JP2022186470A - Two-liquid curable resin composition and shape memory resin - Google Patents

Abstract

To provide a shape memory resin that allows updating of memory.SOLUTION: A two-liquid curable resin composition contains an active hydrogen component and a polyisocyanate component. At least one of the active hydrogen component and the polyisocyanate component has a component having three or more functional groups. The active hydrogen component has at least one of polyamines represented by formula (1) and (2). R1 and R2 independently represent a C4-20 hydrocarbon group, R3-R6 independently represent H or a C1-20 hydrocarbon group, and R7 represents a C1-6 alkanediyl group.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to a two-part curable resin composition and a shape memory resin.

A shape memory resin is a resin that recovers its original shape when heated above a certain temperature even if it is deformed by applying force after molding. Shape memory resins are composed of a stationary phase consisting of physical or chemical bonding sites (crosslinking points) and a reversible phase consisting of non-crosslinked parts that become fluid above a certain temperature. A shape memory resin in which the stationary phase has a crosslinked structure formed by covalent bonds exhibits performance as a thermosetting resin. Therefore, it has the disadvantage that it cannot be remolded.

On the other hand, Patent Document 1, for example, proposes a shape memory resin in which processability as a thermoplastic resin is imparted by introducing a dynamic covalent bond into a crosslinked site. A dynamic covalent bond is a covalent bond that can be reversibly bonded and dissociated. At a temperature above a predetermined temperature, the covalent bond is dissociated and rebonded by cooling. , the workability of the thermoplastic resin can be expressed.

WO2005/056642

When the shape memory resin into which dynamic covalent bonds are introduced is heated to a temperature at which the dynamic covalent bonds dissociate (hereinafter referred to as dissociation temperature Th) or higher, the dynamic covalent bonds dissociate and recombine. By adding deformation under the above heating conditions and then cooling as it is, the deformed shape can be newly memorized. That is, it becomes possible to update the memory.

An object of an embodiment of the present invention is to provide a new shape-memory resin capable of memory updating and a two-component curing resin composition therefor.

式（１）において、Ｒ^１およびＲ^２は、それぞれ独立に炭素数４～２０の一価の炭化水素基を表し、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ独立に水素原子または炭素数１～２０の一価の炭化水素基を表し、式（２）において、Ｒ^７は炭素数１～６のアルカンジイル基を表し、ｎは１～２０の数を表す、二液硬化型樹脂組成物である。 A two-component curable resin composition according to a first embodiment of the present invention is a two-component curable resin composition having an active hydrogen component and a polyisocyanate component, wherein the active hydrogen component and the polyisocyanate component At least one contains a trifunctional or higher functional component, and the active hydrogen component contains one or more polyamines represented by the following formula (1) or formula (2),

In formula (1), R ¹ and R ² each independently represent a monovalent hydrocarbon group having 4 to 20 carbon atoms, and R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or Represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, in formula (2), R ⁷ represents an alkanediyl group having 1 to 6 carbon atoms, n represents a number of 1 to 20, two-component curing type It is a resin composition.

A shape memory resin according to a second embodiment of the present invention is a shape memory resin obtained by reacting an active hydrogen component and a polyisocyanate component, wherein at least one of the active hydrogen component and the polyisocyanate component contains 3 It is a shape memory resin containing a functional or higher component, wherein the active hydrogen component contains one or more polyamines represented by the above formula (1) or formula (2).

In the two-component curable resin composition and the shape memory resin, the polyisocyanate component is one selected from the group consisting of isocyanurate modified products, allophanate modified products, burette modified products, adduct modified products, and carbodiimide modified products. Or two or more kinds may be included.

In the two-component curable resin composition and the shape memory resin, the active hydrogen component may further contain a polyol.

In the two-component curable resin composition and the shape memory resin, the content of the polyamine may be 20 parts by mass or more with respect to 100 parts by mass of the total amount of the polyamine and the polyol.

According to the embodiment of the present invention, it is possible to provide a new shape memory resin whose memory can be updated.

