JPH0660247B2 - Thermoplastic shape memory molding and method of use - Google Patents

Description

Detailed Description of the Invention

[Field of Industrial Application] The present invention provides a thermoplastic shape memory which is useful in various applications such as vehicle materials, mechanical materials, electrical materials, architectural gap fillers, medical materials, decorative materials, and clothing materials. The present invention relates to a molded product and a method of using the molded product. [Prior Art and Problems to be Solved by the Invention] Various proposals have been made for a shape-memory resin molded body. For example, US Pat. No. 4,193,899 discloses a norbornene-based unsaturated terpolymer as a sulfone. That the resin neutralized after the polymerization has a shape memory property, US Pat. Nos. 4,637,944, and 3,563,9
No. 73 describes that shape memory can be achieved by an ethylenic polymer crosslinked by energy irradiation.
The former requires complicated manufacturing of the resin, and it takes a long time to fix the shape and recover the shape, and the latter requires the cross-linking after molding, which is complicated. Further, a shape memory foam containing caprolactam as a main component described in JP-A-60-36538 and a norbornene-based polymer composition described in JP-A-61-188444 are also known. However, these also have problems that they require a special molding method or a cross-linking method, the oil resistance of the molded product is not sufficient, or they cannot be reused as molded products having different shapes. [Means for Solving the Problems] An object of the present invention is to deform at room temperature and fix the deformation at the same time without requiring a complicated manufacturing method or molding method, and after heating and deforming, keep the deformation at room temperature. It is an object of the present invention to provide a shape memory molded article which can be fixed in deformation even by cooling to 1, and can be restored to its original shape by gentle heating. That is, the present invention relates to an organic polyisocyanate and a general formula [Where A ₃ is Provided that 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; 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 or methyl It is a base. ] One or more polyol components selected from the compounds represented by and A thermoplastic shape-memory molded article comprising a polyurethane resin containing at least 15% by weight of the structural unit represented by
Furthermore, a molded body that memorizes a new primitive shape in the molded body,
It is a molded body with fixed deformation, and a method of using the molded body with fixed deformation to recover the deformation. Here, the shape memory referred to in this patent is a primitive shape.

[Molding
The shape of the body as it is, for example (b₁) And MDI
The shape made by completely reacting inside. Or the molded body
Deforms into the desired shape and retains the deformed shape at high temperature
Annealing at (eg 130-230 ℃)
Refers to any of the shapes of the molded body with more deformation stress removed
(Hereinafter referred to as “primitive shape”)
When deformed at a temperature of 0 ° C
It can be fixed by keeping the temperature below ℃, or at room temperature (eg
Deformation is fixed at 40 ° C or below)
Short time by heating the mold (for example, 40 ℃ or more)
A series of properties that can be restored to its original shape (for example, within 5 minutes)
Say Normal plastics and rubbers have the above-mentioned shape memory characteristics.
Does not have. For example, plastic has a fixed deformation
Although it can be heated, it does not recover to its original shape when heated to 40 ° C or higher
However, rubber cannot be fixed by deformation at room temperature. The organic polyisocyanate used in the present invention [hereinafter referred to as (I)
Note] is 4,4′-diphenylmethanediiso
Cyanate, 2,4-tolylene diisocyanate, 2,
6-tolylene diisocyanate, 2,4-tolylene diisocyanate
Mixing of cyanate and 2,6-tolylene diisocyanate
Compound, xylylene diisocyanate, modified polyisocyanate
Nate [4,4'-diphenylmethane diisocyanate
And carbodiimide group, uretdione group,
Polyisocyanate modified to contain a min group
Aromatic polyisocyanates such as; hexamethylene
Diisocyanate, hexamethylene diisocyanate
Aliphatic polyisocyanates such as water-crosslinked polyisocyanates
4,4'-methylenebis (cyclohexyl isocyanate)
Alienate), isophorone diisocyanate, etc.
Formula polyisocyanates and mixtures of two or more thereof
Can be given. Polyisocyanate component preferred from the viewpoint of shape memory
As 4,4'-diphenylmethane diisocyanate
G, 2,4-tolylene diisocyanate, 2,6-tri
Diisocyanate, 2,4-tolylene diisocyanate
Mixture of bisphenol and 2,6-tolylene diisocyanate,
4,4'-methylenebis (cyclohexyl isocyanate
G), isophorone diisocyanate, etc. and these
Examples include a mixture of two or more kinds. More preferably 4,
4'-diphenylmethane diisocyanate, and 4,
4'-methylenebis (cyclohexyl isocyanate)
Is. For the polyol component of the general formulas (1), (2) and (3)
A₁， A₂As the alkylene group having 2 to 4 carbon atoms,
Ethylene group, propylene group, butylene group, etc.
