JPH02225531A - Thermoplastic shape memory molding and using method thereof - Google Patents

Abstract

PURPOSE:To obtain the title molding which can be fixed in the shape given after being deformed by heating and can restore its original shape by gentle heating by molding a thermoplastic polyurethane resin containing specified structural units in addition to an organic polyisocyanate component and a specified polyol component. CONSTITUTION:The title molding produced from a polyurethane resin essentially consisting of an organic polyisocyanate and at least one polyol component selected from among compounds of formulas I, II and III [wherein A3 is a group of formula IV, V or VI (wherein R1 and R2 are each H, a 1-3C alkyl, F or Cl); A1 and A2 are each a 2-4C alkylene; 2<=m+n<=10; 0<=o+p<=10; and 0<=q+r<=10] and containing at least 15wt.% structural units of formulas VII, VIII and IX. This molding can be deformed at a temperature <=130 deg.C, can be fixed in this shape at room temperature and can restore its original shape by gentle heating, so that it is useful as a filler for construction, sealing material for construction, medical material, coating agent for the outside and inside of a pipe or the like, fastener, mold, car body member, bumper, housing of an electronic appliance, etc.

Description

[Detailed description of the invention]

The present invention relates to a molded article having thermoplastic shape memory properties that is useful for various uses such as vehicle materials, mechanical materials, electrical materials, building gap filling materials, medical materials, decorative materials, clothing materials, etc., and a method for using the same. It is related to. [Prior Art] Various proposals have been made regarding shape-memory resin moldings. For example, in U.S. Pat. No. 4,193.899, a resin obtained by sulfonating and neutralizing a norbornene-based unsaturated terpolymer has a shape-memory resin molded body. Having memorability, U.S. Pat. Nos. 4,637°944 and 3,563,9
No. 73 describes that shape memory is caused by an ethylenic polymer crosslinked by energy irradiation, but
The former requires complicated resin production and takes a long time to fix and recover the shape, while the latter requires complicated crosslinking after molding. Also known are a shape-memory foam containing caprolactam as a main component as described in JP-A-60-36538, and a norbornene-based polymer composition as described in JP-A-61-188444. However, these also have problems, such as requiring special molding and crosslinking methods, insufficient oil resistance of the molded product, and the inability to reuse the molded product in a different shape. The object of the present invention is to be able to simultaneously fix deformation at room temperature without requiring complicated manufacturing or molding methods, and also to fix deformation by cooling to room temperature while maintaining the deformation after heating. An object of the present invention is to provide a shape-memory molded body whose shape can be restored to its pre-deformation shape by gentle heating. Here, shape memory in this patent refers to

[The shape of the molded object as it is, for example, the shape made by completely reacting (b,) and MDI in a mold. Alternatively, it refers to any shape of a molded product obtained by deforming the molded product into a desired shape and removing deformation stress by annealing at a high temperature (for example, 130 to 230°C) while maintaining the deformed shape (hereinafter referred to as the original shape). )] 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),
In addition, we have developed a series of properties that allow fixed deformation to be maintained at room temperature (e.g., below 40°C), and the ability to restore the original shape in a short period of time (e.g., within 5 minutes) by heating (e.g., above 40°C) a molded object with fixed deformation. To tell. Ordinary plastics and rubbers do not have the above-mentioned shape memory properties. 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. These and further objects of the invention will become apparent from the description below. That is, the present invention is an organic polyisocyanate with the general formula R7, R2 is hydrogen, an alkyl group having 1 to 3 carbon atoms, fluorine,
Or chlorine. A1 and A2 are alkylene groups having 2 to 4 carbon atoms. m and n are positive integers satisfying 2≦m+n≦10. 0 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 or a methyl group. A thermoplastic shape memory molded body made of a polyurethane resin containing at least 15% by weight of one or more polyol components selected from the group consisting of These methods include a molded body whose original shape has been memorized, a molded body whose deformation has been fixed, and a method for recovering the deformation of a molded body whose deformation has been fixed. The organic polyisocyanates [hereinafter referred to as (I)] used in the present invention include 4,4-diphenylmethane diisocyanate, 2.4-)lylene diisocyanate, 2.
