JPS61195117A - Moisture-permeable and gas-permeable film - Google Patents

Abstract

PURPOSE:To provide the titled film having excellent moisture permeability and gas-permeability, and useful as a water-proofing cloth, etc., by using a copolymer containing a specific crystalline segment and an amorphous segment, as a main component. CONSTITUTION:The objective film contains, as a main component, a copolymer containing (A) a crystalline segment composed of at least one kind of the recurring unit selected from polyester unit, polyamide unit and polyurethane unit, and (B) at least a pair of amorphous segments selected from each of (i) an organopolysiloxane having reactive group and a polyalkylene ether glycol (modified aliphatic polyester) (the carbon number of the alkylene oxide recurring unit is 2-4) and (ii) an organosilane having reactive group, a polyalkylene ether glycol (the carbon number of the alkylene oxide recurring unit is 5-8) and an aliphatic polyester which is not modified with polyalkylene ether glycol.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polymer film, and more particularly to a polymer film having moisture permeability and gas permeability.

[Conventional technology]

Conventionally, plastic films with high moisture permeability and L?
It, polyvinyl alcohol, cellulose acetate, cellulose triacetate, nylon.

Polyurethane, etc. are known, and as glass films with high gas permeability, polyethylene, polystyrene, cellulose acetate, polycarbonate films, etc. are known.

[Problem that the invention seeks to solve]

The moisture permeability and N permeability of each plastic film are as follows:
Neither can be said to be sufficient.

In view of these points, the present invention aims to provide a film having sufficient moisture permeability and gas permeability.

[Means for solving problems]

The present invention provides a crystalline segment consisting of repeating polyester positions, polyamide dislocations, and polyurethane units, and the following (at least one selected from the four groups, or at least one selected from the following group (A) and two): This is a moisture-permeable and gas-permeable film characterized by containing as a main component a copolymer containing at least one selected amorphous segment.

(2) Reactive group-containing organopolysiloxanes, polyalkylene ether glycols, and polyalkylene ether glycol-modified aliphatic polyesters (provided that the number of carbon atoms in the alkylene oxide repeating unit is in the range of 2 to μ).

(2) Organosilanes containing a broadening group, polyalkylene ether glycols (provided that the number of carbon atoms in the alkylene oxide repeating unit is in the range of ! to g), and aliphatic polyesters not modified with polyalkylene ether glycols.

The crystalline segment of the polymer film in the present invention is
Polyester unit, Bolioid degree.

Composed of repeating polyurethane units.

Specifically, combinations of polyester segments mainly composed of aromatic polyester units such as polyethylene terephthalate, polytetramethylene terephthalate, polyparaoxybenzoate, polyethylene terephthalate, -ethylene isophthalate, and polyethylene terephthalate-tetramethylene terephthalate are mentioned. It will be done.

Lactones such as Snake-caprolactone can also be used.

Others include nylon 6, nylon & otsu, nylon 4ri, nylon 410. Examples include polyamide segments such as metaxylylene group-containing polyamides, and aromatic polyurethane segments composed of aromatic polyisocyanates and low-molecular-weight diamines, diols, water, and the like.

Group (A) amorphous segments include reactive group-containing organopolysiloxanes, polyalkylene ether glycols, and polyalkylene ether glycol-modified aliphatic polyesters (provided that the number of carbon atoms in the alkylene oxide repeating unit is 2 to t). things within the range).

Specifically, the reactive group-containing organopolysiloxane includes a hydroxyl group in the side chain or terminal.

It is an organopolysiloxane containing at least 7, preferably 2 or more, amino groups, epoxy groups, alkoxy groups, carboxyl groups, active hydrogen atoms, etc. Examples include compounds having the following structure: (CHa) mO-( CM
! 10) s H Tadama (here, R is a methyl or ethyl group, Rr is a hydrogen atom, a hydroxyl group, an alkoxy group, an aryl group,
A vinyl group, an alkyl group having less than or equal to 1 carbon atoms, and a hydrocarbon group having a substituent 1 For example, an alkoxyalkoxy group,
Fluoroalkyl 11s Diorganosiloxane group, hydroxyalkyl group, aminoalkyl group, dialkylaminoalkyl group.

trialkylammonium alkyl group, mercaptoalkyl group, carboxyalkyl group, epoxyalkyl group,
These include polyoxyalkyl groups.

