JP3115792B2 - Active energy ray-curable resin composition, method for producing the same, molded cured product of active energy ray-curable resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention is characterized by being cured by irradiation with active energy rays, and having excellent transparency, toughness, scratch resistance, water resistance, and low curing shrinkage. The present invention relates to a photocurable resin composition capable of providing a cured product having the same. SUMMARY OF THE INVENTION An object of the present invention is to provide a new material that is useful mainly for producing paints (inks), adhesives, cast products, stereolithography products, and the like.

[0002]

2. Description of the Related Art Conventionally, photocurable compositions have been employed mainly for the production of paint inks, adhesives and cast products for the following reasons. (A) Since the photocurable composition has a high curing speed, the productivity can be improved. (B) Since no solvent or water is generated during curing, the working environment is excellent. (C) Since it can be handled at room temperature, the photocurable composition can be applied to a substrate unstable to heat, It is advantageous for mixing or embedding heat-labile drugs or substances. (D) When the photocurable composition is cured, the surface hardness of the cured product can be increased. In recent years, taking advantage of these advantages, application of a photocurable composition to a sheet or a film has been devised, and the study stage has begun. It is known that by curing this type of photocurable resin composition, a cured product having relatively good transparency, high hardness and scratch resistance can be obtained.

[0003]

However, the present inventor has
When examining conventional photocurable compositions, the cured products tend to be hard, brittle, and difficult to elongate, so that cracks or breaks easily occur in the cured film due to relatively small external force such as impact. There was a tendency. Further, the time required for curing the photocurable composition is as short as several seconds, so that the shrinkage during curing is high, so that it becomes difficult to improve the dimensional accuracy of the product, and the appearance of the product becomes wrinkled. In some cases or lack adhesion to the adherend.

[0004] The object of the present invention is, in addition to good transparency,
An object of the present invention is to provide an active energy ray-curable resin composition which can form a cured product having higher toughness and has a small degree of curing shrinkage.

[0005]

As a result of various studies on a photocurable resin composition which can satisfy the above-mentioned various performances, the present inventor has found that the photocurable resin composition containing a thermoplastic polyurethane elastomer has the above-mentioned properties. Surprisingly, it was found that a cured product having shape memory properties was formed, and the present invention was achieved.

That is, the present invention relates to (a) a thermoplastic polyurethane elastomer, and (b) a t-butyl metaacrylate.
G, benzyl methacrylate and N- (meth) acro
It is characterized by containing one or more monofunctional monomers selected from the group consisting of ilmorpholine, and (c) a urethane (meth) acrylate oligomer compatible with the thermoplastic polyurethane elastomer (a) after curing. And an active energy ray-curable resin composition.

[0007] In particular, the thermoplastic polyurethane elastomer is of a solventless type. Also, a mixture 100 composed of a thermoplastic polyurethane elastomer, a monofunctional monomer and a urethane (meth) acrylate oligomer
0 to 20 parts of a photopolymerization initiator, 0 parts of a photosensitizer,
-20 parts, thermosetting component 0-10 parts, additive 0-10 parts,
0 to 60 parts of a coloring agent can be added.

In order to produce the active energy ray-curable resin composition, (1) a molecular weight of 500 or more and 400
A thermoplastic polyurethane elastomer is produced by addition-polymerizing a polyol having a terminal active hydrogen of 0 or less, (2) a low molecular weight glycol or a low molecular weight diamine having a molecular weight of 490 or less, and (3) an organic diisocyanate. It can be dissolved in a monofunctional monomer together with the urethane (meth) acrylate oligomer. Or addition polymerization of (1) a polyol having a terminal active hydrogen having a molecular weight of 500 or more and 4000 or less, (2) a low-molecular glycol or low-molecular diamine having a molecular weight of 490 or less, and (3) an organic diisocyanate in the monofunctional monomer. By doing so, it is possible to produce a thermoplastic polyurethane elastomer, dissolve the thermoplastic polyurethane elastomer in the monofunctional monomer, and dissolve the urethane (meth) acrylate oligomer in the monofunctional monomer.