It Of these, the ethylene group is preferred from the viewpoint of shape memory.
Yes. M and n in the general formula (1) are preferably 2 ≦ m + n ≦ 4.
Is a positive integer that satisfies
Shape memory is poor. More preferably in terms of shape fixability
It is a positive integer that satisfies 2 ≦ m + n ≦ 2.5. (here
And m + n = 2.5 is, for example, 2 mol adduct and 3 mol adduct.
Represents a mixture in an equimolar amount) and o and p in the general formula (2) are preferably 0 ≦ o + p ≦ 4.
Is 0 or a positive integer that satisfies, and o + p is 4 or more.
Then, the shape memory property deteriorates. Even better in terms of shape stability
It is preferably 0. Q and r in the general formula (3) are preferably 0 ≦ q + r ≦ 4.
0 or a positive integer that satisfies
It is 0. When q + r is 4 or more, the shape memory property deteriorates.
It R in the general formulas (1), (2), and (3)₁, R₂of
As the alkyl group having 1 to 3 carbon atoms, methyl group, ethyl group
Group, butyl group and the like. Of these, the methyl group is the shape
It is preferable from the viewpoint of memory. As the constituent component represented by the general formula (1), for example, 4,
4'-methylenebisphenol, 4,4-isopropylidene
Denbisphenol, 4,4'-hydroxybisphe
Nole, 4,4'-sulfonyl bisphenol,
Bisphenes such as 4,4'-dihydroxybenzophenone
Ethanol in the norls or mixtures of two or more of these
Oxide, propylene oxide, butylene oxide
Run alkylene oxides having 2 to 4 carbon atoms such as
By ring-opening addition reaction in the form of a dam or block
You can get what you get. Of these, ethylene
A ring-opened addition is particularly preferable from the viewpoint of shape memory.
Good The number of added moles of these alkylene oxides is
1 mol or more per 1 OH group of sphenols
That is all. Shape memory when the number of added moles becomes too large
4 mols per 1 mol of bisphenols, since the properties deteriorate
The following are preferred. Specifically, 4,4'-methylenebisulfate
Ethylene oxide 2 mol adduct of enol, 4,4 '
-Propylene oxide 2 methylene bisphenol
Addition product, ethyl 4,4'-methylenebisphenol
2 moles of oxides and 2 moles of propylene oxide
, 4,4'-methylenebisphenol butylene oki
Side 4 mol adduct, 4,4'-isopropylidene bis
Ethylene oxide 2 mol adduct of phenol, 4,
4'-dihydroxybenzophenone propylene oxide
2 mol addition product and the like. Shown by general formula (2)
The diol component to be used is a vinyl compound in the case of the above general formula (1).
A compound of the type in which the benzene nucleus of a sphenol is hydrogenated,
Nawachi bis (4-hydroxycyclohexyl) methane,
2,2-bis (4-hydroxycyclohexyl) propa
3,3-bis (4-hydroxycyclohexyl) pe
Compounds such as methane, or these bishydroxy
Compounds and mixtures of two or more of these can be represented by the general formula
Add alkylene oxide as in the case of (1)
The obtained product can be used. Of alkylene oxide
The number of moles added is 1 gram per mole of bishydroxy compound.
If it becomes too large, the shape memory will become worse.
The non-adduct is particularly preferable. Formula (2) above
Specifically, the alkylene oxide adduct of
(4-hydroxycyclohexyl) methane ethylene oxide
2 mol of oxidant, 2,2-bis (4-hydroxy)
Cyclohexyl) propane propylene oxide 4
Adduct, 3,3-bis (4-hydroxycyclohexyl)
2) Butylene oxide 2 mol adduct of pentane
can give. The diol component represented by the general formula (3) is cyclohexane.
Dimethanol or alkylene oxide
It was obtained by adding. Addition of alkylene oxide
If the number of moles is 4 moles or more, the shape memory property becomes poor. Special
Especially preferred is cyclohexanedimethanol. one
Specific examples of the alkylene oxide adduct of the general formula (3)
Cyclohexanedimethanol is ethylene oxide
2 mol adduct of cyclohexanedimethanol
Examples thereof include a 2 mol lenoxide adduct. Further, these are represented by the general formulas (1), (2) and (3).
The compound can be used as a mixture of two or more kinds. Due to the general formulas (1), (2) and (3) which are essential components
Coming unitand The amount of any one or more of the constitutional units in the polyurethane resin
At least 15% by weight, preferably 20% by weight or more,
More preferably 25% by weight or more and less than 15% by weight
Does not provide sufficient shape memory. Shape memory performance of the obtained shape memory polyurethane resin
Improve outside performance, such as impact resistance, cold resistance, etc.
