JP2002264210A - Heat shrinkable aromatic polyester tube and product made of inorganic material having surface covered with the tube - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat shrinkable aromatic polyester tube having a utility value of a general purpose electrical insulation material, a heater-coating material or the like having excellent heat resistance when an electronic component is mounted on a printed board after the component is covered with the polyester tube, excellent shrinkage characteristics and openability. SOLUTION: A stretched tube is obtained by stretching an unstretched tube made of a resin composition mainly containing a thermoplastic resin (component A) which contains an aromatic polyester resin of 70 wt.% or more. The stretched tube is the heat shrinkable aromatic polyester tube having (1) a crystallinity when the stretched tube is heat treated at 105 deg.C for 30 min in the air of 16% or less, and (2) a peak temperature of a melting point of the aromatic polyester resin obtained by a DSC measurement according to JIS K 7121 of 220 deg.C or higher.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-shrinkable aromatic polyester tube formed from a resin composition mainly containing a thermoplastic resin containing 70% by weight or more of an aromatic polyester resin, and to its use. More specifically, a stretched tube obtained by stretching an unstretched tube, wherein the stretched tube has a crystallinity under a specific heat treatment condition of a specific value or less, and a melting point peak of a specific temperature or more. The present invention relates to a heat-shrinkable aromatic polyester tube having the same. Furthermore, when coated on electronic components, etc., it has excellent shrinkage characteristics and opening properties, and also has a good coated state even when exposed to extremely high temperatures in surface mounting processing of electronic components, for example, in a solder reflow furnace. The present invention relates to a heat-shrinkable aromatic polyester tube excellent in heat resistance capable of retaining the heat resistance, and an inorganic material product whose surface is covered with the tube.

[0002]

2. Description of the Related Art Heretofore, as a heat-shrinkable tubular electrical insulating material used for capacitor coating, a heat-shrinkable tube mainly made of polyvinyl chloride has been widely used. 2. Description of the Related Art In recent years, electronic components such as capacitors have often been used in high-temperature states due to their high densities in order to reduce the weight and size of products. Fields with high operating temperatures, such as automotive electrical components, are also rapidly expanding. For this reason, good heat resistance is also required for heat-shrinkable tubes.
Heat resistance of a heat-shrinkable tube made of polyvinyl chloride is insufficient. Also, it has been pointed out that if a special combustion furnace is not used when burning and discarding, the combustion furnace is likely to be damaged and harmful substances are easily generated, which requires labor for disposal management. From such a viewpoint, a heat-shrinkable tube made of a polyester resin has come to be used as an alternative to the polyvinyl chloride tube.

The following characteristics are mainly required of a heat shrinkable tube for covering an electronic component such as a capacitor. First, the heat shrinkable tube has good coating processability. Second, the machinability of the heat-shrinkable tube is good.

In a heat-shrinkable tube made of polyester resin, Japanese Patent Application Laid-Open No.
No. 224723 discloses that the crystallinity of a tube is 4 to 4.
Heat shrinkable polyester tubes that are 20% have been proposed. To improve the second characteristic, Japanese Patent Application Laid-Open No. Hei 4-303620 proposes a method for producing a copolymerized polyester tube containing fine particles and a heat-shrinkable polyester tube having specific characteristics.

However, particularly in the case of chip capacitors of the surface mount type, the tubes proposed above have not yet had sufficient heat resistance. In other words, when the condenser coated on the tube is passed through a solder reflow furnace for mounting, a part of the tube swells and the coating is detached. This is considered to be because the tube covered by the capacitor does not yet have sufficient heat resistance. Further, in a conventionally used heat-shrinkable polyester tube obtained by stretching at a high magnification, swelling does not occur, but secondary shrinkage occurs, and sufficient coating is not performed. Therefore, there has been a demand for a heat-shrinkable tube which has good heat resistance when subjected to surface mounting and does not cause swelling or secondary shrinkage.

[0006]

An object of the present invention is to provide a general-purpose electric insulation which is excellent in heat resistance when mounting a heat-shrinkable aromatic polyester tube on an electronic component and then mounted on a printed circuit board, and which has excellent shrinkage characteristics and openability. An object of the present invention is to provide a heat-shrinkable aromatic polyester tube having a value of use such as a material and a heating element covering material.

[0007] The present inventors have conducted intensive studies to achieve the above object. In particular, the aromatic polyester tube is considered to crystallize due to the heat applied during the surface mounting process, but the difference in properties related to such crystallization is considered to affect the heat resistance after final coating. Study was carried out. As a result, a stretched tube obtained by stretching a polyester tube surprisingly has a crystallinity of not more than a specific value after heat-treating the stretched tube at 105 ° C. for 30 minutes, and The present inventors have found that a heat-shrinkable aromatic polyester tube that satisfies that the peak temperature corresponding to the melting point of the aromatic polyester resin in the DSC measurement is equal to or higher than a specific value can solve the above object, and has completed the present invention.

[0008]

Means for Solving the Problems The present invention is obtained by stretching an unstretched tube composed of a resin composition mainly comprising (A) a thermoplastic resin containing 70% by weight or more of an aromatic polyester resin (component (A)). A stretched tube, wherein (1) the stretched tube is placed in air at 105 ° C.
Crystallinity after heat treatment for 30 minutes at 16% or less (hereinafter referred to as "condition 1"), and (2) JIS K7
A heat-shrinkable aromatic polyester tube characterized in that the melting point peak temperature of the aromatic polyester resin determined by DSC measurement according to 121 is 220 ° C. or higher (hereinafter referred to as “condition 2”). .

In the present invention, preferably, the resin composition further comprises 0.02 to 4 parts by weight of (B) an inorganic lubricant (component B) and / or (C) an organic lubricant (100 parts by weight of component A). (C component) The present invention relates to a heat-shrinkable aromatic polyester tube which is a resin composition containing 0.02 to 4 parts by weight.

Further, in the present invention, preferably, the above-mentioned stretched tube is formed so that the unstretched tube is 1.2 to 3 in the radial direction of the tube.
The present invention relates to a heat-shrinkable aromatic polyester tube obtained by stretching the tube in a length direction of 1 to 1.5 times.

Further, in the present invention, preferably, the above-mentioned stretched tube is formed such that an unstretched tube is 1.2 to 1..
The present invention relates to a heat-shrinkable aromatic polyester tube that is obtained by stretching to 7 times and an area magnification of 1.5 to 1.8 times.