6-) lylene diisocyanate, 2.4-) lylene diisocyanate, a mixture of 2゜6-tolylene diisocyanate, xylylene diisocyanate, modified polyisocyanate (4,4-diphenylmethane diisocyanate, etc.) with carposiimide group, uretdione group, Aromatic polyisocyanates such as polyisocyanates modified to contain uretdione groups; hexamethylene diisocyanate, hexamethylene diisocyanate I.
Aliphatic polyisocyanates such as water-crosslinked polyisocyanate; cycloaliphatic polyisocyanates such as 4,4-methylenebis(cyclohexylisocyanate-1.), isophorone diisocyanate, and mixtures of two or more thereof. Preferred polyisocyane-1 components from the viewpoint of shape memory are 4,4-diphenylmethane diisocyanate and 2.4-)lylene diisocyanate!・、2.61
-lylene diisocyanate, a mixture of 2°4-tolylene diisocyanate and 2,6-)lylene diisocyanate, 4,4-methylenebis(cyclohexyl isocyanate), isophorone diisocyanate, and mixtures of two or more of these. More preferably 4
゜4--diphenylmethane diisocyanate-1, and 4
．． 4--methylenebis(cyclohexyl isocyanate). In the polyol components of general formulas (1), (2) and (3), A1. Examples of the alkylene group having 2 to 4 carbon atoms in A2 include an ethylene group, a propylene group, and a butylene group. Among these, ethylene group is preferable from the viewpoint of shape memory properties. m and n in general 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 fixity, it is more preferably a positive integer satisfying 2≦m+n≦2.5. (Here, m+n: 2.5 refers to a mixture of, for example, a 2-molar adduct and a 3-molar adduct in equimolar proportions) O and p in general formula (2) are preferably O≦0+p≦4
It is 0 or a positive integer that satisfies the following, and when O0p is 4 or more, shape memory properties deteriorate. More preferably, it is 0 in terms of shape fixation. q and r in general formula 3) are preferably 0≦q+r≦4
0 or a positive integer that satisfies the following, more preferably O. When q+r is 4 or more, shape memory properties deteriorate. In general formulas (1), (2), and (3), R4, R
Examples of the alkyl group having 1 to 3 carbon atoms in 2 include a methyl group, an ethyl group, and a butyl group. Among these, methyl group is preferable from the viewpoint of shape memory properties. The constituents represented by the general formula (1) include, for example, 4,
4-methylenebisphenol, 4,4-isopropylidenebisphenol, 4,4-hydroxybisphenol, 4,4-sulfonylbisphenol, 4
, 4-dihydroxybenzophenone, or a mixture of two or more thereof, with an alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, etc., ring-opened in a random or block manner. Examples include those obtained by addition reaction. Among these, those prepared by ring-opening addition of ethylene oxide are particularly preferred 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, shape memory properties will deteriorate, so it is preferably 4 moles or less per mole of bisphenol. Specifically, 4,4--methylene bisphenol adduct with 2 moles of ethylene oxide, 4.4--
2 moles of propylene oxide adduct of methylene bisphenol, 2 moles of ethylene oxide and 2 moles of propylene oxide adduct of 4,4-methylene bisphenol, 4 moles of butylene oxide adduct of 4,4-methylene bisphenol, 4.4-1 2 mole ethylene oxide adduct of isobropylidene bisphenol, 4,4
--Dihydroxybenzophenone propylene oxide 2 mole adduct and the like. The diol component represented by the general formula (2) is a compound obtained by hydrogenating the benzene nucleus of the bisphenol in the case of the above general formula (1), that is, bis(4-hydroxycyclohexyl)methane,
Compounds such as 2,2-bis(4-hydroxycyclohexyl)propane and 3゜3-bis(4-hydroxycyclohexyl)pentane may be used as they are, or these bishydroxy compounds and mixtures of two or more thereof may be added with the general formula ( 1
) can be used by adding alkylene oxide. If the number of moles of alkylene oxide added is too large relative to 1 mole of the bishydroxy compound, 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 the above general formula (2) is bis(4-
