JP2001240648A - Elastomer film or sheet and laminated film or sheet using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an elastomer film or sheet that has excellent mechanical properties, for example, strength, flexibility and the like and heat resistance as well as excellent water impermeability and excellent moisture permeability and laminated film or sheet using the same. SOLUTION: This elastomer is a block copolymer that comprises (A) a polyester copolymer that is constituted with the repeated units of short-chain polyester component represented by general formula (1): -CO-R0-CO-O-R1-O- (wherein R0 is a 6-12C divalent aromatic hydrocarbon group and R1 is a 2-8C alkylene group) and with the recurrent units of the long-chain polyester component represented by general formula (2): -CO-R0-CO-O-R3-O- [wherein R0 is a 6-12C divalent aromatic hydrocarbon group; R3 represents the component that is constituted with the recurrent units represented by the general formula: R4-O- (wherein R4 is a 2-8C alkylene group) and has a number-average molecular weight of 500-5,000] and (B) a polyether that is constituted with the recurring units represented by general formula (3): -R3-O- (wherein R3 is a 2-8C alkylene group), in which the polyester copolymer (A) and the polyether (B) are bridged with the urethane bond component (C) represented by formula (4) -CO-O-NH-R4- NH-CO-O- (wherein R4 represents a 2-15C alkylene group, phenylene group, or methylene group or a functional group to which the above-stated alkylene group and phenylene group are bonded) and the amounts of the components (B) and (C) are characteristically 50-150 pts.wt. and 10-300 pts.wt. per 100 pts.wt. of the component (A), respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an elastomer film or sheet having excellent mechanical properties such as strength and flexibility, heat resistance, water impermeability (water stoppage) and excellent moisture permeability. It relates to the laminated film or sheet used.

[0002]

2. Description of the Related Art Conventionally, as a material of a film or a sheet, a crystalline aromatic polyester such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) constitutes a hard segment, and polylactone constitutes a soft segment. Polyester type thermoplastic elastomers are known (see, for example, JP-A-57-133302), and films or sheets made of such elastomers are said to be excellent in mechanical properties and thermal stability. . Although this film or sheet is certainly excellent in thermal stability, there is room for improvement in flexibility, and there is a problem that it is difficult to provide the film or sheet in a field where stretchability is required. A film or sheet having both heat resistance and mechanical properties such as flexibility has not been known.

[0003] On the other hand, asphalt and asphalt roofing, which have been used as a waterproof sheet on the walls of general houses and roofing materials, are waterproof, but have little or no moisture permeability. When the temperature difference is large, water vapor condenses on the side of the room of these waterproof sheets, which causes molds and damages the wood of the support in contact with the surface where the condensation occurs. There was a problem that was also bad. In order to solve this problem, a lightweight, non-woven, water-permeable polyolefin-based nonwoven sheet has also been developed, but when it is used as a roofing material or a house wrap, it is used for fixing. Since it is quite common to use tuckers and nails, in that case, as a result of the gaps and holes opened by the tuckers and nails in the nonwoven sheet, rainwater infiltrated from the gaps of the tiles and the outer wall passes through the gaps and holes, There was a problem that the wood (for example, a bar, a field board) or the like in contact with the sheet was corroded.

[0004]

SUMMARY OF THE INVENTION In view of the characteristics of the above-mentioned conventional film or sheet, the present invention is excellent in mechanical properties such as strength and flexibility, heat resistance, and water impermeability (water stoppage). It is an object of the present invention to provide an elastomer film or sheet having a combined moisture permeability and a laminated film or sheet using the same.

[0005]

The elastomer film or sheet according to the first aspect of the present invention comprises a short-chain polyester component represented by the general formula (1) and a long-chain polyester component represented by the general formula (2). A polyester copolymer (A) comprising 50 to 100% by weight of the short-chain polyester component and 50 to 0% by weight of the long-chain polyester component, and a repeating unit represented by the general formula (3). A block copolymer of a polyether (B) composed of units, comprising a polyester copolymer (A) and a polyether
(B) is bound by a urethane binding component (C) represented by the general formula (4), and is a polyester-based copolymer (A) 10
0 to 1 part by weight of the polyether (B) is 50 to 1500
Parts by weight and 10 to 300 parts by weight of the urethane binding component (C).

[0006]

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[0007]

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[0008]

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[0009]

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[0010] The elastomer film or sheet according to the second aspect of the present invention is the elastomer film or sheet according to the first aspect, wherein the polyester-based copolymer (A) has a number average molecular weight of 300 to 5,000. is there.

The elastomeric film or sheet according to the third aspect of the present invention is the elastomeric film or sheet according to the first or the second aspect, wherein the polyester-based copolymer (A) has an intrinsic viscosity of 0.05 to 1. It is 0.

[0012] The elastomer film or sheet according to claim 4 is the elastomer film or sheet according to claim 1, 2 or 3, wherein the polyether (B) has a number average molecular weight of 500 to 5000. It is.

The elastomer film or sheet according to the fifth aspect of the present invention is the elastomer film or sheet according to the first to third or fourth aspects, wherein the elastomer film or the sheet has a moisture permeability of 300.
g / m ² · 24 hours or more.

The elastomer film or sheet according to claim 6 is the elastomer film or sheet according to claim 1 to 4 or 5, wherein the thickness of the elastomer film or sheet is 0.01 or less.
５5 mm.

A laminated film or sheet according to the invention of claim 7 is obtained by laminating a nonwoven fabric on at least one surface of the elastomer film or sheet of claims 1 to 5 or 6.

The laminated film or sheet of the invention according to claim 8 is the laminated film or sheet according to claim 7, wherein the thickness of the nonwoven fabric is 0.03 to 5 mm.

The laminated film or sheet according to the ninth aspect of the present invention is the laminated film or the sheet according to the seventh or eighth aspect, wherein the nonwoven fabric is a polyolefin-based nonwoven fabric.