[0012] The present invention also relates to a heat-shrinkable polyester tube, wherein the stretched tube preferably has a crystallinity of 6% or less.

In the present invention, more preferably, the above resin composition is prepared by adding 100 parts by weight of component A to an inorganic lubricant (component B).
0.05 to 1 part by weight and (C) an organic lubricant (component C)
The present invention relates to a heat-shrinkable aromatic polyester tube containing 0.05 to 1 part by weight.

Furthermore, the present invention is preferably carried out in water at 100 ° C.
The heat shrinkage when immersed for 0 seconds is 30 in the radial direction of the tube.
The heat-shrinkable aromatic polyester tube according to the present invention, wherein the heat-shrinkable aromatic polyester tube has a length of 1 to 40% and a length of the tube of 1 to 10%.

Further, the present invention preferably relates to an inorganic material product whose surface is covered with the above-mentioned heat-shrinkable aromatic polyester tube.

Further, the present invention relates to an inorganic material product, the surface of which is coated with the heat-shrinkable polyester tube, wherein the inorganic material product is subjected to a heat treatment in a solder reflow soldering apparatus.

Further, the present invention relates to the above heat-shrinkable aromatic polyester tube, wherein the heat-shrinkable aromatic polyester tube is for covering a chip type capacitor.

Hereinafter, the present invention will be described in detail.

The aromatic polyester resin referred to in the present invention (hereinafter may be simply referred to as "polyester resin").
Is 70% of 100 mol% of the dicarboxylic acid component of the dicarboxylic acid component and the diol component forming the polyester resin.
A polyester resin in which at least mol%, preferably at least 90 mol%, most preferably at least 99 mol% is an aromatic dicarboxylic acid.

Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2,5-
Dichloroterephthalic acid, 2-methylterephthalic acid, 4,
4-stilbene dicarboxylic acid, 4,4-biphenyl dicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, 4,4-diphenoxyethane dicarboxylic acid, 5
-Na sulfoisophthalic acid, ethylene-bis-p-benzoic acid and the like. These dicarboxylic acids can be used alone or in combination of two or more.

The polyester resin of the present invention can be copolymerized with less than 30 mol% of an aliphatic dicarboxylic acid component in addition to the above aromatic dicarboxylic acid. Specific examples thereof include adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4
-Cyclohexanedicarboxylic acid and the like.

The diol component of the present invention includes, for example, ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol,
2-dimethyl-1,3-propanediol, trans-
Or -2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-
Hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylene diol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis (2-hydroxyethyl Ether) and the like.
These can be used alone or in combination of two or more.

The kind and composition ratio of the aromatic dicarboxylic acid, aliphatic dicarboxylic acid and diol component are selected so as to satisfy the melting point peak temperature condition of the present invention.

As the aromatic polyester resin comprising the dicarboxylic acid component and the diol component, specifically, a polyethylene terephthalate resin, a polybutylene terephthalate resin, a polyethylene isophthalate resin,
Examples include polyethylene naphthalate resin, polybutylene naphthalate resin, polyethylene terephthalate / isophthalate copolymer resin, and polyethylene / neopentyl terephthalate copolymer resin.

Among them, polyethylene terephthalate resin,
Polyethylene naphthalate resin, polyethylene terephthalate / isophthalate copolymer resin, and polyethylene / neopentyl terephthalate copolymer resin are preferred.

Further, polyethylene terephthalate resin,
Polyethylene terephthalate / isophthalate copolymer resin and polyethylene / neopentyl terephthalate copolymer resin are more preferred.

The most preferred embodiment is a polyethylene terephthalate resin.

These resins may be used alone or in combination of two or more. Polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene isophthalate resin, polyethylene terephthalate / isophthalate copolymer resin, and polyethylene / neopentyl terephthalate copolymer resin have the purpose of further improving heat resistance while maintaining heat shrinkage properties. 10 to 3 polyethylene naphthalate resin and polybutylene naphthalate resin
0% by weight can be mixed.

The polyethylene terephthalate resin of the present invention (hereinafter sometimes abbreviated as PET resin) is a resin substantially comprising terephthalic acid as a dicarboxylic acid component and ethylene glycol as a diol component.

Further, a PET resin in which polyethylene glycol is slightly copolymerized as a diol component can also be used.
The molecular weight of polyethylene glycol is 150 to 6,
A range of 000 is preferred.

The composition ratio of the polyethylene glycol component is preferably 5% by weight or less, more preferably 3% by weight or less, even more preferably 2% by weight or less in 100% by weight of the diol component. On the other hand, the lower limit is preferably 0.5% by weight or more, more preferably 1% by weight or more.

The introduction of the polyethylene glycol component has the advantage of increasing the mobility of the molecular chain and increasing the entropy elasticity required for the heat shrinkage characteristics. On the other hand, if too much is contained, the heat resistance tends to decrease or the crystallinity tends to increase (condition 1).
Are difficult to satisfy).

Further, in PET resin, about 0.5% of diol component is usually contained as a by-product during polymerization.
Contains at least mol% of a diethylene glycol component. As the ratio of the diethylene glycol component,
6 mol% or less is preferable in 100 mol% of diol components,
5 mol% or less is more preferable, and 4 mol% or less is further preferable.

The ratio of terephthalic acid and isophthalic acid of the dicarboxylic acid component constituting the polyethylene terephthalate / isophthalate copolymer resin (hereinafter sometimes abbreviated as TA / IA copolymer resin) of the present invention is determined by the total dicarboxylic acid 80 to 9 terephthalic acid when the component is 100 mol%
It is 9.9 mol%, preferably 85-99 mol%, more preferably 90-99 mol%. The isophthalic acid content is 0.1 to 20 mol%, preferably 1 to 15 mol%, and more preferably 1 to 10 mol%.

The TA / IA copolymer resin includes naphthalenedicarboxylic acid other than terephthalic acid and isophthalic acid.
The aromatic dicarboxylic acid can be copolymerized with 10 mol% or less, preferably 5 mol% or less, and the aliphatic dicarboxylic acid such as adipic acid can be copolymerized with 5 mol% or less, preferably 3 mol% or less. However, it is most preferable that the dicarboxylic acid component consist of only terephthalic acid and isophthalic acid.