2 moles of ethylene oxide adduct of hydroxycyclohexyl)methane, 4 moles of propylene oxide adduct of 2,2-bis(4-hydroxycyclohexyl)propane, 2 moles of butylene oxide adduct of 3,3-bis(4-hydroxycyclohexyl)pentane Things can be given. 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 general formula (3) include an adduct of 2 moles of ethylene oxide of cyclohexane dimetatool and a 2 mole adduct of propylene oxide of cyclohexane dimetatool. Moreover, the compounds represented by these general formulas (1), (2) and (3) can also be used in a mixture of two or more. The amount of the structural units derived from the general formulas (1), (2) and (3), which are essential components, is such that at least 15% by weight, preferably 20% by weight or more of any one or more of the structural units is present 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 following general formulas (1), (2) and (3). A long chain polyol component [hereinafter referred to as (b2)] having an average molecular weight of 500 to 8000 (this molecular weight is determined from Or-1-V of the polyol component) is used in combination with the polyol component [hereinafter referred to as (bl)]. . Examples of (b2) include polyether diols, polyester diols, polybutadiene glycols, hydrogenated polybutadiene glycols, and mixtures of two or more of these. Examples of polyether diols include polyethylene ether glycol, polypropylene ether glycol, polyethylene-bolybrobylene (block and/or random) ether glycol, polytetramethylene ether glycol, polytetramethylene-ethylene (block and/or random) Examples include ether glycol, polytetramethylene-propylene (block and/or random) ether glycol, polyhexamethylene ether glycol, and mixtures of two or more thereof. Examples of polyester diols include polyester diols obtained by reacting low molecular weight diols and/or polyether diols with molecules of 411,000 or less with dicarboxylic acids, polylactone diols obtained by ring-opening polymerization of lactones, polycarbonate diols, etc. The low-molecular diols mentioned above include ethylene glycol,
Examples include diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1°6-hexanediol, and mixtures of two or more of these. Examples of polyether diols having a molecular weight of 1000 or less include polyethylene glycol, polytetramethylene glycol, polypropylene glycol, triethylene glycol; and mixtures of two or more thereof. In addition, 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 mixtures of two or more of these. 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-1, Examples include polydiethylene acybate, poly(polytetramethylene ether) adipate, polyethylene azelate, polyethylene sebacate, polybutylene azelate, polybutylene sebacate, polycaprolactone diol; and mixtures of two or more of these. Polybutadiene polymers include hydroxyl-terminated polybutadiene homopolymer types, hydroxyl-terminated polybutadiene copolymer types (styrene-butadiene copolymer, acrylonitrile-butadiene copolymer), etc.
Examples include mixtures of two or more of these. Specific examples include the Po1yBd series manufactured by ARCO in the United States and the G series of Nl5SO-PB manufactured by Nippon Soda Co., Ltd. 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 Soda Co., Ltd.'s Nl5SO
-PB's CI series is an example. Furthermore, polymer diols obtained by polymerizing these long-chain diol components with 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, (bl) should be added to an average molecular weight of ff1400 (this molecular weight is higher than the OH-V of the polyol component). The following low molecular polyol [hereinafter referred to as (b3)] is used in combination. (b3) includes ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1゜4-butanediol, neopentyl glycol, 1,6-hexanediol, glycerin, trimethylolpropane, penta Nilthritol, etc., or a mixture of two or more of these can be used. In addition to these, monoethanolamine, jetanolamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, isophoronediamine, 4,4-diphenylmethanediamine, 4,4
--Polyamine compounds such as methylenebis(cyclohexylamine) and mixtures of two or more thereof can also be used for the same purpose as (b3) as long as the shape memory properties are not impaired. A catalyst is used if necessary in the production of polyurethane resin. Catalysts include salts of metals and organic and inorganic acids such as lead octylate, dibutyltin dilaure-1, and stannous octoate-1, and organic metal derivatives; organic tertiary amines such as triethylenediamine and triethylamine, and diazabicyclone. Examples include decene catalysts. In the production of polyurethane resins or molded products, 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. Examples of dyes include direct dyes, acid dyes, basic dyes, reactive dyes, and metal complex dyes. As a pigment,