In order to achieve the above, the general formulas (1), (2) and (3) are used.
The polyol component [hereinafter (b₁)]], The average
Molecular weight 500-8000 (This molecular weight is
OH-V) long-chain polyol component [below
(B_TwoTogether]. (B_Two), As polyether diol, polyester
Ludiol, polybutadiene glycol, hydrogenated polybuta
Diene glycol, and mixtures of two or more of these
can give. Examples of polyether diols include polyethylene diol.
Ether glycol, polypropylene ether glyco
Polyethylene-polypropylene (block and /
Or random) ether glycol, polytetramethy
Renether glycol, polytetramethylene-ethylene
(Block and / or random) ether glyco
, Polytetramethylene-propylene (block and
And / or random) ether glycol, polyhexa
Methylene ether glycol, and two or more of these
A mixture of Polyester diols include low molecular weight diols and
And / or polyether diol having a molecular weight of 1000 or less
Polyester diester obtained by reacting carboxylic acid with dicarboxylic acid
Polylace obtained by ring-opening polymerization of oar or lactone
Includes tondiol, polycarbonate diol, etc.
Examples of the above low molecular diol include ethylene glycol and di
Ethylene glycol, propylene glycol, dipropyi
Lenglycol, 1,4-butanediol, 1,3-butane
Tandiol, neopentyl glycol, 1,6-hex
Zandiol, and mixtures of two or more of these.
Be done. As a polyether diol with a molecular weight of 1000 or less
For polyethylene glycol, polytetramethylene
Recall, polypropylene glycol, triethylene glycol
Recall; and mixtures of two or more of these
It Further, as the dicarboxylic acid, an aliphatic dicarboxylic acid is used.
(Succinic acid, adipic acid, sebacic acid, glutaric acid,
Zelaic acid, maleic acid, fumaric acid, etc.), aromatic dica
Rubonic acid (terephthalic acid, isophthalic acid, etc.) and
Examples thereof include a mixture of two or more kinds. As a lactone
Is ε-caprolactone. Specific examples of these polyester diols include poly
Ethylene adipate, polybutylene adipate, poly
Xamethylene adipate, polyneopentyl adipate
Polyethylene polypropylene adipate, polyethylene
Lenbutylene adipate, polybutylene hexamethylene
Adipate, polydiethylene adipate, poly (polyte
(Tramethylene ether) adipate, polyethylene aze
Rate, polyethylene sebacate, polybutylene azere
, Polybutylene sebacate, polycaprolactone di
Oars; and mixtures of two or more of these
It Hydroxyl terminated polybutadiene as polybutadiene glycol
Diene homopolymer type, and hydroxyl-terminated polybutane
Diene copolymer type (styrene-butadiene copolymer
, Acrylonitrile butadiene copolymer),
Examples include a mixture of two or more of these. Specifically
ARCO Poly Bd series and Japan
Soda Co., Ltd.'s NISSO-PB G series is mentioned.
It As the hydrogenated polybutadiene glycol, the
Some or all of the unsaturated double bonds in tadiene glycol
Hydrogenated, and mixtures of two or more of these
And so on. Specifically, NIS of Nippon Soda Co., Ltd.
The GI series of SO-PB is mentioned. In addition, these long-chain diol components and ethylenically unsaturated monomer
Polymerize the oligomer (acrylonitrile, styrene, etc.)
The resulting polymeric diol can also be used. Also, the shape memory of the obtained shape memory polyurethane resin is
Improve performance other than performance, such as hardness and heat resistance
To do this, (b₁), The average molecular weight is 400 (this molecular weight is
Low content of less than (determined from OH-V of polyol component)
Child polyol [below (b₃).] Are used together. (B₃), Ethylene glycol, diethylene glycol
Cole, propylene glycol, dipropylene glycol
1,3-butanediol, 1,4-butanedio
Le, neopentyl glycol, 1,6-hexanedio
Le, glycerin, trimethylolpropane, pentael
It uses sitol, etc., or a mixture of two or more of these.
Rukoto can. In addition to these, monoethanolamine
Amine, diethanolamine, ethylenediamine, hexamer
Tolylenediamine, Diethylenetriamine, Isophoronedi
Amine, 4,4'-diphenylmethanediamine, 4,
4'-methylenebis (cyclohexylamine), etc.
Shaped Liamine Compounds and Mixtures of Two or More of These
To the extent that it does not interfere with memory (b₃) Is used for the same purpose
You can A catalyst is used if necessary in the production of polyurethane resin.
