JPH02167349A - Porous sheet and use thereof - Google Patents

Abstract

PURPOSE:To obtain a porous sheet useful as clothing material, medical material, etc., fixing deformation at normal temperature, restoring shape to a shape before deformation by mild heating in case of necessity, comprising an organic diisocyanate and a specific polyol component as essential components. CONSTITUTION:A solution of a polyurethane resin comprising an organic diisocyanate and one or more polyol components selected from compounds shown by formula I-formula III [A3 is group shown by formula IV (R1 and R2 are H, 1-3C alkyl, etc.); A1 and A2 are 2-4C alkylene; 2<=m+n<=10; 0<=0+p<=10, 0<=q+<=410; X is H, chlorine, etc.] as essential components and containing >=15wt.% constituent unit shown by formula VI in an organic solvent is applied to a substrate or base material, brought into contact with a non- solvent which has affinity for the organic solvent and nonaffinity for polyurethane and the organic solvent is transferred to the non-solvent to give the aimed sheet.

Description

[Detailed description of the invention]

[Industrial Application Fields] The present invention is a porous material with shape memory that is useful in various applications such as clothing materials, medical materials, decorative materials, vehicle materials, mechanical materials, electrical materials, and building gap filling materials. sheet and
It concerns how to use it. [Prior art] Regarding conventional porous sheets, for example, Japanese Patent Publication No. 54-2055
A porous sheet etc. obtained by applying a solvent solution of a polyurethane resin made from polycaprolactone, 4゜4゛-diphenylmethane diisocyanate and ethylene glycol to a substrate and treating it with a non-solvent of the polyurethane resin described in Publication No. 7 is available. Are known. [Problems to be Solved by the Invention] However, although these have excellent air permeability, they have almost no shape memory effect. [Issues to be solved by the inventionffl] The inventors of the present invention have air permeability, can fix the deformation for convenience in use, and can recover the shape before deformation by gentle heating when necessary. As a result of repeated research on shape-memory porous sheets that can Here, shape memory in this patent refers to

[The shape of the manufactured sheet is the same. Alternatively, it refers to any shape created by deforming a 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 the original shape). If the sheet is deformed at a temperature from around room temperature to 130°C, the deformation can be fixed by bringing it to room temperature (for example, below 40°C), and the deformation can be maintained at room temperature (for example, below 40°C), and the deformation can be fixed by heating the sheet. Refers to a series of characteristics that allow recovery to the original shape within a short period of time (for example, within 5 minutes) by heating (for example, at 40° C. or higher). Suitable plastics and rubbers do not have the shape memory properties mentioned above. For example, although plastic can be fixed in deformation, it will not recover to its original shape even if heated above 40°C, and rubber cannot be fixed in deformation at room temperature. [Means for Solving the Problems] That is, the present invention uses an organic diisocyanate and the general formula Rh, where R* is hydrogen, an alkyl group having 1 to 3 carbon atoms, fluorine,
or chlorine; Ah At is an alkylene group having 2 to 4 carbon atoms; m and n
is a positive integer that satisfies 2≦m+n≦10; 0 and p are 0 or positive integers that add % O:S o 10 to t; q and r satisfy 0≦Q+r≦10 0 or a positive integer; X is hydrogen, chlorine, bromine or a methyl group. ] A shape-memory porous sheet made of a polyurethane resin containing at least 15ffIm% of polyol components selected from the compounds represented by the following as an essential component; A memory method that memorizes new primitive shapes in
These are a method for fixing deformation and a method for recovering from deformation. The organic diisocyanates [hereinafter referred to as CI] used in the present invention include 4.4-diphenylmethane diincyanate isocyanate), 2. 8-) Lylene diisocyanate)
, 2. 4-) lylene diisocyanate, mixture of 2゜6-lylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate), 4. Examples include 4-methylenebis(cyclohexyl isocyanate), inphorone diisocyanate, and mixtures of two or more thereof. Preferred organic diisocyanate components from the viewpoint of shape memory include 4,4'-diphenylmethane diisocyanate, 2.4-)lylene diisocyanate), 2. 8-
) lylene diisocyanate, a mixture of 2.4-) lylene diisocyanate and 2.8-) lylene diisocyanate, 4.4''-methylenebis(cyclohexyl isocyanate), inphorone diincyanate, and mixtures of two or more thereof. More preferably 4.