[0018] The laminated film or sheet of the invention according to claim 10 is the laminated film or sheet according to claim 7 or 8, wherein the nonwoven fabric is a polyester-based nonwoven fabric.

The laminated film or sheet of the invention according to claim 11 is the laminated film or sheet according to claim 7 or 8, wherein the nonwoven fabric is a polyamide-based nonwoven fabric.

According to a twelfth aspect of the present invention, there is provided the laminated film or sheet according to any one of the seventh to tenth or eleventh aspects, wherein the laminated film or the sheet has a moisture permeability of 200 g / m ² · 24 hrs or more. It is.

In the present invention, the polyester-based copolymer (A) is constituted by repeating a short-chain polyester component represented by the general formula (1) and a long-chain polyester component represented by the general formula (2). Is done. The above general formula (1) and general formula
In (2), examples of the dicarboxylic acid containing a divalent aromatic hydrocarbon group R ⁰ include terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethyl isophthalate, orthophthalic acid, dimethyl orthophthalate, naphthalenedicarboxylic acid, and naphthalene And dimethyl dicarboxylate.

Examples of the diol component containing an alkylene group R ¹ of 2-8 carbon atoms constituting the short-chain polyester component, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3 -Butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol and the like. Diol component containing an alkylene group R ² of the 2 to 8 carbon atoms constituting the long-chain polyester component may include the same diols as R ^1. Examples of the polyether constituting these long-chain polyester components include polyethylene glycol and poly (1,3-
Polytetramethylene glycols such as propanediol), poly (1,2-propanediol) and poly (1,4-butanediol), and polyhexamethylene glycols such as poly (1,6-hexanediol). Can be These low molecular weight diols and high molecular weight polyether components may be used alone or in combination of two or more.

As the polyether for obtaining the polyester-based copolymer (A), polytetramethylene glycol is preferable among them because of its excellent mechanical properties and weather resistance.
Examples of commercially available products include “PTHF” manufactured by BASF and “PTMG” manufactured by Mitsubishi Chemical Corporation. Polyethylene glycol is suitably used because it can impart excellent moisture permeability.

The above polyether has a number average molecular weight of 50.
Those having about 0 to 5000 are preferable. When the number average molecular weight of R ² in the general formula (2) is smaller than 500,
The blocking property of the obtained polyester copolymer (A) is lowered, the melting point is lowered, and the mechanical strength of the ester elastomer at high temperatures is lowered. If it is larger than 5000,
Since the compatibility with the polyether (B) is low, the degree of polymerization of the ester elastomer does not increase, and an elastomer having sufficient strength cannot be obtained. More preferably, the number average molecular weight is 5
What is 00-2000 is used.

The polyester copolymer (A) can be polymerized by the following method. For example, terephthalic acid dimethyl ester is mixed with polyether and excess low molecular weight diol at 200 ° C. in the presence of a catalyst.
To carry out a transesterification reaction, followed by a polycondensation reaction at 240 ° C. under reduced pressure, whereby a polyester copolymer (A) can be obtained.
The proportion of the short-chain polyester component in the constituent components of the polyester-based copolymer (A) is 50 to 100% by weight. When the amount of the short-chain polyester component is less than 50% by weight, the melting point of the polyester copolymer (A) is low, which adversely affects the mechanical strength of the ester elastomer at high temperatures. Preferably 70 to 100% by weight is used.

The number average molecular weight of the polyester copolymer (A) is preferably from 300 to 5,000. When the number average molecular weight is less than 300, the blockability of the obtained ester elastomer becomes low, which adversely affects the mechanical strength at high temperature. When it exceeds 5,000, the compatibility with the polyether (B) is low. Therefore, the degree of polymerization of the ester elastomer does not increase, and sufficient strength cannot be obtained.

If the intrinsic viscosity of the polyester-based copolymer (A) is too low, the blockability of the ester-based elastomer is lowered, which adversely affects the mechanical strength at high temperatures. Is preferably 0.05 to 1.0, more preferably 0.2 to 0.6, since the compatibility of the ester-based elastomer decreases and the degree of polymerization of the ester-based elastomer decreases, and sufficient strength cannot be obtained. The intrinsic viscosity of the polyester copolymer (A) is a value measured at 25 ° C. using orthochlorophenol as a solvent.

The number average molecular weight of the above polyether (B) is
Preferably it is 500-5000. The above polyether
When the number average molecular weight of (B) is less than 500, the obtained ester elastomer has poor flexibility, and furthermore, it is not possible to obtain sufficient moisture permeability. On the other hand, when it is larger than 5000, the degree of polymerization of the obtained ester elastomer does not increase because the compatibility with the polyether (B) becomes low,
Sufficient strength cannot be obtained. More preferably, those having a number average molecular weight of 500 to 2,000 are used.

The polyether (B) used in the present invention is
It is composed of a repeating unit represented by the general formula (3). As such a polyether, for example, the same polyether as that used for obtaining the above-mentioned polyester-based copolymer (A) is suitably used.

The ester elastomer used in the present invention comprises the above polyester copolymer (A) and a polyether
A block copolymer with (B), wherein the polyester copolymer (A) and the polyether (B) are represented by the above general formulas (4), (5) and (6) Urethane binding component
(C) and so on. The urethane binding component
In order to obtain an ester elastomer bonded by (C), a polyester copolymer (A) and a polyether
(B) may be reacted with, for example, a diisocyanate compound.

The polyester copolymer (A) and the polyether (B) usually have hydroxyl groups at both ends, but may partially have carboxyl groups. At this time, when both terminal functional groups reacting with the diisocyanate compound are hydroxyl groups, the urethane binding component (C) of the general formula (4), and when one is a hydroxyl group and the other is a carboxyl group, the urethane of the general formula (5) Linked by the linking component (C). When the terminal functional group of the polyester-based copolymer (A) is a carboxyl group, the urethane-binding component (C) partially includes a portion bonded by the diisocyanate compound of the general formula (6). You may.