carbon black, titanium oxide, iron oxide, chromium oxide,
Examples include inorganic pigments such as mica, zinc oxide, and navy blue, and organic pigments such as coupled azo-based, condensed azo-based, anthraquinone-based, perylene-based, quinacridone-based, thioindigo-based, dioxazine-based, and phthalocyanine-based pigments. Examples of the inorganic filler include lucium carbonate, silica, talc, and glass peas. Examples of the organic filler include fine powders, beads, and hollow beads of fluorocarbon resin, silicone resin, polyamide resin, styrene resin, urethane resin, and the like. Examples of organic modifiers 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. can give. As a weather resistance improver, hindered phenol type,
Antioxidants such as phosphite type and thioether type, ultraviolet absorbers such as benzophenone type, benzotriazole type, oxalic acid anilide type, salicylate type, and salicylate group, light stabilizers such as hindered amine type, hydrazine type, semicarbacilyl type, etc. Examples include NOx gas stabilizers, nickel complex-based metal deactivators, and organic halogen-based flame retardants. Examples of plasticizers include dibutyl phthalate and dioctyl phthalate. Examples of the crosslinking agent include the above-mentioned isocyanates, melamine, organic polyamines, getimine 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 polyurethane resin, it is an essential component (b,)
The usage rate of (b2) and/or b3) is
At least 15 structural units derived from (b,) in the resin
If it is % by weight, preferably 20% by weight or more, more preferably 25% by weight or more, it may be changed according to the shape memory properties of the shape memory polyurethane resin to be obtained and the requirements for performance other than shape memory. . Molar ratio of polyol component (b,) to component (b2) and/or component (b3) used in combination [(b+):
The ratio of (b2) + (b3) is usually 1:0 to 1, preferably 1:0 to 0.5. In addition, a total polyol component consisting of one and/or all of (b2) and (b3), which has the NCO group of organic polyisocyanate component (1) and (b,) as essential components [co-component hereinafter referred to as (B)] The equivalent ratio of active hydrogen groups capable of reacting with isocyanate is usually 0.9 to 1.1:1, preferably substantially 1:1. Shape-memory polyurethane resin can be produced by conventional methods, such as a one-shot method in which all components (I) and (B) are reacted simultaneously, or a method in which components (1) and (B) are reacted simultaneously.
), such as a method in which a part of the component (b2) is reacted to produce a prepolymer, and then the prepolymer is reacted with the component (bl). The shape memory polyurethane resin can be produced in the presence of a solvent that is inert to isocyanate 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 (dimethylsulfoxide, 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 carbonization Hydrogen solvents (n-hexane, etc.), alcohol solvents (isopropyl alcohol, ethyl alcohol, etc.)
and mixtures of two or more of these. Preferred are amide solvents and sulfoxide solvents,
DMF is particularly preferred. The urethane resin concentration in the solvent is 10 to 90% by weight, preferably 20 to 60% by weight. The shape memory molded body can be manufactured by a known method. For example, when a solvent-free polyurethane resin is used, it can be manufactured by methods such as injection molding, extrusion molding, blow molding, inflation molding, and calendering. The molding temperature is usually 100 to 250°C. When the polyurethane resin is a solvent solution, it can be produced by casting on the surface of a release paper, metal plate, glass plate, plastic film, etc. with a doctor knife, and then evaporating the solvent. In this case, 1 is easy to process using the same solvent as used in the above reaction.
Can be adjusted at any time. Also, the processing temperature is usually 60~200″C
It is. The thermoplastic shape-memory molded article of the present invention can be heated to 130 to 230"C in a desired shape, and the shape is shaped normally for 1 to 2 minutes.
By holding it for 0 hours, preferably 5 minutes to 10 hours, the shape can be memorized as the original shape. Furthermore, the molded product of the present invention is preferably 130°C or lower, preferably 8°C or lower.
