JPH0618919B2 - Porous sheet and its use - Google Patents

Description

Detailed Description of the Invention

INDUSTRIAL APPLICABILITY The present invention is a porous material having a shape memory property useful in various applications such as clothing materials, medical materials, decorative materials, vehicle materials, mechanical materials, electrical materials, and gap fillers for construction. The present invention relates to a seat and a method of using the seat. [Prior Art] Regarding a conventional porous sheet, for example, Japanese Patent Publication No. 54-2055.
A porous sheet obtained by applying a solvent solution of a polyurethane resin from polycaprolactone, 4,4′-diphenyl-methan diisocyanate and ethylene glycol described in JP-A No. 7 to a substrate and treating the substrate with a non-solvent of the polyurethane resin is disclosed. Are known. [Problems to be Solved by the Invention] However, although these have excellent breathability, they have almost no effect of shape memory. [Problems to be Solved by the Invention] The present inventors have breathability and can fix deformation for convenience of use, and when necessary, recover the shape before deformation by gentle heating. The present invention has been achieved as a result of repeated research on a shape-memory porous sheet that can be used. Here, the shape memory referred to in this patent is a primitive shape.

[Shape of the manufactured sheet as it is. Alternatively, a sheet having a shape obtained by deforming the sheet into a desired shape and heating it to a high temperature (for example, 130 to 230 ° C.) while maintaining the deformed shape (hereinafter referred to as a primitive shape)] When deformed from around room temperature at a temperature of 130 ° C, the deformation can be fixed at room temperature (for example, 40 ° C or less),
It also refers to a series of characteristics that can maintain the fixation of deformation at room temperature (for example, 40 ° C or less) and can recover the original shape in a short time (for example, within 5 minutes) by heating the sheet with the deformation fixed (for example, 40 ° C or less). . Ordinary plastics and rubbers do not have the above-mentioned shape memory characteristics. For example, plastic can fix deformation, but it does not recover its original shape when heated to 40 ° C. or higher, and rubber cannot fix deformation at room temperature. [Means for Solving the Problems] That is, the present invention relates to an organic diisocyanate and a general formula [Wherein A ₃ is Or Provided that R ₁ and R ₂ are hydrogen, an alkyl group having 1 to 3 carbon atoms, fluorine, or chlorine; A ₁ , A ₂ are alkylene groups having 2 to 4 carbon atoms; and m and n are 2 ≦ m + n ≦ 10. O and p are 0 or positive integers satisfying 0 ≦ o + p ≦ 10; q and r are 0 or positive integers satisfying 0 ≦ q + r ≦ 10; X is hydrogen, chlorine, It is a bromine or methyl group. ] One or more polyol components selected from the compounds represented by and A shape-memory porous sheet made of a polyurethane resin containing at least 15% by weight of the structural unit represented by
It is a memory method for storing a new primitive shape in the shape-memory porous sheet, a fixing method for deformation, and a restoring method for deformation. Examples of the organic diisocyanate [hereinafter referred to as (I)] used in the present invention include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6
-Tolylene diisocyanate, 2,4-tolylene diisocyanate, a mixture of 2,6-tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, 4,4'-methylene bis ( Cyclohexyl isocyanate), isophorone diisocyanate, and the like, and mixtures of two or more thereof. Preferred organic diisocyanate components from the viewpoint of shape memory property are 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate and 2,6- A mixture of tolylene diisocyanates,
4,4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate and the like
Examples include a mixture of two or more species. More preferably 4,
4'-diphenylmethane diisocyanate, and 4,
4'-methylenebis (cyclohexyl isocyanate)
Is. In the polyol component of the general formulas (1), (2) and (3), examples of the alkylene group having 2 to 4 carbon atoms of A ₁ and A ₂ include ethylene group, propylene group and butylene group. Of these, an ethylene group is preferable from the viewpoint of shape memory. X in the general formulas (1) and (2) is preferably hydrogen or a methyl group from the viewpoint of shape memory property. M and n in the general formula (1) are preferably 2 ≦ m + n ≦ 4.
Is a positive integer that satisfies the above condition, and when m + n is 4 or more, the shape memory property deteriorates. More preferably 2 in terms of shape memory
It is a positive integer that satisfies ≦ m + n ≦ 2.5. (Here, m + n = 2.5 means, for example, a mixture of 2 mol adduct and 3 mol adduct in an equimolar ratio.) O and p in the general formula (2) are preferably 0 ≦ o + p ≦ 4.
0 or a positive integer that satisfies the above condition, and if o + p is 4 or more, the shape memory property deteriorates. It is more preferably 0 in terms of shape memory. Q and r in the general formula (3) are preferably 0 ≦ q + r ≦ 4.