The structure of the isocyanate compound is not particularly limited as long as it is a compound having two isocyanate groups in the same molecule, and three or more isocyanate groups may be used as long as the fluidity of the formed polyester elastomer is maintained. May be used. When an isocyanate compound having three or more isocyanate groups is used, it is preferable to use a diisocyanate compound having two isocyanate groups in combination. The average number of isocyanate groups per molecule of the isocyanate compound is preferably 2.0 to 2.2.

As the diisocyanate, for example,
Aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate; 1,2-ethylene diisocyanate, 1,3-propylene diisocyanate, 1,4-butane diisocyanate, 1,6-hexamethylene Diisocyanate, 1,
Examples thereof include aliphatic diisocyanates such as 4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, isophorone diisocyanate, and hydrogenated 4,4'-diphenylmethane diisocyanate.

A typical example of the isocyanate compound having an average number of isocyanate groups per molecule of more than 2.0 is polymeric MDI, and commercially available products include, for example, "Millionate MR" manufactured by Nippon Polyurethane Co., Ltd.
200 "(average number of isocyanate groups = 2.8). Other isocyanate compounds having an average number of isocyanate groups per molecule larger than 2.0 include other triphenylmethane triisocyanate (3 isocyanate groups), tris (isocyanatephenyl) thiophosphate (3 isocyanate groups), hexamethylene triisocyanate ( 3) isocyanate group and the like.

The above-mentioned ester-based elastomer in the present invention contains 50 to 1500 parts by weight of the polyether (B) and 10 to 300 parts by weight of the urethane binding component (C) based on 100 parts by weight of the polyester-based copolymer (A). Be composed. The reason is that when the amount of the polyether (B) is less than 50 parts by weight, the ester-based elastomer cannot obtain sufficient creep resistance, and cannot obtain sufficient moisture permeability.
If the amount is more than 500 parts by weight, sufficient mechanical strength cannot be obtained, and preferably 100 parts by weight to 900 parts by weight.

When the amount of the urethane binding component (C) is 10
If it is less than 10 parts by weight, the ester-based elastomer will not be a high molecular weight substance and will have low mechanical strength, and if it is more than 300 parts by weight, the ester-based elastomer will have poor creep resistance, Is because sufficient moisture permeability cannot be obtained.
It is composed of 00 parts by weight.

In order to improve the reactivity between the polyester copolymer (A) and the polyether (B) and obtain an ester elastomer having excellent mechanical strength, the terminal of the polyester copolymer (A) must be increased. The functional group is preferably a hydroxyl group. When the terminal functional group is, for example, a carboxyl group, a polymer having a sufficient high molecular weight cannot be obtained due to poor reactivity with an isocyanate group, resulting in poor mechanical strength. Further, it is necessary to take a process countermeasure for suppressing or preventing the generation and foaming of carbon dioxide due to the reaction between the carboxyl group and the isocyanate group.

The isocyanate group of the urethane binding component (C) and the terminal functional group equivalent ratio of the polyester copolymer (A) and the polyether (B) are preferably 0.95 to 1.1. If the above-mentioned equivalence ratio largely deviates from the above-mentioned range, a polymer having a sufficient high molecular weight cannot be obtained, resulting in poor mechanical strength.

The polyester elastomer in the present invention can be obtained, for example, by melt-mixing the polyester copolymer (A), the polyether (B) and the diisocyanate compound and reacting them. A preferred method of melt mixing includes, for example, a method of melt mixing in an extruder, and a preferable extrusion temperature is 150 to 260 ° C. 1
When the temperature is lower than 50 ° C., the reactivity becomes difficult because the polyester copolymer (A) does not melt, and it is difficult to obtain a high-molecular-weight ester elastomer. When the temperature exceeds 260 ° C., the polyester copolymer (A) And the diisocyanate compound is decomposed, and it is difficult to obtain an ester elastomer having sufficient strength. A more preferred range of the melt mixing temperature is 200 to 2
40 ° C.

In the present invention, a catalyst may be used during the melt mixing. As the catalyst, diacyl stannous,
Tetanacyl stannic, dibutyltin oxide, dibutyltin dilaurate, dimethyltin malate, tin dioctanoate, tin tetraacetate, triethyleneamine, diethyleneamine, triethylamine, metal naphthenate,
Metal octylate, triisobutylaluminum, tetrabutyltitanate, calcium acetate, germanium dioxide, antimony trioxide and the like are preferred. Two or more of the above catalysts may be used in combination.

A stabilizer may be used in the ester elastomer of the present invention.
-Trimethyl-2,4,6-tris (3,5-di-t-
Butyl-4-hydroxybenzyl) benzene, 3,9-
Bis {2-3- (3-t-butyl-4-hydroxy-5)
-Methylphenyl) -propionyloxy] -1,1-dimethylethyl {-2,4,8,10-tetraoxaspiro [5,5] undecane and the like; a hindered phenolic antioxidant; tris (2,4 -Di-t-butylphenyl) phosphite, trilauryl phosphite, 2-t-butyl-α- (3-t-butyl-4-hydroxyphenyl)
-P-cumenylbis (p-nonylphenyl) phosphite, dimyristyl 3,3'-thiodipropionate,
And heat stabilizers such as distearyl 3,3'-thiodipropionate, pentaerythryltetrakis (3-laurylthiopropionate), and ditridecyl 3,3'-thiodipropionate.

The above-mentioned ester-based elastomer in the present invention may contain, as needed, during or after production, a cell nucleating agent, a fiber, a flame retardant, an ultraviolet absorber, an antistatic agent, an inorganic filler and other inorganic substances, and a higher fatty acid. An additive such as a salt may be added. In general, the bubble nucleating agent preferably has a particle size of 500 μm or less, for example, calcium carbonate, talc, clay, magnesium oxide, zinc oxide, carbon black, silicon dioxide, titanium oxide, sodium bicarbonate, citric acid, ortho acid, and the like. Examples include boric acid and alkaline earth metal salts of fatty acids. Examples of the fibers include inorganic fibers such as glass fibers, carbon fibers, boron fibers, silicon carbide fibers, alumina fibers, amorphous fibers, and silicon / titanium / carbon fibers; and organic fibers such as aramid fibers.