Conceptual diagram for explaining shape memory and memory update of shape memory resin according to the embodiment Schematic side view showing the bending state of the test piece in the shape memory and memory renewal evaluation test

The two-component curable resin composition according to the present embodiment contains an active hydrogen component (A) and a polyisocyanate component (B), and usually contains a first liquid containing the active hydrogen component (A), and a second liquid containing the polyisocyanate component (B).

<First liquid>
[Active hydrogen component (A)]
The active hydrogen component (A) contained in the first liquid is a component containing active hydrogen groups such as amino groups and hydroxyl groups, and is also called an active hydrogen group-containing compound. In this embodiment, the active hydrogen component (A) contains one or more of polyamines (A1) represented by the following formula (1) or formula (2).

Polyamines represented by formula (1) are secondary diamines with bulky substituents. A urea bond formed by reaction between an amino group having such a bulky substituent and an isocyanate group is thermoreversibly bond-dissociable, ie, a dynamic covalent bond. The polyamine represented by the formula (2) is not a secondary amine having bulky substituents, but is a urea compound formed by reacting an amino group and an isocyanate group by withdrawing electrons from an ester bond attached to a benzene ring. It is believed that the bond is thermoreversibly bond-dissociable, ie dynamic covalent bond.

In formula (1), R ¹ and R ² each independently represent a monovalent hydrocarbon group having 4 to 20 carbon atoms. The hydrocarbon group may be a saturated or unsaturated aliphatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, or an aromatic hydrocarbon group. The number of carbon atoms in the hydrocarbon group is preferably 4-12, and may be 4-8. In one embodiment, when R ¹ and R ² are aliphatic hydrocarbon groups, they preferably have a branched chain, for example, R ¹ and R ² are each independently a branched aliphatic group having 4 to 12 carbon atoms. Hydrocarbon groups are preferred, and branched saturated hydrocarbon groups each independently having 4 to 8 carbon atoms are more preferred.

In Formula (1), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group may be a saturated or unsaturated aliphatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, or an aromatic hydrocarbon group. The number of carbon atoms in the hydrocarbon group may be 1-12, or 1-8. In one embodiment, R ³ , R ⁴ , R ⁵ and R ⁶ are preferably hydrogen atoms.

In formula (2), R ⁷ represents an alkanediyl group having 1 to 6 carbon atoms. R ⁷ more preferably represents an alkanediyl group having 3 to 5 carbon atoms, more preferably a butanediyl group having 4 carbon atoms. When there are a plurality of oxyalkylene groups OR ⁷ in formula (2) (that is, n≧2), the plurality of oxyalkylene groups OR ⁷ may be of the same type, or two or more types may be combined.

In formula (2), n represents a number from 1 to 20. n may be 2-15, or 5-12. In formula (2), the positions of the amino groups bonded to the benzene rings at both ends are not particularly limited, but are preferably para positions with respect to the ester bond.

Specific examples of the polyamine represented by formula (2) include "Elastomer 250P" (R ⁷ = tetramethylene, n = 3) and "Elastomer 650P" (R ⁷ = tetramethylene, n = 9), “Elastomer 1000P” (R = tetramethylene, n = ¹⁴ ), “Porea SL-100A” (R = tetramethylene and ³ -methyltetramethylene, molecular weight 1238), “CUA-4” (R ⁷ = trimethylene, n=1), etc. are commercially available and can be used.

The active hydrogen component (A) may consist of the polyamine (A1) alone, or may contain a polyol (A2) together with the polyamine (A1). By using the polyol (A2) together, embrittlement when heated to the dissociation temperature Th or higher can be suppressed and flexibility can be imparted. Here, when the active hydrogen component (A) consists only of the polyamine (A1), the resin obtained by the reaction with the polyisocyanate component (B) is a polyurea resin, and the active hydrogen component (A) is combined with the polyamine (A1). When the polyol (A2) is included, the resulting resin is a polyurethaneurea resin. Hereinafter, these polyurea resins and polyurethane urea resins may be collectively referred to as polyurethane-based resins.