[0009] The present invention also relates to a cured product formed by irradiating the active energy ray-curable resin composition with an active energy ray.

The thermoplastic polyurethane elastomer (a) used in the composition of the present invention comprises (1) a molecular weight of 500 or more;
A polyol having a terminal active hydrogen of 4000 or less,
It can be produced by addition polymerization of (2) a low molecular weight glycol or a low molecular weight diamine having a molecular weight of 490 or less, and (3) an organic diisocyanate. This thermoplastic polyurethane elastomer is basically a linear polymer, has rubber elasticity by itself, and has no polymerizability by active energy rays. The molecular weight is preferably 10,000 or more, but the upper limit is usually 500,000. If this is less than 10,000, sufficient strength cannot be obtained. If this exceeds 500,000, the viscosity of the composition becomes too high, and the composition does not cast during casting.

(1) The polyol having a terminal active hydrogen having a molecular weight of 500 or more and less than 4000 can be exemplified as follows. Polyoxyalkylene polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol: These are esterification products of these polyoxyalkylene polyols with polycarboxylic acids such as succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid. Polyether polyester-modified polyols: 1,6-hexanediol, 1,4-butanediol, 1,2-propylene glycol, ethylene glycol, neopentyl glycol, 2-methyl-
An alkylene diol such as 1,3-propanediol;
Condensed polyester polyols by any combination with dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and dodecane dicarboxylic acid; polyester polyols such as polycarbonate diols composed of lactone polyols; other commercially available acrylic polyols; Polyols generally used in the field of elastomers, such as polybutadiene-based polyols, polyisoprene-based polyols, polyolefin-based polyols, saponified ethylene vinyl acetate, phosphorus-containing polyols, and halogen-containing polyols. One or more of these polyols can be used.

The glass transition point Tg of these polyols
Is preferably −20 ° C. or lower. Tg is -20
When the temperature exceeds ℃, the flexibility of the polyol is lost and the cured product does not exhibit toughness because it has no properties as an elastomer.

(2) Examples of the low molecular weight glycol having a molecular weight of less than 490 include glycols such as ethylene glycol, 1,4-butanediol, bis (hydroxyethyl) hydroquinone, pentaethylene glycol and tetraethylene glycol. . In addition, molecular weight 49
Examples of the low-molecular diamine less than 0 include aromatic amines such as hydrazine, ethylenediamine, butylenediamine, diaminodiphenylmethane, and P-phenylenediamine. One or more of these low-molecular glycols and low-molecular diamines can be used as a chain extender.

(3) Examples of the organic diisocyanate include tolylene diisocyanate, 4,4'-genyl methane diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, isophorone diisocyanate, lysine diisocyanate and hydrogenated xylylene. One or more organic diisocyanates selected from the group consisting of range isocyanates can be used.

In the reaction of the raw materials (1), (2) and (3) to obtain a thermoplastic polyurethane elastomer, the reaction method and reaction conditions are not particularly limited, and a known method is employed. can do.

Known production methods include, for example, (A) a one-shot method in which these three components are mixed together and reacted, and (B) a polyol of (1) and an organic diisocyanate of (3) in advance. And react to this reactant
There is a two-shot method in which a low molecular glycol or a low molecular diamine is mixed and reacted in (2).

In order to control the reactivity, it is preferable to use a reaction solvent and a reaction catalyst. As the reaction solvent, any solvent capable of uniformly dissolving the raw materials may be used, and organic solvents not containing hydrogen that is reactive with diisocyanate, such as toluene, ethyl acetate, methyl ethyl ketone, dioxane, isophorone, dimethylformamide, and dimethyl sulfoxide. Use the required amount.