It Lead octylate, dibutyltin dilaurate as catalyst
And organic metals such as stannous octoate and organic
Organic acid salts and organometallic derivatives; triethylenediami
Organic tertiary amines such as amine and triethylamine, diaza
Examples thereof include bicycloundecene catalyst. When manufacturing polyurethane resin or molded products
Auxiliary compounds can be used within the range that does not hinder the shape memory performance.
Wear. Colorants such as dyes, pigments, fillers, modification
Agents, weather resistance improvers, plasticizers, crosslinking agents and the like.
Direct dyes, acid dyes, basic dyes, reactive dyes
Examples include dyes and metal complex dyes. As a pigment,
Carbon black, titanium oxide, iron oxide, chromium oxide,
Inorganic pigments and cups such as mica, zinc oxide, navy blue
Ring azo type, condensed azo type, anthraquinone type, berylle
Quinone, quinacridone, thioindigo, dioxazine
Examples of organic pigments include phthalocyanine pigments and phthalocyanine pigments. Nothing
Machine fillers include calcium carbonate, silica, tar
Ku, glass beads and the like. As an organic filler
Is fluorine resin, silicone resin, polyamide resin, styrene
Fine powder of resin, urethane resin, beads, hollow body
Examples include beads. Polychlorinated organic modifier
Vinyl, polyacrylic ester, polystyrene, poly
Acrylonitrile, acrylonitrile-vinylidene chloride
Copolymer, acrylonitrile-styrene copolymer, chloride
Examples of thermoplastic resins such as vinyl-vinyl acetate copolymer
To be Hindered phenol as a weather resistance improver
-Based, phosphite-based, thioether-based, etc. antioxidants
Agent, benzophenone type, benzotriazole type, oxalic acid
UV of nilide, salicylate, salicylate, etc.
Ray absorber, light stabilizer such as hindered amine, hydra
NOx gas stabilizers such as gin type and semicarbazilo type
Such as metal shell deactivator, organic halogen-based
Examples include flame retardants. Dibutyl phthalate as a plasticizer
Examples include tallate and dioctyl phthalate. Rack
As the crosslinking agent, the above-mentioned isocyanates, melamine, organic
Polyamine, organic polyamine and methyl ethyl ketone, etc.
Trimine, a ketimine compound obtained from the ketone compounds of
Polyfunctional glycos such as tylol propane and glycerin
And epoxy compounds. When obtaining polyurethane resin, it is an essential component (b₁)
And, (b₂) And / or (b₃The usage rate of) is (b₁)
Structural units derived fromand Of at least 15% by weight in the polyurethane resin,
Preferably 20% by weight or more, more preferably 25% by weight
%, The shape memory polyurethane to be obtained
To meet the demands of resin shape memory and performance other than shape memory
You can change it. Polyol component (b₁), And used together (b₂) Ingredients
And / or (b₃) Component molar ratio [(b₁): (B₂) +
(B₃] Is usually 1: 0 to 1, preferably 1: 0 to 0.5
is there. In addition, NC of the organic polyisocyanate component (I)
O group and (b₁) Is an essential ingredient, (b₂) And (b₃)of
All polyol components consisting of one and / or all [[
Below (referred to as (B)]] An activity capable of reacting with the isocyanate of the component
The equivalence ratio of the basic hydrogen group is usually 0.9 to 1.1: 1, preferably
Substantially 1: 1. The shape memory polyurethane resin is manufactured by an ordinary method.
For example, all of (I) component and (B) component
One-shot method of simultaneously reacting with (I) component
Part of the component (B), for example (b₂) React the ingredients
A polymer is prepared and then (b₁) React the ingredients
Method. Isocyanate is used to manufacture shape memory polyurethane resins.
It can be carried out in the presence of a solvent inert to the groups.
In the case of no solvent, it is often used like a kneader or an extruder.
Polymerize using a device that can stir and create with a pelletizer, etc.
It can be manufactured by granulating or crushing with a freeze crusher.
It When polymerizing in a solvent, the amide solvent is used as the solvent.
[Dimethylformamide (hereinafter abbreviated as DMF), dimethy
Luacetamide, etc.], sulfoxide-based solvent (dimethyl
Sulfoxide), lactam solvent (n-methyl-2)
-Pyrrolidone, etc., ether solvents (dioxane, te
Trahydrofuran, etc., ester-based solvents (ethyl acetate)
Solvent, cellosolve acetate, etc., ketone-based solvent (shiku)
Rohexanone, methyl ethyl ketone), methyl isobuty
Such as ketones), aromatic hydrocarbon solvents (such as toluene)
Etc.), aliphatic hydrocarbon solvents (2-hexane, etc.),
Rucol solvent (isopropyl alcohol, ethyl alcohol
Cole, etc.) and mixtures of two or more of these.
