JP2015120838A - Porous sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a porous sheet that uses a resin derived from biomass as a raw material, satisfies flexibility and moisture permeability and has excellent durability.SOLUTION: The porous sheet is produced by melt molding a resin composition including a resin and not less than 20 pts.mass to not more than 300 pts.mass of a filler based on 100 pts.mass of the resin to form a raw fabric sheet and stretching the raw fabric sheet. The resin is produced by subjecting a dicarboxylic acid component including a dicarboxylic acid compound having a furan ring and a diol and/or a diamine to condensation and has a content of the dicarboxylic acid compound having a furan ring in the dicarboxylic acid component exceeding 90 mol%.

Description

  The present invention relates to a porous sheet excellent in durability while satisfying flexibility and moisture permeability.

  In recent years, as environmentally friendly materials, resins using biomass-derived raw materials and resins having biodegradability have been developed and put into practical use. Patent document 1 has a furan structure and a reduced viscosity (ηsp) with the object of providing a thermoplastic resin having a sufficient molecular weight that is excellent in heat resistance, mechanical properties, and weather resistance using biomass as a raw material. A thermoplastic resin having a / C) of 0.48 dL / g or more and a terminal acid value of less than 200 μeq / g is disclosed.

  In Patent Document 2, it is obtained from an aliphatic dicarboxylic acid, a polyfunctional aromatic acid, and a diol for the purpose of providing a resin for versatile use including a film or a sheet using a fatty-aromatic biodegradable polyester. A biodegradable polyester of the fatty-aromatic type is disclosed in which the aromatic acid is a dicarboxylic acid derived from a renewable resource.

JP 2008-291243 A Special table 2011-520005 gazette

  A porous sheet is known as one of materials using a resin, and the porous sheet is used as, for example, a sanitary material, a medical material, a clothing material, a separation filter, a battery material, and the like.

  However, a porous sheet manufactured using polylactic acid (PLA) as a biomass-derived polyester resin has poor durability. Although there is a description in Patent Document 2 that may be used for a porous sheet, aliphatic dicarboxylic acid is used, and when processed into a porous sheet, the durability cannot be said to be sufficient.

  Accordingly, an object of the present invention is to provide a porous sheet that uses a biomass-derived resin as a raw material and is excellent in durability while satisfying flexibility and moisture permeability.

That is, the gist of the present invention is as follows.
A porous sheet formed by melt-molding a resin composition containing a resin and a filler containing 20 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the resin, and stretching the original sheet There,
The resin is a resin obtained by condensing a dicarboxylic acid component containing a dicarboxylic acid compound having a furan ring and a diol and / or diamine, and the amount of the dicarboxylic acid compound having a furan ring in the dicarboxylic acid component is 90%. The present invention relates to a porous sheet, which is a resin exceeding mol%.

  The porous sheet of the present invention exhibits the effect of being excellent in durability while satisfying flexibility and moisture permeability.

  In the present invention, by using a flanged carboxylic acid compound that exceeds 90 mol% in the dicarboxylic acid component, when the porous sheet is formed, the durability of the resin, that is, the hydrolysis resistance is unexpectedly improved, and the flexibility and permeability are improved. It was found that the moisture was also satisfied. This is presumably because the furan ring resin has an appropriate elastic modulus, and therefore when it is made porous by adding a filler and stretching, it satisfies moisture permeability and develops flexibility. Moreover, it is thought that it is because it is excellent in the hydrolysis resistance after the high temperature preservation | save of the dicarboxylic acid compound which has a furan ring in a dicarboxylic acid component that it is excellent in durability.

  The present invention is obtained by melt-molding a resin composition containing a resin and a filler of 20 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the resin, and stretching the original sheet. It is a porous sheet, and the resin is a resin obtained by condensing a dicarboxylic acid component containing a dicarboxylic acid compound having a furan ring and a diol and / or a diamine, and has a furan ring in the dicarboxylic acid component. It is a porous sheet which is resin in which the quantity of a dicarboxylic acid compound exceeds 90 mol%.

  The resin in the present invention is not particularly limited as long as it is a resin obtained by condensing a dicarboxylic acid component containing a dicarboxylic acid compound having a furan ring and a diol and / or diamine, but the specific resin used in the present invention is not limited. Examples of the resin include condensation polymers such as polyester, polyamide, and polyester carbonate. Among them, polyester and polyamide are suitable resins.

  Hereafter, each component used for manufacture of resin of this invention is demonstrated.

[Dicarboxylic acid component (hereinafter also simply referred to as acid component)]
From the viewpoint of the durability of the resulting porous sheet, the amount of the dicarboxylic acid compound having a furan ring in the dicarboxylic acid component used as the raw material for the resin is more than 90 mol%, preferably 93 mol% or more, more preferably 95. More preferably, mol% or more, still more preferably 98 mol% or more, still more preferably 99 mol% or more, and substantially 100 mol%.

  The dicarboxylic acid compound having a furan ring may be a petroleum-derived raw material or a biomass-derived raw material, but it is preferable to use a biomass-derived raw material. In addition, the component as used in this invention is synonymous with a raw material.

  Examples of the dicarboxylic acid compound having a furan ring include furan-2,5-dicarboxylic acid (also referred to as 2,5-furandicarboxylic acid), furan-2,4-dicarboxylic acid, furan-2,3-dicarboxylic acid, A furancarboxylic acid compound such as furan-3,4-dicarboxylic acid can be used, and furan-2,5-dicarboxylic acid is preferable from the viewpoint of durability and flexibility of the porous sheet to be obtained.

  As the dicarboxylic acid compound having a furan ring, only one component may be used, or a plurality of components may be used in combination. In the present specification, the “carboxylic acid compound” includes not only a carboxylic acid but also an ester of the carboxylic acid and an alcohol having 1 to 3 carbon atoms, and an acid anhydride of the carboxylic acid.

  The acid component can contain a carboxylic acid compound other than the dicarboxylic acid compound having a furan ring as long as the effects of the present invention are not impaired. Examples of such carboxylic acid compounds include aliphatic dicarboxylic acid compounds. As the aliphatic dicarboxylic acid compound, a linear aliphatic dicarboxylic acid is more preferable from the viewpoint of flexibility. Such a carboxylic acid compound may use only one component, and may use a some component together.

  The aliphatic dicarboxylic acid compound is preferably an aliphatic dicarboxylic acid having 2 or more carbon atoms, more preferably 6 or more from the viewpoint of flexibility, and preferably 12 or less, more preferably 10 or less from the viewpoint of durability. An acid compound is mentioned. Specifically, oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, and acid anhydrides thereof (1 to 1 carbon atoms) 3) alkyl esters and the like.

  From the viewpoint of durability of the produced porous sheet, the aliphatic dicarboxylic acid compound is preferably less than 10 mol%, more preferably 7 mol% or less, still more preferably 5 mol% or less, and still more preferably in the dicarboxylic acid component. Preferably it is 2 mol% or less, More preferably, it is 1 mol% or less, More preferably, it is 0 mol%.

  Other dicarboxylic acid components include aromatic dicarboxylic acid compounds such as terephthalic acid.