As a reaction catalyst, a tertiary amine such as triethylamine, tetramethylbutanediamine, 1,4-diaza (2,2,2) bicyclooctane, or dibutyltin dilaurate is used in a urethanization reaction. The required amount of reaction catalyst is used.

The reaction temperature is usually from 40 to 100 ° C, preferably from 60 to 80 ° C. In the present invention, a thermoplastic polyurethane elastomer obtained by such a general method can be used.

To produce the composition of the present invention, the thermoplastic polyurethane elastomer obtained as described above can be dissolved together with a urethane (meth) acrylate oligomer in a monofunctional monomer. However, the composition according to the present invention is a solventless composition, and when the above-mentioned organic solvent is used, removal of the organic solvent must be considered. In addition, even when an organic solvent is not used, since the obtained thermoplastic polyurethane elastomer is solid, a solid thermoplastic polyurethane elastomer is used,
A step of dissolution in other components of the composition is required, and this step requires a lot of time and effort.

Therefore, in the monofunctional monomer (b),
The aforementioned polyurethane raw materials (1), (2), (3)
Can be reacted. This reaction step
The one-shot method or the two-shot method described above may be used. At this time, a reaction catalyst can be added to the monofunctional monomer, and reaction conditions such as a reaction temperature are appropriately selected. According to this method, the thermoplastic polyurethane elastomer can be obtained in a solution state in which the thermoplastic polyurethane elastomer is dissolved in the monofunctional monomer (b).

However, in this method, the upper limit of the reaction temperature must be kept at 80 to 100 ° C. Otherwise, there is a risk that the monofunctional monomer (b) may initiate thermal polymerization. In this case, it is effective to add a small amount of a thermal polymerization inhibitor in order to prevent the monofunctional monomer from causing thermal polymerization. As such a thermal polymerization inhibitor, hydroquinone, t-butylhydroquinone, phenothiazine, hydroquinone monomethyl ether and the like are used.

The present inventor has determined that the thermoplastic polyurethane elastomer thus introduced imparts toughness, abrasion resistance, and low curing shrinkage of a cured product of the present composition, and further exhibits shape memory. I found

The shape memory will be described. By irradiating the composition of the present invention with an active energy ray, the composition is cured to obtain a cured product. At this stage, the cured product is given a predetermined shape. The cured product is heated, softened and deformed. Or, it is deformed by applying an external force. Thereafter, when the deformed cured product is cooled, the once deformed shape is maintained. Next, the cured product after the deformation is heated again to soften, and when the external force is removed, the shape at the time of the initial polymerization reaction is restored again.

The monofunctional monomer (b) used in the present invention is one or more monofunctional monomers whose homopolymer has a glass transition point Tg of 50 ° C. or higher.

When the Tg of the monofunctional monomer is less than 50 ° C., tack tends to remain on the surface of the cured product of the present invention, and the tensile strength of the cured product decreases. That is, the present inventor has found that at room temperature, the polymerization reaction product of the component (b) solidifies into a glass state and has a sufficient cohesive force, so that the cured product of the present invention exhibits toughness, transparency, and resistance to heat. They have found that they show balanced performance such as abrasion.

The polymer of the monofunctional monomer (b) is
When heated to a temperature in the vicinity of g or more, it is easily deformed. The monofunctional monomer having a homopolymer Tg of 50 ° C. or higher is generally a low-viscosity photocurable monomer and is used as a photopolymerization component.

As mentioned above, the monofunctional monomer (b) can be used as a solvent in the polyurethane reaction for producing the thermoplastic polyurethane elastomer (a). However, in the molecule of the monofunctional monomer,
When the compound contains hydrogen active in the reaction with a diisocyanate such as a hydroxyl group or an amino group, it cannot be used as such a reaction solvent.