Be done. Preferred are amide-based solvents and sulfoxide-based
It is a solvent, and DMF is particularly preferable. Urethane in solvent
Resin concentration is 10 to 90% by weight, preferably 20 to 60%
The amount is%. The shape memory molded body can be manufactured by a known method. For example
When using a solventless polyurethane resin, injection molding or pressing
Demolding, blow molding, inflation processing, calendar
-Can be manufactured by a method such as processing. Molding temperature is usually 100
~ 250 ° C. Polyurethane resin is a solvent solution
In case of release paper, metal plate, glass plate, plastic film
After casting with a doctor knife on the surface of
Can be produced by a method such as evaporating. In this case
The same solvent as that used for the reaction was used to adjust the concentration to facilitate processing.
Can be adjusted. The processing temperature is usually 60 to 200 ° C. The thermoplastic shape memory molding of the present invention has a desired shape.
It is heated to 130 to 230 ° C and its shape is usually 1 minute to 20 minutes.
By holding for a time, preferably 5 minutes to 10 hours
You can also memorize the shape as a primitive shape.
It Further, the molded body of the present invention has a temperature of 130 ° C. or lower, preferably
Deforms at a temperature of 80 ° C or less, 40 ° C while maintaining the deformation
If it is cooled to the temperature below, the deformation will be
It is fixed and maintained as it is. Furthermore, fixing the variant of the invention
The molded body is heated to 40 ° C or higher, preferably 45 ° C or higher.
By restoring the deformed shape that has been sustained to the original shape
To do. [Examples] The present invention will be described below with reference to Examples.
It is not limited. (Parts shown in the examples are parts by weight.
[Materials used] 1, Polyisocyanate A (MDI): 4,4'-diphenylmethane diisocyanate (H-MDI): 4,4'-methylenebis (cyclohexyl ether)
Socyanate) 2, Polyol component (b₁) (B₁-1): of 4,4'-isopropylidene bisphenol
Ethylene oxide adduct Average number of moles added: 2.3 Average molecular weight: 330 Hydroxyl value: 340 (b₁-2): of 4,4'-isopropylidene bisphenol
Propylene oxide adduct Average number of moles added: 2.3 Average molecular weight: 361 Hydroxyl value: 311 (b₁-3): Ethyl 4,4'-sulfonylbisphenol
Renoxide adduct Average number of moles added: 2.3 Average molecular weight: 351 Hydroxyl value: 319 (b₁-4): 2,2-bis (hydroxycyclohexyl) p
Lopan molecular weight: 246 (b₁-5): Cyclohexane dimethal Molecular weight: 144 (b₁-6): of 4,4'-isopropylidene bisphenol
Ethylene oxide adduct Average number of moles added: 18.1 Average molecular weight: 1020 Hydroxyl value: 110.1 3, Polyol component (b₂) (B₂-1): Polybutylene adipate Average molecular weight: 2000 Hydroxyl value: 56.1 (b₂-2): Polyoxytetramethylene ether glycol Average molecular weight: 2030 Hydroxyl value: 55.3 (b₂-3): Polycarbonate diol Average molecular weight: 1020 Hydroxyl value: 110.0 (b₂-4): Polycarbonate diol, propylene oxa
Id adduct (polycarbonate diol molecule before addition)
Amount: 3000) Average molecular weight: 6720 Hydroxyl value: 16.7 (b₂-5): Polycarbonate diol Average molecular weight: 1500 Hydroxyl value: 74.8 (b₂-6): Polycarbonate diol Average molecular weight: 3000 Hydroxyl value: 37.4 (b₂-7): Polybutylene adipate Average molecular weight: 2500 Hydroxyl value: 44.9 4, Polyol component (b₃) (B₂-3): Ethylene glycol (b₂-2): 1.4-butanediol 5, solvent (DMF): dimethylformamide Example 1 (b₁-1) 171 parts and (MDI) 129 parts (DM
F) The reaction was carried out in 700 parts at 80 ° C. and the resin concentration was 30%.
Polyurethane resin with a viscosity of 560 poise at 20 ° C (b₁
A skeleton derived from the components: 39% by weight) was obtained. This melt
The solution is cast on a glass plate to evaporate 120 ° C (DMF).
