a diol component mainly composed of an alicyclic hydrocarbon diol derivative, and 2) an aromatic dicarboxylic acid. A copolymer of a dicarboxylic acid component mainly composed of an acid component and a saturated aliphatic dicarboxylic acid component and a diol component mainly composed of a saturated aliphatic diol, 3) mainly composed of an aromatic dicarboxylic acid component and a saturated aliphatic dicarboxylic acid component A copolymer of a dicarboxylic acid component having the following formula and a diol component having a saturated aliphatic diol as a main component, 4) a diol component having an aromatic diol component as a main component,
A copolymer of a saturated aliphatic dicarboxylic acid-based dicarboxylic acid component and a saturated aliphatic polylactone;
And 5) at least one selected from the group consisting of a copolymer of a dicarboxylic acid component mainly containing an aromatic dicarboxylic acid component, a diol component mainly containing a saturated aliphatic diol and a saturated aliphatic polyether. A polyester stretch label characterized by comprising a polyester copolymer.