4--diphenylmethane diincyanate 1,! =4
．． 4--methylenebis(cyclohexyl isocyanate). In the polyol components of general formulas (1), (2) and (3), examples of the alkylene group having 2 to 4 carbon atoms in A+*Al1 include ethylene group, propylene group, and butylene group. Among these, ethylene group is preferable from the viewpoint of shape memory properties. - Formulas (1) and (2) or hydrogen or methyl groups are preferred from the viewpoint of shape memory properties. - m and n in formula (1) are preferably 2≦m+n≦4
It is a positive integer that satisfies the following, and when m + n is 4 or more, shape memory properties deteriorate. In terms of shape memory, it is more preferably a positive integer satisfying 2≦m+n≦2.5. (
Here m+n=2. '5 refers to an equimolar mixture of a 2-mole adduct and a 3-mole adduct, for example) 0 and p in general formula (2) are preferably O: 5゜10p≦
It is O or a positive integer that satisfies 4, and when 00p is 4 or more, the shape memory property becomes worse. O is more preferred in terms of shape memory. - q and r in formula (3) are preferably O1q+r≦4
O or a positive integer that satisfies the following, more preferably 0. When Q+r is 4 or more, shape memory properties deteriorate. In general formulas (1), (2), and (3), Rh
The alkyl group having 1 to 3 carbon atoms in Rg is a methyl group,
Examples include ethyl group and butyl group. Among these, methyl group is preferable from the viewpoint of shape memory properties. -For example, the component represented by formula (1) is 4
．． 4-methylenebisphenol, 4゜4-impropylidenepisphenol, 4゜4゛-hydroxybisphenol, 4.4-sulfonylbisphenol,
4.4-dihydroxybenzophenone, 4.4″-isopropylidene bis(3,5-dichlorophenol)
, 4.4-isopropylidene bis(3,5-dibromophenol), 4.4-isopropylidene bis(3,5-dibromophenol),
Bisphenols such as (5,3-5-tetrabromophenol) or mixtures of two or more of these with alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, etc., in a random or block form. Examples include those obtained by ring-opening addition reaction. Among these, those prepared by ring-opening addition of ethylene oxide are particularly preferable from the viewpoint of shape memory properties. The number of moles of these alkylene oxides added is 1 mole or more per OHHI3 of bisphenols. If the number of moles added is too large, the shape memory will deteriorate, so 4 to 1 mole of bisphenols is added.
It is preferably less than mol. Specifically, 2 moles of ethylene oxide adduct of 4,4'-methylenebisphenol; 4.
2 mol adduct of 4'-methylene bisphenol with propylene oxide, 4. 2 mol adduct of 4-methylene bisphenol with 2 mol of ethylene oxide, 2 mol adduct of propylene oxide, 4. 4 mol adduct of butylene oxide with 4-methylene bisphenol, 4. 4--Impropylidene bisphenol adduct with 2 moles of ethylene oxide, 4
゜4゛-dihydroxybenzophenone propylene oxide 2 mole adduct, 4.4-isopropylidene bis(
2 mole ethylene oxide adduct of 3,5-dichlorophenol), 4,4-isopropylidene bis(3,
2 mole ethylene oxide adduct of 5-dibromophenol), 4,4-impropylidene bis(3,5,3-
, 5-tetrabromophenol) with 2 moles of ethylene oxide. As the diol component represented by the general formula (2), the above-
Compounds in which the benzene nucleus of bisphenols in the case of formula (1) is hydrogenated, namely 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゜5-dibromo-4-hydroxycyclohexyl)ketone or the like, or by adding an alkylene oxide to these bishydroxy compounds or a mixture of two or more thereof in the same manner as in the case of general formula (1). You can use what is provided. If the number of moles of alkylene oxide added is too large relative to 1 mole of the bishydroxy compound, the shape memory properties will deteriorate, so it is preferably 4 moles or less, and unadducted products are particularly preferred. Specifically, the alkylene oxide adduct of formula (2) above is ethylene oxide 2 of bis(4-hydroxycyclohexyl)methane.
molar adduct, propylene oxide 4 molar adduct of 2,2-bis(4-hydroxycyclohexyl)propane,
3. 2-mol butylene oxide adduct of 3-bis(4-hydroxycyclohexyl)pentane, bis(3,5-
Examples include an adduct of 2 moles of ethylene oxide of dichloro-4-hydroxycyclohexyl) sulfone, and an adduct of 2 moles of ethylene oxide of bis(3,5-dibrom-4-hydroxycyclohexyl)ketone. The diol component represented by the general formula (3) is cyclohexane dimetatool or one obtained by adding alkylene oxide to it. When the number of moles of alkylene oxide added is 4 moles or more, shape memory properties deteriorate. Particularly preferred is cyclohexane dimetatool. −
Specific examples of the alkylene oxide adduct of the formula (3) include an adduct of cyclohexane dimetatool with 2 moles of ethylene oxide, and an adduct of 2 moles of propylene oxide with cyclohexane dimetatool. Moreover, the compounds represented by these formulas (1), (2) and (3) can also be used in a mixture of two or more. The amount of the structural units derived from general formulas (1), (2) and (3) which are essential components is such that any one or more of the structural units is at least 15% by weight, preferably 20% by weight or more, in the polyurethane resin.
More preferably, the content is 25% by weight or more, and if it is less than 15% by weight, sufficient shape memory properties cannot be obtained. In order to further improve the properties other than the shape memory performance of the obtained shape memory polyurethane resin, such as impact resistance and cold resistance, it is necessary to use the polyol components represented by the above formulas (1), (2) and (3). [Hereinafter referred to as (b+), a long chain polyol component [hereinafter referred to as (b2)] having an average molecular weight of ff1500 to 8000 (the molecular weight is determined from 0H-V of the polyol component) is used in combination. (Examples of polyether diol include polyether diol, polyester diol, polybutadiene glycol, hydrogenated polybutadiene glycol, and mixtures thereof. Examples of polyether diol include polyethylene ether glycol. , polypropylene ether glycol, polyethylene-polypropylene (block and/or random) ether glycol, polytetramethylene ether glycol, polytetramethylene-ethylene (block and/or random) ether glycol, polytetramethylene-propylene (block and/or random) ) Ether glycol, polyhexamethylene ether glycol A mixture of two or more of these can be mentioned. Polyester diols include polyesters obtained by reacting low molecular weight diols and/or polyether diols with a molecular weight of mtooo or less with dicarboxylic acids. Examples of the low molecular diols include diols, polylactone diols obtained by ring-opening polymerization of lactones, polycarbonate diols, etc., such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1.4-butanediol, 1.