To obtain a film-shaped molded body having a thickness of 0.2 mm. This
Molded product (1 cm wide and 10 cm long)
Was bent 180 ° at 27 ° C. This is warm water of 800 ℃
When soaked in, it completely recovered to its original shape within 2 seconds
It was 1 piece for another section that was left bent at about 30 ℃
It was still bent after a month, but soaked in warm water at 80 ℃
And within 2 seconds, it was completely restored to its original shape. Example 2 (b_Two-1) 2000 parts and (MDI) 4604 parts 70
The reaction is continued for 2 hours while maintaining at ℃
A quasi-prepolymer having groups was obtained. This pseudo-prepolymer
And (b₁-2) is heated to 70 ℃ and 120 ℃ respectively
100.0 g / min by a metering pump, and 95.
Twin screw extruder through the mixer at a speed of 2 g / min
It is continuously fed while being heated and kneaded at a maximum of 200 ° C.
I let it react and took it out like a string. Pellet after aging for 15 hours at 25 ℃
Polyurethane resin (b₁Derived from ingredients
Pellets having a skeleton of 31% by weight) were obtained. This perez
The viscosity of a 30% (DMF) solution of gypsum is 760 poise at 20 ° C.
It was. This pellet was heated to 190 ° C
Film-shaped molded product with a thickness of 0.3 mm processed with a dar roll
Got This molding (cut into 1 cm width and 10 cm length)
Shape) by bending and deforming the
While maintaining the shape, the deformation was fixed by cooling to 25 ° C. this
When immersed in 80 ° C warm water, the original
It recovered to its shape. Another cut left at 25 ° C while folded
The piece remained bent after 1 month, but the temperature was 80 ° C.
When immersed in water, the original shape was completely restored within 2 seconds. Example 3 (b₁-3) 136.2 copies, (b_Two-2) 27.3 copies
And (b_Three-1) 7.2 copies and (MDI) 129.3 copies
(DMF) Reacted in 700 parts at 80 ° C. to obtain resin concentration
Polyurethane resin with a viscosity of 820 poise at 20% at 30%
Fat (b₁Framework derived from the components: 32% by weight) to obtain a solution
It was This solution was cast on a glass plate at 120 ° C. (DM
F) is evaporated to form a film-shaped molded body having a thickness of 0.2 mm.
Obtained. This molded body (width 1 cm, length 10 cm cut
Was bent 180 ° at 27 ° C. 80 ° C
When soaked in warm water, it will return to its original shape completely within 2 seconds.
I restored it. The other section left bent at 25 ° C is 1
It was still bent after 10 months, but immersed in warm water at 80 ℃.
Then, it was completely restored to its original shape. Example 4 (b₁-4) 122.2 parts and (b_Two-3) 38 copies
(H-MDI) 139.9 parts with dibutyltin dilaurate
In 700 parts of (DMF) to which 0.1 part of (catalyst) was added
After reacting at 80 ° C, the viscosity of 20% at 30% resin concentration
560 poise polyurethane resin (b₁Derived from ingredients
A skeleton: 40% by weight) was obtained. Place this solution on a glass plate
And cast it at 120 ° C to evaporate (DMF) to thicken it.
A 0.2 mm film-shaped molded product was obtained. This molded body
(Cut width 1 cm, length 10 cm) at 27 ℃
It was bent 180 degrees. When this was immersed in warm water at 80 ° C
Around 2 seconds, it completely recovered to its original shape. Folding
Another section left to stand at about 25 ° C is bent even after 1 month
It was still up, but within 2 seconds when immersed in 80 ° C warm water
It was completely restored to its original shape. Example 5 As in Example 2, (b_Two-4) 672 copies and (MD
I) 4567 parts were reacted to obtain a quasi-prepolymer. This
Pseudoprepolymer of (b₁-5) at 70 ° C and
100 g / min by a metering pump under heating to 120 ° C,
And through a mixer at a speed of 49.4 g / min.
It is sent to the Liu extruder and heated and kneaded at a maximum temperature of 200 ° C.
Continuously react from above and take out in a string shape, and at 25 ℃ for 15 hours
After aging, cut with a pelletizer to cut polyurethane resin (b₁
Pellets having a skeleton derived from the components: 33% by weight) were obtained.
The viscosity of a 30% (DMF) solution of these pellets at 20 ° C
It was 620 poise. This pellet is
Linder temperature: 200 ℃, Resin temperature: 215 ℃ Injection pressure
Power: 80kgf / cm^Two) Processed with 3mm thick sheet
A shaped body was obtained. This molded product (width 1 cm, length 10 cm
(Cut into pieces) and bend it to 180 ° at 80 ° C
Then, while maintaining its shape, cool it to 25 ° C to fix the deformation.
It was Immerse it in warm water at 80 ℃ and complete it within 1 minute.
It has recovered to its original shape. Leave it bent at 25 ° C
The other section that was left bent after one month
Completely recovers the original shape within 1 minute when immersed in warm water at 80 ℃
did. Example 6 (b₁-1) 162 parts and (b_Three-2) 4 copies and (MD
I) 134 parts were reacted in 700 parts (DMF) at 80 ° C.