Examples of the flame retardant include hexabromocyclododecane, tris- (2,3-dichloropropyl)
Phosphate, pentabromophenyl allyl ether and the like. Examples of the ultraviolet absorber include p
-Tert-butylphenyl salicylate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-
Methoxy-2'-carboxybenzophenone, 2,4
5-trihydroxybutyrophenone and the like. Examples of the antistatic agent include N, N-bis (hydroxyethyl) alkylamine, alkylallyl sulfonate, and alkyl sulfanate.

Examples of the inorganic filler include calcium carbonate, titanium oxide, mica, and talc.
Other inorganic substances include, for example, barium sulfate, alumina, silicon oxide, and the like. Examples of the higher fatty acid salt include sodium stearate, barium stearate, sodium palmitate and the like.

The above-mentioned ester-based elastomer in the present invention may be used after modifying the properties thereof by mixing a thermoplastic resin or a rubber component other than those described above. Examples of such a thermoplastic resin include polyolefin, modified polyolefin, polystyrene, polyvinyl chloride, polyamide, polycarbonate, polysulfone, and polyester. As the rubber component, for example, natural rubber, styrene-butadiene copolymer, polybutadiene, polyisoprene, acrylonitrile-butadiene copolymer, ethylene-propylene copolymer (EPM, EPDM), polychloroprene, butyl rubber, acrylic Examples include rubber, silicone rubber, urethane rubber, olefin-based thermoplastic elastomer, styrene-based thermoplastic elastomer, PVC-based thermoplastic elastomer, ester-based thermoplastic elastomer, and amide-based thermoplastic elastomer.

The method for producing the elastomer film or sheet according to the present invention from the ester-based elastomer is not particularly limited, and a conventionally known method can be employed.

For example, (1) an unstretched sheet or film may be obtained and used as it is, or (2) an unstretched sheet or film may be uniaxially or biaxially stretch-formed.
In addition, examples of the laminating method in the case of a multilayer structure include a co-extrusion method and a laminating method.

The unstretched sheet or film can be obtained, for example, by sufficiently drying the above-mentioned ester-based elastomer, supplying it to an extruder, and extruding it on a casting drum. A uniaxially stretched sheet or film, for example, is usually obtained by sandwiching an unstretched sheet between two different pairs of pinch rolls and pulling the sheet in the length direction in a heated state, whereby the sheet is strongly oriented only in the uniaxial direction. . In this case, the rotational speed ratio between the roll on the take-up side and the roll on the pay-out side becomes the stretching ratio.

A biaxially stretched sheet or film is usually obtained by stretching an unstretched sheet simultaneously or sequentially in a biaxial direction to orient in that direction. Also,
In the case of sequential biaxial stretching, the stretching may be performed in the order of the sheet in the longitudinal direction and the width direction, or vice versa. Furthermore, in simultaneous biaxial or sequential biaxial stretching, stretching in the longitudinal direction and width direction can be performed two or more times. The stretching ratio in the longitudinal direction and width direction of the sheet or film can be arbitrarily set according to the degree of orientation, strength, elastic modulus, etc. of the target sheet or film, but is preferably 2.5 to 5. It is set to 0 times. Either the stretching ratio in the longitudinal direction or the stretching direction in the width direction may be higher, and may be the same. The stretching temperature can be any temperature as long as it is equal to or higher than the glass transition temperature (Tg) of the ester-based elastomer and equal to or lower than the crystallization temperature, but is preferably 80 to 180 ° C.

After the biaxial stretching, the sheet or the film can be subjected to a heat treatment. This heat treatment can be performed by any conventionally known method such as in an oven or on a heated roll. The heat treatment temperature can be any temperature from the crystallization temperature of the ester-based elastomer to the softening point, but is preferably from 120 to 240 ° C. Further, the heat treatment time can be arbitrarily set, but is preferably 1 to 60 seconds. The heat treatment may be performed while relaxing the sheet or film in the longitudinal direction and / or the width direction.

The moisture permeability of the elastomer film or sheet of the present invention is a value measured according to JIS Z 0208. The moisture permeability of the elastomer film or sheet of the present invention is 300 g / m ² · 24 hours or more, preferably 500 g / m ² · 24 hours or more, more preferably 1000 g / m ² · 24 hours or more.

The thickness of the elastomer film or sheet of the present invention is preferably from 0.01 to 5 mm, more preferably from 0.01 to 3 mm, because if it is too thin, it is easily broken, and if it is too thick, the moisture permeability decreases. More preferably, it is 0.02 to 2 mm.

The elastomer film or sheet of the present invention may be composed of a single layer, or may be a composite film or sheet of two or more layers. 2 above
In a composite film or sheet having more than one layer, a film or sheet made of a polyester resin may be laminated, for example, a polyolefin resin, a film or a non-polyester resin such as a polyamide resin, or the like. Sheets may be laminated.

By laminating the elastomer film or sheet of the present invention with a nonwoven fabric, the mechanical strength and the water stopping property can be further improved. The nonwoven fabric is not particularly limited, for example, a nonwoven fabric obtained by a dry process such as a needle punch method, a spunlace method, a spun bond method or a melt blow method,
Examples of the nonwoven fabric include a nonwoven fabric obtained by a wet process such as a papermaking method, a nonwoven fabric obtained by combining a dry process and a wet process, and a laminate of the nonwoven fabric obtained by both processes.