Examples include 3-butanediol, neopentyl glycol 6-hexanediol, and mixtures of these with 2Ni or more. Examples of polyether diols having a molecular ffi of 1000 or less include polyethylene glycol, polytetramethylene glycol, polypropylene glycol, triethylene glycol; and mixtures of two or more thereof. Dicarboxylic acids include 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 2111 Examples include mixtures of the above. Examples of lactones include ε-caprolactone. Specific examples of these polyester diols include polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, polyethylene polypropylene adipate, polyethylene butylene adipate, polybutylene hexamethylene adipate, polydiethylene adipate, poly( Polytetramethylene ether) adipate, polyethylene azelate, polyethylene sepacate, polybutylene azelate, polybutylene sebacate, polycaprolactone diol; and mixtures of these with a size of 2 m or more. Examples of polybutadiene glycol include hydroxyl-terminated polybutadiene homopolymer types, hydroxyl-terminated polybutadiene copolymer tights (styrene-butadiene copolymer, acrylonitrile-butadiene copolymer), etc.
Examples include mixtures of 28 or more of these. Specifically, the PolV Bd series manufactured by ARCO Corporation in the United States and the G series NISSO-PB manufactured by Nippon Soda Co., Ltd. are mentioned. Examples of the hydrogenated polybutadiene glycol include those obtained by hydrogenating some or all of the unsaturated double bonds of the above-mentioned polybutadiene glycol, and mixtures of two or more thereof. Specifically, Nippon Shuta Co., Ltd.'s Nl5SO
-PB's Gl series is mentioned. Furthermore, polymer diols obtained by polymerizing these long-chain diol components and ethylenically unsaturated monomers (acrylonitrile, styrene, etc.) can also be used. In addition, in order to further improve the properties other than the shape memory performance of the obtained shape memory polyurethane resin, such as hardness and heat resistance, it is necessary to increase the average A low-molecular polyol [hereinafter referred to as (bl)] having a molecular weight of m400 or less (the molecular weight is determined from 0H-V of the polyol component) is used in combination. Examples of (bl) include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1゜4-butanediol, neopentyl glycol, 1,6-hexanediol, and two types thereof. Mixtures of the above can be used. In addition to these, monoethanolamine 1,
Polyamine compounds such as ethylenediamine, hexamethylenediamine, diethylenetriamine, inphorondiamine, 4.4-dibuenylmethanediamine, 4.4-methylenebis(cyclohexylamine), and mixtures of two or more of these also impede shape memory. within the range (b
It can be used for the same purpose as l). A catalyst is used if necessary in the production of polyurethane resin. Catalysts include salts of metals and organic and inorganic acids and organometallic derivatives such as lead octylate, dibutyltin dilaurate, stannath octoate; organic tertiary amines such as triethylenediamine and triethylamine; diazabicycloundecene catalysts, etc. can be given. In the production of polyurethane resins or porous sheets, auxiliary compounding agents can be used to the extent that they do not interfere with the shape memory performance. Examples include coloring agents such as dyes and pigments, fillers, modifiers, weather resistance improvers, plasticizers, and crosslinking agents. Dyes include direct dyes, acid dyes, basic dyes,
Examples include reactive dyes and metal complex salt materials. Pigments include inorganic pigments such as carbon black, titanium oxide, iron oxide, chromium oxide, mica, zinc oxide, navy blue, and coupled azo, condensed azo, anthraquinone,
Organic pigments include perylene-based, quinacridone-based, thioindigo-based, dioxazine-based, and butalocyanine-based pigments. Fillers include inorganic fillers such as rhusium carbonate, silica, talc, and glass beads, fine powders such as fluorocarbon resin, silicone resin, polyamide resin, styrene resin, urethane resin, and organic fillers such as beads and hollow beads. Medications can be given. Modifiers include polyvinyl chloride, polyacrylic acid ester, polystyrene, polyacrylonitrile, acrylonitrile-vinylidene chloride copolymer,
Examples include thermoplastic resins such as acrylonitrile-styrene copolymer and vinyl chloride-vinyl acetate copolymer. Weather resistance improvers include antioxidants such as hindered phenols, phosphites, and thioethers; ultraviolet absorbers such as benzophenones, benzotriazoles, oxalic acid anilides, salicylates, and salicylates; and hindered amines. Examples include light stabilizers, NOx gas stabilizers such as hydrazine type and semicarbacilyl type, metal deactivators such as nickel complex salts, and flame retardants such as organic halogen types. Examples of plasticizers include dibutyl phthalate and dioctyl phthalate. Examples of the crosslinking agent include the above-mentioned incyanates, melamine, organic polyamines, ketimine compounds obtained from organic polyamines and ketone compounds such as methyl ethyl ketone, polyfunctional glycols such as trimethylolpropane and glycerin, and epoxy compounds. When obtaining a shape-memory polyurethane resin, the proportion of the essential components (bl), (b2) and/or (bl) used is at least 15% by weight in the constituent unit resin derived from (bl), Preferably 20% by weight or more, more preferably 2 parts 5% by weight or more,
It may be changed according to the shape memory property of the shape memory polyurethane resin to be obtained and the required degree of performance other than shape memory. When obtaining a shape memory polyurethane resin, the molar ratio of the polyol component (bl) and the (be) component and/or (bs) component used in combination [(b+):(be)+(b
s)] is usually 1:0 to 1, preferably 1:0 to 0.