Further, RL is a direct bond or a covalent organic group such as lower alkylene, R9 is a hydrogen atom or a lower alkyl group, and R4 is a hydrogen atom, a methyl group, or a mixed group thereof.

Further, n is a positive integer of 0 or/to SOO, 1m is an integer of 0 or/to 10, and γ is a positive integer of / to 500. ] In addition, the polyalkylene ether glycol and hyphoralkylene ether glycol-modified aliphatic polyesters include alkylene oxide repeating units such as polyethylene ether glycol, polyalkylene ether glycol, polytetramethylene ether glycol, or copolymers of these glycols. Polyalkylene ether glycols having 2 to 1 carbon atoms, and these polyalkylene ether glycols and polyethylene sebacate.

Examples include copolymers with 9WI aliphatic polyesters such as polypropylene adipate, polytetramethylene adipate, and polytetramethylene sepacate.

In addition, as the amorphous segment of the group (A), organosilanes containing reactive 11 groups, polyalkylene ether glycols (provided that the number of carbon atoms in the alkylene oxide repeating unit is in the range of 5 to 1 g) and polyalkylene ether glycols It is an unmodified aliphatic polyester.

5EGC property 11-containing organosilane is an organosilane having at least two, and preferably different types of reactive groups in the molecule.1For example, an alkoxy group, a P-a-alkoxyethoxy group, a vinyl group, a methacrylic group, an epoxy group. It is an organosilane having an amino group, a mercapto group, a carboxyl group, a hydroxyl group, etc.

Specifically, t-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ
- methacryloxypropyltrimethoxysilane, l r
-Aminopropyltriethoxysilane% N-p-(
Aminoethyl] -γ-7minoprobyltriethoxysilane, β-<3-'I-epoxycyclohexyl]dityltrimethoxysilane, vinyltria7toxysilane,
Vinyltriethoxysila/11 Vinyltris-(β-
methoxyethoxy] silane, etc.

Further, the polyalkylene ether glycol is a polyhexamethylene ether glycol having carbon number of 5 to 5 g at the alkylene oxide repeating position.

Furthermore, examples of aliphatic polyesters not modified with polyalkylene ether glycol include polyethylene sepacate, polypropylene adipate, polytetramethylene adipate, polytetramethylene sepacate, and polyesters made of dodecaladicarboxylic acid and tetramethylene glycol. Glycol repeating position carbon number is 2
Examples include aliphatic polyesters of 1 to 2, or their polyester constituents and copolymers, and cyclic ester polymers such as polylactones having 1 to 1 g of carbon atoms can also be used.

The copolymerization ratio of crystalline segment and amorphous segment is
Weight ratio: 20 to 10: O is preferred;
<, 70:30 to 20:IO is particularly preferred.

Also, the ratio of (A) to cB) is 100:O to 2o:tr
.

is preferred, and ioo:o to 30:70 is particularly preferred.

Further, the molecular weight of the copolymer is usually over 2000 bJ, preferably s*j, 000 to 20QOOOm degrees.

Copolymerization methods vary depending on the type of crystalline segment and amorphous segment used; for example, a method in which crystalline segment components and amorphous segment components are simultaneously reacted, a method in which polymer chains constituting the crystalline segment are After formation, the amorphous segment components are subjected to stepwise Cf
How to make it respond.

Examples include a method of manufacturing by depolymerizing a high molecular weight polymer constituting the crystalline segment.

Segments can also be indirectly bonded to each other by adding a reaction accelerating catalyst or using a polyfunctional crosslinking agent, if necessary.

Although the mechanism by which arching properties occur is not clear, this distribution mechanism potentially requires copolymerized amorphous segments to exist independently in crystalline segments with a highly crystalline structure. Therefore, it is necessary that the amorphous segment has a weak affinity with the crystalline segment and has characteristics that make it difficult for them to be uniformly miscible with each other.

As a result, it is thought that micropores at the molecular level are formed in the film, allowing gas molecules to pass through.

In this case, the amorphous segment of
It has the function of increasing the dissolution diffusivity into the membrane.

In addition, by adjusting the polymerization degree and content ratio of the (5) group compound and adjusting the polymerization degree and crystallinity of the crystalline segment, the permeability due to dissolution and diffusion of gas molecules of different 1 molecule volumes into the film can be improved. It can be controlled.