Is 0 or a positive integer satisfying the above condition, and more preferably 0. When q + r is 4 or more, the shape memory property deteriorates. In the general formulas (1), (2), and (3), R ₁ and R
Examples of the alkyl group having ₂ to 3 carbon atoms include a methyl group, an ethyl group and a butyl group. Of these, a methyl group is preferable from the viewpoint of shape memory property. As the constituent component represented by the general formula (1), for example,
4,4'-methylene bisphenol, 4,4'-isopropylidene bisphenol, 4,4'-hydroxy bisphenol, 4,4'-sulfonyl bisphenol, 4,4'-dihydroxybenzophenone, 4,4 '
-Isopropylidene bis (3,5-dichlorophenol), 4,4'-isopropylidene bis (3,5-dibromophenol), 4,4'-isopropylidene bis (3,5,3 ', 5') -Tetrabromphenol) and other bisphenols, or a mixture of two or more thereof, with a ring-opening addition reaction of an alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide and butylene oxide in a random or block form. What can be obtained by. Among these, those obtained by ring-opening addition of ethylene oxide are particularly preferable from the viewpoint of shape memory property. The number of moles of these alkylene oxides added is 1 mole or more per one OH group of the bisphenol. If the number of moles added is too large, the shape memory property deteriorates, so 4 moles or less is preferable for 1 mole of bisphenols. Specifically, 2,4'-methylene bisphenol ethylene oxide 2 mol adduct, 4,4'-methylene bisphenol propylene oxide 2 mol adduct, 4,4'-methylene bisphenol ethylene oxide 2 mol, propylene oxide 2 Mol adduct, 4,4'-methylenebisphenol butylene oxide 4 mol adduct, 4,4'-isopropylidene bisphenol ethylene oxide 2 mol adduct, 4,4'-dihydroxybenzophenone propylene oxide 2 mol adduct, 4 2,4'-isopropylidene bis (3,5-dichlorophenol) ethylene oxide 2 mol adduct, 4,4'-isopropylidene bis (3,5-dibromophenol) ethylene oxide 2 mol adduct, 4 , 4'-isopropylidenebi (3,5,3 ', 5'-tetrabromo phenol), ethylene oxide (2 mol) adduct of the like. The diol component represented by the general formula (2) is a compound of the type obtained by hydrogenating the benzene nucleus of the bisphenol in the case of the general formula (1), that is, bis (4-hydroxycyclohexyl) methane, 2,2-bis ( 4-hydroxycyclohexyl) propane, 3,3-bis (4-hydroxycyclohexyl) pentane, bis (3,5-dichloro-
4-hydroxycyclohexyl) sulfone, bis (3,3
Compounds such as 5-dibromo-4-hydroxycyclohexyl) ketone, or obtained by adding alkylene oxide to these bishydroxy compounds and a mixture of two or more thereof in the same manner as in the case of the general formula (1). Things can be used. If the number of moles of alkylene oxide added is too large with respect to 1 mole of the bishydroxy compound, the shape memory property deteriorates. Specific examples of the alkylene oxide adduct of the general formula (2) include 2 mol of ethylene oxide of bis (4-hydroxycyclohexyl) methane and 4 mol of propylene oxide of 2,2-bis (4-hydroxycyclohexyl) propane. Adjunct,
Butylene oxide 2 mol adduct of 3,3-bis (4-hydroxycyclohexyl) pentane, bis (3,5-
Examples thereof include dichloro-4-hydroxycyclohexyl) sulfone ethylene oxide 2 mol adduct, bis (3,5-dibromo-4-hydroxycyclohexyl) ketone ethylene oxide 2 mol adduct, and the like. The diol component represented by the general formula (3) is obtained by adding cyclohexanedimethanol or alkylene oxide thereto. If the number of moles of alkylene oxide added is 4 moles or more, the shape memory property deteriorates. Particularly preferred is cyclohexanedimethanol. Specific examples of the alkylene oxide adduct of the general formula (3) include an adduct of cyclohexanedimethanol with 2 moles of ethylene oxide and an adduct of cyclohexanedimethanol with 2 moles of propylene oxide. The compounds represented by the general formulas (1), (2) and (3) can also be used as a mixture of two or more kinds. Structural units derived from general formulas (1), (2) and (3) which are essential components and The amount of at least 15% by weight of the constituent units in the polyurethane resin, preferably 20% by weight or more,
More preferably, it is at least 25% by weight, and if it is less than 15% by weight, sufficient shape memory cannot be obtained. In order to further improve performances other than shape memory performance of the obtained shape memory polyurethane resin, such as impact resistance and cold resistance, the polyol component represented by the above general formulas (1), (2) and (3). in the following _{(b 1)} and referred, in combination with average molecular weight 500 to 8000 (the molecular weight determined from OH-V of the polyol component) [hereinafter referred to as _{(b 2)]} a long-chain polyol component. Examples of (b ₂ ) include polyether diol, polyester diol, polybutadiene glycol, hydrogenated polybutadiene glycol, and a mixture of two or more thereof. Examples of the polyester diol include polyethylene ether glycol, polypropylene ether glycol, polyethylene-polypropylene (block and / or
Or random) ether glycol, polytetramethylene ether glycol, polytetramethylene-ethylene (block and / or random) ether glycol, polytetramethylene-propylene (block and / or random) ether glycol, polyhexamethylene-ethylene glycol, and Examples thereof include a mixture of two or more kinds. Examples of the polyether diol include a polyester diol obtained by reacting a low molecular weight diol and / or a polyester diol having a molecular weight of 1,000 or less with a dicarboxylic acid, a polylactone diol obtained by ring-opening polymerization of a lactone, a polycarbonate diol, and the like. Examples of the low molecular weight diol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,6-hexanediol, and two or more of these. A mixture of Examples of the polyether diol having a molecular weight of 1000 or less include polyethylene glycol, polytetramethylene glycol, polypropylene glycol, triethylene glycol; and a mixture of two or more thereof. As dicarboxylic acids, aliphatic dicarboxylic acids (succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, etc.) and these 2 Examples include a mixture of two or more species. Examples of the lactone include ε-caprolactone. Specific examples of these polyether diols include polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, polyethylene polypropylene adipate, polyethylene butylene adipate, polybutylene hexamethylene adipate, polydiethylene adipate, poly (polytetraadipate). Methylene ether) adipate, polyethylene azelate, polyethylene sebacate, polybutylene azelate, polybutylene sebacate, polycaprolactone diol; and mixtures of two or more thereof. As polybutadiene glycol, hydroxyl-terminated polybutadiene homopolymer type, hydroxyl-terminated polybutadiene copolymer type (styrene-butadiene copolymer, acrylonitrile-butadiene copolymer), etc.,
Examples include a mixture of two or more of these. Specific examples thereof include Poly Bd series manufactured by Arco Corp. of America and G series of NISSO-PB manufactured by Nippon Soda Co., Ltd. Examples of the hydrogenated polybutadiene glycol include those obtained by hydrogenating a part or all of the unsaturated double bonds of the above polybutadiene glycol, and a mixture of two or more of these. Specifically, NIS of Nippon Soda Co., Ltd.
