JPH10202811A - Elastomer laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate cloth capable of being recovered as polyester while flexibility is equipped, and moisture permeation waterproof properties are provided. SOLUTION: A sheet of 5-30μm thickness composed of a polymer wherein a melting point of polyester block copolymer of 20-50wt.% of a hard segment having polybutylene terephthalate composed of at least 60mol.% of tetramethylene glycol to terephthalic acid and dicarboxylic acid components as main component, and 80-50wt.% of a soft segment being polyester composed of long chain diol indicated by at least 60mol% of HO(CH2 CH2 O)iH (i=2 to 5) to aromatic dicarboxylate and dicarboxylic acid components, is within a specific range, and a dishcloth of polyester or the like are laminated to prepare an elastomer laminated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an elastomer laminate, and more particularly, to a moisture-permeable and waterproof laminated sheet in which a specific polyester block copolymer and a fabric are laminated.

[0002]

2. Description of the Related Art Heretofore, various methods have been practiced for laminating a film on a fabric and using it as a moisture-permeable waterproof fabric for sportswear, raincoat, etc., for example, by bonding a microporous film of polytetrafluoroethylene. (Eg, commercially available under the trade name of GORE-TEX), and those using a urethane film are well known.

Recently, there has been a strong demand that a polyester-based moisture-permeable waterproof membrane be used for a polyester fabric in the sense that it can be reused when the fabric is discarded. For example, Japanese Patent Publication No. 1-48872 discloses such a fabric. Discloses a form in which a thin film of polytetramethylene terephthalate or the like obtained by copolymerizing poly (oxyalkylene) glycol mainly composed of polyethylene glycol is laminated on a fabric and used.

However, in the case of a polytetramethylene terephthalate film obtained by copolymerizing the poly (oxyalkylene) glycol, if the polyethylene glycol portion is increased in order to increase the moisture permeability, the film itself becomes water-absorbing, and the size of the film becomes large. This is unfavorable because it causes a change and a feeling of stuffiness inside. In addition, the sheet as a whole has a hard feeling, and a sheet laminated with a fabric is not preferred because it has a rough feeling or a hard feeling.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a moisture-permeable and waterproof fabric which can be recovered as the same polyester when used in a fabric made of polyester fibers and the like, and is environmentally preferable. . Furthermore, while having flexibility that conventional product does not have and is superior in moisture permeability,
An object of the present invention is to provide a laminate in which films having low water absorption are laminated.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to obtain a laminate satisfying the above-mentioned problems, and as a result, have prepared a thin film using a specific polyester block copolymer, and The inventors have found that the problem can be solved by stacking, and have reached the present invention.

That is, the present invention relates to 1) 20 to 50% by weight of a hard segment mainly composed of polybutylene terephthalate (PBT) comprising 60% by mole or more of a tetramethylene glycol component per terephthalic acid component and a dicarboxylic acid component. , More than 60 mol% of HO (CH ₂ CH ₂₎ per aromatic dicarboxylic acid component and dicarboxylic acid component
Soft segment 80 made of a polyester consisting of a long chain diol component represented by _{O) i H (i = 2~5} )
50% by weight of a polyester block copolymer having a melting point (T) within the following range, a laminate of a sheet and a cloth having a thickness of 5 to 30 μm, and a waterproof property. An elastomer laminate,

T ₀ -5>T> T ₀ -60 T> T '+ 10 (T ₀ : Melting point of the polymer comprising the hard segment, T': All the components constituting the hard segment and the soft segment Melting point of random copolymer)

Item 2) The item 1 wherein the polyester block copolymer according to item 1 comprises a composition containing less than 50% by weight of PBT obtained by copolymerizing polyethylene glycol having a molecular weight of 500 or more. An elastomer laminate, and

Item 3) An elastomer laminate according to item 1 or 2, wherein the fabric is made of polyester.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester block copolymer of the present invention has a hard segment whose main component is polybutylene terephthalate, and other than terephthalic acid other than aromatic dicarboxylic acid containing benzene or naphthalene ring, An aliphatic dicarboxylic acid of the formulas 4 to 12,
Aliphatic diols having 2 to 12 carbon atoms other than tetramethylene glycol, diols such as alicyclic diols such as cyclohexane dimethanol may be copolymerized, and dicarboxylic acids other than terephthalic acid or diol components other than tetramethylene glycol. Is 40 mol% or less, preferably 30 mol% or less, based on all dicarboxylic acids.