It is 5. In addition, N of the organic diisocyanate component (I)
All polyol components consisting of one and/or all of (be) and (bs) [hereinafter referred to as (B)] having GO groups and (b+) as essential components, active hydrogen groups that can react with the incyanate of the component. The equivalent ratio is usually 0.9 to 1. 1:
1, preferably substantially 1:1. Shape-memory polyurethane resin can be produced by conventional methods, such as the one-shimmit method in which all components (I) and (B) are reacted at the same time, or a part of component (I) and part (B). For example, there is a method in which the (be) component is reacted to produce a prepolymer, and then the (b+) component is reacted with this prepolymer. Further, the thermoplastic shape memory polyurethane resin can be produced in the presence of a solvent that is inert to incyanate groups. In the case of a solvent-free product, it can be produced by polymerizing using a device that can be stirred well, such as a kneader or extruder, and then granulating it with a pelletizer or the like, or pulverizing it with a freeze-pulverizer. When polymerizing in a solvent, amide solvents [dimethylformamide (hereinafter abbreviated as DMF), dimethylacetamide, etc.], sulfoxy solvents (dimethyl sulfoxide, etc.), lactam solvents (n-
methyl-2-pyrrolidone, etc.), ether solvents (dioxane, tetrahydrofuran, etc.), ester solvents (
ethyl acetate, cellosolve acetate, etc.), ketone solvents (cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aliphatic hydrocarbon solvents (n-hexane, etc.)
, alcoholic solvents (isopropyl alcohol, ethyl alcohol, etc.), and mixtures of two or more thereof. Preferred are amide solvents and sulfoxide solvents, and DMF is particularly preferred. The urethane resin concentration in the solvent is 10 to 90% by weight, preferably 20 to 6% by weight.
00-60 weight. The shape-memory porous sheet produced by Zero Hatena can be manufactured by a conventional method. For example, components (1) and (be) are reacted to produce a prepolymer, which is then added with a blowing agent (such as azobisisobutyronitrile or azosica-bonamide) and a foam stabilizer (such as tote silicone). A method of foaming and curing by reacting a (b+) component containing silicone oil SH series, etc., and a method of foaming and curing a shape-memory polyurethane resin in a solvent that is a poor solvent for the polyurethane resin and has a lower boiling point than water. After synthesis, by phase inversion with water, W1
A method is possible in which a type 0 emulsion is prepared, the solvent is preferentially evaporated and water is removed by drying. A preferred method for producing a shape memory porous sheet is to reduce the resin concentration by using a solvent solution of the polyurethane resin produced by the above method, or by using an organic solvent similar to that used in the urethanization reaction, particularly preferably DMF, to reduce the resin concentration. Usually 5
Dilute or dissolve to a concentration of ~40% by weight, preferably 16 to 20% by weight, and add the above-mentioned auxiliary ingredients, surfactants (anionic, cationic, nonionic, silicone, etc.) as necessary, and wet film formation. Contains a sex improver (cellulose powder, etc.). In addition, if you want to add heat resistance to a porous sheet, use a crosslinking agent.