Examples of the mono (meth) acrylate ester having a homopolymer having a Tg of 50 ° C. or higher include the following. Monoacrylates such as isobornyl acrylate (the homopolymer has a Tg of 94 ° C.) and dicyclopentenyl acrylate (the Tg is 120 ° C.). Isobornyl methacrylate (the Tg is 170 ° C.), dicyclopentenyl methacrylate (the Tg is> 12 ° C.)
0 ° C.), dicyclopentanyl methacrylate (the T
g is 95 ° C.), t-butyl methacrylate (the Tg
107 ° C.), cyclohexyl methacrylate (the Tg is 66 ° C.), benzyl methacrylate (the Tg
Is 54 ° C.), methyl methacrylate (the Tg is 10
5 ° C), ethyl methacrylate (the Tg is 65 ° C)
Etc. monomethacrylate. N- (meth) acryloylmorpholine (the Tg is> 60 ° C.), N-vinylpyrrolidone (the Tg is> 60 ° C.), N, N′-dimethyl (meth) acrylamide (the Tg is> 60 ° C.). One or more of these monofunctional monomers can be used.

These monofunctional monomers have a role of dissolving the other components (a) and (c), lowering the viscosity of the composition, and facilitating the handling of the composition. It is necessary to select one with good compatibility.

In these monofunctional monomers, the photopolymerizable group is monofunctional, and when photopolymerized, a linear polymer chain portion is generated to give the cured product a thermoplastic property. or,
Since the homopolymer has a Tg of 50 ° C. or higher, it retains a given shape at room temperature and is easily deformed by an external force at a high temperature of 50 ° C. or higher because it is in a rubbery state.
Further, since Tg is at a high temperature exceeding normal temperature, there is an effect of eliminating stickiness near normal temperature and maintaining a high surface hardness.

The component (c) is a urethane (meth) acrylate oligomer that is compatible with the component (a) after curing. Therefore, an oligomer in which the active hydroxyl group of the same polyol as the component (a) is converted to urethane (meth) acrylate,
It is preferable that the polyurethane has an active hydroxyl group at an end and is an oligomer obtained by urethane (meth) acrylate, and is generally a polyfunctional oligomer having two or more (meth) acryl groups in one molecule. It is.

The polyurethane used here does not need to have the same molecular weight as the component (a). Rather, the molecular weight of the polyol is preferably 500 or more and 3000 or less, and it is necessary to maintain compatibility.

A known method is used for synthesizing the polyurethane (meth) acrylate. That is, a diisocyanate in an equimolar amount to the hydroxyl value of the liquid polyol is added, and if necessary, a urethanation catalyst is added, and 20 to 40
C. to react the diisocyanate with the active hydrogen. Thereafter, an equimolar amount of hydroxylated (meth) acrylate is added and reacted at 40 to 100 ° C. until the isocyanate group disappears.

As the diisocyanate used here,
Tolylene diisocyanate, 4,4'-genyl methane diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, isophorone diisocyanate, lysine diisocyanate, one selected from the group consisting of hydrogenated xylylene diisocyanate or More than one organic diisocyanate can be used.

As the hydroxyalkylated (meth) acrylate, 2-hydroxyethylated (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
One or more (meth) acrylates selected from the group consisting of 1,4-butanediol mono (meth) acrylate, glycerol mono (meth) acrylate, and caprolactone-modified (meth) acrylate can be used.

Further, the component (c) does not need to have a similar chemical structure to the thermoplastic polyurethane elastomer of (a), and as a result, may be compatible with the thermoplastic polyurethane elastomer of (a).

In general, the chemical structural formulas of the commercially available urethane (meth) acrylate oligomers are few in many cases. Therefore, by repeating trial and error, the compatibility with the thermoplastic polyurethane elastomer (a) can be improved. You need to find out.

Of these three components, the two components (a) and (b) are transparently mixed as a composition.
When the composition consisting of only (a) and (b) is polymerized and cured, the cured product becomes cloudy and does not become compatible. here,
When a mixture of the three components (a), (b) and (c) is polymerized and cured, a transparent and flexible cured product is obtained.
It can be seen that the urethane (meth) acrylate oligomer of the component (c) acts as a compatibilizer between the components (a) and (b). In the copolymer of the composition containing the cured products of (a), (b) and (c), the (a) thermoplastic polyurethane elastomer component precipitated near the component (c) having a large molecular weight. It is considered that a micro phase separation structure is formed.