The lower the copolymerization ratio, the higher the melting point, which is preferable. However, copolymerization is also performed to increase flexibility. However, when the copolymerization ratio is increased, crystallization is difficult, and the moldability and the like are deteriorated. Although this copolymerization ratio is difficult to specify in the production of the block copolymer of the present invention, it may be considered that it corresponds to a case where the melting point of the crystal is 160 ° C. or higher, preferably 170 ° C. or higher.

On the other hand, as the soft segment, a polyester mainly composed of terephthalic acid and a long-chain diol of HO (CH ₂ CH ₂ O) _i H (i = 2 to 5) is used. An aromatic dicarboxylic acid other than an acid, an aliphatic or alicyclic dicarboxylic acid, or a copolymer of a short-chain diol may be used. The copolymerization ratio of these components is 40 mol% or less based on the dicarboxylic acid component.

Here, the copolymerizable aromatic dicarboxylic acid, aliphatic dicarboxylic acid or alicyclic dicarboxylic acid includes, for example, isophthalic acid, phthalic acid, naphthalenedicarboxylic acids, linear dicarboxylic acids having 4 to 12 carbon atoms. acid,
Particularly, a linear dicarboxylic acid having 8 to 12 carbon atoms, cyclohexanedicarboxylic acid and the like can be mentioned.

As the diol component, HO having i of 2 to 5 is used.
(CH ₂ CH ₂ O) _i H is used, where i is hard at 1 and hygroscopicity is high at 6 or more, which is unsuitable for the present invention. Preferably, i is 3 to 4 most.

The copolymerizable diols include those having 2 carbon atoms.
To 12 straight-chain aliphatic diols and the like. Also,
Copolymerizing polyoxyalkylene glycol having a relatively low molecular weight of 1200 or less, preferably 100 or less, in an amount of 30% by weight or less, preferably 20% by weight or less based on the whole polymer, improves the low-temperature properties. However, use of more than 30% by weight is not preferable because chemical resistance and the like are reduced.

In the polyester block copolymer of the present invention, the amount ratio (weight ratio) of the hard segment to the soft segment is from 20 to 50 to 80 to 50, preferably 25.
-40 to 75-60. When the amount ratio of these hard segments exceeds the above-mentioned amount, the obtained polyester block copolymer is not preferred because problems such as being hard and difficult to use appear, and when the soft segment exceeds the above-mentioned range, This is because the crystallinity decreases and molding becomes difficult.

The segment length of the soft segment and the hard segment of the polyester block copolymer is preferably about 500, expressed as a molecular weight.
To 7000, more preferably 800 to 5000, but is not particularly limited. Although it is difficult to directly measure the segment length, for example, the composition of the polyester constituting the soft and hard components, the melting point of the polyester composed of the components constituting the hard segment, and the melting point of the obtained polyester block copolymer From these, it can be estimated using Flory's equation.

From these points, the melting point of the polyester block copolymer of the present invention is an important item, and the melting point (T) is between T ₀ -5 and T ₀ -60, preferably T _0.
-10 to T ₀ -50, more preferably T ₀ -1
It should be between 5 and T ₀ -40. This melting point is preferably higher than the melting point (T ') of the random copolymer composed of all the components constituting the hard segment and the soft segment by 10 ° C., preferably 20 ° C. or more, and the melting point of the random copolymer is determined. If not, the melting point should be 150 ° C. or higher, preferably 160 ° C. or higher. Here, T ₀ is the melting point of the (copolymer) polymer composed of the components constituting the hard segment.

When the polymer of the present invention is not a block copolymer but a random copolymer, the polymer is generally amorphous and has a low glass transition temperature. However, what can be used as a practical problem such as wrapping around a roller or sticking to each other even if formed into a sheet, so-called blocking phenomenon or sticky surface cannot be obtained.

As a method for producing such a polyester block copolymer, there is a method in which polymers constituting the soft segment and the hard segment are produced, respectively, and melt-mixed so that the melting point is lower than that of the polyester constituting the hard segment. Can be Since this melting point changes depending on the mixing temperature and time, it is preferable to deactivate the catalyst by adding a catalyst deactivator such as phosphorus oxyacid at the time when the desired melting point is reached.