The resin concentration is 30% and the viscosity at 20 ° C is 560 poise.
Polyurethane resin (b₁Skeleton derived from ingredients: 37 weight
%) Solution was obtained. This solution is cast on a glass plate and 120
0.2mm thick film by evaporating (DMF) at ℃
A shaped body was obtained. This molded product (width 1 cm, length 10 c
(cut to m) was bent 180 ° at 27 ° C.
Soaking this in warm water of 80 ℃, completely within 2 seconds
It has recovered to its original shape. Leave it bent at about 25 ℃
Another slice remained bent after one month, but 8
When immersed in warm water at 0 ° C, it completely recovers its original shape within 2 seconds.
It was Example 7 (b₁-3) 275 parts and (b_Two-5) 111 parts
214 parts of (MDI) in 1400 parts of (DMF) at 80 ° C
And the viscosity at 20 ° C is 820 at a resin concentration of 30%.
Poise polyurethane resin (skeleton derived from component b1:
32 wt%) solution was obtained. This solution is cast on a glass plate.
Then, evaporate (DMF) at 120 ° C.
A film-shaped molded body was obtained. This molding (width 1 cm, length
(10 cm long) is folded 180 ° at 27 ° C.
Bent When immersed in warm water at 65 ° C, within 2 seconds
Completely restored to its original shape. Approximately 25 ℃ while folded
The other section left in place remains bent after 1 month
However, when immersed in warm water at 65 ° C, the original shape was completely achieved within 2 seconds.
Recovered. Example 8 (b₁-2) 149 parts and (b_Two-6) 44 parts and (M
Reaction of 107 parts of DI) in 700 parts of (DMF) at 80 ° C
The resin concentration is 30% and the viscosity at 20 ° C is 700 poises.
Polyurethane resin (skeleton derived from b1 component: 31 layers
% Solution). This solution is cast on a glass plate and
0.2mm thick film by evaporating (DMF) at 0 ° C
A mud-shaped body was obtained. This molded body (width 1 cm, length 10
(Cut out to cm) and fold 180 ° at 27 ℃
It was When it was immersed in warm water at 60 ℃, it was completed within 2 seconds.
It has recovered to its original shape. Release at about 25 ° C while folded
The other section placed was still bent after 1 month
When it is soaked in 60 ° C warm water, it will completely return to its original shape within 2 seconds.
I restored it. Example 9 (b₁-1) 131 parts and (b_Two-7) 58 parts and (H
-MDI) 111 parts dibutyltin dilaurate (touch)
Medium) 0.1 parts (DMF) 700 parts 80 ° C
At a resin concentration of 30% and a viscosity at 20 ° C of 150
Poise polyurethane resin (skeleton derived from component b1:
30% by weight) solution was obtained. This solution is cast on a glass plate.
Then, evaporate (DMF) at 120 ° C.
A film-shaped molded body was obtained. This molding (width 1 cm, length
(10 cm long) is folded 180 ° at 27 ° C.
Bent When immersed in hot water at 70 ° C, within 2 seconds
Completely restored to its original shape. Approximately 25 ℃ while folded
The other section left in place remains bent after 1 month
However, when immersed in hot water at 70 ° C, the original shape was completely achieved within 2 seconds.
Recovered. Example 10 (b₁-1) 134 parts and (b_Two-7) 59 parts and (M
Reaction of 107 parts of DI) in 700 parts of (DMF) at 80 ° C
Allowed to give a resin concentration of 30% and a viscosity of 860 poise at 20 ° C.
Polyurethane resin (skeleton derived from b1 component: 31 layers
% Solution). This solution is cast on a glass plate and
0.2mm thick film by evaporating (DMF) at 0 ° C
A mud-shaped body was obtained. This molded body (width 1 cm, length 10
(Cut out to cm) and fold 180 ° at 27 ℃
It was When this was immersed in warm water at 65 ° C, it was completed within 2 seconds.
It has recovered to its original shape. Release at about 25 ° C while folded
The other section placed was still bent after one month
When it is immersed in warm water of 65 ℃, it will return to its original shape within 2 seconds.
I restored it. Examples 11, 12, and 13 The film-shaped molded products (width 1c) obtained in Examples 1, 2, and 3.
m, 20 cm long)
Wrap it in a coil around a rod (diameter 10 mm) and secure both ends with a string.
After heating at 150 ℃ for 30 minutes, cool to 25 ℃
Then, remove the coiled film from the glass rod.
It was The molded body after heat treatment is coiled at 25 ° C for 10 days.