Polyol (A2) is a compound having a plurality of hydroxyl groups in the molecule, examples of which include polyether polyol, polyester polyol, polycarbonate polyol, castor oil-based polyol, polybutadiene polyol, polyisoprene polyol, dimer acid polyol, polycaprolactone polyol, acrylic polyol and the like. The polyol (A2) may also be a low-molecular-weight polyol generally used as a cross-linking agent, such as a polyol compound having a molecular weight of 300 or less, specifically ethylene glycol, propylene glycol, 1,4-butanediol, , 3-butanediol, nonanediol, octanediol, 3-methyl-1,5-pentanediol, dipropylene glycol, bisphenol A, glycerin, trimethylolpropane and the like. These polyols (A2) can be used either singly or in combination of two or more.

The polyol (A2) is not particularly limited, but preferably has a hydroxyl value (OHV) of 10 to 400 mgKOH/g, more preferably 50 to 350 mgKOH/g, and still more preferably 100 to 400 mgKOH/g. 320 mg KOH/g, and may be 200-300 mg KOH/g. As used herein, the hydroxyl value is measured according to JIS K1557-1:2007, Method A.

In one embodiment, polyol (A2) preferably comprises a polyether polyol. Examples of polyether polyols include polyol compounds such as ethylene glycol, propylene glycol, bisphenol A and glycerin, or polyamine compounds such as ethylenediamine, and alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, either alone or as a mixture, in random or block form. Examples include those obtained by addition. The hydroxyl value of the polyether polyol is not particularly limited, and may be 10-400 mgKOH/g, 50-350 mgKOH/g, 100-320 mgKOH/g, or 200-300 mgKOH/g.

When the active hydrogen component (A) contains the polyol (A2) together with the polyamine (A1), the content of the polyamine (A1) is 20 parts by mass per 100 parts by mass of the total amount of the polyamine (A1) and the polyol (A2). It is preferable that it is above. When the content is 20 parts by mass or more, it is possible to increase the content of the urea bond that becomes a dynamic covalent bond and improve the memory updating property. The content of the polyamine (A1) is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, relative to 100 parts by mass of the total amount of the polyamine (A1) and the polyol (A2), and It may be 90 parts by mass or less, or may be 80 parts by mass or less.

The content of the polyol (A2) is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 100 parts by mass in total of the polyamine (A1) and the polyol (A2). It is 60 parts by mass or less, and may be 10 parts by mass or more, or may be 20 parts by mass or more.

Active hydrogen component (A) may contain active hydrogen group-containing compounds other than polyamine (A1) and polyol (A2) (for example, polyamines other than polyamine (A1)), but preferably active hydrogen component (A ) consists of the polyamine (A1) alone or the polyamine (A1) and the polyol (A2) alone. Therefore, the ratio of the polyamine (A1) in 100% by mass of the active hydrogen component (A) is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more. , Further, it may be 90% by mass or less, or 80% by mass or less. The ratio of the polyol (A2) in 100% by mass of the active hydrogen component (A) is preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, and , 10% by mass or more, or 20% by mass or more. The total ratio of the polyamine (A1) and the polyol (A2) in 100% by mass of the active hydrogen component (A) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 100% by mass.

[Other ingredients]
The first liquid may be composed only of the active hydrogen component (A), but if necessary, for example, a catalyst, an antifoaming agent, an antioxidant, a diluent, a flame retardant, an ultraviolet absorber, a coloring agent, Various additives such as fillers and plasticizers can be added as long as the purpose of the present embodiment is not impaired.

<Second liquid>
[Polyisocyanate component (B)]
Various polyisocyanate compounds having two or more isocyanate groups in one molecule can be used as the polyisocyanate component (B) contained in the second liquid. Examples of the polyisocyanate component (B) include aliphatic polyisocyanate (B1), alicyclic polyisocyanate (B2), and aromatic polyisocyanate (B3), as well as modified and polynuclear compounds thereof. You may use 1 type or you may use 2 or more types together.