[Raw materials used]

1. Organic diisocyanate (■) (MDI): 4,4'' Diphenylmecune diisocyanate (■-MDI): 4,4-methylene oxide (cyclohexyl isocyanate) 2. Polyol component (b+) (b+-1): 4, 4- -Isobu U Virite °
Average number of moles added of ethylene oxide ↑ide adduct of 4,4-isopropylene bisphenol = 2.3 Average molecular ffi: 33G Hydroxyl value = 340 (b, -2): Average addition of ethylene oxide ↑ide adduct of 4,4-isobrohylene phenol Number of moles: 2.3 Average molecule ffi: 3fil Hydroxyl value = 311 (b+-3): Ethylene oxide adduct of 4,4--sulfonyl bisphenol Average number of moles added: 2.3 Average molecular weight: 351 Hydroxyl group Value: 319 (b-4): 2,2-hist(4-hydroxycyclohexyl)propane molecular weight: 246 (bl-5) Dimethanol molecule: 4 (blG): 4.4--If 0%
Average number of added moles of ethylene oxide adduct of bisphenol: 18.1 Average molecule i: 1020 Hydroxyl value: tto, t3, polyol component (b2) (ba-1): Average molecular weight of this ethylene oxide adduct: m :zoo. Hydroxyl value: 5B, 1 (ba-2): Nyrioxytetramethylene ether glycol average molecular weight: 250G : 2030 Water a base value 755.3 (ba-4) : Nelicane nate diol average molecular weight: 1G2G Hydroxyl value 7110.0 (ba-5) : Nelicane nate diol average molecular weight ff1=1500 Hydroxyl value: 74.8 (ba-8): Ne°licane°natediol, Br0runo I! Ide adduct (Neritonetosi 1-# molecular weight before addition: 300G) Average molecular weight: 672G Hydroxyl value: IB, 7 4, Polyol component (BA) (BSI): Ethylene glycol (BA4)
: 1.4-7" Kundiol 5, solvent (D KanF) 2 Dino 9 niNlumamito. Example 1 171 parts of (bl-1) and 129 parts of (MDI) were mixed with (DMF)
) to react at 80°C in 700 parts of polyurethane resin l11 (
A skeleton derived from the bl component: 3El%) solution was obtained. Using the obtained polyurethane resin solution, solutions having various compositions shown in Table 1 were prepared. (Table-1) Polyurethane resin solution = 100 parts (DMF)
: 150 copies Sansurin 0T-70 (
Book 1): Part 2 (11): Sanyo Chemical Industries Co., Ltd. i! 2 Surfactant (sulfosuccinic acid ester salt type)
．． Coated to a thickness of 5 mm, immersed in a 30°C water bath for 60 minutes to solidify, further immersed in a 60°C water bath for 60 minutes, washed, and dried at 120°C for 40 minutes (sheet density: approximately 0.4) L
A porous sheet was obtained by peeling off the polyester film. This porous sheet (cut into pieces 1 cm wide and 10 cm long) was folded and oiled at 80° C. and then cooled to 25° C. to fix the deformation. When this was immersed in warm water at 90°C, it completely recovered to its original shape within 30 seconds. Another section that was left folded at 30°C remained bent even after a week, but when it was immersed in 90°C water,
It completely recovered to its original shape within 0 seconds. Example 2 2000 parts of (bi-1) and 4604 parts of (MDI) were added to 70
The reaction was carried out for 2 hours while maintaining the temperature at °C to obtain a pseudo prepolymer having isocyanate groups at the ends. This pseudo-prepolymer and (bl-2) were heated at 70°C and 120°C, respectively, at 100.0 g/min with a metering pump, and at 95.0 g/min.
The mixture was fed into a twin-screw extruder via a mixer at a rate of 2 g/min, reacted continuously while being heated and kneaded at a maximum temperature of 200° C., and taken out in the form of a string. After aging at 25° C. for 16 hours, the mixture was cut with a pelletizer to obtain pellets of polyurethane resin (31% by weight of the skeleton derived from the b+ acid component). Table 2 Using 1g of polyurethane resin pellets
A solution with the following composition was prepared. (Table-2) Polyurethane resin pellets 2 30 parts (DMF)
: 220 parts Sansrin 0T-70
' 2nd part DILACC0LOR (X2):
8 parts (!2): Colorant manufactured by Dainippon Ink & Chemicals Co., Ltd. The above prepared solution was applied to a support (polyester film)
Coat it on top to a thickness of 1.5 mm, 4゛O℃, 95%RH
It was solidified for 5 minutes under constant temperature and humidity conditions, then immersed in a 70°C hot water bath for 100 minutes, washed, dried at 120°C for 40 minutes, and peeled off from the polyester film to obtain a porous sheet (sheet density: 0.5). Ta. This porous sheet (width 1cm ffh length 10cm
) was bent 180° at 80°C,
The deformation was fixed by cooling to ℃. When this was immersed in warm water at 80°C, it completely recovered to its original shape within 30 seconds. Another section that was left folded at room temperature (approximately 30°C) remained folded even after one week, but when immersed in warm water at 80°C, it completely recovered to its original shape within 30 seconds. Example 3 (b+-3)138. Part 2, (be-3)27.
3 parts and (bi-1) 7.2 parts and (MDI) 129
3 parts of ゜ were reacted in 700 parts of (DMF) at 80°C,
A polyurethane resin solution (skeleton derived from b+acid component = 32% by weight) having a resin concentration of 30% and a viscosity of 820 voids at 20°C was obtained. Using the obtained polyurethane resin solution, solutions having the compositions shown in Table 3 were prepared. (Table-3) Polyurethane resin solution: 100 parts (DMF)
: 150 copies Sansurin 0T-70
° 2 parts Coronate HL (X3)
' Part 3 03) 2 Aliphatic polyfunctional incyanate manufactured by Nippon Polyurethane Industries Co., Ltd. The above prepared solution was placed on a support (polyester film).