The aromatic dicarboxylic acid compound is preferably contained in the dicarboxylic acid component in an amount of 5 mol% or less, more preferably 1 mol% or less, and still more preferably 0 mol%, from the viewpoint of flexibility of the produced porous sheet. .
An acid not included in the dicarboxylic acid, for example, an aromatic tricarboxylic acid compound such as trimellitic acid may be used together with the dicarboxylic acid component. From the viewpoint of flexibility, the aromatic tricarboxylic acid compound is preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less, and even more preferably 5 mol% or less with respect to 100 mol% of the dicarboxylic acid component. Is more preferable, and 0 mol% is more preferable.

[Diol / diamine]
The diol is preferably an aliphatic diol and more preferably a linear aliphatic diol from the viewpoint of excellent flexibility of the produced porous sheet.

  From the viewpoint of flexibility of the obtained porous sheet, the diol has preferably 2 or more, more preferably 4 or more carbon atoms, and from the viewpoint of moisture permeability of the obtained porous sheet, preferably 10 or less, more preferably. Is 8 or less, more preferably 6 or less, still more preferably 4 or less, still more preferably 3 or less, and preferably 2 from the viewpoint of durability of the resulting porous sheet.

  Specific examples of preferred aliphatic diols include, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1 , 5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-butenediol, neopentyl glycol, 2,3-butane Selected from the group consisting of diol, 2,3-pentanediol, 2,4-pentanediol, 2,3-hexanediol, 3,4-hexanediol, 2,4-hexanediol, and 2,5-hexanediol One or more are preferable, and the softness of the porous sheet to be produced is From the viewpoint of durability, durability, and moisture permeability, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol are preferable. 1 or more selected from the group consisting of 1,8-octanediol and 1,10-decanediol, more preferably selected from the group consisting of ethylene glycol, 1,3-propanediol and 1,4-butanediol. 1 or more types are more preferable. As the diol, only one component may be used, or a plurality of components may be used in combination.

  The content of the aliphatic diol in the diol is preferably 40 mol% or more, more preferably 60 mol% or more, and still more preferably 80 mol%, from the viewpoints of flexibility, durability, and moisture permeability of the resulting porous sheet. More preferably, it is 90 mol% or more, still more preferably 95 mol% or more, still more preferably 99 mol% or more, and still more preferably 100 mol%.

  Examples of diols other than aliphatic diols that can be used as diols include hydroxymethylfurfuryl alcohol; aromatic alcohols such as flange alcohol such as dihydroxyfuran. The amount of the aromatic alcohol is preferably 5 mol% or less, more preferably 3 mol% or less, still more preferably 1 mol% or less, and more preferably 0 mol% in the diol, from the viewpoint of flexibility of the resulting porous sheet. Further preferred.

  In addition to the diol, a trihydric or higher polyhydric alcohol other than the diol may be used in combination. Examples of such alcohol include glycerin, pentaerythritol, trimethylolpropane and the like.

  The amount of the trihydric or higher polyhydric alcohol that can be used in combination is preferably 20 mol% or less, more preferably 15 mol% or less, based on 100 mol% of the total diol, from the viewpoint of durability of the resulting porous sheet. More preferably, 10 mol% or less is more preferable, 5 mol% or less is still more preferable, and 0 mol% is more preferable.

  From the viewpoint of durability and flexibility of the resulting porous sheet, the diamine is preferably an aliphatic diamine, and more preferably a linear aliphatic diamine.

  From the viewpoint of flexibility of the obtained porous sheet, the carbon number of the diamine is preferably 2 or more, more preferably 4 or more, and from the viewpoint of moisture permeability of the obtained porous sheet, preferably 10 or less, more preferably. Is 8 or less, more preferably 6 or less, and still more preferably 4 or less.

  Preferred diamines include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,2-butanediamine, 1,3-butanediamine, 1,4-butanediamine, 1,2-pentanediamine, 1 One or more selected from the group consisting of 1,3-pentanediamine, 1,4-pentanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine, and 1,10-decanediamine From the viewpoints of flexibility, moisture permeability, and durability of the resulting porous sheet, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5 are preferable. One or more selected from the group consisting of -pentanediamine, 1,6-hexanediamine, 1,8-octanediamine and 1,10-decanediamine is more preferred, and 1,3-propanediamine and / or 1,4 -Butanediamine is more preferred, 4-propanediamine is even more preferred. As the diamine, only one component may be used, or a plurality of components may be used in combination.

  The content of the aliphatic diamine is preferably 40 mol% or more, more preferably 60 mol% or more, and still more preferably 80 mol% in the diamine, from the viewpoints of flexibility, durability, and moisture permeability of the resulting porous sheet. More preferably, it is 90 mol% or more, still more preferably 95 mol% or more, still more preferably 99 mol% or more, and substantially 100 mol%.

  Examples of diamines other than aliphatic diamines that can be used as diamines include paraphenylenediamine, paraxylylenediamine, 2,4-toluenediamine, 4,4-diaminodiphenyl ether, and 2,2-bis [4- [4. -Aminophenoxy] phenyl] propane, bis [4- [4-aminophenoxy] phenyl] sulfone, 1,3-bis [4-aminophenoxy] benzene, aromatic diamines such as 4,4-diaminodiphenylsulfone, etc. It is done.

  Only one of diol and diamine may be used, or both may be used together. When using a diol and a diamine together, the diamine is preferably used in an amount of 0.01 mol or more, more preferably 0.05 mol or more, preferably 100 mol or less, more preferably 20 mol or less with respect to 1 mol of the diol. .

In this invention, unless the effect of this invention is impaired, you may further use a hydroxycarboxylic acid compound as a raw material of resin.
Examples of the hydroxycarboxylic acid compound include those containing at least one hydroxy group and one or more carboxyl groups in the molecule. The number of carbon atoms of the hydroxycarboxylic acid compound is preferably 3 or more, and more preferably 6 or less. Specifically, lactic acid (carbon number: 3, carboxyl group: 1, hydroxy group: 1), malic acid (carbon number: 4, carboxyl group: 2, hydroxy group: 1), tartaric acid (carbon number: 4, carboxyl) Group: 2, hydroxy group: 2), citric acid (carbon number: 6, carboxyl group: 3, hydroxy group: 1), isocitric acid (carbon number: 6, carboxyl group: 3, hydroxy group: 1), gluconic acid (Carbon number: 6, carboxyl group: 1, hydroxy group: 5) and the like.

  From the viewpoint of durability, the hydroxycarboxylic acid compound is preferably 100 mol% or less, more preferably 50 mol% or less, still more preferably 20 mol% or less, more preferably 10 mol with respect to 100 mol% of the dicarboxylic acid component. % Or less, more preferably 0 mol%.

  Among resins obtained by condensing a dicarboxylic acid component containing a dicarboxylic acid compound having a furan ring and a diol and / or diamine, a resin containing the following structural unit is used to provide durability and flexibility of the resulting porous sheet. From the viewpoints of properties and moisture permeability.

(In the formula, A represents a divalent aliphatic hydrocarbon group which may be substituted.)

  By using furan-2,5-dicarboxylic acid as the dicarboxylic acid compound having a furan ring, a resin containing the structural unit represented by the general formula (1) or (2) can be obtained. Therefore, furan-2,5-dicarboxylic acid is a more preferred compound as the dicarboxylic acid compound having a furan ring from the viewpoint of flexibility and durability of the resulting porous sheet.