The fibers constituting these nonwoven fabrics include:
Although not particularly limited, for example, natural fibers such as cotton, hemp, and wool, regenerated cellulose fibers, polyamide fibers,
Polyester, polyolefin, polystyrene,
Examples thereof include synthetic fibers such as polyacrylic and polyvinyl alcohol, and inorganic fibers such as pulp and glass fiber.
These fibers can be used alone or as a mixture. Among them, polyolefin-based, polyester-based, and polyamide-based synthetic fibers are preferably used because of their excellent durability.

If the thickness of the non-woven fabric is too small, the effect of reinforcing the elastomer film or sheet cannot be sufficiently obtained, and if the thickness is too large, the bulkiness and rigidity will increase even if the reinforcing effect is sufficient. Therefore, the thickness is preferably in the range of 0.03 to 5 mm because the handling property is deteriorated.

The laminated film or sheet of the present invention comprises:
Although the above-described elastomer film or sheet and a nonwoven fabric are laminated, the lamination means is not particularly limited, and examples thereof include an adhesive lamination method using an adhesive, a heat fusion method, and the like. . Among them, industrially, during extrusion molding of a polyester-based elastomer film or sheet, a nonwoven fabric is laminated on the elastomer film or sheet while the elastomer film or sheet has heat fusibility,
An extrusion lamination method in which both are pressed by a roll or the like and laminated is preferably used.

The moisture permeability of the thus obtained laminated film or sheet of the present invention is preferably 200 g /
m ² · 24 hours or more, more preferably 500 g /
m ² · 24 hours or more, more preferably 1000 g / m ²
・ 24 hours or more. The moisture permeability of the laminated film or sheet is a value measured according to JIS Z0208. If the above water vapor permeability is less than 200 g / m ² · 24 hours, sufficient air permeability cannot be obtained. For example, when used as a waterproof sheet for construction, generation of mold on the coated surface due to dew condensation and deterioration of wood members etc. And may cause various troubles due to poor air permeability.

(Function) In the present invention, as described above, an ester-based elastomer having a high blockability of a hard segment component and a soft segment component was studied, and an elastomer film or sheet was obtained. The above-mentioned ester-based elastomer in the present invention exhibits properties as an elastomer by the crystal formed by the short-chain polyester component constituting a cross-linking point. And a long-chain polyether polyester component, that is, a portion having a high proportion of the soft segment component, so that the short-chain polyester component is more crystalline than the conventional ester-based elastomer exhibiting the same degree of creep resistance. As a result, a strong crosslinking point is formed, and excellent mechanical properties at high temperatures can be exhibited.

Further, the presence of a portion having a high proportion of polyether increases the molecular weight between crosslinking points, and as a result,
In addition to exhibiting the characteristics of a highly flexible elastomeric material, the elastomer material has both water impermeability and excellent moisture permeability. Since the ester-based elastomer film or sheet of the present invention uses such an ester-based elastomer, it has excellent mechanical properties such as strength and flexibility and heat resistance, and is a roofing material used under roofs and walls. When used as a material, it has excellent water-blocking properties (impermeability) even when nailed for fixing, and can be widely used as a building material. Covers, raincoats, tents, wet suits, other protective clothing for clean rooms, gloves, various shoes, daily items such as back sheets for disposable diapers, films or sheets for cultivation in agriculture, films or sheets for medical use, strength and flexibility It has excellent mechanical properties such as permeability and heat resistance, and has both water impermeability and excellent moisture permeability. It is one which allows very useful for use in wide range of fields taking advantage of.

Since the laminated film or sheet of the present invention is obtained by laminating the above-mentioned ester-based elastomer film or sheet and a nonwoven fabric, the above-mentioned various properties of the ester-based elastomer film or sheet are strengthened. In addition, it is possible to remarkably improve not only mechanical strength including durability but also particularly moisture permeability and dew condensation prevention.

[0062]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. (Example 1) [Production of polyester-based copolymer (A)] 100 parts by weight of dimethyl terephthalate, 102 parts by weight of 1,4-butanediol, polytetramethylene glycol having a number average molecular weight of about 1000 (manufactured by BASF) PTHF1000 ") (hereinafter referred to as _Mn ≒ 1000), 48 parts by weight, 0.3 parts by weight of tetrabutyl titanate as a catalyst, and 1 part as a stabilizer.
3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene
3 parts by weight and 0.3 parts by weight of tris (2,4-di-t-butylphenyl) phosphite were added, and the reaction system was kept at 200 ° C. for 3 hours under nitrogen to carry out a transesterification reaction.

The progress of the transesterification reaction was confirmed by measuring the amount of methanol distilled off. After the transesterification proceeded, the temperature was raised to 240 ° C. for 20 minutes, and the pressure was reduced. The polymerization system reached a reduced pressure of 2 mmHg or less in 20 minutes. As a result of performing a polycondensation reaction in this state for 20 minutes, 160 parts by weight of a white polyester copolymer was obtained.

(Production of Sheet) 100 parts by weight of the polyester copolymer, 110 parts by weight of the above-mentioned polytetramethylene glycol (M _n ≒ 1000) and 36 parts by weight of 4,4′-diphenylmethane diisocyanate were mixed with a twin-screw extruder ( 220 ° C using L / D = 25 manufactured by Berstolf
(Residence time: 200 seconds), extruded into a sheet, cooled through a cooling drum, wound up by a winder, width 30
An ester-based elastomer sheet having a thickness of 2 cm and a thickness of 2 mm was obtained. From the sheet obtained, JI using a punching press
The S2 dumbbell was punched out and evaluated by the following method.
The results are shown in Table 1. [Surface hardness] Measured according to ASTM D-2240. [Strong elongation] Tensile strength according to ASTM D-638,
The elongation at break was measured. [Heat resistance] After standing at 140 ° C. for 10 minutes, evaluation was made based on the change in shape.

(Example 2) [Production of polyester copolymer (A)] The above polytetramethylene glycol used in Example 1 (M _n ≒ 100)
Example 1 except that the amount of 0) was 12 parts by weight.
In the same manner as in the production of the polyester copolymer in
120 parts by weight of a polyester copolymer was obtained.