Aliphatic polyisocyanates (B1) include, for example, tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine Examples include diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, and the like, and any one or two or more of these may be used in combination.

Examples of the alicyclic polyisocyanate (B2) include isophorone diisocyanate (IPDI), hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3- Bis(isocyanatomethyl)cyclohexane and the like can be mentioned, and any one of them or two or more thereof may be used in combination.

Examples of the aromatic polyisocyanate (B3) include tolylene diisocyanate (TDI, such as 2,4-TDI, 2,6-TDI), diphenylmethane diisocyanate (MDI, such as 2,2'-MDI, 2,4'- MDI, 4,4'-MDI), 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate (XDI), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, triphenyl Methane triisocyanate and the like can be mentioned, and any one of them or two or more of them may be used in combination.

Modified products of these polyisocyanates (B1) to (B3) include, for example, isocyanurate modified products, allophanate modified products, burette modified products, adduct modified products, carbodiimide modified products, etc. Any one of these may be used. Or you may use together 2 or more types.

In one embodiment, as the polyisocyanate component (B), at least one modified material selected from the group consisting of an isocyanurate modified material, an allophanate modified material, a burette modified material, an adduct modified material and a carbodiimide modified material is used. is preferred, more preferably the above modified aliphatic polyisocyanate (B1), more preferably the above modified hexamethylene diisocyanate (HDI).

[Other ingredients]
The second liquid may be composed only of the polyisocyanate component (B), and in addition to the polyisocyanate component (B), if necessary, for example, a catalyst, an antifoaming agent, an antioxidant, a diluent , flame retardants, ultraviolet absorbers, colorants, fillers, plasticizers, and the like can be added to the extent that the purpose of the present embodiment is not impaired.

<Two-component curable resin composition>
The two-component curable resin composition according to the present embodiment is a polyurethane-based resin obtained by the reaction of the active hydrogen component (A) and the polyisocyanate component (B) as described above. It is also called a system resin composition.

In the two-pack curable resin composition, at least one of the active hydrogen component (A) and the polyisocyanate component (B) contains a trifunctional or higher component (monomer). As a result, a crosslinked structure is formed in the polyurethane-based resin after curing, and performance as a thermosetting resin having shape memory can be imparted. In addition, the active hydrogen component (A) contains the polyamine (A1), and the amino groups of the polyamine (A1) react with the isocyanate groups of the polyisocyanate component (B) to form urea bonds as dynamic covalent bonds. Therefore, it is possible to provide memory updatability.

Here, the trifunctional or higher component is a polyamine or polyol having three or more amino groups or hydroxyl groups in one molecule in the case of the active hydrogen component (A), and one molecule in the case of the polyisocyanate component (B). It is a polyisocyanate compound having three or more isocyanate groups in it.

In the two-component curable resin composition, only the active hydrogen component (A) may contain a trifunctional or higher component, only the polyisocyanate component (B) may contain a trifunctional or higher component, and the active hydrogen component ( Both A) and the polyisocyanate component (B) may contain trifunctional or higher functional components. Since the polyamine (A1) is difunctional, it is preferable that the polyisocyanate component (B) contains a trifunctional or higher component, whereby the polyamine (A1) is used as a cross-linking site and dynamically shared at the cross-linking site. Coupling can be introduced.

Examples of polyisocyanate compounds having a functionality of 3 or more include triphenylmethane triisocyanate, polymeric MDI, modified isocyanurate, modified allophanate, modified burette, modified carbodiimide, and a product obtained by reacting isocyanate with a trihydric or higher alcohol. Examples include adduct modified products, and these may be used singly or in combination of two or more.