If it is deformed at a temperature of 0°C or lower and cooled to a temperature of 40°C or lower while maintaining the deformation, the deformation will be fixed and maintained as it is even if the external force is removed. Furthermore, the molded article with fixed deformation of the present invention is heated to 40° C. or higher, preferably 45° C. or higher, so that the sustained deformed shape is restored to the original shape. [Example] The present invention will be explained below with reference to Examples, but the present invention is not limited thereto. (The parts shown in the examples represent parts by weight) [Raw materials used] 1. Polyisocyanate A (MDI): 4,4- diphenylmethane diisocyanate (H-MDI): 4,4- -
Methylene bis(cyclohexyl isocyanate) 2, polyol component (b,) (b+-1): 4,4--isobrobilite°
Base phenol ethylene oxide! Average number of adducts: 2.3 Average molecular weight = 330 Hydroxyl group i: 340 (b, -2): 4.4- Average number of adducts of pyrohylene oxide adduct of isotube 0 birite base phenol Number: 2.3 Average molecular weight: 361 Hydroxyl value: 311 (bl-3): 4.4--Sphenol
Suphenol ethylene oxide! Average number of moles added of the compound = 2.3 Average molecular weight = 351 Hydroxyl value: 319 (b, -4): 2,2-hose (4-hydroxyloxyhexyl) alcohol molecular weight: 24
6 (bl-5)' Cyclohexane methanol molecular weight = 144 (b, -8): Ethylene oxide adduct of 4,4--isobrobilite bisphenol Average number of moles added: 18.1 Average molecular weight: 1020 Hydroxyl group Value: 110.1 3, polyol component (ba) (ba-1) ' This polyethylene azidate average molecular weight: 2000 Hydroxyl value: 5B, 1 (ba-2) ' Polyoxytetramethylene I
-Terquarycol average molecular weight: 2030 Hydroxyl value: 55.3 (BA-3) 'Nelide carbonate diol Average molecular weight: 102G Hydroxyl value: 110.0 (BA-4): Nelycarbonate diol, propylene Oxite adduct (Molecular weight of nelicarbonate sieol before addition: 3000) Average molecular weight: 6720 Hydroxyl value: lB, 7 (ba-5): Average molecular weight of nelicarne nate shiol: 1500 Hydroxyl value: 74. 8 (be-G) ' Nelycarne nate diol average molecular weight: 3000 Hydroxyl value: 37.4 (ba-7) ' Nelyph tylene oxide average molecular weight: 2500 Hydroxyl group @: 44.9 4. Polyol component (b ,) (b3-1): (bs-2)' 5. Solvent (DMF): Dimethyl lumamide ethycin ° recall 1.4-bucundiol Example 1 171 parts of (bl 1) and 129 parts of (MDI) were mixed into ( DM
F) React at 80°C in 700 parts to obtain a resin concentration of 30%.
Polyurethane resin (b
+39% by weight of skeleton derived from acid component) solution was obtained. This solution was cast on a glass plate and the (DMF) was evaporated at 120"C to make it thicker to obtain a 0.2 mm film-like molded body. This molded body (cut into a piece with a width of 1 cm ml and a length of 10 cm) A section) was bent by 180 @ at 27℃. When it was immersed in warm water at 80℃, it completely recovered to its original shape within 2 seconds. Another section, which was left folded at about 30℃, was It remained bent even after several months, but the temperature was 80 degrees Celsius.
When immersed in hot water, it completely recovered to its original shape within 2 seconds. Example 2 2000 parts of (ba-1) and 4804 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 incyanate groups at the ends. This pseudo-prepolymer and (bl-2) were heated at 70'C and 120°C using a metering pump at 100.0 g/min and 9
The mixture was fed into a twin-screw extruder via a mixer at a rate of 5.2 g/min, reacted continuously while heating and kneading at a maximum temperature of 200° C., and taken out in the form of a string. After aging at 25° C. for 15 hours, the pellets were cut with a pelletizer to obtain pellets of polyurethane resin (skeleton derived from the b+ acid component: 31% by weight). The viscosity of the 30% (DMF) solution of this pellet is 20″C
It was 760 boise. This pellet was processed using a calendar roll heated to 190°C to obtain a film-like molded product with a thickness of 0.3 mm. This molded body (width 1 cm ms
(cut to a length of 10 cm) was bent to 180" at 80°C and deformed, then cooled to 25°C while retaining its shape to fix the deformation. When it was immersed in 80°C hot water,
It completely recovered to its original shape within 2 seconds. Another section that was left folded at 25°C remained folded even after one month, but when immersed in warm water at 80°C, it completely recovered to its original shape within 2 seconds. Example 3 (b+-3)136. Part 2, (bz-2)27.