(Production of Sheet) 100 parts by weight of the polyester copolymer, 110 parts by weight of the above polytetramethylene glycol (M _n n1000), and 42 parts by weight of 4,4′-diphenylmethane diisocyanate were mixed with a twin screw extruder ( Using Berstorf L / D = 25), 220
Kneading (residence time 200 seconds) at ℃, extruded into a sheet,
After cooling through a cooling drum, it is wound on a winder and has a width of 3 mm.
An ester-based elastomer sheet having a thickness of 0 cm and a thickness of 2 mm was obtained. The properties of the sheet were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 3 [Production of Polyester Copolymer (A)] The above polytetramethylene glycol used in Example 1 (M _n ≒ 100)
Example 1 except that the amount of 0) was 28 parts by weight.
In the same manner as in the production of the polyester copolymer in
140 parts by weight of a polyester copolymer was obtained.

(Production of Sheet) 100 parts by weight of the polyester copolymer, 110 parts by weight of the above polytetramethylene glycol (M _n n1000), and 42 parts by weight of 4,4′-diphenylmethane diisocyanate were mixed with a twin screw extruder ( Using Berstorf L / D = 25 mm), 2
After kneading (residence time: 200 seconds) at 20 ° C., extruding into a sheet, cooling through a cooling drum, winding the sheet on a winder,
An ester elastomer sheet having a width of 30 cm and a thickness of 2 mm was obtained. The properties of the sheet were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 1 (Production of polyester copolymer) 100 parts by weight of dimethyl terephthalate, 102 parts by weight of 1,4-butanediol, and the above-mentioned polytetramethylene glycol used in Example 1 (M _n ≒ 1000) ) 170 parts by weight, 0.3 parts by weight of tetrabutyl titanate as a catalyst, 1,3,5-
0.3 parts by weight of trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and 0.1 parts of tris (2,4-di-tert-butylphenyl) phosphite. 3 parts by weight, and the reaction system was cooled to 20 under nitrogen.
The mixture was kept at 0 ° C. for 3 hours to carry out a transesterification reaction.

The progress of the transesterification reaction was confirmed by measuring the amount of methanol distilled off. After the transesterification proceeded, the temperature was raised to 240 ° C. for 20 minutes, and the pressure was reduced. The polymerization system reached a reduced pressure of 2 mmHg or less in 20 minutes. As a result of performing a polycondensation reaction in this state for 20 minutes, 283 parts by weight of a white ester elastomer was obtained.

(Production of Sheet) This ester-based elastomer was mixed with a twin-screw extruder (L / D = 25 manufactured by Berstorf Co., Ltd.).
mm) and kneading at 220 ° C. (residence time 200 seconds)
Then, the mixture was extruded into a sheet, cooled through a cooling drum, and wound around a winder to obtain an ester elastomer sheet having a width of 30 cm and a thickness of 2 mm. The properties of the sheet were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2 100 parts by weight of polybutylene terephthalate pellets, 0.08 part by weight of a phosphorus compound of triphenyl phosphite, and 30 parts by weight of ε-caprolactone were mixed with a twin-screw extruder (manufactured by Berstorf, L / D = 25m
m), kneaded at 230 ° C., extruded into a sheet,
After cooling through a cooling drum, it is wound on a winder and has a width of 3 mm.
An ester-based elastomer sheet having a thickness of 0 cm and a thickness of 2 mm was obtained. The properties of the sheet were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[0073]

[Table 1]

Example 4 Production of Polyester Copolymer (A) 100 parts by weight of dimethyl naphthalenedicarboxylate, 81 parts by weight of 1,4-butanediol, polytetramethylene glycol having a number average molecular weight of about 650 ( "PTMG650" manufactured by Mitsubishi Chemical Corporation)
(Hereinafter referred to as _Mn ≒ 650) 12 parts by weight, 0.3 parts by weight of tetrabutyl titanate as a catalyst, and 1,3,5-trimethyl-2,4,6-tris (3,5
-Di-t-butyl-4-hydroxybenzyl) benzene (0.3 part by weight) and tris (2,4-di-t-butylphenyl) phosphite (0.3 part by weight) were added, and the reaction system was heated at 210 ° C. under nitrogen. For 3 hours to carry out a transesterification reaction.

The progress of the transesterification reaction was confirmed by measuring the amount of methanol distilled off. After the transesterification reaction proceeded, the temperature was raised to 250 ° C. in 20 minutes, and a pressure reduction operation was performed. The polymerization system reached a reduced pressure of 2 mmHg or less in 20 minutes. As a result of a polycondensation reaction for 10 minutes in this state, 130 parts by weight of a white polyester copolymer was obtained. The number average molecular weight of the obtained copolymer was 1,300.

(Production of Sheet) 100 parts by weight of the polyester copolymer, 500 parts by weight of polytetramethylene glycol (M _n n1000) and 150 parts by weight of 4,4′-diphenylmethane diisocyanate were mixed in a twin-screw extruder (Berstorff). (L / D = 40), extruded into a sheet, cooled through a cooling drum and wound up on a winder to obtain an ester-based elastomer sheet having a width of 30 cm and a thickness of 0.5 mm. Was.

The tear strength, water vapor permeability and water blocking property (water impermeability) of the obtained sheet were evaluated by the following methods, and the results are shown in Table 2.

[Tear strength] JIS L 1096 A-
The measurement was performed according to the method 1.

[Moisture Permeability] Measured according to JIS Z 0208.