Furthermore, ethylene glycol alone is most preferred as the diol component in the TA / IA copolymer resin, but it is also possible to copolymerize a diol component other than ethylene glycol.

The ratio of ethylene glycol and neopentyl glycol of the diol component constituting the polyethylene / neopentyl terephthalate copolymer resin (hereinafter sometimes abbreviated as EG / NPG copolymer resin) of the present invention is as follows:
Ethylene glycol is 90 to 99 mol%, preferably 95 to 99 mol%, and more preferably 97 to 99 mol% when the total diol acid component is 100 mol%. The content of neopentyl glycol is 1 to 10 mol%, preferably 1 to 10 mol%.
-8 mol%, more preferably 1-5 mol%. It is also possible to copolymerize diol components other than ethylene glycol and neopentyl glycol.

The EG / NPG copolymer resin contains the above-mentioned aromatic dicarboxylic acid such as naphthalenedicarboxylic acid other than terephthalic acid in an amount of 10 mol% or less, preferably 5 mol% or less, and the above-mentioned aliphatic resin such as adipic acid. 5 dicarboxylic acids
Although it is possible to copolymerize at most 3 mol%, preferably at most 3 mol%, it is most preferred that the dicarboxylic acid component be terephthalic acid alone. It is also possible to copolymerize an aliphatic dicarboxylic acid.

The structure of the terminal group of the aromatic polyester resin used in the present invention is not particularly limited. In addition to the case where the ratio of hydroxyl group and carboxyl group in the terminal group is almost the same, when one of the ratios is large. It may be. Further, the terminal groups may be blocked by reacting a compound having reactivity with such terminal groups.

The method for producing the aromatic polyester resin used in the present invention is carried out according to a conventional method in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc., while heating while heating the dicarboxylic acid component and the diol component. And the water or lower alcohol produced as a by-product is discharged out of the system. For example, examples of the germanium-based polymerization catalyst include oxides, hydroxides, halides, alcoholates, and phenolates of germanium, and more specifically, germanium dioxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium, And antimony trioxide.

In the present invention, compounds such as manganese, zinc, calcium, and magnesium used in a transesterification reaction which is a prior step of a conventionally known polycondensation can be used together. Alternatively, it is possible to deactivate such a catalyst with a phosphorous acid compound or the like to perform polycondensation.

The method for producing the aromatic polyester can be any of a batch system and a continuous polymerization system.

The intrinsic viscosity of the aromatic polyester resin is 0.4 to 1.5, and 0.5 to 0.5, as measured at 35 ° C. using o-chlorophenol as a solvent.
1.0 is preferred, 0.55-0.95 is more preferred, 0.6-0.9 is still more preferred, and 0.75-0.9.
Is particularly preferred. If the intrinsic viscosity is less than 0.4, the mechanical properties, rupture strength and elongation of the tube will be low, and if it exceeds 1.5, the melt processability of the tube will be poor, which is not preferable.

The polyester resin constituting the tube of the present invention may be one kind or two or more kinds. For example, a TA / IA copolymer resin may be used alone or PE
The TA / IA copolymer resin and the PET resin can be used in a mixture. The isophthalic acid is 0.1 to 20 mol%, preferably 0.1 to 15 mol in 100 mol% of the total dicarboxylic acid component of the mixed resin of the TA / IA copolymer resin and the PET resin. %, More preferably 0.1 to 10 mol%.

The copolymer of the polyester resin may be a block copolymer or a random copolymer. For example, the TA / IA copolymer resin may be a block copolymer consisting essentially of a polyethylene terephthalate chain and a polyethylene isophthalate chain, or a random copolymer of ethylene terephthalate and ethylene isophthalate.

The aromatic polyester resin, particularly preferably the PET resin, is 100% by weight of the thermoplastic resin of the component A.
The content is 70% by weight or more, more preferably 80% by weight or more.

The thermoplastic resin of the present invention can contain 30% by weight or less of 100% by weight or less of a thermoplastic resin other than the polyester resin. The presence of another thermoplastic resin makes it possible to control the degree of crystallinity under the condition 1, and to impart various properties such as heat resistance, slipperiness, toughness, and tear resistance.

Other thermoplastic resins other than the polyester resin include polysulfone resins, polyether ether ketone resins, polyphenylene sulfide resins, polyphenylene ether resins, polyethylene resins, polyolefin resins such as polypropylene resins, polystyrene resins, ABS resins, and the like. AS resins, styrene resins such as MBS resins, polycarbonate resins, polyamide resins, acrylic resins, and various thermoplastic elastomers (for example, styrene, olefin, urethane, polyester, polyamide, 1,2-polybutadiene, Vinyl chloride type, fluorine type [fluoro rubber], ionomer resin,
Chlorinated polyethylene, silicone, etc.). Further, IPN (Interpenetrating)
Composite rubber of acrylic rubber and silicon rubber using Polymer Networks (interpenetrating network structure) technology. For example, Mitsubishi Rayon Co., Ltd. product name Metablen S-2
001 etc. One or more of these thermoplastic resins other than the polyester resin can be used.

Among these thermoplastic resins other than the polyester resin, a thermoplastic polyester elastomer resin having good compatibility with the polyester resin is preferable from the viewpoint of improving hot water resistance. By including such a small amount of the TPEE resin, the crystallinity under the condition 1 is reduced. Also, the dynamic friction coefficient of the inner surface of the tube decreases.

The thermoplastic polyester elastomer resin (hereinafter sometimes abbreviated as TPEE resin) is:
A resin in which a high melting point and high crystalline aromatic polyester is used for a hard segment and an amorphous polyester or an amorphous polyether is used for a soft segment. The former is a polyester ester resin, and the latter is a polyether ester resin.

When the polyetherester resin is 100% by weight of the polyetherester resin, the hard segment is 5 to 95% by weight and the soft segment is 5 to 95% by weight, and the intrinsic viscosity is 0.4 to 2.0%. Range.

As the aromatic polyester of the hard segment of the polyetherester resin of the present invention, the dicarboxylic acid and diol components constituting the above-mentioned aromatic polyester resin can be used.
C. or higher is preferred.