．． It was applied to a thickness of 5 mm, immersed in a 30°C water bath for 30 minutes to solidify, further immersed in a 70°C water bath for 100 minutes, washed, dried at 120°C for 40 minutes, peeled off from the polyester film, and prepared as a polygonal sheet. Density: about 0.5) was obtained. This porous sheet (width 1 c rrh length 10 c
1800 folds at 25°C. When this was immersed in hot water at 70°C, it completely recovered to its original shape within 30 seconds. Fold it again + ll + leave it at room temperature (
Another section left at 25°C remained folded even after one week, but when immersed in warm water at 70°C, it completely recovered to its original shape within 30 seconds. Example 4 122.2 parts of (b+-4), 38 parts of (ba-4) and 139.9 parts of (H-MDI) in 700 parts of (DMF) to which 0.1 part of dibutyltin dilaurate (catalyst) was added A polyurethane resin solution (skeleton derived from the b+ acid component: 400 mm) having a resin concentration of 30% and a viscosity of 5EIO voids at 20° C. was obtained. Using the obtained polyurethane resin solution, make a solution with the composition shown in Table 4? J″4 was adjusted. (Table-4) Polyurethane resin solution: 100 parts (DMF)
: 150 copies Sansurin 0T-70
° A two-part substrate (polyester brushed woven fabric) was immersed in the above adjustment solution to impregnate it. Next, 40℃, 95%R
After coagulating for 5 minutes under constant temperature and humidity conditions of .7) was obtained.The obtained porous sheet) (1
1+1cm1 (cut into 10cm length) 6
It was folded 90' at 5°C and cooled to 20°C to fix the deformation. When this was heated to 70°C with a dryer, it completely recovered to its original shape within 2 minutes. Another section that was left folded at 25°C remained folded even after a week, but when heated to 70°C with a hair dryer, it completely recovered to its original shape within 2 minutes. Example 5 In the same manner as in Example 2, (ba-6) 372 parts of E and (MD
I) A pseudo prepolymer was obtained by reacting 37 parts of 45E. This pseudo-prepolymer and (b+-5) were heated at 70°C and 120°C, respectively, at 100g/100g/by metering pump.
It is fed into a twin-screw extruder via a mixer at a speed of 49.4 g/min, reacted continuously while heating and kneading at a maximum of 200°C, and taken out in the form of a string at 25°C.
After time aging, cut with a pelletizer to make polyurethane resin (
A pellet of b + skeleton derived from acid component = 33 weight n%) was obtained. The viscosity of a 30% (DMF) solution of the pellets was 620 poise at 20°C. A solution having the composition shown in Table 5 was prepared using the obtained polyurethane resin pellets. (Table-5) Polyurethane resin pellets: 30 parts (DMF)
: 220 parts Sansrin 0T-70
: 2nd part DILACCOLOR:
E! The above prepared solution was applied onto a substrate (polyester woven fabric) to a thickness of 1.2 mm, immersed in a 30° C. water bath for 30 minutes to solidify, and further immersed in a 70° C. water bath for 80 minutes for washing. Next, it was dried at 120° C. for 40 minutes to obtain a porous sheet (sheet density: about 0.5). The obtained porous sheet (cut to 1 cm in width and 10 cm in length) was bent and deformed to 1800 degrees at 80°C, and while the shape was maintained, it was cooled to 25°C to fix the deformation. When this was immersed in warm water at 80°C, it completely recovered to its original shape within 2 minutes. Another section that was left folded at 25°C remained folded even after one month, but the temperature was 80.
When immersed in a warm bath at ℃, it completely recovered to its original shape within 2 minutes. Example 6 182 parts of (b+1) and 4 parts of (b$-2) and (M
134 parts of DI) were reacted at 80°C in 700 parts of (DMF) to obtain a polyurethane resin (skeleton derived from the b+ acid component: 37
% by weight) solution was obtained. Using the obtained polyurethane resin solution, solutions having the compositions shown in Table 6 were prepared. (Table-6) Polyurethane resin solution: 100 parts (DMF)
: 150 copies Sansurin 0T-70
° 2 parts coronet) HL”
Add 3 parts of the above adjustment solution to the base (polyester napkin)
It was coated on top to a thickness of 1.2 mm, immersed in a 30°C water bath for 30 minutes to solidify, and further immersed in a 70°C water bath for 120 minutes for washing. Next, dry at 120℃ for 40 minutes to form a porous sheet (
A sheet density of approximately 0.5) was obtained. The resulting porous sheet (cut into pieces of 1 cm wide and 10 cm long) was bent and deformed at 80° C. by 180°, and while the shape was maintained, the sheet was cooled to 25° C. to fix the deformation. When this was immersed in warm water at 80°C, it completely recovered to its original shape within 2 minutes. Another section that was left folded at 25°C remained folded even after one month, and when r; was immersed in a hot bath at 80°C, it completely recovered to its original shape within 2 minutes. Example 7 171 parts of (b+-1) and 129 parts of (MDI) were mixed into (DMF
) to react at 80°C in 700 parts of polyurethane resin (b+
A solution containing a skeleton derived from an acid component (39% by weight) was obtained. Using the obtained polyurethane resin solution, a solution having the composition shown in Table 7 was prepared. (Table-7) Polyurethane resin solution: ioog (DMF)
: 150 copies Sansurin 0T-70
° Apply 2 parts of the above prepared solution to a thickness of 1.5 mm on a support (polyester film) and heat at 30°C.