  A is preferably 2 or more, more preferably 4 or more from the viewpoint of flexibility of the obtained porous sheet, and preferably 10 or less, more preferably 8 or less, from the viewpoint of moisture permeability of the obtained porous sheet. Further, preferably 6 or less, more preferably 4 or less, from the viewpoint of durability of the resulting porous sheet, preferably 2, a divalent aliphatic hydrocarbon group which may have a substituent. More preferably an alkylene group, and still more preferably a linear alkylene group. Examples of the substituent include a carboxyl group.

  In order to satisfy the formula represented by the general formula (1), the diol described above may be used. From the viewpoint of flexibility, durability, and moisture permeability of the resulting porous sheet, ethylene glycol, 1, From the group consisting of 2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol and 1,10-decanediol One or more selected are preferable, and one or more selected from the group consisting of ethylene glycol, 1,3-propanediol and 1,4-butanediol are more preferable.

  In order to satisfy the formula represented by the general formula (2), the diamine described above may be used. From the viewpoint of flexibility, durability, and moisture permeability, 1,2-propanediamine, 1,3- One or more selected from the group consisting of propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine and 1,10-decanediamine are preferred, 1,3-propanediamine and / or 1,4-butanediamine are more preferred, and 1,4-propanediamine is even more preferred.

  The structural unit represented by the general formula (1) or (2) is present in the resin by introducing it as a copolymerization component or as a main polymerization component in the resin production process as described above. Can do.

[Production method of resin]
As a method for producing the resin in the present invention, known methods relating to the production of thermoplastic resins such as polyester, polycarbonate, polyamide and the like can be employed. Moreover, the polymerization reaction in this case can set the appropriate conditions employ | adopted conventionally, and is not restrict | limited in particular.

  Preferably, the dicarboxylic acid component and the diol and / or diamine are heated by heating the mixture containing the above-mentioned dicarboxylic acid component and diol and / or diamine as essential components and, if necessary, other components such as a catalyst and a plasticizer. Alternatively, it is produced by causing a condensation reaction with diamine. The reaction is carried out until the number average molecular weight of the obtained resin falls within a preferable range described later.

  In the condensation reaction, the total amount of diol and diamine is preferably 1 mol or more with respect to 1 mol of the dicarboxylic acid component, from the viewpoint of increasing the reactivity and improving the durability of the porous sheet to be obtained. Preferably it is 1.2 mol or more, More preferably, it is 1.5 mol or more, Preferably it is 10 mol or less, More preferably, it is 8 mol or less, More preferably, it is 5 mol or less.

  The heating temperature during the condensation reaction is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, further preferably 200 ° C. or higher, more preferably 220 ° C. or higher, preferably 270 ° C. or lower, more preferably 250 ° C. or lower. is there. The setting of the heating temperature is not particularly limited, and for example, it may be set to maintain a substantially constant temperature from the start to the end of the condensation reaction, or the temperature is increased when the condensation reaction has progressed to some extent. It may be a simple setting.

  The time required for the condensation reaction is, for example, preferably 1 hour or longer, more preferably 4 hours or longer, further preferably 6 hours or longer, preferably 15 hours or shorter, more preferably 10 hours or shorter.

The pressure in the reaction vessel during the condensation reaction may be normal pressure, but it is preferable to perform the condensation reaction under reduced pressure. The final degree of vacuum in the reaction vessel is, for example, preferably 1.33 × 10 ³ Pa or less, and more preferably 0.27 × 10 ³ Pa or less.

  It is preferable to proceed the reaction while appropriately removing gas components generated during the condensation reaction. For that purpose, the aspect which collect | recovers the fractions produced | generated with a condensation reaction using the reaction container provided with the cooling pipe, for example is preferable.

  The addition timing of the catalyst is not particularly limited as long as it is before the start of the pressure reduction reaction, and may be added at the time of charging the raw material or may be added at the start of pressure reduction.

  In the production of the resin, chain extenders such as diisocyanate, diphenyl carbonate, dioxazoline, and silicate ester may be used.In particular, when a carbonate compound such as diphenyl carbonate is used, these carbonate compounds are added to the entire resin. It is also preferable to obtain polyester carbonate by adding 20 mol% or less, preferably 10 mol% or less, relative to 100 mol% of the constituent components.

  Moreover, in this invention, you may seal the polyester terminal group of resin with carbodiimide, an epoxy compound, monofunctional alcohol, or carboxylic acid.

  In this case, examples of the carbodiimide compound of the end-capping agent include compounds having one or more carbodiimide groups in the molecule (including polycarbodiimide compounds). Specifically, the monocarbodiimide compound includes dicyclohexylcarbodiimide, diisopropyl. Carbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di-β-naphthylcarbodiimide, N, N′-di-2,6-diisopropylphenylcarbodiimide, etc. Illustrated. These may be used individually by 1 type, and may mix and use 2 or more types.

  When the resin in the present invention is prepared by a condensation reaction, a catalyst may or may not be used depending on the type and combination of raw materials used. Examples of the catalyst include esterification catalysts such as tin compounds and titanium compounds. As the catalyst, only one component may be used, or a plurality of components may be used in combination.

  As the tin compound, a tin (II) compound having a Sn-O bond is more preferable from the viewpoint of polycondensation.

Examples of tin (II) compounds having a Sn-O bond include tin oxalate (II), tin (II) acetate, tin (II) octoate, octylic acid (2-ethylhexanoate) tin (II), and lauric acid. Tin (II) carboxylate having a carboxylic acid group having 2 to 28 carbon atoms such as tin (II), tin (II) stearate, tin (II) oleate; octyloxy tin (II), lauroxy tin (II), Alkoxytin (II) having an alkoxy group having 2 to 28 carbon atoms such as stearoxytin (II) and oleyloxytin (II); tin oxide (II); tin (II) sulfate, etc., Sn-X (X is halogen) Examples of the tin (II) compound having a bond (showing an atom) include tin (II) halides such as tin (II) chloride and tin (II) bromide. Among these, from the viewpoint of durability , (R ² COO) ₂ Sn (wherein R ² represents an alkyl or alkenyl group having 5 to 19 carbon atoms), (R ³ O) ₂ Sn (where R ³ Is Alkoxy tin (II) and tin oxide represented by SnO (II) is preferably represented by an alkyl or alkenyl group of prime 6~20), (R ² COO) fatty tin represented by ₂ Sn ( II) and tin (II) oxide are more preferred, and tin (II) octoate, octylic acid (2-ethylhexanoate) tin (II), tin (II) stearate and tin (II) oxide are more preferred.

Specific examples of titanium compounds include titanium diisopropylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₃ H ₇ O) ₂ ], titanium diisopropylate bisdiethanolamate [Ti (C ₄ H ₁₀ O ₂ N) ₂ (C ₃ H ₇ O) ₂ ], titanium dipentylate bistriethanolaminate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₅ H ₁₁ O) ₂ ], titanium diety rate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (C 2 H 5 O) 2 ], titanium dihydroxy octylate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (OHC 8 H ₁₆ O) ₂ ], titanium distearate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₁₈ H ₃₇ O) ₂ ], titanium triisopropylate triethanolaminate [Ti (C ₆ H ₁₄ O ₃ N) (C ₃ H ₇ O) ₃ ], titanium monopropylate tris (triethanolaminate) [Ti (C ₆ H ₁₄ O ₃ N) ₃ (C ₃ H ₇ Among these, titanium diisopropylate bistriethanolamate, titanium diisopropylate bisdiethanolamate and titanium dipentylate bistriethanolaminate are preferable, and these are, for example, Matsumoto Trading Co., Ltd. Also available as a commercial product.