It retained its shape. Next coil after 10 days storage
The molded body was deformed into a flat plate at 80 ° C and the shape was maintained.
The deformation was fixed as it was by cooling to 25 ° C. These flat plates
The mold remained flat even after 10 days,
When immersed in the bath, it recovered to a coiled shape within 2 seconds. these
The results are shown in (Table-1).Comparative Example 1 (b_Two-1) 1423 copies and (DMI) 1072 copies 70
The reaction is continued for 2 hours while maintaining at ℃
A quasi-prepolymer having groups was obtained. Also (b₁-1) 2
53 parts and (b_Three-2) Mix 253 parts uniformly at 120 ° C.
This was used as solution (B). Next, the pseudoprepolymer and the solution (B)
Each is heated to 70 ℃ and 120 ℃ under constant temperature pump
At a rate of 100 g / min, and 20.2 g / min
Through the machine into a twin-screw extruder, up to 200
While heating and kneading at ℃, react continuously and take out in a string shape.
It was After aging for 17 hours at 25 ° C, cut with a pelletizer and paste.
Polyurethane resin (b₁Skeleton derived from components: 6% by weight)
Of pellets were obtained. 30% (DMF) solution of this pellet
The viscosity of the liquid was 730 poise at 20 ° C. This perez
Thickness is processed with a calendar roll heated to 190 ℃
A 0.3 mm film-shaped molded product was obtained. This molded body (width
1cm, 10cm in length) 1 at 25 ℃
It was bent 80 degrees. When I tried to leave it
It was not possible to fix the bent shape by recovering to the shape of. Comparative Example 2 (b₁-6) 87.1 parts, (b_Two-2) 87.1 parts and
(B_Three-1) 18.6 copies and (MDI) 107.1 copies
(DMF) Reacted in 700 parts at 80 ° C. to obtain resin concentration
Polyurethane resin with a viscosity of 840 poise at 20% at 30%
A solution of fat (skeleton derived from essential components: 6% by weight) was obtained.
This solution was cast on a glass plate and treated with (DMF) at 120 ° C.
Evaporation gave a film-shaped molded product having a thickness of 0.2 mm.
This molded product (width 1 cm, length 10 cm
() Is bent and deformed at 80 ° C to 180 ° and its shape is maintained.
I tried to fix the deformation by cooling it to 25 ℃ while holding it
You can immediately restore the original shape and fix the bent shape.
There wasn't. Comparative Example 3 (b_Two-4) 160.1 parts and (b_Three-1) 25.6
And (H-MDI) 114.3 parts (DMF) 700 parts
Reaction at 80 ° C in a room temperature and at a resin concentration of 30%,
Polyurethane resin with a degree of 810 poise (b₁Contains ingredients
No) solution was obtained. This solution is cast on a glass plate and
0.2mm thick film by evaporating (DMF) at 0 ° C
A mould-shaped body was obtained. This molded product (width 1 cm, length 10 c
(cut to m) was bent 180 ° at 25 ° C.
When I tried to leave it, it immediately recovered to its original shape and folded.
The bent shape could not be fixed. [Effects of the Invention] Shape memory properties made of the thermoplastic polyurethane resin of the present invention
The molded product can be deformed at a temperature of 130 ° C or less, and
It can be fixed at a temperature, and it can be turned into a primitive shape by gentle heating.
Can be recovered. Due to such effects, the shape memory molding of the present invention
The body is a building filler, a building sealant, a decorative material, a medical material
Materials, coating on the inside and outside of pipes, second piping, fixing
Pins, fasteners, temperature sensors, wiring seals for electric wires
Materials, molds, shape-changing toys, accessories, packing and packaging
Which binding materials, sizing materials, artificial flowers, car body parts, bumpers
ー, sealant for automobile machinery, electronic device housing, clothing
It is useful as an interlining material.

Claims (4)

[Claims] 1. An organic polyisocyanate and a general formula [Where A ₃ is Provided that 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; 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 or methyl It is a base. ] One or more polyol components selected from the compounds represented by and A thermoplastic shape-memory molded article comprising a polyurethane resin containing at least 15% by weight of the structural unit represented by. 2. The thermoplastic shape-memory molded article according to claim 1, which has a desired shape and is held at 130 to 230 ° C. to store the shape as a primitive shape. 3. Deformed into a desired shape at about 130 ° C. or lower,
The thermoplastic shape memory molding according to claim 1 or 2, wherein the deformed shape is maintained as it is at about 40 ° C or lower. 4. The method of using a thermoplastic shape memory molded article according to claim 3, wherein the sustained deformed shape is returned to the original shape by heating at about 40 ° C. or higher.