The GI series of SO-PB is mentioned. Further, a polymer diol obtained by polymerizing these long chain diol components and an ethylenically unsaturated monomer (acrylonitrile, styrene, etc.) can also be used. Further, in order to further improve the performance other than the shape memory performance of the obtained shape memory polyurethane resin, such as hardness and heat resistance, (b ₁ ) within a range that does not hinder the shape recovery and the fixed memory of deformation. A low component polyol having an average molecular weight of 400 (this molecular weight is determined from OH-V of the polyol component) or less [hereinafter referred to as (b ₃ )] is used in combination. Examples of (b ₃ ) include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, and the like, and these 2 Mixtures of more than one species can be used. In addition to these, monoethanolamine,
Polyamine compounds such as ethylenediamine, hexamethylenediamine, diethylenetriamine, isophoronediamine, 4,4'-diphenylmethanediamine, 4,4'-methylenebis (cyclohexylamine) and mixtures of two or more of these are also within a range not impairing the shape memory property. (B
It can be used for the same purpose as ₃ ). A catalyst is used if necessary in the production of the polyurethane resin. Examples of the catalysts include salts of organic and inorganic acids with lead octylate, dibutyltin dilaurate, stanna octoauto, and organic metal derivatives; organic tertiary amines such as triethylenediamine and triethylamine, and diazabicycloundecene catalysts. Can be given. In producing a polyurethane resin or a porous sheet, an auxiliary compounding agent can be used within a range not impairing the shape memory performance. Examples thereof include coloring agents such as dyes and pigments, fillers, modifiers, weather resistance improvers, plasticizers and cross-linking agents. Examples of dyes include direct dyes, acid dyes, basic dyes, reactive dyes, and metal complex salt dyes. As the pigment, carbon black, titanium oxide, iron oxide, chromium oxide, mica, zinc oxide, dark blue, and other inorganic pigments and coupling azo-based, condensed azo-based, anthraquinone-based, perylene-based, quinacridone-based, thioindigo-based, Examples of organic pigments include dioxazine-based and phthalocyanine-based pigments. As the filler, calcium carbonate, silica,
Inorganic fillers such as talc and glass beads and fluorine resin,
Examples thereof include fine powders of silicone resin, polyamide resin, styrene resin, urethane resin and the like, and organic fillers such as beads and hollow beads. Examples of the modifier include thermoplastic resins such as polyvinyl chloride, polyacrylic acid ester, polystyrene, polyacrylonitrile, acrylonitrile-vinylidene chloride copolymer, acrylonitrile-styrene copolymer, and vinyl chloride-vinyl acetate copolymer. To be As weather resistance improvers, hindered phenol-based, phosphite-based, thioether-based, etc. antioxidants, benzophenone-based, bendtriazole-based, oxalic acid anilide-based, salicylate-based, salicylate-based UV absorbers, hindered amide-based And the like, NOx gas stabilizers such as hydrazine type and semicarbazilo type, nickel complex salt type metal deactivators, organic halogen type flame retardants and the like. Examples of the plasticizer include diphtyl phthalate and dioctyl phthalate. Examples of the cross-linking agent include the above-mentioned isocyanates, melamine, organic polyamines, methylamine compounds obtained from organic polyamines and ketone compounds such as methyl ethyl ketone, trimethylolpropane, polyfunctional glycols such as glycerin, and epoxy compounds. When obtaining a shape-memory polyurethane resin, the proportion of the essential components (b ₁ ) and (b ₂ ) and / or (b ₃ ) used is such that the structural units derived from (b ₁ ) and Of at least 15% by weight in the polyurethane resin,
The content is preferably 20% by weight or more, and more preferably 25% by weight or more, and may be changed according to the shape memory property of the shape memory polyurethane resin to be obtained and the demand for performance other than shape memory. In the case of obtaining a shape-memory polyurethane resin, the molar ratio of the polyol component (b ₁ ) and the (b ₂ ) component and / or (b ₃ ) component used in combination [(b ₁ ) :( b ₂ ) +
(B ₃ )] is usually 1: 0 to 1, preferably 1: 0 to 0.