3 parts and (ba-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 the b+ acid component: 32% by weight) having a resin concentration of 30% and a viscosity of 820 voids at 20° C. was obtained. This solution was cast onto a glass plate at 120°C.
(DMF) was evaporated to obtain a film-like molded product with a thickness of 0.2 mm. This molded body (width I Crrh length 10
180" was bent at 27°C. When it was immersed in warm water at 80°C, it completely recovered to its original shape within 2 seconds. Another section was left folded at 25°C. remained bent even after one month, but 8
When immersed in warm water at 0°C, it completely recovered to its original shape. Example 4 122.2 parts of (b+-4) and 38 parts of (b23) and (
8 in 700 parts of (DMF) to which 0.1 part of dibutyltin dilaurate (catalyst) was added.
The reaction was carried out at 0°C, and the viscosity at 20°C was 5 at a resin concentration of 30%.
A 60 poise polyurethane resin (skeleton derived from the b+ acid component: 40% by weight) solution was obtained. This solution was cast onto a glass plate and the (DMF) was evaporated at 120°C to make it thicker.
．． A 2 mm film-like molded body was obtained. This molded body (cut into pieces with a width of I Q ffh and a length of 10 cm) was bent 180" at 27°C. When it was immersed in warm water at 80°C, it completely recovered to its original shape within 2 seconds. Bending Another section left at about 25°C remained bent after one month, but when immersed in warm water at 80°C, it completely recovered to its original shape within 2 seconds.Example 5 Example 2 Similarly, (b2-4) 672 copies and (MDI
) 4587 parts were reacted to obtain a pseudo prepolymer. This pseudo-prepolymer and (b+5) were heated at 70°C and 120°C, respectively, at 100 g/min using a metering pump.
The mixture was fed into a twin-screw extruder via a mixer at a rate of 49.4 g/min, reacted continuously while being heated and kneaded at a maximum of 200°C, taken out into a string cane, aged at 25°C for 15 hours, and then processed into a pelletizer. Cut and use polyurethane resin (b+
A pellet containing a skeleton derived from an acid component (33% by weight) was obtained. The viscosity of a 30% (DMF) solution of this pellet was 620 voids at 20°C. This pellet was processed using an injection molding machine (cylinder temperature: 200° C., resin temperature: 215° C., injection pressure 80 kgf/cm 2 ) to obtain a sheet-like molded product with a thickness of 3 mm. This molded body (cut to a width of 1crrh and a length of 10cm) was bent and deformed at 80°C to a shape of 1808, and while maintaining its shape, it was cooled to 25"C to fix the deformation. When this was immersed in hot water at 80°C, ,
It completely recovered to its original shape within 1 minute. Another section that was left folded at 25°C remained folded even after one month, but when immersed in a hot bath at 80°C, it completely recovered to its original shape within 1 minute. Example 6 182 parts of (b+-1) and 4 parts of (ba-2) and (MD
I) 134 parts of (DMF) were reacted in 700 parts of (DMF) at 80°C to obtain a polyurethane resin with a viscosity of 580 poise at 20'C at a resin concentration of 30% (b + skeleton derived from acid component = 3
7% by weight) solution was obtained. This solution was cast on a glass plate, and (DMF) was evaporated at 120° C. to obtain a film-like molded product with a thickness of 0.2 mm. This molded body (width 1cm5
A piece cut to a length of 10 cm) was bent 180'' at 27°C. When it was immersed in warm water at 80°C, it completely recovered to its original shape within 2 seconds. Another section that was left folded at about 25°C remained folded even after one month, but when immersed in warm water at 80°C, it completely recovered to its original shape within 2 seconds. Example 7 275 parts of (b, -3) and 111 parts of (be 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%.