[Waterproof] On a 1 cm thick wood board, nails (length 125 mm, head diameter 10.5 mm, trunk diameter 4.6 m)
In m), the sample sheet is nailed and fixed. At the nailed area on the fixed sheet, a glass tube (2
(0 mm, height 300 mm), and the nail head is arranged at the center of the bottom of the glass tube. In order to seal the bottom of the glass tube and the sheet surface in a watertight manner, the outer periphery of the bottom of the glass tube is sealed with a sealing material. Seal and fill with water to a height of 250 mm and test whether the injected water leaks through the sheet from the nailed area. In addition, in order to prevent evaporation of water from the upper part of the glass tube, the glass tube was covered with an upper lid and allowed to stand. A sample having a water loss of 1 milliliter or less for 24 hours after standing was evaluated as "water-static", and the number of samples was 1
The test was performed with 0 pieces, and the superiority of the water stoppage was evaluated by the number of “waterproof” / the number of test pieces.

(Example 5) [Polyester copolymer]
Production of (A)] In the production of the polyester copolymer of Example 4, polytetramethylene glycol (M _n n65
Except that 0) was not used, 118 parts by weight of a polyester-based copolymer was obtained in the same manner as in Example 4. The number average molecular weight of the obtained copolymer was 1200.

(Production of Sheet) The same procedure as in Example 4 was repeated except that the obtained polyester copolymer was used and the number average molecular weight of the polytetramethylene glycol in Example 4 was changed to about 1500. , Thickness 0.1mm
Was obtained. The properties of the sheet obtained in the same manner as in Example 4 were evaluated, and the results are shown in Table 2.

Example 6 The same as Example 4 except that the polytetramethylene glycol (M _n ≒ 650) of Example 4 was replaced by 500 parts by weight of polyethylene glycol having a number average molecular weight of about 1,000. To obtain a polyester copolymer, and an ester elastomer sheet having a width of 30 cm and a thickness of 0.1 mm was obtained using the polyester copolymer. The properties of the sheet obtained in the same manner as in Example 4 were evaluated, and the results are shown in Table 2.

(Comparative Example 3) The same asphalt roofing sheet as in Example 4 was evaluated using 22 kg of commercially available asphalt roofing, and the results are shown in Table 2.
It was shown to.

[0085]

[Table 2]

(Example 7) The ester-based elastomer sheet obtained in Example 5 and a polyester-based non-woven fabric having a thickness of 0.11 mm (“Estal E01015” manufactured by Asahi Kasei Corporation) were heated at 230 ° C. using a “heat press”. To form a laminated sheet having a thickness of 0.16 mm. The tear strength, moisture permeability, and water stoppage (water impermeability) of the obtained laminated sheet were evaluated in the same manner as in Example 4. The results are shown in Table 3.

(Example 8) In the step of melt-extruding an ester-based elastomer sheet of Example 5, while the above-mentioned melt-extruded sheet has a state of heat-sealing property, the same polyester-based nonwoven fabric as used in Example 7 ( 0.29mm thick)
Were supplied in layers and pressed between the laminating rolls to produce a laminated sheet having a thickness of 0.37 mm. The tear strength, moisture permeability, and water stoppage (water impermeability) of the obtained laminated sheet were evaluated in the same manner as in Example 4. The results are shown in Table 3.

[0088]

[Table 3]

[0089]

Since the elastomer film or sheet according to the first aspect of the present invention is constituted as described above, a hard segment component comprising a short-chain polyester component represented by the general formula (1) and (2) or general formula
(3) It is made of an ester-based elastomer that has high blockability with the soft segment component represented by (3), and also has excellent elongation in addition to heat resistance, and has both mechanical properties such as strength and flexibility and heat resistance. Elastomer film or sheet. They are suitably used particularly for industrial packaging applications such as adhesive tape materials and cable covers, packaging applications for foods and the like.

Further, as described above, the elastomer film or sheet of the present invention can be used as a highly flexible elastomeric material in which the presence of a portion having a high proportion of polyether increases the molecular weight between crosslinking points. In addition to exhibiting the characteristics, it has both water impermeability and excellent moisture permeability.

The elastomer film or sheet of the present invention is excellent in mechanical properties such as strength and flexibility and heat resistance in addition to the applications in the above-mentioned fields. When used as a base material such as for example, excellent waterproofness (water impermeability) is secured even by nailing for fixing, and it can be widely used as a building material. As interior materials, body covers, raincoats, tents, wetsuits, other protective clothing for clean rooms, gloves, various shoes, daily items such as backsheets for disposable diapers, various cultivation films or sheets in agriculture, various medical films or sheets It is excellent in mechanical properties such as strength, flexibility, etc. and heat resistance, and has both water impermeability and excellent moisture permeability. It is intended to enable a very useful use in the lend wide range of fields.

The elastomer film or sheet according to the second aspect of the present invention is configured as described above. Therefore, in the elastomer film or sheet according to the first aspect, particularly, mechanical properties such as strength and flexibility, and heat resistance. It has excellent water permeability and excellent water permeability and excellent moisture permeability, and enables extremely useful use in a wide range of fields.

Since the elastomer film or sheet according to the third aspect of the present invention is configured as described above, the elastomer film or sheet according to the first aspect of the present invention particularly has mechanical properties such as strength and flexibility. It has excellent heat resistance, and has both water impermeability and excellent moisture permeability, and enables extremely useful use in a wide range of fields.

The elastomer film or sheet according to the fourth aspect of the present invention is configured as described above. Therefore, in the elastomer film or the sheet according to the first aspect, particularly, mechanical properties such as strength and flexibility are provided. It has excellent heat resistance, and has both water impermeability and excellent moisture permeability, and enables extremely useful use in a wide range of fields.

Since the elastomer film or sheet according to the fifth aspect of the present invention is configured as described above, the elastomer film or sheet according to the first aspect of the present invention particularly has excellent moisture permeability. Provide a comfortable living environment as a building material to breathe or as an interior material for vehicles, and discomfort when wearing clothing such as humid or wet or rash on weak skin such as infants as various protective clothing and protective equipment to breathe Without, it gives a comfortable feeling of use, moreover, enables efficient execution of forcing cultivation and suppression cultivation as a production material of respiring agriculture, forestry and fishery materials, and furthermore, these fresh food products, flowers, The present invention enables extremely useful use in a wide range of fields, such as a packaging material for seeds and seedlings, and as various breathable medical films or sheets.