  The amount of the catalyst present is preferably 0.0001 parts by mass or more, more preferably 0.001 parts by mass or more, and still more preferably 0.01 parts by mass with respect to 100 parts by mass of the total amount of the diol and diamine and the dicarboxylic acid component. It is above, Preferably it is 2.0 mass parts or less, More preferably, it is 1.5 mass parts or less, More preferably, it is 1.0 mass part or less, More preferably, it is 0.1 mass part or less. Here, the amount of the catalyst present means the total amount of the catalyst subjected to the condensation polymerization reaction.

[Physical properties of resin]
The number average molecular weight of the resin used in the present invention is preferably 10,000 or more, more preferably 20,000 or more, and even more preferably 30,000 or more, from the viewpoint of durability, moisture permeability and flexibility of the obtained porous sheet. Further, it is preferably 40,000 or more, and from the viewpoint of productivity of the porous sheet, it is preferably 150,000 or less, more preferably 100,000 or less, further preferably 80,000 or less, and further preferably 60,000 or less.

  The glass transition point (Tg) of the resin used in the present invention is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, and further preferably 20 ° C. from the viewpoint of improving the moisture permeability and durability of the resulting porous sheet. As described above, it is more preferably 40 ° C. or higher, further preferably 60 ° C. or higher, and preferably 100 ° C. or lower, more preferably 90 ° C. or lower, from the viewpoint of flexibility of the obtained porous sheet.

The melting point (Tm) of the resin used in the present invention is preferably 130 ° C. or higher, more preferably 140 ° C. or higher, more preferably 150 ° C. or higher, from the viewpoint of improving the heat resistance and durability of the resulting porous sheet. More preferably 160 ° C. or higher, more preferably 170 ° C. or higher, more preferably 180 ° C. or higher, more preferably 190 ° C. or higher. From the viewpoint of moldability of the resulting porous sheet, preferably 250 ° C. or lower, more preferably Is 230 ° C. or lower, more preferably 220 ° C. or lower.
The molecular weight, melting point, and glass transition point of the resin used in the present invention can be determined by the method described in the examples described later.

(Resin composition)
The resin composition used in the present invention is a composition containing a resin and a filler. Such a resin composition has a filler of 20 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the resin. It is preferable that a plasticizer is further contained.

  The filler used in the present invention is a component that constitutes the resin composition together with the resin. By using the filler, the sheet obtained by the stretching treatment is made porous and has moisture permeability. it can. As the filler, an inorganic filler and / or an organic filler can be used.

  Examples of inorganic fillers include calcium carbonate, gypsum, talc, clay, kaolin, silica, diatomaceous earth, magnesium carbonate, barium carbonate, magnesium sulfate, barium sulfate, calcium phosphate, aluminum hydroxide, zinc oxide, titanium oxide, alumina, Examples include mica, zeolite, carbon black, aluminum powder, iron powder and the like. Among these fillers, from the viewpoint of improving flexibility, it is preferable to use calcium carbonate or barium sulfate, and it is more preferable to use calcium carbonate.

  Examples of the organic filler include granular materials such as crosslinked polystyrene beads, crosslinked silicone beads, and crosslinked polymethyl methacrylate.

  The various fillers mentioned above can be used singly or in combination of two or more.

  The average particle size of the filler is preferably 0.1 μm or more, more preferably 0.3 μm or more, further preferably 0.5 μm or more, and further preferably 1 μm, from the viewpoint of moisture permeability of the porous sheet to be obtained. From the viewpoint of durability and flexibility of the resulting porous sheet and prevention of sheet breakage during production, it is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less.

  The content of the filler in the resin composition is 20 parts by mass or more, preferably 50 parts by mass or more, more preferably 80 parts by mass with respect to 100 parts by mass of the resin from the viewpoint of moisture permeability of the obtained porous sheet. Part or more, more preferably 100 parts by weight or more, more preferably 130 parts by weight or more, and from the viewpoint of durability and flexibility of the obtained porous sheet, it is 300 parts by weight or less, preferably 250 parts by weight or less, More preferably, it is 200 mass parts or less, More preferably, it is 180 mass parts or less.

  In the present invention, it is preferable that the resin composition further contains a plasticizer from the viewpoint of improving flexibility while maintaining the durability of the porous sheet.

  Preferred plasticizers include polyester plasticizers, polyhydric alcohol ester plasticizers, polycarboxylic acid ester plasticizers and phosphate esters from the viewpoint of improving flexibility while maintaining the durability of the porous sheet. 1 or more types selected from the group consisting of plasticizers.

  Specific examples of the polyester plasticizer include succinic acid, glutaric acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid and the like, preferably a dicarboxylic acid having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, Propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, etc., preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms Polyesters with the dialcohol can be mentioned. Further, it may be a compound in which a hydroxyl group or a carboxy group at a polyester terminal is esterified with a monocarboxylic acid or a monoalcohol and blocked.

  Specific examples of the polyhydric alcohol ester plasticizer include polyhydric alcohols such as polyethylene glycol, polypropylene glycol, glycerin, and the above dialcohol or their (poly) oxyalkylene adducts, preferably 1 to 12 carbon atoms, more preferably May include mono-, di- or triesters with monocarboxylic acids having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.

  As the polyvalent carboxylic acid ester plasticizer, a polyvalent carboxylic acid such as trimellitic acid and the above dicarboxylic acid, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to carbon atoms. And mono-, di- or triesters with 4 monoalcohols or their (poly) oxyalkylene adducts. Specifically, phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, and butyl benzyl phthalate; tributyl trimellitic acid, trioctyl trimellitic acid, tri Trimellitic acid esters such as trihexyl melitrate; Adipic acid esters such as diisodecyl adipate and octyldecyl adipate; Citric acid esters such as triethyl acetyl citrate and tributyl acetyl citrate; Azelaic acid such as di-2-ethylhexyl azelate Esters; sebacic acid esters such as dibutyl sebacate and di-2-ethylhexyl sebacate; polyethylene glycol monomethyl ether having an average addition mole number of succinic acid and ethylene oxide of 2 to 3 (hydroxyl group 1 The per ethylene oxide can be given 2-3 mols) esters of such.

  Examples of the phosphoric ester plasticizer include mono-, di- or triesters of phosphoric acid and the above monoalcohol or its (poly) oxyalkylene adduct. Specific examples include tributyl phosphate, tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, diphenyl-2-ethylhexyl phosphate, tricresyl phosphate, tris (ethoxyethoxyethyl) phosphate, and the like. it can.

  As the plasticizer, from the viewpoint of improving flexibility while maintaining durability, an ester compound having a (poly) oxyalkylene group is preferable, and a polyester plasticizer having a (poly) oxyalkylene group, a polyhydric alcohol One or more selected from the group consisting of ester plasticizers, polycarboxylic acid ester plasticizers and phosphate ester plasticizers are more preferred. The (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group. As the oxyalkylene group, an oxyethylene group, an oxypropylene group or an oxybutylene group is preferable, and an oxyethylene group or an oxypropylene group is more preferable.

  The content of the plasticizer is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, still more preferably 50 parts by mass or more, and still more preferably 70, from the viewpoint of improving flexibility with respect to 100 parts by mass of the resin. From the viewpoint of suppressing a decrease in durability, it is preferably 120 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 90 parts by mass or less, and still more preferably 88 parts by mass. It is not more than part by mass, more preferably not more than 85 parts by mass.