Boy's polyurethane resin (skeleton derived from BL component:
32% by weight) solution was obtained. This solution was cast on a glass plate, and (DMF) was evaporated at 120° C. to obtain a film-like molded product with a thickness of 0.2 mm. This molded body (cut into a piece with a width of I cm and a length of 10 cm) was bent 180° at 27°C. This is 65
When immersed in warm water at ℃, it completely recovered to its original shape within 2 seconds. Another section that was left folded at about 25°C remained folded even after one month, but when immersed in warm water at 85°C, it completely recovered to its original shape within 2 seconds. Example 8 149 parts of (b+2) and 44 parts of (b2-6) and (
107 parts of MDI) were reacted at 80°C in 700 parts of (DMF) to produce a polyurethane resin with a resin concentration of 30% and a viscosity of 700 poise at 20°C (skeleton derived from the BL component = 3).
1% by weight) solution was obtained. This solution was cast onto a glass plate and the (DMF) was evaporated at 120''C to obtain a film-like molded body with a thickness of 0.2 mm.
(cut into 10cm length) at 27℃ for 1800℃.
Folded. When this was immersed in warm water at 60°C, it completely recovered to its original shape within 2 seconds. Another section that was left folded at approximately 25°C remained folded even after one month.
When immersed in warm water at 0°C, it completely recovered to its original shape within 2 seconds. Example 9 To 131 parts of (t)+-1) and 5811 (b27), 111 parts of (H-MDI) was added to dibutyltin dilaurate (
80 in 700 parts of (DMF) with the addition of 0.1 part of catalyst)
The viscosity at 20°C is 15 when the resin concentration is 30%.
A 0 poise polyurethane resin (skeleton derived from bl component: 30% by weight) solution was obtained. This solution was cast onto a glass plate and (DMF) was evaporated at 120°C to a thickness of 0.2 m.
A film-like molded body of m was obtained. This molded body (width 1 c
mt (cut to a length of 10 cm) was bent 1801 times at 27°C. When this was immersed in hot water at 70°C, it completely recovered to its original shape within 2 seconds. Another section that was left folded at about 25°C remained folded even after one month, but when immersed in hot water at 70°C, it completely recovered to its original shape within 2 seconds. Example 10 134 parts of (b+-1) and 59 parts of (ba 7) and (
107 parts of MDI) were reacted at 80°C in 700 parts of (DMF) to obtain a polyurethane resin (skeleton derived from 11 parts of b) having a resin concentration of 30% and a viscosity of 860 voids at 20°C: 3
1% by weight) solution was obtained. This solution was cast on a glass plate, and (DMF) was evaporated at 120° C. to obtain a film-like molded product with a thickness of 0.2 mm. This molded body (cut into a piece with a width of 1 cm and a length of 10 cm) was bent 180° at 27°C. When this was immersed in warm water at 65°C, it completely recovered to its original shape within 2 seconds. Another section that was left folded at approximately 25°C remained folded even after one month.
When immersed in warm water at 5°C, it completely recovered to its original shape within 2 seconds. Example 11.12.13 Film-like molded product obtained in Example 1.2.3 (width 1
cmz cut to a length of 20cm) is wound into a coil around a glass rod (of diameter 10mm), fixed with a string at both ends, heat-treated at 150℃ for 30 minutes, cooled to 25℃, and turned into a coil. The film was removed from the glass rod. The molded body after the heat treatment retained its coiled shape even after 10 days at 25°C. Next, the coiled molded body 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 flat molded bodies retained their flat shape even after 10 days, but 80
When immersed in a hot water bath at °C, it recovered to its coiled shape within 2 seconds. These results are shown in (Table 1). (Table-1) Comparative Example 1 (bz 1) 1423 parts and (MDI) 1072 parts 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. Also (bl 1)
253 parts of (bz-2) and 253 parts of (bz-2) were uniformly mixed at 120°C to obtain 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 20
The mixture was reacted continuously while being heated and kneaded at 0° C. and taken out in the form of a string. After aging at 25° C. for 17 hours, the pellets were cut with a pelletizer to obtain pellets of polyurethane resin (6% by weight of the skeleton derived from the b+ acid component). 30% of this pellet (DMF
) The viscosity of the solution was 730 poise at 20°C. This pellet was processed with a calender roll heated to 190°C to a thickness of 0. A 3 mm film-like molded body was obtained. This molded body (cut to a width ICm1 and a length of 10 cm) was iso' bent at 25°C. When I tried to leave it alone, it immediately returned to its original shape and the bent shape could not be fixed. Comparative Example 2 (bl-6)87. 1 part, (t)2 2)87.