It was immersed in a water bath at 80° C. for 60 minutes to solidify, and then immersed in a hot bath at 80° C. for 60 minutes for washing. Next, the porous sheet peeled off from the support was dried at 110°C to obtain a porous sheet (sheet density: about 0.4). This porous sheet (width I cms
(cut into 10cm length) at 40℃ for 180℃
It was bent to zero and cooled to 25°C to fix the deformation. When this was immersed in warm water at 80°C, it completely recovered to its original shape within 5 seconds. Another section that was left unfolded at room temperature (approximately 25°C) remained bent even after a week, but when immersed in 80°C water, it completely recovered to its original shape within 5 seconds. Example 8 275 parts of (b+-3) and 111 parts of (b2-'5) and 214 parts of (MDI) were mixed in 1400 parts of (DMF) at 80°C.
The viscosity at 20°C was 820 at a resin concentration of 30%.
Poise polyurethane resin (skeleton derived from b + acid component =
32% by weight) solution was obtained. Using the obtained polyurethane resin solution, a solution having a composition as shown in Table 8 was prepared. (Table-8) Polyurethane resin solution: 100 parts (DMF)
: 150 copies Sansurin 0T-70
° Part 2 DILACCOLOR:
A 6-part substrate (polyester napkin) was immersed in the above-mentioned liquid mixture to impregnate it. Next, immerse in a 30°C water bath for 60 minutes to solidify.
Furthermore, it was immersed in a 60° C. water bath for 60 minutes and washed. Next 1
Dry at 20℃ to form a porous sheet (sheet density: approx. 0.5)
I got it. The obtained porous sheet (cut to a width of 2 cm ml and a length of 10 cm) was deformed by folding at 45° C. at 90° C., and while the shape was maintained, the sheet was cooled to 20° C. 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 that was folded and left at room temperature (approximately 25 degrees Celsius) remained folded even after one week, but when heated to approximately 70 degrees Celsius with a hair dryer, it completely recovered to its original shape within 20 seconds. Example 9 134 parts of (b+-1) and 59 parts of (b*-2) and (M
107 parts of DI) were reacted at 80°C in 700 parts of (DMF) to obtain a polyurethane resin with a resin concentration of 30% and a viscosity of 860 voids at 20°C (skeletal structure derived from the b+ acid component).
% by weight) solution was obtained. Using the obtained polyurethane resin solution, a solution having the composition shown in Table 9 was prepared. (Table-9) Polyurethane resin solution: 100 parts (DMF)
: 150 copies Sansurin 0T-7
0 ° 2 parts Coronate HL °
3 parts The above solution was applied to a substrate (polyester woven fabric), immersed in a 20° C. water bath for 60 minutes to solidify, and further immersed in a 70° C. water bath for 80 minutes for washing. Next 110
It was dried at ℃ to obtain a porous sheet (sheet density: about 0.5). Obtained porous sheet (width lCm1 length 10c
(cut into a length of m) was deformed by 90° at room temperature (approximately 25°C). When this was heated to about 80° C. with a dryer, it completely recovered to its original shape within 25 seconds. Another section that was left folded at room temperature (approximately 25°C) remained folded even after a week, but it was removed with a hair dryer for about 80 minutes.
When heated to 0°C, it completely recovered to its original shape within 25 seconds. Example 1011L 12 Porous sheet obtained in Example 1.2.5 (width lCms
Each piece (cut into a length of 20 cm) was wound into a coil shape around glass 111 (diameter 10 mm), and both ends were fixed with a string, heated at 150°C for 30 minutes, cooled to 25°C, and coiled into a porous coil. The quality sheet was removed from the glass rod. The porous sheet after the heat treatment retained its coiled form even after 10 days at 25°C. Next, the coiled molded product stored for 10 days was deformed into a flat plate shape at 80°C, and while the shape was maintained, it was cooled to 25°C to fix the deformation. These plate-shaped molded products retained their plate-like shape even after 10 days, but when immersed in a hot water bath at 80° C., they recovered to their coil-like shape within 2 seconds. These results are shown in (Table 10). (Table-10) Comparative Example 1 (b2-1) 1423 parts and (MDI) 1072 parts were added to 70
The reaction was carried out for 2 hours while maintaining the temperature at °C to obtain a pseudo prepolymer having incyanate groups at the ends. Also (b+-1)2
53 parts of (bs-2) and 253 parts of (BS-2) were uniformly mixed at 120°C to form liquid B). Next, the pseudo prepolymer and liquid (B) were heated to 70°C and 120°C, respectively, and passed through a mixer at a rate of 100 g/min and 20.2 g/min using a metering pump into a twin screw extruder. up to 200
The mixture was reacted continuously while heating and kneading at ℃ and taken out in the form of a string. After aging at 25°C for 17 hours, the polyurethane resin (skeleton derived from b + acid component = 6% by weight) was cut with a pelletizer.
) pellets were obtained. 30% of this pellet (DMF)
The viscosity of the solution was 730 voids at 20°C. A solution having the composition shown in Table 11 was prepared using the obtained polyurethane resin pellets. (Table 11) Polyurethane resin pellets: 30 parts (DMF) 220 parts Sanmorin 0T-70° 2 parts DILACC0LOR: 6 parts
．． It was applied to a thickness of 5 mm, solidified for 5 minutes under constant temperature conditions of 40°C and 195% RH, and then placed in a hot water bath at 70°C for 10 minutes.