Specifically, polybutylene terephthalate or polybutylene naphthalate consisting essentially of 1,4-butanediol and terephthalic acid or naphthalenedicarboxylic acid is preferred. Such polybutylene terephthalate or polybutylene naphthalate may contain other diols other than 1,4-butanediol, for example, ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, cyclohexanedimethanol, etc. in 100 mol% of all diol components. 5 mol% or less can be copolymerized, and other dicarboxylic acids other than terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc.
Preferably, isophthalic acid can be copolymerized with 100 mol% or less and 10 mol% or less of all dicarboxylic acid components. Most preferred is polybutylene terephthalate consisting solely of 1,4-butanediol and terephthalic acid.

In the soft segment of the polyetherester resin of the present invention, the alkylene portion has 3 to 12 carbon atoms.
Mainly composed of a polyether glycol which is an alkylene or a cycloalkylene having 4 to 10 carbon atoms. Typical examples of such polyether glycols include polyether glycols such as polypropylene glycol, polytrimethylene glycol, and polytetramethylene glycol, or copolyethylene-propylene glycol, copolyethylene-tetramethylene glycol [provided that ethylene oxide units are 50% by weight or less of ether glycol], copolytetramethylene-1,2-cyclohexylene dimethylene glycol [where the 1,2-cyclohexylene dimethylene oxide unit comprises 1 to 20 mol% of copolyether glycol] ] And other copolyether glycols. Of these, polytetramethylene glycol is preferred.

Further, when the polyester ester resin of the present invention is 100% by weight of the polyester ester resin,
5 to 95% by weight of hard segment, 5 of soft segment
９５95% by weight, with an intrinsic viscosity in the range of 0.4-2.0.

As the aromatic polyester of the hard segment of the polyester ester resin of the present invention, the dicarboxylic acid and diol components constituting the above-mentioned aromatic polyester resin can be used, and the melting point of this segment is 100 ° C.
The above is preferred.

More specifically, polybutylene terephthalate consisting essentially of 1,4-butanediol and terephthalic acid is preferred. Such polybutylene terephthalate includes
Diols other than 1,4-butanediol, such as ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, cyclohexane dimethanol, etc., can be copolymerized in an amount of 5 mol% or less based on 100 mol% of all diol components. A dicarboxylic acid other than terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, or the like, preferably isophthalic acid, can be copolymerized with 100 mol% or less and 10 mol% or less of all dicarboxylic acid components. Most preferred is polybutylene terephthalate consisting solely of 1,4-butanediol and terephthalic acid.

The soft segment of the polyester ester resin of the present invention includes polycaprolactone, an aliphatic polyester (for example, polyethylene adipate) from the above-mentioned aliphatic dicarboxylic acid and aliphatic diol, and a dicarboxylic acid component whose main component is an aromatic dicarboxylic acid. A polyester ether (hereinafter referred to as aromatic polyester ether) with a diol component mainly composed of a polyether glycol in which the alkylene moiety is an alkylene having 3 to 12 carbon atoms or a cycloalkylene having 4 to 10 carbon atoms. ). Among them, aromatic polyester ethers are preferred.

As the dicarboxylic acid component of such an aromatic polyester ether, an aromatic dicarboxylic acid is preferably 70 mol% or more, more preferably 80 to 99 mol%, and most preferably 90 to 90 mol% in 100 mol% of the dicarboxylic acid component. 98 mol%. As such aromatic dicarboxylic acids, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid are preferred, and isophthalic acid is most preferred.
In addition, as the aliphatic dicarboxylic acid, adipic acid, sebacic acid, azelaic acid and the like, preferably adipic acid is copolymerized in less than 30 mol%, more preferably 1 to 20 mol%, most preferably 2 to 10 mol%. it can. On the other hand, typical examples of the diol component of the aromatic polyester ether include polyether glycols such as polypropylene glycol, polytrimethylene glycol, and polytetramethylene glycol, or copolyethylene-propylene glycol, copolyethylene-tetramethylene glycol [however, ethylene Oxide units comprise 50% by weight or less of copolyether glycol], copolytetramethylene-1,2-cyclohexylene dimethylene glycol [provided that 1,2-cyclohexylene dimethylene oxide units are 1 to 20% of copolyether glycol. Mol%]. Of these, polytetramethylene glycol is preferred.

The TPEE resin is 100% by weight of the component A.
And preferably 0.1 to 10% by weight,
The content is more preferably from 5 to 5% by weight, and still more preferably from 1 to 3% by weight.

The resin composition of the present invention is provided with an inorganic lubricant (component B) and / or an organic lubricant (component C) in order to impart lubricating properties to obtain good opening properties and good finishing properties when coated. Preferably. More preferably, it comprises a specific amount of a combination of an inorganic lubricant and an organic lubricant.

As the inorganic lubricant of the component B of the present invention, for example, kaolin, clay, calcium carbonate, silicon oxide,
Examples include inorganic inert external particles such as calcium terephthalate, aluminum oxide, titanium oxide, calcium phosphate, and lithium fluoride. The average particle size of the inorganic inert external particles is 0.01 to 10 μm, preferably 0.1 to 10 μm.
And more preferably 4 to 10 μm. Here, the average particle size of the inorganic inert external particles is the particle size when the cumulative weight distribution of the weight distribution measured using a laser diffraction method (SALD-1100 manufactured by Shimadzu Corporation) becomes 50%.
As the particle size distribution, it is extremely preferable to contain large inorganic inert particles having a particle size in the range of 4 to 30 μm.
In such a range, even if the tube has a small thickness, a defect does not occur in the tube, and a good opening property can be achieved. The content of the large-diameter inorganic inert external particles is preferably from 2 to 80% by weight, more preferably from 10 to 70% by weight, most preferably from 20 to 60% by weight based on 100% by weight of all the inorganic inert external particles. is there.

The effect of the inclusion of the large-sized inorganic inert external particles is as follows.
In particular, it is remarkable in a tube having a low stretching ratio in which projections of large-diameter inorganic inert external particles due to stretching hardly occur. In addition, since these tubes are expanded by applying internal pressure to the unstretched tube and the diameter is regulated by the stretched tube, the outer surface in contact with the stretched tube has small projections of large-diameter inorganic inert external particles and has good printability. . On the other hand, on the inner surface of the tube that does not come into contact with the stretched tube, projections of large-diameter inorganic inert external particles are likely to appear, and therefore the opening property is improved.