It is 5. In addition, N of the organic diisocyanate component (I)
Active hydrogen capable of reacting with isocyanates of all polyol components [hereinafter referred to as (B)] component consisting of one and / or all of (b ₂ ) and (b ₃ ) containing a CO group and (b ₁ ) as essential components The equivalent ratio of the groups is usually 0.9 to 1.1: 1.
It is preferably substantially 1: 1. The shape-memory polyurethane resin can be produced by a usual method. For example, a one-shot method in which all of the components (I) and (B) are reacted at the same time, a part of the components (I) and (B), for example, the component (b ₂ ) is reacted to prepare a prepolymer, which is then prepared. And the component (b ₁ ) is reacted with. Further, the production of the thermoplastic shape memory polyurethane resin can be carried out in the presence of a solvent inert to the isocyanate group. In the case of using no solvent, polymerization can be carried out by a method of polymerizing using a well-stirring device such as a kneader or an extruder and granulating with a pelletizer or crushing with a freeze crusher. In the case of polymerizing in a solvent, an amide-based solvent [dimethylformamide (hereinafter abbreviated as DMF), dimethylacetamide, etc.], a sulfosulfide-based solvent (dimethylsulfoxide, etc.), a lactam-based solvent (n-methyl-2-pyrrolidone, etc.), Ether-based solvents (dioxane, tetrahydrofuran, etc.), ester-based solvents (ethyl acetate, cellosolve acetate, etc.), ketone-based solvents (cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aliphatic carbonization Examples thereof include hydrogen solvents (n-hexane and the like), alcohol solvents (isopropyl alcohol, ethyl alcohol and the like), and mixtures of two or more thereof. Amide solvents and sulfoxide solvents are preferable, and DMF is particularly preferable. The concentration of urethane resin in the solvent is 10 to 90% by weight, preferably 20 to 60% by weight. The shape memory porous sheet of the present name can be produced by a usual method. For example, (I) component and (b ₂₎ and the component are reacted to produce a pre-polymer then this foaming agent (azobisisobutyronitrile, Azojika - Bon'amido etc.), and a foam stabilizer [doo - Les Silicone oil SH series etc. of Silicone Co., Ltd.] and a method of reacting the component (b ₁ ) to carry out foam curing, or a shape memory polyurethane resin is a poor solvent for the polyurethane resin and lower than water. After synthesizing in a solvent having a boiling point, a W / O type emulsion is obtained by inversion with water, and the solvent is preferentially removed by evaporation, and then water is removed by drying. As a preferred method for producing the shape-memory porous sheet, a solvent solution of the polyurethane resin produced by the above-mentioned method, or the same organic solvent as that used for the urethanization reaction of pellets or powder, particularly preferably DMF with a resin concentration of Usually 5
To 40 wt%, preferably 15 to 20 wt%, diluted or dissolved, and if necessary, the auxiliary compounding agent, surfactant (anion type, cation type, nonion type, silicon type, etc.), wet film formation Add a property improver (cellulose powder, etc.). When it is desired to add heat resistance to the porous wet sheet, a crosslinking agent

[Raw materials used]

1, organic diisocyanate (I) (MDI): 4,4′-diphenylmethane diisocyanate (H-MDI): 4,4′-methylenebis (cyclohexylisocyanate 2, polyol component (b ₁ ) (b _{1 1} -1): 4,4'-isopropylidene bisphenol ethylene oxide adduct Average number of moles added: 2.3 Average molecular weight: 330 Hydroxyl value: 340 (b ₁ -2): 4,4'-isopropylidene bis Propylene oxide adduct of phenol Average number of moles added: 2.3 Average molecular weight: 361 Hydroxyl value: 311 (b ₁ -3): 4,4'-Sulfonylbisphenol ethylene oxide adduct Average number of moles added: 2.3 Average molecular weight: 351 Hydroxyl value: 319 (b ₁ -4): 2,2-bis (4-hydroxycyclohexyl) propane Molecular weight: 246 (b ₁ -5): Cyclohexane dimethanol Molecular weight: 144 (b ₁ -6) ): 4,4'-isopropylidene bisphenol Tylene oxide adduct Average number of moles added: 18.1 Average molecular weight: 1020 Hydroxyl value: 110.1 3, Polyol component (b ₂ ) (b ₂ -1): Polybutylene adipate Average molecular weight: 2000 Hydroxyl value: 56.1 (b ₂ -2): polybutylene adipate - DOO average molecular weight: 2500 hydroxyl value: 44.9 (b ₂ -3): polyoxytetramethylene et - Teruguriko - Le-average molecular weight: 2030 hydroxyl value: 55.3 (b ₂ -4): polycarbonate -Bone-todionol Average molecular weight: 1020 Hydroxyl value: 110.0 (b ₂ -5): Polycarbone-Bone-todiole Average molecular weight: 1500 Hydroxyl value: 74.8 (b ₂ -6): Polycarbone-Bonet-dioyl , Propylene oxide adduct (Polycarbone-todiol molecular weight before addition: 3000) Average molecular weight: 6720 Hydroxyl value: 16.7 4, Polyol component (b ₃ ) (b ₃ -1): Ethylene glycol (b ₃ -2): 1.4-Butadiol 5, solvent (DMF): dimethylform Amide Example 1 171 parts of (b ₁ -1) and 129 parts of (MDI) were added to (DM