In the two-component curable resin composition, the ratio of the active hydrogen component (A) and the polyisocyanate component (B) is not particularly limited. Component (B) may be 30 to 150 parts by mass, or may be 40 to 120 parts by mass. Further, NCOV/OHV (index), which is the ratio of the isocyanate value (NCOV) (mgKOH/g) of the polyisocyanate component (B) to the hydroxyl value (OHV) (mgKOH/g) of the active hydrogen component (A), is, for example, It may be 0.7 to 1.5, 0.9 to 1.2, or 1.0 to 1.1.

As used herein, the isocyanate value (mgKOH/g) is calculated by the following formula from the isocyanate content (NCO%) obtained by measuring the isocyanate content in accordance with JIS K1603-1:2007 A method. .
Isocyanate value = (NCO% x 56110) / (42.02 x 100)

The two-component curable resin composition according to the present embodiment is usually composed of a first liquid containing the active hydrogen component (A) and a second liquid containing the polyisocyanate component (B), but optional components You may provide the thing containing the said other component as a 3rd liquid.

The two-pack curable resin composition can be produced by preparing the first liquid and the second liquid, that is, the first liquid and the second liquid may be filled in separate containers. . The first liquid and the second liquid filled in separate containers are mixed at the time of use, whereby the active hydrogen component (A) and the polyisocyanate component (B) react to form a polyurethane-based resin and harden. may At that time, it may be cured by heating. The two-pack curable resin composition according to the embodiment may be obtained by mixing the first liquid and the second liquid, may be in a liquid state before curing, or may be in a cured state.

<Shape memory resin>
The shape memory resin according to the present embodiment is a polyurethane-based resin obtained by reacting the active hydrogen component (A) and the polyisocyanate component (B). Anything you can get is fine. At least one of the active hydrogen component (A) and the polyisocyanate component (B) contains a trifunctional or higher component in the shape memory resin, thereby imparting shape memory properties. Since the urea bond formed by the reaction of the polyamine (A1) and the polyisocyanate component (B) contained in is a dynamic covalent bond that can be reversibly bonded and dissociated, memory update is possible.

Specifically, the shape memory resin is composed of a stationary phase composed of a crosslinked portion and a reversible phase composed of a non-crosslinked portion that becomes fluid above the glass transition temperature Tg, and is heated above the glass transition temperature Tg. As a result, the reversible phase is softened and deformed while maintaining the stationary phase. In addition, since the urea bond is dissociated by heating to a dissociation temperature Th or higher at which the urea bond, which is a dynamic covalent bond, is dissociated, and rebonds during cooling, deformation is applied under a heating condition of the dissociation temperature Th or higher, and the product is left as it is. By cooling, the deformed shape can be newly memorized.

FIG. 1 is a conceptual diagram for explaining shape memory and memory update of a shape memory resin according to an embodiment. The state (1) in FIG. 1 will be described as a starting point. In the state (1), the molded body of the shape memory resin has the shape A as the memory shape, and is in the state of the shape A when the ambient temperature T is lower than the glass transition temperature Tg (T<Tg). From this state, the compact is heated to the glass transition temperature Tg or higher (Tg≦T<Th) (state (2)), and the compact is further deformed into shape B as shown in (3). When this deformed state is cooled to T<Tg, it is fixed as it is and becomes a compact having shape B as shown in (4). However, since the shape A is memorized, when heated to Tg≦T<Th, the shape A is restored as shown in (2). Therefore, if the product is cooled as it is, it returns to the initial state of (1).

On the other hand, when the state of (3) deformed to the shape B is heated to a dissociation temperature Th or higher (T ≥ Th), the urea bond, which is a dynamic covalent bond, dissociates as shown in (5) to dissociate the amino group and the isocyanate group. become. After that, when the state of shape B is cooled below the dissociation temperature Th (Tg≦T<Th), the amino group and the isocyanate group recombine to form a urea bond as shown in (6), and shape B is newly memorized. , that is, memory update occurs. Therefore, if it is cooled to T<Tg as it is, it becomes a compact having shape B as shown in (7). Since this compact remembers the shape B, even if it is heated to Tg≤T<Th, it remains in the shape B as shown in (6) and does not restore to the shape A shown in (2). From the state of (6), the compact is deformed into shape C as shown in (8), and when cooled to T<Tg in this deformed state, a compact having shape C is obtained as shown in (9). Since the memory shape of the compact of shape C is shape B, it is restored to shape B as shown in (6) when heated to Tg≦T<Th.