The organic lubricant of the component C of the present invention includes hydrocarbon lubricants such as paraffin and polyethylene wax, higher fatty acid lubricants such as stearic acid, metal soap lubricants such as calcium stearate, and ester lubricants such as montanic acid wax. And organic fine particles such as a crosslinked acrylic resin containing benzoguanamine or polymethyl methacrylate as a main component. In particular, an organic lubricant which has a synergistic effect with an inorganic lubricant is optimally one which improves external lubricity and has good compatibility with a resin. In addition, it is necessary to satisfy conditions such as having thermal stability at the time of extrusion. For a resin composition containing 70% by weight or more of a polyester resin, montanic acid wax is particularly preferable.

The montanic acid wax is a fossil wax montan wax mainly containing fatty acids and fatty alcohols having 21 to 34 carbon atoms obtained by solvent extraction of lignite, and a wax obtained by esterifying or partially saponifying the montan wax. It is. Specifically, Hoechst WAX S (Hoechs WAX) obtained by oxidizing montan wax
Hoechs, a montanic acid diester obtained by esterifying montan wax with ethylene glycol.
t WAX E (manufactured by Hoechst), montanic acid diester Hostalub WE40 (manufactured by Hoechst), which is obtained by esterifying montan wax with glycerin, and montan wax partially esterified with butylene glycol, and the remainder is saponified with calcium hydroxide. Hoechst is a partially saponified montanic acid ester
WAX OP (manufactured by Hoechst), among which Hoechst WAX E, HostalubW
E40 is preferred.

Inorganic lubricant (component B), organic lubricant (component C)
Is added to each of 100 parts by weight of the component A.
It is preferably from 02 to 4 parts by weight, more preferably from 0.1 to 2.5 parts by weight. In a more preferred embodiment, 0.05 to 1 part by weight of the component B and 0.0 part by weight of the component C are added to 100 parts by weight of the component A
It is a resin composition comprising 5 to 1 part by weight.

By combining an organic lubricant and an inorganic lubricant, effective formation of particle projections and surface lubricity can be improved without problems such as a decrease in heat resistance, and an improvement in opening property can be achieved. Further, when cutting, covering, and shrinking the tube with the automatic mounting machine, the close contact of the cut portion is reduced, and the insertability of the coated body into the tube is improved, so that stable processing can be performed.

Such a heat-shrinkable tube is often folded into a tape, wound up on a reel, and then shipped as a product. At this time, if the surface of the tube has poor lubricity, it often occurs with a polyester film or the like. In some cases, a blocking phenomenon occurs, and the tubes adhere to each other so that they do not come off. This resin composition can also improve such a problem.

The most preferred embodiment of the method for producing the tube of the present invention is a method in which an unstretched tube is extruded using a ring die and then stretched to form a heat-shrinkable tube. In addition, there is a method in which a film extruded and stretched using a T-die or an I-die is bonded to the tube by fusion, welding or adhesion to form a tube, and a method in which the tube or film is bonded in a spiral shape to form a tube. .

Here, the method of extruding an unstretched tube using a ring die and then stretching it to form a heat-shrinkable tube will be described in further detail. The resin composition comprising the aromatic polyester resin is heated and melted to a temperature equal to or higher than the melting point by a melt extruder, continuously extruded from a ring die, then forcibly cooled and molded into an unstretched tube. As a means for forced cooling, a method of immersing in low-temperature water, a method using cooling air, or the like can be used. Among them, a method of immersing in low-temperature water is effective because the cooling efficiency is high.
The unstretched tube may be continuously supplied to the next stretching step, or may be wound once into a roll and then used as a raw material in the next stretching step. From the viewpoint of production efficiency and thermal efficiency, a method in which an unstretched tube is continuously supplied to the next stretching step is preferable.

The unstretched tube thus obtained is biaxially stretched by applying a pressure from the inside of the tube with a compressed gas. Although the stretching method is not particularly limited, for example, pressure is applied from one end of an unstretched tube by a compressed gas to the inside of the tube while being sent at a constant speed, and then preheated with hot water or an infrared heater, and the like. It is placed in a stretching tube heated to a stretching temperature that regulates the stretching ratio, and biaxial stretching is performed. Temperature conditions and the like are set so that stretching is performed at an appropriate position in the stretching tube. After stretching, it is cooled, and is taken up and wound up as a stretching tube while holding the stretching pressure while being sandwiched between a pair of nip rolls. Stretching may be performed in either the longitudinal direction or the radial direction, but is preferably performed simultaneously.

The stretching ratio in the length direction is determined by the ratio between the feed speed of the unstretched tube and the nip roll speed after stretching, and the stretching ratio in the radial direction is determined by the ratio of the unstretched outer diameter to the stretched tube outer diameter. . As another stretching pressurizing method, a method in which both the unstretched tube delivery side and the stretched tube take-up side are sandwiched between nip rolls to maintain the internal pressure of the compressed gas sealed therein can be employed.

The stretching conditions vary depending on the properties of the polymer to be used and the heat shrinkability of the target tube, but the stretching temperature is usually equal to or higher than the glass transition temperature to 105 ° C., preferably 70 ° C.
１００100 ° C.

The heat-shrinkable aromatic polyester tube of the present invention is obtained by reducing the unstretched tube by 1.2 to 3 times in the radial direction.
And what was obtained by extending 1 to 1.5 times in the length direction is preferable. Further, the stretching ratio in the radial direction of the tube is 1.
It is preferably from 3 to 2 times, more preferably from 1.4 to 1.7 times. The stretching ratio in the length direction of the tube is 1.02 to 1.3.
Times is preferable, and 1.02 to 1.15 times is more preferable.

If the stretching ratio in the radial direction of the tube is less than 1.2 times, a sufficient amount of shrinkage may not be obtained. If it exceeds three times, it may be difficult to satisfy the conditions 1 and 2 at the same time. Further, it is difficult to control the stretching ratio in the longitudinal direction of the tube.

If the stretching ratio in the length direction of the tube exceeds 1.5 times, the amount of shrinkage in the length direction becomes large, and it becomes difficult to cover the electronic parts stably, and the yield of the electronic parts decreases. May be.