  In view of the above matters, the content of the resin in the resin composition used in the present invention is preferably 15% by mass or more, more preferably 20% by mass or more, and still more preferably, from the viewpoint of production of the porous sheet. From the viewpoint of containing a filler and a plasticizer, it is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 35% by mass or less. Further, the content of the filler in the resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more from the viewpoint of improving moisture permeability. From the viewpoint of enhancing the properties, it is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less. Further, the content of the plasticizer in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more from the viewpoint of flexibility, and from the viewpoint of durability. Preferably, it is 50 mass% or less, More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less.

  In order to improve the flexibility of the porous sheet, there is a policy of adopting a resin using a diol having a long-chain alkylene group, but the porous sheet obtained in this way has reduced moisture permeability and durability. Tend to. On the other hand, by using ethylene glycol as the diol and further using a plasticizer, a porous sheet in which all three of flexibility, moisture permeability, and durability are more excellent can be obtained.

  Accordingly, one aspect of satisfying the durability and flexibility of the obtained porous sheet at a high level is that the resin contains a structural unit represented by the general formula (1) or (2), Is a porous sheet obtained by using a plasticizer with respect to the resin, and in this case, the amount of the plasticizer is flexible with respect to 100 parts by mass of the resin. From a viewpoint, Preferably it is 50 mass parts or more, More preferably, it is 70 mass parts or more, More preferably, it is 75 mass parts or more, From a viewpoint of suppressing a durable fall, Preferably it is 120 mass parts or less, Preferably it is 100 mass parts. Hereinafter, it is preferably 90 parts by mass or less, more preferably 88 parts by mass or less, and still more preferably 85 parts by mass or less.

  The resin composition used in the present invention may contain other components other than those described above as long as the effects of the present invention are not hindered. For example, an antistatic agent, an antifogging agent, a light stabilizer, and an ultraviolet absorber. , Pigments, crystal nucleating agents, fungicides, antibacterial agents, foaming agents, flame retardants, and the like.

(Porous sheet)
The porous sheet of the present invention is obtained by melt-molding the above resin composition into a raw sheet, and stretching the raw sheet.

  Although there is no limitation in the method of melt-molding the said resin composition and obtaining a raw fabric sheet, Preferably, it can manufacture efficiently, for example with the following method.

  First, each component constituting the resin composition described above is premixed using a Henschel mixer, a super mixer, or the like, and then kneaded with a single screw or twin screw extruder to be pelletized. Next, after the obtained pellets are melted, a film is formed by a molding machine to obtain a film (raw sheet). As the molding machine, a T-die type and an inflation type can be used, and a T-die type molding machine is preferably used.

  The elastic modulus of the film (raw sheet) thus obtained is preferably 0.1 GPa or more, more preferably 0.3 GPa or more, and still more preferably 0.5 GPa, from the viewpoint of strength when a porous sheet is formed. Above, more preferably 0.7 GPa or more, from the viewpoint of flexibility when the porous sheet is made, preferably 5 GPa or less, more preferably 3 GPa or less, still more preferably 2.5 GPa or less, more preferably 2 GPa or less, More preferably, it is 1.5 GPa or less, More preferably, it is 1.3 GPa or less. The measuring method of the elastic modulus of the film (raw sheet) is the method described in the examples.

  Next, the obtained film (raw fabric sheet) is uniaxially or biaxially stretched to cause interfacial peeling between the resin and the filler to make it porous. A roll method or a tenter method is preferably used for this stretching. In this way, the porous sheet of the present invention is obtained.

  The raw sheet is preferably stretched at least 1.1 times in the uniaxial direction. From the viewpoint of flexibility of the obtained porous sheet, the draw ratio is preferably 1.1 or more, more preferably 1.5 or more, still more preferably 1.8 or more, still more preferably 2.0 or more. From the viewpoint of the strength and durability of the porous sheet to be produced, it is preferably 5 or less, more preferably 4 or less, further preferably 3 or less, and further preferably 2.5 or less.

  The durability of the porous sheet of the present invention thus obtained is evaluated as hydrolysis resistance indicated by a value obtained by the method described in Examples. In the present invention, from the viewpoint of hydrolysis resistance of the porous sheet, the higher the value, the more preferable. Specifically, it is preferably 70% or more, more preferably 75% or more, and still more preferably 80%. That's it.

  The moisture permeability of the porous sheet is evaluated by a value obtained by the method described in the examples. From the viewpoint of use as a sanitary material, the moisture permeability of the porous sheet is preferably as high as possible, specifically 1.6 or more, more preferably 1.8 or more, and even more preferably 1. 9 or more.

  The flexibility of the porous sheet is evaluated by a method required by the method described in the examples. When the evaluation result is A, B or C, it can be said that there is sufficient flexibility as a porous sheet. In the case of A or B, it can be said that it is superior to the conventional product. It can be said that it is particularly superior to the product.

  The present invention further discloses the following items, manufacturing methods, and uses with respect to the above-described embodiments.

[1] A porous sheet formed by melt-molding a resin composition containing 20 parts by mass or more and 300 parts by mass or less of a resin and a resin and 100 parts by mass of the resin, and then stretching the original sheet Sex sheet,
The resin is a resin obtained by condensing a dicarboxylic acid component containing a dicarboxylic acid compound having a furan ring and a diol and / or diamine, and the amount of the dicarboxylic acid compound having a furan ring in the acid component is 90 mol. Porous sheet, which is a resin exceeding%.

[2] The amount of the dicarboxylic acid compound having a furan ring in the dicarboxylic acid component is preferably 93 mol% or more, more preferably 95 mol% or more, further preferably 98 mol% or more, more preferably 99 mol% or more, More preferably, the porous sheet according to [1], which is substantially 100 mol%.
[3] The group in which the dicarboxylic acid compound having a furan ring is composed of furan-2,5-dicarboxylic acid, furan-2,4-dicarboxylic acid, furan-2,3-dicarboxylic acid and furan-3,4-dicarboxylic acid. The porous sheet according to [1] or [2], which is one or more selected from the above.
[4] The dicarboxylic acid component preferably further contains an aliphatic dicarboxylic acid compound having 2 or more carbon atoms, more preferably 6 or more carbon atoms, preferably 12 or less carbon atoms, more preferably 10 or less carbon atoms. ] To [3] Any one porous sheet.
[5] The aliphatic dicarboxylic acid compound is preferably oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, acids of these acids The porous sheet according to the above [4], which is one or more aliphatic dicarboxylic acid compounds selected from the group consisting of anhydrides and alkyl esters of 1 to 3 carbon atoms of these acids.
[6] The amount of the aliphatic dicarboxylic acid compound in the dicarboxylic acid component is preferably less than 10 mol%, more preferably 7 mol% or less, still more preferably 5 mol% or less, even more preferably 2 mol% or less, and more The porous sheet according to [4] or [5], more preferably 1 mol% or less, and still more preferably 0 mol%.