In this case, the influence of the film forming operation is important.

The film strength of the polymer can be adjusted by adjusting the degree of polymerization, the content of amorphous segments, etc.

〔Effect of the invention〕

The film obtained by the present invention has excellent moisture permeability and gas permeability, so it can be used in many fields that require both mono- and amphoteric properties.

〔Example〕

The present invention will be explained below with reference to Examples.

In the Examples and Comparative Examples, "parts" means parts by weight, and the reduced viscosity (Frib) is Fe/-#/
Using a mixed solvent of tetrachloroethane MRA/4<, polyurethane lightness is 0. Measured at 30"C with lIQ/100ml.

Example/ 132 parts of dimethyl terephthalate, average molecular weight approximately 200
500 parts of polyethylene ether glycol and 366 parts of ethylene glycol were charged into an autoclave together with o and t o parts of titanium tetrabutoxide catalyst, and the temperature was brought to an internal temperature of 22.0''C in 0 minutes.

At this time, methano-y was distilled out by transesterification. For another 60 minutes, the pressure in the system was reduced to 0. ．． 2 fi IIIF
At the same time, the temperature was raised to 230'Cvc, and polymerization was carried out for /110 minutes to obtain a copolymer with a reduced viscosity of /23.

This polymer was prepared as a chloroform solution of 10% by weight,
It was coated on release paper with a doctor knife and dried for 6000.3 minutes to obtain a film with a thickness of about 30 folds.

The moisture permeability of this film was determined according to JIS-Z-0201 (temperature =
Ito'c, relative humidity: measured from 011.3 K-, 1,200 sbA, 14! It was hr.

Example Koshimethyl terephthalate 527 parts, average molecular weight approximately YOO
Part of polytetramethylene ether glyco-kSOO of O and 3tt part of ethylene glycol were charged into an autoclave together with 0g0 part of titanium tetrabutoxide catalyst, and a copolymer having a reduced viscosity of 233 was obtained by the same operation as in Example.

The moisture permeability of this polymer is 000 f/m”-4Zh.
It was r.

Example 3 3/lr part of dimethyl terephthalate and 341l part of ethylene glycol were combined with titanium tetrabutoxide catalyst QlrO
The mixture was placed in an autoclave, and the internal temperature was raised to 220"CE over 20 minutes.

Methanol was distilled out through transesterification.

Here, 500 parts of the following silicon diol having an average molecular weight of about 2300 was added, and the pressure in the system was gradually reduced.

0.2tllH9 over 40 minutes and %21Ij
CE temperature was raised. Polycondensation was continued in this state for 1 lIO minutes to obtain a copolymer with a reduced viscosity of /.30.

The moisture permeability of this polymer was measured in the same manner as in Example/, and it was found that:
Tsuta.

-(CHaCHlo)L H Example 1 J/part of dimethyl terephthalate, 3t3!11% of ethylene glycol, 230 parts of polytetramethylene ether glycol having an average molecular weight of about 2000, and 250 parts of silicone diol similar to the silicone diol used in Example 3. A copolymer having a reduced viscosity of /, 11 was obtained by charging 0 g of titanium tetrabutoxide as a catalyst into an autoclave and carrying out the same operation as in Example.

The moisture permeability of this polymer is 009/m”・2 phr
Met.

Example j Dimethyl terephthalate 3/lr, ethylene glycol cock part, polyethylene ether glyco-klAOO part with an average molecular weight of about 2000, and 200 parts of silicon diol similar to the silicon diol used in Example 3, 010 parts of titanium tetrabutoxide as a catalyst. was charged into an autoclave, and by the same operation as in Example/, reduced viscosity/3
g of copolymer was obtained.

This poly! -The moisture permeability of Z Otobe 0f/m', 21I
Example 2 1120 parts of dimethyl terephthalate, 5 parts of ethylene glycol 2, 300 parts of polyethylene ether glycol having an average molecular weight of about 2000, and 200 parts of the following silicon diol having an average molecular weight of about 3.200.

100 parts of polyhexamethylene ether glycol having an average molecular weight of about 2,000 and 0 g of titanium tetrabutoxide as a catalyst were charged into an autoclave, and a copolymer with a reduced viscosity of /, 2/ was obtained by the same operation as in Example /. .