Further, in a preferred embodiment of the present invention,
A stretched tube stretched in an area ratio (a product of a stretch ratio in the tube radial direction and a stretch ratio in the tube length direction) of 1.2 to 3 times is more preferable.
The area magnification is in the range of 1.3 to 2 times, and more preferably in the range of 1.5 to 1.8 times.

In the heat-shrinkable aromatic polyester tube of the present invention, the condition 1 is as follows:
Crystallinity when heat-treated at 5 ° C. for 30 minutes is 16% or less. Further, the crystallinity after such heat treatment is preferably 10% or less, more preferably 7% or less, and still more preferably 5% or less. The crystallinity is a value determined by a density gradient tube method. In order to obtain such a degree of crystallinity, the structure of the component A, the method of producing the tube, and the like are important factors.

Regarding the structure of the component A, it is important that factors that enhance crystallinity, for example, a long-chain diol component, are not increased more than necessary. As the component A, a PET resin is preferable. The diethylene glycol content is preferably about 0.5 to 5 mol% in 100 mol% of the diol component. For the purpose of further lowering the crystallinity, it is preferable to mix a small amount of TPEE resin.

An important factor in the production method is the draw ratio during the production of the drawn tube. In other words, in the stretched tube having a high stretch ratio, the molecular chain is relatively elongated,
The movement to shrink becomes more active. Such movement of the molecular chains leads to high crystallinity. Therefore, the condition 1 becomes more difficult to satisfy as the stretching ratio increases.

Heat treatment temperature of condition 1 of the present invention (105 ° C.)
Can be said to be relatively low as a temperature for crystallizing an aromatic polyester resin having a melting point of 220 ° C. or higher and a glass transition temperature of about 70 ° C. If the movement of molecular chains is so active that crystallization relatively progresses in such a temperature range, effective heat resistance cannot be obtained in the coated tube, which is an important technical finding found in the present invention. This is one of the findings. Although the reason for this is not clear at this time, he considers as follows.

That is, the heat-shrinkable aromatic polyester tube coated on a product such as an electronic component is firstly subjected to a heat treatment at the time of coating (many times in a hot air environment of about 300 ° C. for several seconds). Next, when performing surface mounting processing, first, preheating is performed (the processing is often performed for about 2 minutes in an atmosphere of about 180 ° C.). Thereafter, a heat treatment for surface mounting is performed in a solder reflow furnace (the processing is performed for about one minute in an atmosphere at about 300 ° C.). Therefore, it is subjected to two heat treatments before the solder reflow furnace treatment in which swelling actually occurs.
Naturally, crystallization of the polyester resin proceeds by such heat treatment. Here, as described above, the higher the molecular chain movement, the higher the crystallinity.

Here, consider the behavior due to the heat treatment in the solder reflow furnace. It is considered that crystallization of the polyester resin having a low crystallinity further proceeds even in the heat treatment in the solder reflow furnace. Although the progress of crystallization results in a movement of contracting the volume, the movement of the contraction of the tube is restrained by the electronic component to be coated, and as a result, the tube is firmly fixed.

On the other hand, in the case of a polyester resin which has already been crystallized by coating treatment or preheating treatment for surface mounting,
It is considered that the crystallization that proceeds during the heat treatment in the solder reflow furnace is relatively small. On the other hand, since the crystal itself thermally expands, the expansion movement of the tube becomes larger than the contraction movement. Such expansion movement is free because it is not restricted at all. In particular, the portion once separated from the surface of the electronic component is released from frictional resistance and the like, so that free deformation is possible. Such behavior is expected to be a phenomenon of blistering when processed in a solder reflow furnace.

That is, the higher the crystallinity before being put into the solder reflow furnace, the more easily the polyester resin is liable to undergo thermal expansion, and the more likely it is to cause poor swelling. Therefore, it is considered desirable that the crystallinity at this point is as low as possible, and the present inventor has found that Condition 1 is suitable as an index for this.

In order to satisfy Condition 1, the crystallinity of the drawn tube itself is also important. This is because if the degree of crystallinity is high at this point, the degree of crystallinity also becomes high under condition 1. The crystallinity of the drawn tube itself is preferably 6% or less, more preferably 5% or less, and 4% or less.
% Or less is more preferable, and 3.5% or less is particularly preferable.

The heat-shrinkable aromatic polyester tube of the present invention has an aromatic polyester resin having a melting point peak temperature of 220 ° C. or higher determined by DSC measurement (differential scanning calorimetry) in accordance with JIS K7121. That is, the melting point peak of the aromatic polyester resin, which is the main component of the component A, needs to be higher than a specific temperature. Preferably, such a melting point peak is at least 230 ° C, more preferably at least 240 ° C.

Since the melting point peak temperature substantially depends on the resin composition constituting the tube, in particular, the aromatic polyester resin of the component A, it is important to appropriately select such a structure. Examples of such a suitable aromatic polyester resin include PET resin as described above.

The heat-shrinkable polyester tube of the present invention obtained as described above is widely used for various uses. However, particularly in a field where heat resistance is required, it is desirable that the heat shrinkage be in a specific range. As described above, the stretching ratio is important to satisfy the condition 1 of the present invention. However, since such a stretching ratio has a large effect on the heat shrinkage ratio, the required heat shrinkage ratio is achieved with the lowest possible stretching ratio. It is necessary to do.

From this point of view, a stretched tube satisfying conditions 1 and 2 of the tube of the present invention,
The heat shrinkage when immersed in water at 0 ° C. for 30 seconds is 30 to 40% in the radial direction of the tube, and 1 to 10 in the length direction of the tube.
% Is a preferred embodiment of the present invention. Such a shrinkage range is
It provides both good coating and heat resistance for the electronic components to be coated. More preferably, the heat shrinkage is 32 to 38% in the radial direction of the tube and 1 to 8% in the longitudinal direction of the tube.

The resin composition of the present invention may be used by mixing the above-mentioned components in advance using a mixer such as a tumbler, a V-type blender, a Nauter mixer, a Banbury mixer, a kneading roll, and an extruder. The measured components may be directly supplied to a supply port of an extruder that extrudes a stretching tube, or separately measured components may be supplied to each supply port of an extruder having two or more supply ports.