[7] The carbon number of the diol is preferably 2 or more, more preferably 4 or more, preferably 10 or less, more preferably 8 or less, still more preferably 6 or less, still more preferably 4 or less, and still more preferably The porous sheet according to any one of [1] to [6], which is 3 or less.
[8] The porous sheet according to any one of [1] to [7], wherein the diol is preferably an aliphatic diol, more preferably a linear aliphatic diol.
[9] Diol is ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-butenediol, neopentyl glycol, 2,3-butanediol, 2,3- One or more selected from the group consisting of pentanediol, 2,4-pentanediol, 2,3-hexanediol, 3,4-hexanediol, 2,4-hexanediol and 2,5-hexanediol are preferred, Ethylene glycol, 1,2-propanediol, 1,3-propanediol, One selected from the group consisting of 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol and 1,10-decanediol More preferably, one or more selected from the group consisting of ethylene glycol, 1,3-propanediol and 1,4-butanediol is more preferable. .
[10] The amount of the aliphatic diol in the diol is preferably 40 mol% or more, more preferably 60 mol% or more, still more preferably 80 mol% or more, further preferably 90 mol% or more, further preferably 95 mol%. The porous sheet according to any one of [1] to [9] above, more preferably 99 mol% or more, and still more preferably substantially 100 mol%.

[11] The carbon number of the diamine is preferably 2 or more, more preferably 4 or more, preferably 10 or less, more preferably 8 or less, still more preferably 6 or less, and still more preferably 4 or less. 1]-[10] Any one porous sheet.
[12] The porous sheet according to any one of [1] to [11], wherein the diamine is preferably an aliphatic diamine, more preferably a linear aliphatic diamine.
[13] diamine is ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,2-butanediamine, 1,3-butanediamine, 1,4-butanediamine, 1,2-pentanediamine, One selected from the group consisting of 1,3-pentanediamine, 1,4-pentanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine and 1,10-decanediamine Preferably, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine, and 1, One or more selected from the group consisting of 10-decanediamine is more preferable, 1,3-propanediamine and / or 1,4-butanediamine is more preferable, and 1,4-propanediamine is still more preferable. 1]-[12] Any one porous sheet.
[14] The amount of the aliphatic diamine in the diamine is preferably 40 mol% or more, more preferably 60 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more, further preferably 95 mol%. As described above, the porous sheet according to any one of [1] to [13], more preferably 99 mol% or more, and still more preferably substantially 100 mol%.
[15] As a raw material of the resin, a hydroxycarboxylic acid compound is preferably 100 mol% or less, more preferably 50 mol% or less, further preferably 20 mol% or less, further preferably 100 mol% or less with respect to 100 mol% of the dicarboxylic acid component. The porous sheet according to any one of [1] to [14], which is used in an amount of 10 mol% or less, more preferably substantially 0 mol%.

[16] The resin is represented by the following general formula (1) or (2):

(Wherein A represents a divalent aliphatic hydrocarbon group which may be substituted), any one of the aforementioned [1] to [15], which is a porous sheet comprising a structural unit represented by Porous sheet.
[17] A is preferably a substituent having 2 or more carbon atoms, more preferably 4 or more carbon atoms, preferably 10 or less carbon atoms, more preferably 8 or less, still more preferably 6 or less, and even more preferably 4 or less. The divalent aliphatic hydrocarbon group which may have, more preferably an alkylene group, and still more preferably a linear alkylene group, any one of the aforementioned [1] to [16] porosity Sheet.
[18] The resin is produced by heating a mixture containing a dicarboxylic acid component and a diol and / or diamine to cause a condensation reaction between the dicarboxylic acid component and the diol and / or diamine, [1] to [17] Any one porous sheet.
[19] The total amount of diol and diamine is preferably 1 mol or more, more preferably 1.2 mol or more, still more preferably 1.5 mol or more, preferably 10 mol with respect to 1 mol of the dicarboxylic acid component. The porous sheet according to any one of [1] to [18], which is more preferably 8 mol or less, and still more preferably 5 mol or less.
[20] The heating temperature during the condensation reaction is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, further preferably 200 ° C. or higher, more preferably 220 ° C. or higher, preferably 270 ° C. or lower, more preferably 250 The porous sheet according to [18] or [19], wherein the porous sheet has a temperature of 0 ° C or lower.

[21] A condensation reaction is carried out using one or more esterification catalysts selected from the group consisting of tin compounds and titanium compounds, and the amount of the catalyst is 100 parts by mass of the total amount of diol, diamine and dicarboxylic acid component Is preferably 0.0001 parts by mass or more, more preferably 0.001 parts by mass or more, further preferably 0.01 parts by mass or more, preferably 2.0 parts by mass or less, more preferably 1.5 parts by mass. The porous sheet according to any one of [18] to [20], wherein the porous sheet is not more than part by mass, more preferably not more than 1.0 part by mass, and further preferably not more than 0.1 part by mass.
[22] The number average molecular weight of the resin is preferably 10,000 or more, more preferably 20,000 or more, further preferably 30,000 or more, further preferably 40,000 or more, preferably 150,000 or less, more preferably 100,000. Hereinafter, the porous sheet according to any one of [1] to [21], more preferably 80,000 or less, and further preferably 60,000 or less.
[23] The glass transition point (Tg) of the resin is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, further preferably 20 ° C. or higher, more preferably 40 ° C. or higher, more preferably 60 ° C. or higher, The porous sheet according to any one of [1] to [22], which is preferably 100 ° C or lower, more preferably 90 ° C or lower.
[24] The melting point (Tm) of the resin is preferably 130 ° C. or higher, more preferably 140 ° C. or higher, further preferably 150 ° C. or higher, more preferably 160 ° C. or higher, further preferably 170 ° C. or higher, and more preferably 180 ° C. As described above, the porous sheet according to any one of [1] to [23], which is preferably 190 ° C. or higher, preferably 250 ° C. or lower, more preferably 230 ° C. or lower, and further preferably 220 ° C. or lower.
[25] The content of the filler in the resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, preferably 70% by mass or less, more preferably The porous sheet according to any one of [1] to [24], which is 60% by mass or less, more preferably 50% by mass or less.

[26] The content of the filler in the resin composition is preferably 50 parts by mass or more, more preferably 80 parts by mass or more, further preferably 100 parts by mass or more, and further preferably 130 parts by mass with respect to 100 parts by mass of the resin. The porous sheet according to any one of [1] to [25], which is not less than 250 parts by weight, preferably not more than 200 parts by weight, and more preferably not more than 180 parts by weight.
[27] The filler is preferably an inorganic filler and / or organic filler, calcium carbonate, gypsum, talc, clay, kaolin, silica, diatomaceous earth, magnesium carbonate, barium carbonate, magnesium sulfate, barium sulfate, calcium phosphate One or more selected from the group consisting of aluminum hydroxide, zinc oxide, titanium oxide, alumina, mica, zeolite, carbon black, aluminum powder, iron powder, crosslinked polystyrene beads, crosslinked silicone beads, and crosslinked polymethyl methacrylate The porous sheet according to any one of [1] to [26], more preferably calcium carbonate and / or barium sulfate, and still more preferably calcium carbonate.
[28] The average particle size of the filler is preferably 0.1 μm or more, more preferably 0.3 μm or more, further preferably 0.5 μm or more, more preferably 1 μm or more, preferably 10 μm or less, more preferably The porous sheet according to any one of [1] to [27], which is 5 μm or less, more preferably 3 μm or less.