F) React in 700 parts at 80 ° C., resin concentration 30%
Polyurethane resin with a viscosity of 560 poise at 20 ℃ (b
A skeleton derived from _one component: 39% by weight) was obtained. A solution having the composition shown in Table 1 was prepared using the obtained polyurethane resin solution. (Table-1) Polyurethane resin solution: 100 parts (DMF): 150 parts Sanmorin OT-70 (* 1): 2 parts (* 1): Sanyo Chemical Industries, Ltd. surfactant (sulfosuccinate salt side) The prepared solution is applied on a support (polyester film) to a thickness of 1.5 mm, immersed in a water bath at 30 ° C. for 60 minutes for coagulation, further immersed in a water bath at 60 ° C. for 60 minutes, and washed at 120 ° C. Dry for 40 minutes (sheet density: 0.4)
Then, it was peeled from the polyester film to obtain a porous sheet. This porous sheet (cut into a width of 1 cm and a length of 10 cm) was bent 180 ° at 80 ° C and cooled to 25 ° C to fix the deformation. When this was immersed in 90 ° C. warm water, the original shape was completely recovered within 30 seconds. Also, another section that was left bent at 30 ° C. was still bent after 1 week, but when immersed in warm water at 90 ° C. 3
The original shape was completely restored within 0 seconds. Example 2 _(b 2 -1) and 2000 parts (MDI) 4604 parts of 70
The reaction was carried out for 2 hours while maintaining at 0 ° C. to obtain a pseudo prepolymer having an isocyanate group at the terminal. This quasi-prepolymer and (b _1-2 ) were heated to 70 ° C. and 120 ° C., respectively, by a metering pump at 100.0 g / min, and 95.
The mixture was fed at a rate of 2 g / min into a twin-screw extruder through a mixer, and continuously reacted while being heated and kneaded at a maximum temperature of 200 ° C. and taken out in a string shape. (Backbone derived from b ₁ component: 31 wt%) cut into the polyurethane resin by 15 hours aging after pelletizer at 25 ° C. to obtain a pellet. Using the obtained polyurethane resin pellets, a solution having a composition shown in Table 2 was prepared. (Table-2) Polyurethane resin pellets: 30 parts (DMF): 220 parts Sanmorin OT-70: 2 parts DILAC COLOR (* 2): 6 parts (* 2): Colorant manufactured by Dainippon Ink and Chemicals, Inc. above The adjusted solution is applied on a support (polyester film) to a thickness of 1.5 mm, coagulated for 5 minutes under constant temperature and humidity conditions of 40 ° C. and 95% RH, and further immersed in a water bath at 70 ° C.
After dipping for 00 minutes, washing, and drying for 40 minutes at 120 ° C., peeling from the polyester film and then removing the porous sheet (sheet density:
0.5) was obtained. This porous sheet (width 1 cm, length 1
It was cut at 0 cm) and bent at 80 ° C by 180 ° and cooled to 25 ° C to fix the deformation. When this was immersed in warm water at 80 ° C., the original shape was completely recovered within 30 seconds. Another section left bent at room temperature (about 30 ° C) remained bent even after 1 week at 80 ° C.
When it was soaked in warm water, the original shape was completely recovered within 30 seconds. Example 3 (b _1-3 ) 136.2 parts, (b _2-3 ) 27.3 parts and (b ₃ -1) 7.2 parts and (MDI) 129.3 parts in (DMF) 700 parts. in it reacted at 80 ° C., a viscosity of 20 ° C. at a resin concentration of 30% (backbone derived from _{b 1} component: 32 wt%) polyurethane resin 820 poise to obtain a solution. Using the obtained polyurethane resin solution, a solution having the composition shown in Table 3 was prepared. (Table-3) Polyurethane resin solution: 100 parts (DMF): 150 parts Sanmorin OT-70: 2 parts Coronate HL (* 3): 3 parts (* 3): Aliphatic polyfunctional isocyanate manufactured by Nippon Polyurethane Industry Co., Ltd. The prepared solution is applied on a support (polyester film) to a thickness of 1.5 mm, immersed in a water bath at 30 ° C. for 30 minutes for coagulation, and further immersed in a water bath at 70 ° C. for 100 minutes,
After washing, it was dried at 120 ° C. for 40 minutes and peeled from the polyester film to obtain a porous sheet (sheet density: about 0.5). This porous sheet (width 1 cm, length 10 cm was cut) was bent 180 ° at 25 ° C. This is 7
When immersed in warm water of 0 ° C., the original shape was completely recovered within 30 seconds. Further, another piece left bent at room temperature (25 ° C.) remained bent even after 1 week, but when immersed in hot water at 70 ° C., it completely recovered to its original shape within 30 seconds. Example 4 _(b 1 -4) 122.2 parts and _(b 2 -4) 38 parts of (H-MDI) 139.9 parts of dibutyltin dilaurate (catalyst) was added 0.1 parts (DMF) 700 80 are reacted in ° C. in parts, the viscosity of 20 ° C. 30% resin concentration (backbone derived from b ₁ component: 40 wt%) polyurethane resin 560 poise to obtain a solution. The resulting polyurethane resin solution was used to prepare a solution having the composition shown in Table-4. (Table-4) Polyurethane resin solution: 100 parts (DMF): 150 parts Sanmorin OT-70: 2 parts A substrate (polyester raised woven fabric) was dipped and impregnated in the above adjustment solution. Next, it is solidified for 5 minutes under constant temperature and humidity conditions of 40 ° C. and 95% RH, further immersed in a 70 ° C. water bath for 120 minutes, washed, dried at 80 ° C. for 20 minutes, and further 120 ° C. 40