Further, various additives and inorganic fillers may be added in such an amount that the effect is exhibited, as long as the object of the present invention is not impaired. Various additives include flame retardants (brominated bisphenol, brominated polystyrene, carbonate oligomer of brominated bisphenol A, triphenyl phosphate, resorcinol bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate), red phosphorus, etc.) , Flame retardant aids (such as sodium antimonate and antimony trioxide), anti-dripping agents (such as polytetrafluoroethylene having fibril forming ability), antioxidants (such as hindered phenol compounds), ultraviolet absorbers, and mold release Agents, lubricants, coloring agents and the like. Examples of the inorganic filler include glass beads, talc, and mica.

The resin composition of the present invention has a water content of 0.1% by weight or less in order to prevent hydrolysis of the polyester resin.
Preferably, it is dried so as to be 0.05% by weight or less. For example, drying is performed under conditions of 170 ° C. for 3 hours, 150 ° C. for 12 hours, and vacuum at 120 ° C. for 24 hours.

Thus, according to the present invention, there is also provided a product obtained by coating the surface of various inorganic material products using the heat-shrinkable aromatic polyester tube. The target product is the properties of the aromatic polyester resin as the main component (mechanical properties such as insulation, heat resistance, chemical resistance, and high elastic modulus).
Any material can be used, and examples thereof include metal material products and glass products. Specifically, examples of the metal material product include a capacitor, an electric wire (round wire, square wire), a dry battery, a secondary battery such as a lithium ion battery, a steel pipe, and an electric device. As the electric device, a motor coil end, It can cover the entire small motor, including transformers and leads. Further, as the glass product, for example, a light bulb and a fluorescent lamp are shown, and particularly, it can be used as a fluorescent lamp coated tube of a facsimile or an image scanner.

Among the above, the heat-shrinkable aromatic polyester tube of the present invention is preferably used for electronic parts typified by capacitors, particularly those subjected to high-temperature heat treatment in a solder reflow soldering apparatus for surface mounting. is there. That is, according to the present invention, there is provided an inorganic material product whose surface is coated with the heat-shrinkable polyester tube of the present invention, which is heated in a solder reflow soldering apparatus. More preferably, there is provided a capacitor product having a surface coated with the heat-shrinkable polyester tube of the present invention, which is heat-treated in a solder reflow soldering device, and still more preferably, heat-treated in a solder reflow soldering device. The present invention provides a chip-type capacitor product for surface mounting treatment, the surface of which is covered with the heat-shrinkable polyester tube of the present invention.

That is, according to the present invention, there is provided a heat-shrinkable aromatic polyester tube which is extremely suitable for coating a chip type capacitor.

[0097]

The present invention will be described in more detail with reference to the following examples. In addition, the typical physical property in an Example was measured by the following method.

(1) Heat Shrinkage Rate A heat-shrinkable tube having a length of 10 cm was placed in boiling water at 100 ° C.
The length before and after the immersion for 0 second and the outer diameter were measured with a digital caliper, and calculated by the following formula. Five samples were measured and the average was calculated.

[0099]

(Equation 1)

(2) Heat resistance test when mounting on a printed circuit board (solder reflow test of a capacitor) A chip type aluminum electrolytic capacitor is covered with a heat-shrinkable tube, and then a solder reflow tester TPF manufactured by Asahi Engineering Co., Ltd. Using −20 L, soldering was performed, and swelling of the tube, melting, and detachment of the shoulder due to secondary shrinkage were visually evaluated. Evaluation is 50 for each sample
I went in pieces.

The solder reflow consists of a preheat portion and a reflow portion. After preheating in the preheat portion, soldering was performed in the reflow portion. The conditions are as follows. Preheat section: furnace temperature 180 ° C, condenser passage time 120 seconds Reflow section: furnace temperature 310 ° C, condenser passage time 6
0 seconds Maximum surface temperature of substrate; 270 ° C, Maximum temperature of capacitor surface; 250 ° C Conveyor speed; 0.6 m / min Number of test samples; No change in the heat-shrinkable tube was observed in all of the coated capacitors. Δ: After the solder reflow test, some changes in the heat-shrinkable tube such as swelling, melting and secondary shrinkage of the tube were observed. However, this is a level that does not cause any problem in the function as a product. ×: After the solder reflow test, changes in the heat-shrinkable tube such as swelling or secondary shrinkage of the tube have occurred, and some may cause problems in the function as a product. did.

(3) Crystallinity (before heat treatment of the stretched tube,
And after the heat treatment of Condition 1) The stretched tube was placed in a drier set at 110 ° C for 30 minutes, and heat-treated, and determined by a density gradient tube method. The crystallinity of the stretched tube before the heat treatment was also measured.

(4) Melting point Measured according to JIS K7121. The measurement was carried out using a DSC measuring machine (manufactured by TA Instruments) at a heating rate of 20 ° C./min. The melting point of the sample of Comparative Example 4 was not recognized.

(5) Dynamic friction coefficient The dynamic friction coefficient between the inner surfaces was measured with a contact force of 1.96 N (200 gf) using a surface property measuring device manufactured by HEIDON in accordance with ASTM-D1894.

(6) Opening property The rolled tube was folded in parallel with the length direction after pressure bonding with a roll so that air did not remain on the inner surface of the stretched tube, and evaluated as follows. ；: Mouth opened with only one bend and good opening. △; Mouth opened two times. ×; Mouth did not open even after three or more turns, resulting in poor opening.

[Examples 1 to 8 and Comparative Examples 1 to 4] The resin compositions shown in Table 1 were melted by an extruder set at a cylinder temperature of 270 ° C, extruded through a ring die, immersed in water, cooled and solidified. The unstretched tube obtained at 90 ° C
In hot water, use an extension tube with an inner diameter of 8.6 mmφ, 49 kP
a (0.5 kg / cm ² ), pressurized air was applied to the tube, stretched under the conditions shown in Table 1 and cooled with water.
m or 50 μm stretched heat-shrinkable tube was obtained. Table 1 shows the shape and characteristics of the obtained heat-shrinkable tube.