The glass transition temperature Tg of the shape memory resin according to the present embodiment is not particularly limited as long as it is lower than the dissociation temperature Th. °C or higher, or 50 °C or higher. Also, the glass transition temperature Tg may be 150° C. or lower, 130° C. or lower, 120° C. or lower, 100° C. or lower, or 80° C. or lower. As used herein, the glass transition temperature Tg is a value determined by dynamic viscoelasticity measurement.

The dissociation temperature Th of the shape memory resin according to the present embodiment is not particularly limited as long as it is higher than the glass transition temperature Tg. In this specification, the dissociation temperature Th is measured as follows. That is, in the memory update possibility evaluation test (flat → bending) in the example described later, the heating temperature in (2) was changed to a temperature higher than the glass transition temperature Tg in increments of 10 ° C., and the other memory update was performed. A test similar to the possibility evaluation test (flat to bending) is performed to calculate the deformation rate, and the minimum temperature at which the calculated deformation rate becomes 30% or more is defined as the dissociation temperature Th.

The two-component curable resin composition and shape memory resin according to the present embodiment can be used to produce various resin molded bodies by general resin molding methods such as injection molding, film molding, and blow molding. . Moreover, its use is not particularly limited, and for example, it can be used for various uses such as electric and electronic parts.

The present invention will be described in more detail based on examples below, but the present invention is not limited thereto.

Raw materials used in Examples and Comparative Examples are shown below.
[Polyamine (A1)]
・ Polyamine 1: "Etacure 420" manufactured by Mitsui Chemicals Fine Co., Ltd., a polyamine represented by the following formula

- Polyamine 2: "Elastomer 650P" manufactured by Kumiai Chemical Industry Co., Ltd., a polyamine represented by the following formula (n = 9)

[Polyol (A2)]
・ Polyol 1: polyoxypropylene bisphenol A ether, hydroxyl value 211 mgKOH / g, functional group number 2, manufactured by Sanyo Chemical Industries, Ltd. "Newpol BP-5P"
· Polyol 2: polypropylene glycol, hydroxyl value 281 mgKOH / g, functional group number 2, AGC Co., Ltd. "Exenol 420"

[Polyisocyanate component (B)]
· Polyisocyanate 1: hexamethylene diisocyanate (HDI) modified product, isocyanate value 259 mgKOH / g, manufactured by Tosoh Corporation "Coronate 2770"
· Polyisocyanate 2: HDI isocyanurate modified product, isocyanate value 309 mgKOH / g, functional group number 3, "HT-600" manufactured by Wanhua Chemical Co., Ltd.

[Other ingredients]
・ Defoamer: "Disparon P-450" manufactured by Kusumoto Kasei Co., Ltd.
・Catalyst: Nitto Kasei Co., Ltd. “Neostan U-810”

A method for measuring the glass transition temperature Tg of the shape memory resin is as follows.
[Glass transition temperature Tg]
Using a predetermined test piece (length 20 mm × width 5 mm × thickness 2 mm), using Rheogel E-4000 manufactured by UBM Co., Ltd., the distance between chucks is 20 mm, the fundamental frequency is 10 Hz, and the strain is set to the glass transition temperature Tg in the automatic control mode. It was measured.