After drying for a minute, a porous sheet (sheet density: about 0.7) was obtained. The obtained porous sheet (cut to a width of 1 cm and a length of 10 cm) was bent 90 ° at 65 ° C and cooled to 20 ° C to fix the deformation. When this was heated to 70 ° C. with a dryer, the original shape was completely recovered within 2 minutes. In addition, the other section that was left at 25 ° C after bending was 1
After a week, it was still bent, but with a dryer at 70 ℃
When heated up to, the original shape was completely recovered within 2 minutes. Example 5 (b ₂ −6) 672 parts and (MD
I) 4567 parts were reacted to obtain a quasi-prepolymer. The pseudo prepolymer and (b ₁ -5) were heated to 70 ° C. and 120 ° C., respectively, by a metering pump at 100 g / min,
And sent to a twin-screw extruder through a mixer at a speed of 49.4 g / min, continuously react while heating and kneading at a maximum of 200 ° C., and take out in a string shape, and after aging at 25 ° C. for 15 hours, with a pelletizer. Cut the polyurethane resin (b ₁
Pellets having a skeleton derived from the components: 33% by weight) were obtained.
The viscosity of a 30% (DMF) solution of the pellets was 620 poise at 20 ° C. Using the obtained polyurethane resin pellets, a solution having a composition shown in Table 5 was prepared. (Table-5) Polyurethane resin pellets: 30 parts (DMF): 220 parts Sanmorin OT-70: 2 parts DILAC COLOR: 6 parts The above adjustment solution had a thickness of 1.
It was applied to 2 mm, immersed in a 30 ° C. water bath for 30 minutes to coagulate, and further immersed in a 70 ° C. water bath for 80 minutes and washed. Next, it was dried at 120 ° C. for 40 minutes to obtain a porous sheet (sheet density: about 0.5). Obtained porous sheet (width 1c
m, 10 cm in length) 180 at 80 ℃
It was bent and deformed at a temperature of 25 ° C., and while maintaining its shape, it was cooled to 25 ° C. to fix the deformation. When this was immersed in warm water at 80 ° C., the original shape was completely recovered within 2 minutes. Another piece left bent at 25 ° C. was still bent even after one month, but when immersed in a warm bath at 80 ° C., it completely recovered to its original shape within 2 minutes. Example 6 _(b 1 -1) 162 part and _(b 3 -2) 4 parts of (MD
I) 134 parts of (DMF) and reacted at 80 ° C. in 700 parts of backbone viscosity 20 ° C. at a resin concentration of 30% is derived from the polyurethane resin _{(b 1} component of 560 poise: 37 wt%) solution to give the It was Using the obtained polyurethane resin solution, a solution having the composition shown in Table 6 was prepared. (Table-6) Polyurethane resin solution: 100 parts (DMF): 150 parts Sanmorin OT-70: 2 parts Coronate HL: 3 parts The above adjustment solution was applied on a substrate (polyester raising cloth) to a thickness of 1.2 mm, and 30 It was immersed in a water bath at a temperature of 30 ° C. for 30 minutes to be solidified, and further immersed in a water bath at a temperature of 70 ° C. for 120 minutes for cleaning. Next, it was dried at 120 ° C. for 40 to obtain a porous sheet (sheet density: about 0.5). Obtained porous sheet (width 1c
m, 10 cm in length) 180 at 80 ℃
It was bent and deformed at a temperature of 25 ° C., and while maintaining its shape, it was cooled to 25 ° C. to fix the deformation. When this was immersed in warm water at 80 ° C., the original shape was completely recovered within 2 minutes. Another piece left bent at 25 ° C. was still bent even after one month, but when immersed in a warm bath at 80 ° C., it completely recovered to its original shape within 2 minutes. Example 7 _(b 1 -1) 171 parts of the (MDI) 129 parts (DM
F) React in 700 parts at 80 ° C., resin concentration 30%
Polyurethane resin with a viscosity of 760 poise at 20 ℃ (b
A skeleton derived from _one component: 39% by weight) was obtained. The resulting polyurethane resin solution was used to prepare a solution having the composition shown in Table 7. (Table-7) Polyurethane resin solution: 100 parts (DMF): 150 parts Sanmorin OT-70: 2 parts The above adjusting solution was applied on a support (polyester film) to a thickness of 1.5 mm, and a water bath at 30 ° C was used. It was immersed for 60 minutes in an aqueous solution to solidify, and further immersed in a hot water bath at 60 ° C. for 60 minutes for cleaning. Next, the porous sheet peeled from the support was heated at 110 ° C.