1 part and (ba-1) 18.6 parts and (MDI) 107
゜1 part was reacted in 700 parts of (DMF) at 80°C,
A polyurethane resin solution (skeleton derived from essential components: 6% by weight) having a resin concentration of 30% and a viscosity of 840 voids at 20°C was obtained. This solution was cast onto a glass plate at 120°C (D
MF) was evaporated to obtain a film-like molded product with a thickness of 0.2 mm. When this molded body (cut into pieces 1 cm wide and 10 cm long) was bent at 180° at 80'C and then cooled to 25°C while retaining its shape to fix the deformation, it immediately recovered to its original shape. The bent shape could not be fixed. Comparative Example 3 160.1 parts of (bz-4) and 25°6 parts of (bi 1) and 114.3 parts of (H-MDI) were added to 700 parts of (DMF).
A polyurethane resin solution (containing no b+ acid component) having a resin concentration of 30% and a viscosity of 810 poise at 20°C was obtained. This solution was cast onto a glass plate and 1
(DMF) was evaporated at 20° C. to obtain a film-like molded product with a thickness of 0.2 mm. This molded body (width I Crl'h
(cut into 10cm length) at 25℃ for 1800℃.
Folded. When I tried to leave it alone, it immediately returned to its original shape and the bent shape could not be fixed. [Effects of the Invention] The shape-memory molded body made of the thermoplastic polyurethane resin of the present invention can be deformed at a temperature of 130'C or less, the deformation can be fixed at room temperature, and it can be restored to its original shape by gentle heating. be able to. Because of these effects, the shape-memory molded product of the present invention can be used as architectural filling materials, architectural sealing materials, decorative materials, medical materials, internal and external coatings for pipes, piping starters, fixing pins, fasteners, etc. Sensors Wiring/ruling materials for electric wires, molds, shape-changing toys, accessories - Binding materials for packing, bundling materials, artificial flowers, car body parts, bumpers
It is useful for automotive machinery sealing materials, electronic device housings, clothing interlining materials, etc.

Claims (6)

[Claims] (1), Organic polyisocyanate and general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2), and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (3), A_3 in the formula is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲Mathematical formulas, chemical formulas,
There are 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 or positive integers satisfying 0≦o+p≦10. q and r are 0 or positive integers satisfying 0≦q+r≦10. X is hydrogen or a methyl group. The essential component is one or more polyol components selected from the group consisting of ▲Mathematical formulas, chemical formulas, tables, etc.
A thermoplastic shape-memory molded body made of a polyurethane resin containing at least 15% by weight of the structural units shown in ▼ and ▲Mathematical formulas, chemical formulas, tables, etc.▼. (2) The thermoplastic shape-memory molded article according to claim (1), which has a desired shape and is memorized as an original shape by being maintained at 130 to 230°C. (3) The thermoplastic shape-memory molding according to claim (1), which is deformed into a desired shape at a temperature of about 130°C or less, and maintains the deformed shape as it is at a temperature of about 40°C or less. body. (4) The thermoplastic shape memory molding according to claim (2), which is deformed into a desired shape at a temperature of about 130°C or less, and maintains the deformed shape as it is at a temperature of about 40°C or less. body. (5) The method for using the thermoplastic shape memory molded article according to claim (3), which comprises heating to about 40° C. or higher to return the sustained deformed shape to its original shape. (6) The method for using the thermoplastic shape memory molded article according to claim (4), which comprises heating to about 40° C. or higher to return the sustained deformed shape to its original shape.