Since the elastomer film or sheet according to the sixth aspect of the present invention is configured as described above, the elastomer film or sheet according to any one of the first to third aspects exhibits mechanical properties such as strength and flexibility and the like. It maximizes various properties such as heat resistance and water impermeability and moisture permeability.

The laminated film or sheet according to the seventh aspect of the present invention is constructed as described above, so that the elastomer film or the sheet according to the first aspect of the invention has excellent mechanical strength and flexibility. In addition to the excellent properties of having both properties and heat resistance as well as water impermeability and moisture permeability, the properties of the nonwoven fabric such as strength and cushioning properties are organically combined, and these effects can be significantly enhanced. Things.

Since the laminated film or sheet of the invention according to claim 8 is configured as described above, particularly,
It also has excellent moisture permeability, provides a comfortable living environment as a building material to breathe and interior materials such as vehicles, as well as various protective clothing and protective equipment to breathe, against stuffy or wet skin or weak skin such as infants There is no discomfort when wearing clothes such as rash, and it gives a comfortable feeling of use.Moreover, it enables efficient cultivation such as forcing cultivation or suppression cultivation as a production material of respiring agriculture, forestry and fishery materials. It enables extremely useful use in a wide range of fields, such as packaging materials for these fresh foods, flowers, seeds and seedlings, and various respirable medical films or sheets.

Since the laminated film or sheet according to the ninth aspect of the present invention is constructed as described above, the strength, flexibility, etc., of the elastomer film or sheet and the laminated film or the sheet according to the preceding aspects are exhibited. This ensures that the various properties such as mechanical properties and heat resistance, and water impermeability and moisture permeability are exhibited.

Since the laminated film or sheet according to the tenth aspect of the present invention is constituted as described above, the strength, flexibility and the like which the elastomer film or the sheet and the laminated film or the sheet according to the preceding aspects play. In addition to the mechanical properties, heat resistance, and various properties such as water impermeability and moisture permeability, it is lightweight, has good handling properties such as rich slipperiness, and imparts excellent durability. It is.

Since the laminated film or sheet according to the eleventh aspect of the present invention is constituted as described above, the strength, flexibility and the like that the elastomer film or the sheet and the laminated film or the sheet according to the preceding aspects play. In particular, it imparts high strength and excellent durability in addition to the mechanical properties and heat resistance, and various properties such as water impermeability and moisture permeability.

Since the laminated film or sheet according to the twelfth aspect of the present invention is constructed as described above, the strength, flexibility and the like of the elastomer film or sheet and the laminated film or the sheet according to the preceding aspects are exhibited. In addition to the mechanical properties and heat resistance, and various properties such as water impermeability and moisture permeability, the present invention particularly provides excellent heat resistance such as cold resistance and heat resistance and weather resistance.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shigeichi Fukaya 2-1 Shimomotocho Hyakuyama, Mishima-gun, Osaka Sekisui Chemical Co., Ltd. (72) Inventor Shoji Nori 2- Hyakuyama, Shimamotocho, Mishima-gun, Osaka 1 F-term in Sekisui Chemical Co., Ltd. (reference) 4F071 AA53 AA81 AA88 AF09 AF15 AF21 AF25 AF45 AH03 BB06 BC01 BC10 BC12 4F100 AK03B AK41A AK41B AK46B AK51A AK54A AL01A AL05A AL09A BA02J15Y15Y04 J15Y15Y15 BA07 DA01 DB03 DB04 DC02 DC43 DC50 DF01 DF14 DF16 DF21 DG02 DH02 DH06 DH10 HA01 HA06 HA07 HA11 HC03 HC12 HC22 HC71 JA01 QB15 QB19 RA05 RA09

Claims (12)

[Claims] 1. A short-chain polyester component represented by the following general formula (1) and a long-chain polyester component represented by the following general formula (2):
0 to 100% by weight, and the long-chain polyester component is 50 to
0% by weight of a polyester copolymer (A) and a general formula
A block copolymer of a polyether (B) composed of the repeating unit represented by (3), wherein the polyester copolymer (A) and the polyether (B) are represented by the general formula (4). The polyether (B) is 50 to 1500 parts by weight and the urethane binding component (C) is 10 to 300 parts by weight based on 100 parts by weight of the polyester copolymer (A). An elastomer film or sheet comprising parts by weight. Embedded image Embedded image Embedded image Embedded image 2. The elastomer film or sheet according to claim 1, wherein the polyester-based copolymer (A) has a number average molecular weight of 300 to 5,000. 3. The elastomer film or sheet according to claim 1, wherein said polyester copolymer (A) has an intrinsic viscosity of 0.05 to 1.0. 4. The elastomer film or sheet according to claim 1, wherein the number average molecular weight of the polyether (B) is from 500 to 5,000. 5. The elastomer film or sheet according to claim 1, wherein the moisture permeability of the elastomer film or sheet is 300 g / m ² · 24 hours or more. 6. The elastomer film or sheet according to claim 1, wherein said elastomer film or sheet has a thickness of 0.01 to 5 mm. 7. A laminated film or sheet obtained by laminating a nonwoven fabric on at least one surface of the elastomer film or sheet according to claim 1. 8. The nonwoven fabric having a thickness of 0.03 to 5 mm
The laminated film or sheet according to claim 7, wherein 9. The laminated film or sheet according to claim 7, wherein the nonwoven fabric is a polyolefin-based nonwoven fabric. 10. The laminated film or sheet according to claim 7, wherein the nonwoven fabric is a polyester-based nonwoven fabric. 11. The laminated film or sheet according to claim 7, wherein the nonwoven fabric is a polyamide-based nonwoven fabric. 12. The transparent film or sheet of the laminated film.
Humidity 200g / m ^Two· It is 24 hours or more.
12. The laminated film or sheet according to 10 or 11.