[Examples 1 to 12 and Comparative Example 1]
According to the composition (parts by mass) shown in Table 1 below, the first liquid and the second liquid were prepared, and both were mixed at the mass ratio shown in Table 1 (parts by mass of the second liquid to 100 parts by mass of the first liquid). Using the mixed liquid obtained by mixing, a test piece having a length of 20 mm, a width of 5 mm, and a thickness of 2 mm was formed. Table 1 also shows the index NCOV/OHV, which is the ratio of the isocyanate value (NCOV) of the polyisocyanate component (B) to the hydroxyl value (OHV) of the active hydrogen component (A). The specimen was cured at 120°C for 3 hours to complete curing. In addition, in Comparative Example 1 in which no polyamine was blended, curing was completed by curing at 80° C. for 16 hours.

The obtained test piece was measured for the glass transition temperature Tg, and evaluated for shape memory property and shape memory renewability. The updateability of shape memory was evaluated for the possibility of memory update and the repeatability of memory update. The evaluation method is as follows.

[Shape memory]
(1) A flat test piece is heated to T = 100°C (Tg ≤ T < Th), attached to a jig as shown in Fig. 2, and subjected to bending deformation (bending angle θ = 60°) and held for 1 hour. did.
(2) The test piece was cooled to T<Tg (T=5° C. in Comparative Example 1, T=15° C. in other cases) while bending deformation was applied. It was removed from the jig and set in a free state, and it was confirmed whether or not the test piece maintained bending deformation.
(3) Then, by heating the bent test piece to T=100° C. (Tg≦T<Th), it was confirmed whether the test piece restored to its original flat shape.
(4) A test piece that maintained bending deformation in the above (2) restored to a flat shape in the above (3) was evaluated as having shape memory and was evaluated as "Good". Other than that, it was evaluated as "×" as no shape memory property.

[Possibility of memory update]
(flat → bending)
(1) A flat test piece was heated to T=100° C. (Tg≦T<Th), attached to a jig as shown in FIG. 2, and subjected to bending deformation (bending angle θ=60°).
(2) Heated to T=150° C. (T≧Th) while bending deformation was applied, and held for 3 hours.
(3) After 3 hours, the temperature was set to 100° C., the test piece was removed from the jig, and held in a free state for 1 hour.
(4) After that, the test piece was cooled to T<Tg (T=5° C. in Comparative Example 1, T=15° C. in other cases), and the bending angle of the test piece was measured. Using the measured bending angle A1 (°), the ratio (A1/60) × 100% to the initial bending angle θ = 60° was calculated as the deformation rate, and those with a deformation rate of 70% or more were evaluated as “○” ( Excellent memory renewability), 30% or more and less than 70% were evaluated as "Δ" (with memory renewability), and less than 30% were evaluated as "x" (no memory renewability).

(bending → flat)
(5) The bent test piece obtained above was heated to T=100° C. (Tg≦T<Th), sandwiched between flat molds, and deformed to be flat. At that time, a spacer was inserted between the molds so that the test piece would not deform due to malleability, and the thickness between the molds was 2 mm, which was the same as the thickness of the test piece.
(6) Heated to T=150° C. (T≧Th) while being deformed, and held for 3 hours.
(7) After 3 hours, the temperature was set to 100° C., the test piece was removed from the mold, and held in a free state for 1 hour.
(8) After that, the test piece was cooled to T<Tg (T=5° C. in Comparative Example 1, T=15° C. in other cases), and the bending angle of the test piece was measured. Using the measured bending angle A2 (°) and the above A1 (°), {(A1-A2) / A1} × 100% is calculated as a deformation rate, and a deformation rate of 70% or more is given as "○" ( Excellent memory renewability), 30% or more and less than 70% were evaluated as "Δ" (with memory renewability), and less than 30% were evaluated as "x" (no memory renewability).

[Repeatability of memory update]
(1) to (8) of the above "Evaluation of possibility of memory update" are repeated once more, and "○" is given when both the evaluations in (4) and (8) of the second time are "○" (Excellent repeatability of memory update), "x" for those evaluated as "x" in either one of (4) and (8) (poor repeatability of memory update), and others " △”.