As the polyester block copolymer of the present invention, those having an intrinsic viscosity of 0.6 or more, preferably 0.8 to 1.5, measured at 35 ° C. in orthochlorophenol can be used. If the intrinsic viscosity is lower than this, the strength is lowered, which is not preferable.

The polyester block copolymer of the present invention is formed into a sheet as a composition which may contain other polymers, stabilizers, pigments, dyes, flame retardants, nucleating agents, lubricants and other additives. .

In particular, other polymers having a molecular weight of 500
As described above, preferably polybutylene terephthalate obtained by copolymerizing polyethylene glycol of 1000 to 6000 (for example, containing 30 to 70% by weight of polyethylene glycol)
Less than 50% by weight, preferably 20-45% by weight
Although the added composition has improved moisture permeability and is a polymer having high water absorption by itself, this composition is characterized in that it shows almost the same water absorption as the polyester block copolymer of the present invention.

As the cloth used in the present invention, a cloth having characteristics required by the application should be selected.
For example, when used as sportswear, a fabric that expands and contracts with movement is used, and when used as a tent, a strong fabric is used.

Further, the elastomer laminate of the present invention naturally includes a case where the polyester block copolymer layer is on the front surface, a case where the polyester block copolymer layer is on the back surface, and a case where the polyester block copolymer layer is in the middle of the fabric.

Such a laminate can be produced, for example, by making a film of a polyester block copolymer and sticking it. At this time, it is preferable to use an adhesive made of, for example, a polyester having a low melting point, since the whole can be made of polyester. The melting point or softening point at this time is less than 150 ° C, preferably 140 to 100 ° C. In addition, as a bonding method, so as not to impair the moisture permeability as much as possible,
Preferably, point or line bonding is achieved. This is because the effect of the present invention is halved if the adhesive adheres to the whole because the adhesive has poor moisture permeability.

The film of the polyester block copolymer has a thickness of 5 to 30 μm, preferably 10 to 30 μm.
２５25 μm is used. The method of producing this film may be any method, for example, by extruding from a circular die and putting gas inside, an inflation film forming method of forming a film in a balloon shape, extruding a molten polymer from a slit die, A method of cooling and solidifying with a cooling roller is used, and release paper is used as necessary.

Further, since the film of the present invention is thin, blocking often becomes a problem. As a countermeasure, it is a good method to add an internal lubricant or a crystallization accelerator. For example, silica, kaolin, calcium carbonate, talc, fatty acid metal salts and the like are often added. This amount is generally at most 5%, preferably at most 2%.

[0030]

The present invention will be described below in detail with reference to examples. In the examples, “parts” indicates “parts by weight”.

Reference Example 1 Dimethyl terephthalate 194
Part and 160 parts of triethylene glycol (107 mol% based on the dicarboxylic acid component) were transesterified with a dibutyltin diacetate catalyst, and then polycondensed under reduced pressure to obtain a syrupy polyester having an intrinsic viscosity of 0.76. . A polybutylene terephthalate chip having an intrinsic viscosity of 0.98, which was separately obtained by polycondensation with the polyester, was dried to obtain 10
After adding 7 parts and reacting at 250 ° C. for further 75 minutes,
The reaction was stopped by adding 0.1 part of phenylphosphonic acid. The polyester block copolymer (hard segment: soft segment = 28: 72 (weight ratio)) was taken out and formed into chips to obtain a film raw material.
The melting point of the chip was 176 ° C. and the intrinsic viscosity was 0.83.

Reference Example 2 Dimethyl terephthalate 180
Part, 20 parts of dimethyl sebacate, 140 parts of tetraethylene glycol (72 mol% based on the dicarboxylic acid component) and 40 parts (38 mol% based on the dicarboxylic acid component) of a transesterification reaction with a dibutyltin diacetate catalyst. Polycondensed below to give an intrinsic viscosity of 1.0
6 was obtained. Reference Example 1
After blocking as described above, chips were formed (polyester block copolymer, hard segment: soft segment = 27: 73 (weight ratio)).

Reference Example 3 Dimethyl terephthalate 25
Parts, polyethylene glycol (average molecular weight 3000) 6
0 parts and 35 parts of tetramethylene glycol were polymerized by a conventional method using tetrabutoxytitanate as a catalyst to obtain a polyethylene glycol copolymerized polybutylene terephthalate having an intrinsic viscosity of 1.72.