And dried to obtain a porous sheet (sheet density: about 0.4). This porous sheet (cut to a width of 1 cm and a length of 10 cm) was bent 180 ° at 40 ° C and cooled to 25 ° C to fix the deformation. When this was immersed in warm water of 80 ° C., the original shape was completely recovered within 5 seconds. Further, another piece left bent at room temperature (about 25 ° C.) remained bent even after 1 week, but when immersed in warm water of 80 ° C., it completely recovered to its original shape within 5 seconds. Example 8 _(b 1 -3) 275 part and _(b 2 -5) 111 parts of the (MDI) 214 parts (DMF) 80 ° C. in 1400 parts of
And the viscosity at 20 ° C is 820 at a resin concentration of 30%.
Skeleton derived from the polyurethane resin (b ₁ component of poise:
32 wt%) solution was obtained. The resulting polyurethane resin solution was used to prepare a solution having the composition shown in Table-8. (Table-8) Polyurethane resin solution: 100 parts (DMF): 150 parts Sanmorin OT-70: 2 parts DILACCOLOR: 6 parts A substrate (polyester raising cloth) was dipped and impregnated in the above-mentioned liquid mixture. Then, soak in a water bath at 30 ° C for 60 minutes to solidify,
Further, it was immersed in a hot water bath at 60 ° C. for 60 minutes and washed. Then 1
Porous sheet dried at 20 ° C (sheet density: about 0.5)
Got The obtained porous sheet (width 2 cm, length 10 c
It was bent and deformed at 45 ° C. to 90 ° and cooled to 20 ° C. while maintaining its shape to fix the deformation. When this was heated to about 70 ° C with a dryer,
It completely recovered to its original shape within 20 seconds. Another section left at room temperature (about 25 ° C.) while folded was still bent after one week, but when heated to 70 ° C. with a dryer, it completely recovered to its original shape within 20 seconds. Example 9 _(b 1 -1) 134 part and _(b 2 -2) 59 parts of (M
107 parts of DI) was reacted in 700 parts of (DMF) at 80 ° C. to obtain a solution of a polyurethane resin (skeleton derived from component b ₁ : 31% by weight) having a resin concentration of 30% and a viscosity of 860 poise at 20 ° C. It was A solution having the composition shown in Table 9 was prepared using the obtained polyurethane resin solution. (Table-9) Polyurethane resin solution: 100 parts (DMF): 150 parts Sanmorin OT-70: 2 parts Coronate HL: 3 parts The above-mentioned compounded liquid was applied to a substrate (polyester woven fabric), and 20
It was immersed in a water bath at 60 ° C. for 60 minutes to be solidified, and further immersed in a water bath at 70 ° C. for 80 minutes for cleaning. Next, it was dried at 110 ° C. to obtain a porous sheet (sheet density: about 0.5). The obtained porous sheet (cut to a width of 1 cm and a length of 10 cm) was bent and deformed by 90 ° at room temperature (about 25 ° C).
When this was heated to about 80 ° C with a dryer,
Within a second, it was completely restored to its original shape. Another section left at room temperature (about 25 ° C.) while folded was still bent after one week, but when it was heated to about 80 ° C. with a dryer, it completely recovered to its original shape within 25 seconds. Examples 10, 11, 12 Porous sheets obtained in Examples 1, 2, 5 (width 1 cm,
Each 20 cm long piece was wound around a glass rod (diameter 10 mm) in a coil shape, both ends were fixed with a string, and heat-treated at 150 ° C. for 30 minutes, then cooled to 25 ° C.,
The coiled porous sheet was removed from the glass rod. The heat-treated porous sheet retained the coil-like form even after 10 days at 25 ° C. Next, the coil-shaped molded product after storage for 10 days was deformed into a flat plate shape at 80 ° C. and cooled to 25 ° C. while maintaining the shape to fix the deformation. These flat plate-shaped products retained their plate-like shapes even after 10 days,
When it was soaked in the hot water bath, it recovered to a coil shape within 2 seconds. These results are shown in (Table-10). Comparative Example 1 _(b 2 -1) and 1423 parts (MDI) 1072 parts of 70
The reaction was carried out for 2 hours while maintaining at 0 ° C. to obtain a pseudo prepolymer having an isocyanate group at the terminal. The _(b 1 -1) 2
53 parts and 253 parts of (b ₃ −2) were uniformly mixed at 120 ° C. to obtain a liquid (B). Then, the pseudo prepolymer and the liquid (B) were heated in a temperature of 70 ° C. and 120 ° C., respectively, in a twin screw extruder through a mixer at a rate of 100 g / min by a metering pump and 20.2 g / min. Up to 200
The mixture was allowed to react continuously while being heated and kneaded at ℃, and was taken out in the form of a string. 25 ° C. and cut with 17 hours aging after pelletizer with polyurethane resin (backbone derived from b ₁ Ingredients: 6 wt%)
Of pellets were obtained. The viscosity of a 30% (DMF) solution of the pellets was 730 poise at 20 ° C. Using the obtained polyurethane resin pellet, a solution having a composition as shown in Table-11 was prepared. (Table-11) Polyurethane resin pellets: 30 parts (DMF): 220 parts Sanmorin OT-70: 2 parts DILAC COLOR: 6 parts The above adjustment solution was applied onto a support (polyester film) to a thickness of 1.5 mm. , Coagulate for 5 minutes under constant temperature and humidity conditions of 40 ° C and 95% RH, and then bath in a water bath at 70 ° C for 1
After dipping for 00 minutes, washing, and drying for 40 minutes at 120 ° C., peeling from the polyester film and then removing the porous sheet (sheet density:
About 0.6) was obtained. When this porous sheet (cut to a width of 1 cm and a length of 10 cm) was bent 180 ° at 80 ° C. and cooled to 25 ° C. to fix the deformation,
The original shape was restored and the deformation could not be fixed. Comparative Example 2 _(b 1 -6) 87.1 _parts, (b 2 -3) 87.1 parts and _(b 3 -1) 18.6 parts of a (MDI) 107.1 parts (DMF) in 700 parts of At 80 ° C. to obtain a polyurethane resin solution having a resin concentration of 30% and a viscosity of 840 poise at 20 ° C. (skeleton derived from essential components: 6% by weight).