Is the moisture permeability of this polymer Otsu 2009/r? -2≠hr.

Example 7 320 parts of dimethyl terephthalate, 332 parts of hecubutanediol, and Qt part of titanyl magnesium oxalate were charged into an autoclave, and heated to /30" under a nitrogen gas atmosphere.
``CC heated.

The temperature was raised to 2t6c over a period of 0 minutes, and transesterification was carried out.

Here, 500 parts of polyethylene ether glycol having an average molecular weight of about 2000 was added, the pressure in the system was gradually reduced, and 40 parts of polyethylene ether glycol was added.
Polycondensation was carried out for 10 minutes, resulting in a reduced viscosity of 2S4! A copolymer was developed.

The moisture permeability of this polymer is amazing! rOOg/♂・Jph
It was r.

Comparative Example: 520 parts of dimethyl terephthalate, 33 parts of ethylene glycol, 500 parts of polyhexamethylene ether glycol with an average molecular weight of about , a copolymer with a reduced viscosity of 2S2 was obtained.

Konohori w-tvm humidity ha/, soo g/m1.24
It was chr.

Comparative Example 2 Dimethyl terephthalate S/part Otsu, ethylene glycol 3 Otsu 3 parts, polycaprolact 7 having an average molecular weight of about 3000
500 parts, titanium tetrabutoxide QlrO as a catalyst
A copolymer having a reduced viscosity of Z/3 was obtained by the same procedure as in Example.

This poly! The moisture permeability of - is /, 7009 parts m', 21
It was r.

The composition, reduced viscosity, and moisture permeability of the polymer synthesized above are shown in the following table.

(Note 7) The numbers in C) in the table indicate the content in weight percent relative to the polymer.

(Note 2) pmT: Polyethylene terephthalate FB'l': Polyethylene terephthalate P]! :G
: Bo! I Ethylene ether glycol PTMG: Polytetramethylene ether glycol PHMG: Polyhexamethylene ether glycol Silicon diol 0- (p! IJ: CH30) (Mr. Patent Office Examiner) 1. Indication of the case Patent Application Sho/,! > -j7jA-ρ No. 2,
Tara 04 14 years old
ti + t Quil Input 3, Person making the amendment Relationship to the case (patent applicant) Name To j 1
Daimoku bha 11 Kyourei 4, agent/920 ff762
-31-%216, number of inventions increased by amendment
() A crystalline segment consisting of repeating at least one of polyester units, boria 1-ide positions, and polyurethane units, and at least one member selected from both groups below, or at least one member selected from group (5) below. 1. A moisture-permeable and gas-permeable film characterized by containing as a main component a copolymer comprising at least one amorphous segment selected from Group (B).

(A) Reactive group-containing organopolysiloxane, polyalkylene ether glycol, and polyalkylene ether glycol-modified aliphatic polyester (provided that the number of carbon atoms in the alkylene oxide repeating unit is in the range of 2 to 1).

(B) An aliphatic polyester that is not modified with a reactive group-containing organosilane, a polyalkylene ether glycol (alkylene ether glycol), and a polyalkylene ether glycol.

0 Detailed Description of the Invention - On page 3, line 12 of the specification tube, insert "at least one type of polyurethane" after "polyurethane unit."

OBI11mWI, page 1 II/, line ``Can be used.'' Next, ``For example, a film obtained by the present invention is laminated to a fabric, or a solution of this polymer in a suitable solvent is dry-coated on a fabric.'' can be used in the field of comfortable clothing as a waterproof fabric with high moisture permeability.''

Claims (1)

[Claims] A crystalline segment consisting of repeating polyester units, polyamide units and polyurethane units, and the following (
At least one selected from group A) or the following (A)
A moisture-permeable and gas-permeable film characterized by containing as a main component a copolymer comprising at least one amorphous segment selected from the group (B) and at least one amorphous segment selected from the group (B). (A) Reactive group-containing organopolysiloxane, polyalkylene ether glycol, and polyalkylene ether glycol-modified aliphatic polyester (provided that the number of carbon atoms in the alkylene oxide repeating unit is in the range of 2 to 4). (B) An aliphatic polyester that is not modified with a reactive group-containing organosilane, a polyalkylene ether glycol (provided that the number of carbon atoms in the alkylene oxide repeating unit is in the range of 5 to 8), and a polyalkylene ether glycol.