The results are shown in Table 1. In Comparative Example 1, no dynamic covalent bond was formed because the polyamine (A1) represented by formula (1) or (2) was not used as the active hydrogen component (A). Therefore, although the shape memory property was shown, when the free state was set in (3) above in the memory update possibility evaluation, it returned to a flat state close to the initial shape, and the memory update to the bent shape was performed. I didn't.

On the other hand, in Examples 1 to 12, the shape memory property was exhibited, and the polyamine (A1) represented by the formula (1) or (2) was included in the active hydrogen component (A). In the update possibility evaluation, the bent shape was maintained when the free state was set in the above stage (3), and the memory was updated from the flat shape to the bent shape. In addition, the flat shape was maintained in the free state at the stage (7), and the memory was updated from the bent shape to the flat shape. Moreover, by increasing the amount of the polyamine (A1) contained in the active hydrogen component (A), the memory update repeatability was excellent.

For Examples 3 and 7, in order to investigate the temperature at which memory update occurs, the heating temperature in (2) above was changed in the range of 110°C to 150°C in increments of 10°C. The same test as the property evaluation test (flat → bending) was performed, and the ratio (A1/60) to the initial bending angle θ = 60° using the bending angle A1 (°) of the test piece measured in (4) above. 100% was calculated as a deformation rate. The results are shown in Table 2 below.

As shown in Table 2, it can be seen that memory update can be performed at a lower temperature in the third embodiment than in the seventh embodiment. Moreover, in both Example 3 and Example 7, complete memory update was possible at 150° C. or higher. From the results shown in Table 2, the dissociation temperature Th of the shape memory resin of Example 3 was 120°C, and the dissociation temperature Th of the shape memory resin of Example 7 was 130°C.

Although several embodiments of the invention have been described above, these embodiments are presented by way of example and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, replacements, and modifications can be made without departing from the scope of the invention. These embodiments, their omissions, replacements, modifications, etc., are included in the invention described in the scope of claims and equivalents thereof, as well as being included in the scope and gist of the invention.

Claims (8)

A two-part curable resin composition having an active hydrogen component and a polyisocyanate component,
At least one of the active hydrogen component and the polyisocyanate component contains a trifunctional or higher component,
The active hydrogen component contains any one or more polyamines represented by the following formula (1) or formula (2),

In formula (1), R ¹ and R ² each independently represent a monovalent hydrocarbon group having 4 to 20 carbon atoms, and R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, in formula (2), R ⁷ represents an alkanediyl group having 1 to 6 carbon atoms, n represents a number of 1 to 20,
A two-component curable resin composition. 2. The two according to claim 1, wherein the polyisocyanate component contains one or more selected from the group consisting of isocyanurate modified products, allophanate modified products, buret modified products, adduct modified products, and carbodiimide modified products. A liquid curing resin composition. 3. The two-component curable resin composition according to claim 1, wherein said active hydrogen component further contains a polyol. 4. The two-component curable resin composition according to claim 3, wherein the content of said polyamine is 20 parts by mass or more with respect to 100 parts by mass of said polyamine and said polyol. A shape memory resin obtained by reacting an active hydrogen component and a polyisocyanate component,
At least one of the active hydrogen component and the polyisocyanate component contains a trifunctional or higher component,
The active hydrogen component contains any one or more polyamines represented by the following formula (1) or formula (2),

In formula (1), R ¹ and R ² each independently represent a monovalent hydrocarbon group having 4 to 20 carbon atoms, and R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, in formula (2), R ⁷ represents an alkanediyl group having 1 to 6 carbon atoms, n represents a number of 1 to 20,
Shape memory resin. 6. The shape of claim 5, wherein the polyisocyanate component comprises one or more selected from the group consisting of isocyanurate modifications, allophanate modifications, burette modifications, adduct modifications, and carbodiimide modifications. memory resin. 7. The shape memory resin of claim 5 or 6, wherein said active hydrogen component further comprises a polyol. 8. The shape memory resin according to claim 7, wherein the polyamine content is 20 parts by mass or more with respect to 100 parts by mass of the total amount of the polyamine and the polyol.

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