The resulting polyurethane resin solution was used to prepare a solution having the composition shown in Table-12. (Table-12) Polyurethane resin solution: 100 parts (DMF): 150 parts Sanmorin OT-70: 2 parts Coronate HL: 3 parts The above adjustment solution was applied on a support (polyester film) to a thickness of 1.5 mm. , Soak in a water bath at 30 ° C for 30 minutes to solidify, and then soak in a water bath at 70 ° C for 100 minutes,
After washing, it was dried at 120 ° C. for 40 minutes and peeled from the polyester film to obtain a porous sheet (sheet density: about 0.7). When this porous sheet (cut to a width of 1 cm and a length of 10 cm) was bent 180 ° at 25 ° C., the original shape was restored and the deformation could not be fixed. Comparative Example 3 _(b 2 -6) 160.1 parts and _(b 3 -1) 25.6
The parts and (H-MDI) 114.3 parts (DMF) and reacted at 80 ° C. in 700 parts, viscosity of 20 ° C. at a resin concentration of 30% (not including _{b 1} component) polyurethane resin of 810 poise solution Got Using the obtained polyurethane resin solution, a solution having the composition shown in Table 13 was prepared. (Table 13) Polyurethane resin solution: 100 parts (DMF): 150 parts Sanmorin OT-70: 2 parts A substrate (polyester raised woven fabric) was dipped and impregnated in the above adjustment solution. Next, it is solidified for 5 minutes under constant temperature and humidity conditions of 40 ° C. and 95% RH, further immersed in a water bath at 70 ° C. for 120 minutes, washed, dried at 80 ° C. for 20 minutes, and further dried at 120 ° C. for 4 minutes.
It was dried for 0 minutes to obtain a porous sheet (sheet density: about 0.4). Obtained porous sheet (width 1 cm, length 10 cm
(Cut it into pieces) and fold it 90 degrees at 65 ℃, 20 ℃
When I tried to fix the deformation by cooling it to the original shape, it recovered to the original shape and could not fix the deformation. [Effects of the Invention] The shape-memory porous sheet of the present invention can be deformed at room temperature or a temperature around room temperature, can be fixed at room temperature, and can be restored to its original shape by heating during use. . In addition, a new original shape can be stored by heating at 130 to 230 ° C. in a desired shape. Since the porous sheet of the present invention exerts such effects, it is a material for clothing, an interlining material, a brassiere, a medical material, a cast, a corset, a decorative material, a vehicle material, a building interior material, a sports protector, a toy, an artificial flower. It is useful for

Claims (6)

[Claims] 1. An organic diisocyanate and a general formula [Where A ₃ is Or Provided that R ₁ and R ₂ are hydrogen, an alkyl group having 1 to 3 carbon atoms, fluorine, or chlorine; A ₁ , A ₂ are alkylene groups having 2 to 4 carbon atoms; and m and n are 2 ≦ m + n ≦ 10. O and p are 0 or positive integers satisfying 0 ≦ o + p ≦ 10; q and r are 0 or positive integers satisfying 0 ≦ q + r ≦ 10; X is hydrogen, chlorine, It is a bromine or methyl group. ] One or more polyol components selected from the compounds represented by and A shape-memory porous sheet comprising a polyurethane resin containing at least 15% by weight of the structural unit represented by. 2. A solution of the polyurethane resin according to claim 1 in an organic solvent is adhered to a support and brought into contact with a non-solvent having an affinity with the organic solvent and a non-affinity with the polyurethane resin. The shape memory porous sheet obtained by transferring the organic solvent to the non-solvent to form a porous sheet, and then separating the support. 3. An organic solvent solution of the polyurethane resin according to claim 1 is adhered to a substrate and brought into contact with a non-solvent having an affinity with the organic solvent and an incompatibility with the polyurethane resin. And a shape-memory porous sheet obtained by transferring the organic solvent to the non-solvent. 4. The shape-memory porous sheet according to claim 1, which has a desired shape and is held at 130 to 230 ° C. so that the shape is stored as a primitive shape. 5. Deformed into a desired shape at about 130 ° C. or lower,
The shape-memory porous sheet according to any one of claims 1 to 4, wherein the deformed shape is maintained as it is at about 40 ° C or lower. 6. The method for using the shape-memory porous sheet according to claim 5, wherein the sustained deformed shape is returned to the original shape by heating at about 40 ° C. or higher.