[29] The porous sheet according to any one of [1] to [28], wherein the resin composition further contains a plasticizer.
[30] The content of the plasticizer in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, preferably 50% by mass or less, more preferably The porous sheet according to any one of [1] to [29], which is 40% by mass or less, more preferably 30% by mass or less.
[31] The plasticizer content is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, still more preferably 50 parts by mass or more, further preferably 70 parts by mass or more, relative to 100 parts by mass of the resin. Preferably it is 75 parts by mass or more, preferably 120 parts by mass or less, more preferably 100 parts by mass or less, further preferably 90 parts by mass or less, more preferably 88 parts by mass or less, and further preferably 85 parts by mass or less. [1] to [30] Any one porous sheet.
[32] The plasticizer is one or more selected from the group consisting of a polyester plasticizer, a polyhydric alcohol ester plasticizer, a polycarboxylic acid ester plasticizer, and a phosphate ester plasticizer [1] ] To [31] Any one porous sheet.
[33] A polyester plasticizer having a (poly) oxyalkylene group as a plasticizer, a polyhydric alcohol ester plasticizer having a (poly) oxyalkylene group, a polyvalent carboxylic acid ester system having a (poly) oxyalkylene group The porous sheet according to any one of [1] to [32], which is at least one selected from the group consisting of a plasticizer and a phosphoric ester plasticizer having a (poly) oxyalkylene group.
[34] The resin content in the resin composition is preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, preferably 60% by mass or less, more preferably 40% by mass. The porous sheet according to any one of [1] to [33], which is not more than mass%, more preferably not more than 35 mass%.

[35] The resin contains a structural unit represented by the general formula (1) or (2), wherein A in these formulas is an ethylene group, and the compounding amount of the plasticizer is 100 parts by mass of the resin. On the other hand, it is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, further preferably 75 parts by mass or more, preferably 120 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 90 parts by mass or less, The porous sheet according to any one of [1] to [34], more preferably 88 parts by mass or less, and still more preferably 85 parts by mass or less.
[36] The above [1] to [35], wherein the durability indicated by the value obtained by the method described in the examples is preferably 70% or more, more preferably 75% or more, and further preferably 80% or more. Any one porous sheet.
[37] The moisture permeability of the porous sheet evaluated by the value obtained by the method described in the examples is preferably 1.6 or more, more preferably 1.8 or more, and further preferably 1.9 or more. The porous sheet according to any one of [1] to [36].

[38] The flexibility of the porous sheet evaluated by the method required by the method described in Examples is preferably A, B or C, more preferably A or B, and even more preferably A. The porous sheet according to any one of [1] to [37].
[39] The elastic modulus of the raw fabric sheet is preferably 0.1 GPa or more, more preferably 0.3 GPa or more, further preferably 0.5 GPa or more, further preferably 0.7 GPa or more, preferably 5 GPa or less, more The porosity of any one of [1] to [38], preferably 3 GPa or less, more preferably 2.5 GPa or less, more preferably 2 GPa or less, more preferably 1.5 GPa or less, and further preferably 1.3 GPa or less. Sex sheet.
[40] The stretching of the raw sheet is at least uniaxially, preferably 1.1 or more, more preferably 1.5 or more, further preferably 1.8 or more, more preferably 2.0 or more, preferably The porous sheet according to any one of [1] to [39], which is obtained by stretching to 5 or less, more preferably 4 or less, further preferably 3 or less, and still more preferably 2.5 or less.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited at all by the Example. “Part” means part by mass.

Production Example 1
In a 2 L reaction vessel equipped with a stirring blade, a nitrogen inlet and a condenser, 2,5-furandicarboxylic acid 300 g (1.92 mol), ethylene glycol 358 g (5.77 mol) and tin octylate 0.3 g (0. 00074 mol) was measured and added. While stirring was started and nitrogen was introduced, the mixture was heated to 180 ° C. While maintaining this temperature, the fraction produced by the condensation reaction was recovered over 3 hours. Next, the mixture was further heated to raise the temperature in the reaction vessel to 230 ° C., and the pressure was gradually reduced to collect the fraction. After reaching 230 ° C., this temperature was maintained, and polymerization was continued for 6 hours under reduced pressure (pressure 50 Pa) to obtain a polyester resin in the reaction vessel.

Production Example 2
A polyester resin was obtained by performing the same operation as in Production Example 1 except that 358 g of ethylene glycol in Production Example 1 was changed to 439 g (5.77 mol) of 1,3-propanediol.

Production Example 3
A polyester resin was obtained by performing the same operation as in Production Example 1 except that 358 g of ethylene glycol in Production Example 1 was changed to 520 g (5.77 mol) of 1,4-butanediol.

Production Example 4
A polyester resin was obtained in the same manner as in Production Example 1 except that 358 g of ethylene glycol in Production Example 1 was changed to 682 g (5.77 mol) of 1,6-hexanediol.

Production Example 5
A polyamide resin was obtained in the same manner as in Production Example 1 except that 358 g of ethylene glycol in Production Example 1 was changed to 509 g (5.77 mol) of 1,4-diaminobutane.

Production Example 6
A reaction vessel in which 358 g of ethylene glycol of Production Example 1 was changed to 546 g (6.06 mol) of 1,4-butanediol and 20.4 g (0.101 mol) of sebacic acid together with 2,5-furandicarboxylic acid and the like A polyester resin was obtained in the same manner as in Production Example 1 except that the polyester resin was added. The molar ratio of 2,5-furandicarboxylic acid to sebacic acid (2,5-furandicarboxylic acid / sebacic acid) was 95/5.

Production Example 7
A reaction vessel in which 358 g of ethylene glycol in Production Example 1 was changed to 611 g (6.78 mol) of 1,4-butanediol and 68.5 g (0.339 mol) of sebacic acid together with 2,5-furandicarboxylic acid, etc. A polyester resin was obtained in the same manner as in Production Example 1 except that the polyester resin was added. The molar ratio of 2,5-furandicarboxylic acid to sebacic acid (2,5-furandicarboxylic acid / sebacic acid) was 85/15.

Production Example 8
358 g of ethylene glycol in Production Example 1 was changed to 865 g (9.60 mol) of 1,4-butanediol, and 259 g (1.28 mol) of sebacic acid was added to the reaction vessel together with 2,5-furandicarboxylic acid and the like. Except that, polyester resin was obtained in the same manner as in Production Example 1. The molar ratio of 2,5-furandicarboxylic acid to sebacic acid (2,5-furandicarboxylic acid / sebacic acid) was 60/40.

Measurement of molecular weight The molecular weight of the resin was measured under the following conditions.
Analytical instrument: manufactured by Tosoh Corporation, HLC-8320GPC
Detector: Differential refraction detector Eluent: Hexafluoroisopropanol solution having a concentration of 5 mM sodium trifluoroacetate Flow rate: 1.0 ml / min
Column temperature: 40 ° C
Molecular weight standard: A polymethyl methacrylate (PMMA) standard was used, and the number average molecular weight was determined to obtain the molecular weight of the resin.

Measurement of Melting Point and Glass Transition Temperature The melting point (Tm) and glass transition temperature (Tg) of the resin were measured under the following conditions.
Apparatus name: Differential scanning calorimetry apparatus manufactured by TA Instruments Pan: Platinum pan Sample mass: 10 mg
Temperature increase rate: 10 ° C / min

  Table 1 shows the molecular weight, Tg, and Tm of the resins obtained in Production Examples 1-8.