Reference Example 4 Dimethyl terephthalate 65
Parts, polyethylene glycol (average molecular weight 2000) 6
0 parts and 61 parts of tetramethylene glycol were polymerized by a conventional method using tetrabutoxytitanate as a catalyst to obtain a polyethylene glycol copolymerized polybutylene terephthalate having an intrinsic viscosity of 1.22.

Reference Example 5 Dimethyl terephthalate 175
Part, dimethyl isophthalate 19 parts and hexamethylene glycol 180 parts were subjected to a polycondensation reaction using a titanium tetrabutoxide catalyst by a conventional method to give an intrinsic viscosity of 0.89.
A polyester was obtained.

Example 1 The polyester block copolymer of Reference Example 1 and the polyethylene glycol copolymerized polybutylene terephthalate of Reference Example 3 were mixed at a ratio of 55:45 (weight ratio) and passed through a T-die from an extruder. Extruded and cooled with a cooling roll at 40 ° C. to a thickness of 13 μm
Sheet was obtained. Film formation was easy and there was no particular problem.

The sheet obtained had a water absorption of 1.2% after immersion in water at 23 ° C. for 24 hours, and a gap of 20 mm between chucks.
The tensile elasticity modulus (JIS 7127) measured at a tensile speed of 500 mm / min was 25 MPa.

A laminate obtained by thermally bonding the polyester taffeta to this sheet at 170 ° C. with an adhesive obtained by pulverizing the polyester of Reference Example 5 at a temperature of 170 ° C. has moisture permeability (JIS L-1099).
(A-1 method), it was 8900 g / 24 hours / m ² , and was soft and had a very little stiff feeling. Further, a water pressure of 10 m water column was applied by a method similar to the method A- (b) of JIS L1092, but no water leakage was observed.

On the other hand, the polymer ratio of Reference Examples 1 and 3 was 40:
When it was set to 60, the water absorption was 6.3, and the water absorption was much higher than the above-mentioned ratio.

Example 2 Using the polyester block copolymer of Reference Example 2, a sheet having a thickness of 14 μm was prepared in the same manner as in Example 1, and a laminate with a fabric was prepared. The sheet had a water absorption of 1.3% and a tensile modulus of 23 MPa. The laminate has a moisture permeability of 7700 g / 24 hours / m
² , and the water pressure resistance was 10 m or more.

Comparative Example 1 A 12 μm sheet similar to that of Example 1 was prepared using the polymer of Reference Example 4, and a test similar to that of Example 1 was performed. As a result, the water absorption was 12%.
It is clear that the water absorption is larger than that of Example 1,
The tensile modulus of the sheet was 95 MPa. Also,
At the time of sheet preparation, the adhesion of the roller was large, and the sheeting was often interrupted. The moisture permeability of the laminate is 4800 g / 2
4 hours / m ² .

[0042]

According to the present invention, it is possible to obtain a laminated fabric having excellent moisture permeability, and it is more flexible than conventional products, so that it has less stiffness and less moisture absorption, so that the laminate has less stickiness. Can be obtained. The elastomer laminate of the present invention can be suitably used as a moisture-permeable waterproof fabric for sportswear, raincoats, tents and the like. In particular, a laminate with a polyester fabric has the advantage that it can be recovered and used as polyester.

Claims (3)

[Claims] 1. A hard segment composed mainly of polybutylene terephthalate (PBT) comprising at least 60 mol% of a tetramethylene glycol component per terephthalic acid component and a dicarboxylic acid component, and an aromatic dicarboxylic acid component. dicarboxylic acid component per 60 mol% or more of _{HO (CH 2 CH 2 O)} i H polyester block as a soft segment 80-50 wt% of polyester consisting of a long chain diol component represented by (i = 2 to 5) The copolymer is a polyester block copolymer having a melting point (T) in the following range, and has a thickness of 5 to 3
A waterproof elastomer laminate, which is a laminate of a sheet having a thickness of 0 μm and a fabric. _{T 0 -5>T> T 0} -60 T> T '+ 10 (T 0: the melting point of the polymer composed of components constituting the hard segment, T': random copolymer consisting of whole components constituting the hard segment, the soft segment Melting point of polymer) 2. The polyester block copolymer according to claim 1, which comprises a composition containing less than 50% by weight of PBT copolymerized with polyethylene glycol having a molecular weight of 500 or more. Elastomer laminate. 3. The elastomer laminate according to claim 1, wherein the fabric is made of polyester.