After being immersed for 0 minutes and washed, it was dried at 120° C. for 40 minutes and then removed from the polyester film to obtain a porous sheet (sheet density: approximately 0.6). When this porous sheet (cut to 1 cm wide and 10 cm long) was folded 180 degrees at 80°C and cooled to 25°C to fix the deformation, it recovered to its original shape and the deformation could not be fixed. I could not do it. Comparative example 2 (b+-8)87. Part 1, (b2-3)87. 1
part and (bs-1) 18.8 parts and (MD I ), 1
1 part of 07° was reacted at 80°C in 700 parts of (DMF) to produce a polyurethane resin with a resin concentration of 30% and a viscosity of 840 voids at 20°C (skeletal double plate% derived from essential components).
A solution was obtained. The obtained polyurethane resin solution was mixed around to prepare a solution having the composition shown in Table 12. (Table-12) Polyurethane resin solution: 100 parts (DMF)
: 150 copies Sansurin 0T-70
' 2nd part corone) HL
3 parts of the above prepared solution was applied to a support (polyester film) to a thickness of 1.5 mm, immersed in a 30°C water bath for 30 minutes to solidify, and then immersed in a 70°C water bath for 100 minutes.
After soaking for 1 minute, washing at 120°C for 40 minutes, and peeling off the polyester film b, a porous sheet (sheet density: approx. 0
．． 7) was obtained. This porous sheet (width I Crrh
When a piece cut to a length of 10 cm) was bent 180 degrees at 25°C, it recovered to its original shape and the deformation could not be fixed. Comparative Example 3 (b2-6) 180.1 parts and (bs-1) 25°6
and 114.3 parts of (H-MDI) in 700 parts of (DMF) at 80°C to form a polyurethane resin (b+ acid component free) solution with a resin concentration of 30% and a viscosity of 810 voids at 20°C. Obtained. 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 Sansurin 0T-70°
A two-part substrate (polyester brushed woven fabric) was immersed in the above adjustment solution to impregnate it. Next, it was coagulated for 5 minutes under constant temperature and humidity conditions of 40℃ and 95% RH, then immersed in a 70℃ water bath for 120 minutes, washed, dried at 80℃ for 20 minutes, and then further heated to 120℃ for 4 minutes.
After drying for 0 minutes, a porous sheet (sheet density: about 0.4) was obtained. Obtained porous sheet (width I cms length 1
0cm) was folded 90° at 66°C,
When we tried to fix the deformation by cooling it to 20°C, it recovered to its original shape and the deformation could not be fixed. [Effects of the Invention] The Fuji-shaped memory porous sheet of the present invention can be deformed at room temperature or near room temperature, can fix the deformation at room temperature, and can be restored to its pre-deformation shape by heating during use. I can do it. Further, a new original shape can be memorized by heating the desired shape to 130 to 230°C. Because of these effects, the porous sheet of the present invention can be used as clothing materials, interlining materials, brassiere medical materials, casts, corsets, decorative materials, vehicle materials, building interior materials, sports protectors, toys, artificial flowers, etc. Useful.

Claims (1)

[Claims] 1. Organic diisocyanate and general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2), and ▲ Numerical formulas, chemical formulas, tables, etc. There is ▼ (3), [A_3 in the formula ▲ includes mathematical formulas, chemical formulas, tables, etc. ▼, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, however, R_1 and R_2 are hydrogen,
an alkyl group having 1 to 3 carbon atoms, fluorine, or chlorine; A_1 and A_2 are alkylene groups having 2 to 4 carbon atoms; m and n are positive integers satisfying 2≦m+n≦10; o and p are 0 0 or a positive integer satisfying ≦o+p≦10; q and r are 0 or a positive integer satisfying 0≦q+r≦10; X is hydrogen, chlorine, bromine or a methyl group. ] One or more polyol components selected from the compounds represented by are essential components, and ▲There are mathematical formulas, chemical formulas, tables, etc.
Shape-memory porous sheet made of polyurethane resin containing at least 15% by weight of the structural units shown in ▼ and ▲Mathematical formulas, chemical formulas, tables, etc.▼. 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 that has an affinity for the organic solvent and has no affinity for the polyurethane resin, A 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. A solution of the polyurethane resin according to claim 1 in an organic solvent is attached to a substrate, and the solution has affinity with the organic solvent;
A shape-memory porous sheet obtained by bringing the organic solvent into contact with a non-solvent that has no affinity with the polyurethane resin and transferring the organic solvent to the non-solvent. 4. The desired shape was kept at 130 to 230°C, so that the shape was memorized as the original shape.
The shape memory porous sheet according to any one of claims 1 to 3. 5. The shape-memory porous sheet according to any one of claims 1 to 4, which is deformed into a desired shape at a temperature of about 130°C or less, and maintains the deformed shape at a temperature of about 40°C or less. 6. The method of using the shape memory porous sheet according to claim 5, wherein the deformed shape that has been maintained is returned to its original shape by heating to about 40° C. or higher.