Examples 1-10, Comparative Examples 1-5
(Preparation of resin composition)
With the compounding ratio shown in Table 2, in Production Examples 1 to 8 or 100 parts of a commercially available resin, calcium carbonate (manufactured by Sankyo Seiko Co., Ltd., Escalon # 2000, average particle size: 1.1 μm) as a filler, As a plasticizer, a polycondensate of adipic acid and alkylene glycol having a molecular weight of about 1100 (PN-170, manufactured by Asahi Denka Co., Ltd.) was added and premixed with a Henschel mixer (250 rpm, 60 seconds). Next, the mixture was taken out and melt-kneaded using a twin screw extruder with the head set at 220 ° C. to obtain a pelletized resin composition (1). Polylactic acid (PLA) [LACEA H-400 manufactured by Mitsui Chemicals, Inc.] was used as a commercially available resin.

[Production of porous sheet]
It was obtained as described above using a T-die film forming apparatus comprising a single-screw extruder (L / D = 28) having a screw diameter of 50 mm and a T-die having a width of 500 mm (die lip clearance: 1.5 mm). The resin composition (1) was melt-molded to obtain a film (raw sheet) having a thickness of 70 μm and a width of 300 mm. The basis weight of any film was in the range of 70 to 130 g / m ² . The set temperature of the T die during melt molding was 220 ° C., and the molding speed was 8 m / min.

  The obtained film was stretched using a roll uniaxial stretching machine to obtain a porous sheet. The draw ratio was x2.1. The preheating temperature was 100 ° C., the stretching temperature was 90 ° C., and the annealing temperature was 100 ° C.

〔Measurement item〕
(1) Elastic modulus In the blending ratio shown in Table 2, the polyester (PN-170, manufactured by Asahi Denka Co., Ltd.) as a plasticizer was added to Production Examples 1 to 8 or 100 parts of a commercially available resin, and a Henschel mixer was added. (250 rpm, 60 seconds). Next, the mixture was taken out and melt-kneaded using a twin screw extruder with the head set at 220 ° C. to obtain a pelletized resin composition (2). Polylactic acid (PLA) [LACEA H-400 manufactured by Mitsui Chemicals, Inc.] was used as a commercially available resin.

The resin composition (2) was heated and melted by an auto press molding machine (manufactured by Toyo Seiki Co., Ltd.) and cooled after pressurization to obtain a sheet (heating temperature 230 ° C., pressure 200 kg / cm ² , 3 minutes; 15 (Cooled for 3 minutes at 0 ° C.) A 1 × 10 cm strip-shaped test piece was cut out from this sheet, and the elastic modulus was measured with Tensilon (tensile speed: 1 cm / min).

(2) Durability The porous sheet obtained above was allowed to stand for 1 week in an environment of 80 ° C. and 95% RH. The durability as hydrolysis resistance was determined by the following formula. In addition, about the molecular weight of the sheet | seat, the sheet | seat of measurement object was made into a solution with the solvent (The hexafluoro isopropanol solution which is a density | concentration of 5 mM sodium trifluoroacetate), and the molecular weight was calculated | required by the same method as said resin then.
Durability = (Molecular weight of the sheet after storage) / (Molecular weight of the sheet before storage) × 100

(3) Flexibility Regarding the porous sheet obtained above, ten panelists have a tentacle test, and it is softer than Tokuyama's Porum PH-35 (polyethylene-based inorganic filler-added stretched film). Depending on the number of respondents, the evaluation was as follows.

When all (10) respondents answered that it is softer ... A (very soft)
7 to 9 people: B (pretty soft)
For 4 to 6 people ... C (equivalent)
In the case of 3 or less ... D (Inferior in flexibility)

(4) Moisture permeability About the porous sheet obtained above, moisture permeability was measured according to the method of JIS-Z0208. However, the temperature was 30 ° C. and the humidity was 90% RH.

  Table 2 shows the composition and evaluation results of each example.

[Discussion]
When Example 1 and 6-8 are compared, when the carbon number of aliphatic diol becomes long, it exists in the tendency for the moisture permeability of the manufactured porous sheet to fall, but it turns out that a softness | flexibility tends to improve.

  When Examples 2, 4, and 5 are compared, it can be seen that when the amount of the filler is increased, the moisture permeability of the produced porous sheet is improved, but the durability tends to be lowered along with the flexibility.

  When Examples 1 to 3 are compared, it can be seen that the addition of the plasticizer improves the flexibility although the durability of the produced porous sheet is slightly lowered. From Example 3, by using ethylene glycol as the diol, and further using a plasticizer, a porous sheet with superior flexibility, moisture permeability and durability of the produced porous sheet was obtained. I understand that.

  Comparing Examples 7 and 9, it can be seen that aliphatic diamines are more durable than the aliphatic diols.

  Comparing Examples 1 and 10 with Comparative Examples 2 and 3, it can be seen that when the content of furandicarboxylic acid in the acid component is 90 mol% or less, the durability of the produced porous sheet is significantly reduced. .

  As in Comparative Example 1, it can be seen that the porous sheet produced from PLA has low durability and flexibility. As in Comparative Examples 4 and 5, when the amount of the filler is outside the scope of the present application, the durability and flexibility of the produced porous sheet are both low.

  The porous sheet of the present invention is used as, for example, sanitary materials, medical materials, clothing materials, and the like. Moreover, the porous sheet of this invention can also be used as said material with the form of the composite sheet bonded together with fiber sheets, such as a nonwoven fabric, on the one surface. In particular, since the porous sheet of the present invention has moisture permeability as described above, it is used as it is or as a composite sheet bonded with a fiber sheet, such as disposable diapers, sanitary napkins, panty liners (orimono sheets). ), When used as a constituent material of an absorbent article such as an incontinence pad, it is possible to prevent an increase in humidity in the wearing and effectively prevent a rash from occurring on the wearer's skin. These absorbent articles generally include a liquid-permeable top sheet, a liquid-impermeable (including poorly permeable) back sheet, and a liquid-retaining absorbent disposed between the two sheets. A porous sheet or a composite sheet obtained by laminating this with a fiber sheet is particularly preferably used as the back sheet. In addition, the porous sheet of the present invention or the composite sheet obtained by bonding the fiber sheet to the fiber sheet is used as a material for components other than the back sheet in the absorbent article, taking advantage of its good flexibility and moisture permeability. For example, it can also be used as a material such as a three-dimensional gather or a waist barrier sheet.

Claims (6)

A porous sheet formed by melt-molding a resin composition containing a resin and a filler containing 20 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the resin, and stretching the original sheet There,
The resin is a resin obtained by condensing a dicarboxylic acid component containing a dicarboxylic acid compound having a furan ring and a diol and / or diamine, and the amount of the dicarboxylic acid compound having a furan ring in the dicarboxylic acid component is 90%. A porous sheet which is a resin exceeding mol%. The resin is represented by the following general formula (1) or (2):

The porous sheet according to claim 1, comprising a structural unit represented by (wherein A represents an optionally substituted divalent aliphatic hydrocarbon group).   The porous sheet according to claim 2, wherein A is an alkylene group having 2 to 10 carbon atoms.   The porous sheet according to any one of claims 1 to 3, obtained by further blending a resin composition with a plasticizer of 20 parts by mass or more and 120 parts by mass or less with respect to 100 parts by mass of the resin.   The porous sheet according to claim 4, wherein the plasticizer is an ester compound having a (poly) oxyalkylene group.   The A according to any one of claims 2 to 5, wherein A is an ethylene group, and is obtained by further blending a resin composition with a plasticizer of 50 to 120 parts by mass with respect to 100 parts by mass of the resin. Porous sheet.