The abbreviations in Table 1 mean the following. (A component) (A-1) Aromatic polyester resin PET-1: Polyethylene terephthalate resin with [η] = 0.85 (dicarboxylic acid component is 100 mol% terephthalic acid, diol component is 96.7 mol% ethylene glycol, PET-2: neopentyl copolymerized polyethylene terephthalate resin with [η] = 0.71 (100% by mole of terephthalic acid for the dicarboxylic acid component, 88% by mole of ethylene glycol for the diol component, and 12 moles of neopentyl glycol) %) PET-3: amorphous polyethylene terephthalate resin with [η] = 0.78 (the dicarboxylic acid component is terephthalic acid 1)
00 mol%, the diol component is ethylene glycol 68 mol%, 1,4 cyclohexanedimethanol 30 mol%,
PEN: polyethylene naphthalate resin with [η] = 0.60

(A-2) Polyester elastomer resin TPE-1: a polyetherester having a hard segment of polybutylene terephthalate and a soft segment of polytetramethylene glycol manufactured by Teijin Limited under the trade name Nuberan, grade name B4032ZN Resin TPE-2: manufactured by Teijin Limited whose hard segment is polybutylene terephthalate and whose soft segment is aromatic polyester ether, trade name Nubelan,
Polyester ester resin with grade name B4110ZN

(B) Inorganic lubricant Inorganic lubricant; average particle size 4.8 μm, particle size 4.0 to 5.3 μm
m of the large external inert particles of 13.4% by weight, 5.3 to 5.3%
7.5 μm at 16.2 wt%, 7.5 to 11.0 μm at 15.0 wt%, 11 to 16 μm at 10.4 wt%, 1
2.6% by weight of 6 to 22 μm, 0.2% by weight of 22 to 30 μm
Wt% kaolin (total inert external particles 100
57. large inert inert particles of 4-30 μm in weight%
8% by weight). (C) Organic lubricant Organic lubricant; Hoechst WAX E, a montanic acid diester obtained by esterifying montanic acid with ethylene glycol, manufactured by Hoechst.

[0110]

[Table 1]

[0111]

As is clear from Table 1, the heat-shrinkable aromatic polyester tube of the present invention has the following characteristics. (1) The stretched tube has a crystallinity of 16% or less when heat-treated in air at 105 ° C. for 30 minutes. A heat-shrinkable tube that satisfies (2) that the melting point peak temperature of the aromatic polyester resin determined by DSC measurement according to JIS K7121 is 220 ° C. or higher is excellent in heat resistance. The coated electronic component does not cause any problem in the solder reflow furnace treatment. Therefore, it is suitable for coating various kinds of inorganic material products such as electronic components which are subjected to a heat treatment in a solder reflow soldering device or a heat treatment similar thereto. Further, the heat-shrinkable aromatic polyester tube of the present invention can be used as a coating material or a protective material utilizing its combustion resistance, electric properties, and chemical resistance. Therefore, the present invention
Further, the present invention provides an inorganic material product such as an electronic component that is heat-treated in a solder reflow soldering apparatus coated with the heat-shrinkable aromatic polyester tube of the present invention,
Further, the present invention provides various tube coating products having excellent chemical resistance and the like. Specific examples of such tube-coated products include capacitors (for the purpose of insulating coating and the like), fluorescent lamps (for the purpose of improving safety, improving design, and changing light distribution), and lithium-ion batteries. Applications such as a secondary battery (for the purpose of insulating coating and the like) and the like can be cited, and among them, a chip type capacitor can be most preferably cited.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) F16L 11/04 F16L 11/04 H01G 4/224 B29K 67:00 // B29K 67:00 105: 02 105: 02 B29L 23 : 00 B29L 23:00 H01G 1/02 J F term (reference) 3H111 AA02 BA15 BA34 DA11 DA26 DB27 EA04 4F071 AA45 AA84 AB26 AC09 AE11 AF11Y AF15 AF16 AF21 AF27 AF45 AF61Y AH12 BA01 BB09 BC05 4F210 AA02 AB07 AE03 RC RG07 RG30 RG43 4J002 AE032 BB032 BG062 CC192 CF041 CF051 CF061 CF071 CF081 DD046 DE136 DE146 DE236 DH046 DJ016 DJ036 EG037 FD172 FD176 FD177 GQ00

Claims (10)

[Claims] 1. A stretched tube obtained by stretching an unstretched tube made of a resin composition mainly comprising a thermoplastic resin (A component) containing (A) 70% by weight or more of an aromatic polyester resin, The stretched tube has (1) a crystallinity of 16% or less when heat-treated at 105 ° C. for 30 minutes in air, and (2) JIS K71.
21. A heat-shrinkable aromatic polyester tube, wherein the aromatic polyester resin has a melting point peak temperature of 220 ° C. or higher determined by DSC measurement based on No. 21. 2. The above resin composition is used in an amount of 0.02 to 4 parts by weight of (B) an inorganic lubricant (Component B) and / or 0.02 to 4 parts by weight of (C) an organic lubricant (Component C) based on 100 parts by weight of Component A. The heat-shrinkable aromatic polyester tube according to claim 1, which is a resin composition containing 4 parts by weight. 3. The stretched tube is obtained by stretching an unstretched tube 1.2 to 3 times in the radial direction of the tube and 1 to 1.5 times in the length direction of the tube. The heat-shrinkable aromatic polyester tube according to any one of 1 and 2. 4. The stretched tube is obtained by stretching an unstretched tube in a radial direction of the tube to 1.2 to 1.7 times and an area ratio of 1.5 to 1.8 times. The heat-shrinkable aromatic polyester tube according to claim 1. 5. The stretched tube has a crystallinity of 6%.
The heat-shrinkable aromatic polyester tube according to any one of claims 1 to 4, which is: 6. The resin composition contains 0.05 to 1 part by weight of an inorganic lubricant (component B) and 0.05 to 1 part by weight of an organic lubricant (component C) based on 100 parts by weight of component A. The heat-shrinkable aromatic polyester tube according to any one of claims 1 to 5, comprising: 7. The stretching tube is placed in water at 100 ° C. for 30 minutes.
Heat shrinkage when immersed for 30 seconds in the radial direction of the tube
The heat-shrinkable aromatic polyester tube according to any one of claims 1 to 6, wherein the heat-shrinkable aromatic polyester tube is 40% and 1 to 10% in a length direction of the tube. 8. An inorganic material product, the surface of which is coated with the heat-shrinkable aromatic polyester tube according to claim 1. 9. The inorganic material product according to claim 8, wherein the inorganic material product is subjected to heat treatment in a solder reflow soldering apparatus. 10. The heat-shrinkable aromatic polyester tube according to claim 1, wherein the heat-shrinkable aromatic polyester tube is for covering a chip type capacitor.