As described above, the polymer of the component (b) agglomerated into a glass, the urethane (meth) acrylate polymer of the component (c) copolymerized and bonded to the polymer, and the self-cohesive force The toughness is exhibited by the combination of the strong thermoplastic polyurethane (a) with the micro aggregates.

The main components of the composition of the present invention (a),
The mixing ratio of (b) and (c) is preferably as follows.

[0042]

(A) 5 to 60 parts by weight of a thermoplastic polyurethane (b) 5 to 50 parts by weight of a monomer having a homopolymer Tg of 50 ° C. or more (c) Urethane (meth) acrylate oligomer compatible with (a) 5-60 parts by weight ─────────────────────────────────── Total 100 parts by weight

The components (a), (b) and (c) are combined to make up to 100 parts by weight. Of these, component (a) and component (c)
The mixing ratio with the components is preferably close to the same amount.
Even when the amount of (c) increases, a cured product having excellent transparency can be obtained, but the crosslink density increases and the material becomes hard, so that the proportion of the component (c) exceeds 60 parts by weight. Is not preferred. When the proportion of the component (c) is less than 5 parts by weight, it is difficult to be compatible with the component (a).

When the proportion of the component (a) exceeds 60 parts by weight, high strength cannot be obtained even if the elongation of the cured product becomes large. From this viewpoint, it is more preferable that the amount be 40 parts by weight or less. When the amount of the component (a) is less than 5 parts by weight,
Shape memory is no longer exhibited in the cured product. If the proportion of the monofunctional monomer component (b) is less than 5% by weight, a cured product having sufficient strength cannot be obtained, and if it exceeds 50% by weight, the cured product becomes hard and brittle.

In the present invention, the monofunctional monomer component (b) is preferably blended in an amount of 0.5 to 2 parts by weight per 1 part by weight of the component (a). If the amount of the monofunctional monomer component (b) exceeds 2 parts by weight with respect to 1 part by weight of the component (a), the cured product becomes hard and brittle, and if less than 0.5 part by weight. In this case, the viscosity of the composition becomes high, it is difficult to handle, and the workability deteriorates. That is, the amount of the component (b) is set as long as there is no workability problem.
It is desirable to use the minimum amount.

A thermosetting component can be added to the resin composition of the present invention. For example, 2-hydroxyalkyl (meth) acrylate and the diisocyanates described in (3) above; 2-hydroxyalkyl (meth) acrylate and melamines such as tributoxymelamine and trimethoxymelamine; (meth) acrylic acid and diglycidyl Bisphenol A; glycidyl (meth) acrylate and diaminobenzene; diamines such as 3,3'-dichloro-4,4'-diaminodiphenylmethane; (meth) acryloylethyl isocyanate and 2-hydroxyalkyl (meth) acrylate; Isocyanate / 2-hydroxyethyl (meth) acrylate adduct and 2-hydroxyalkyl (meth) acrylate; isophorone diisocyanate / 2-hydroxyethyl (meth) acrylate adduct and 2-hydroxyalkyl Meth) acrylate; have each combination of such.

When the total amount of the components (a), (b) and (c) is 100 parts by weight, 0 to 10 parts by weight of these thermosetting components can be added. If it exceeds 10 parts by weight, it becomes hard and shape memory properties are not exhibited. These thermosetting components may be omitted, but by adding the thermosetting components, the strength of the cured product and the stickiness of the surface can be improved. The addition amount of the thermosetting component is
More preferably, the content is 3 to 5 parts by weight.

Examples of the photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-
Phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1
Acetophenones such as -one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2- Benzoin-based compounds such as dimethoxy-2-phenylacetophenone;
Benzophenone, hydroxybenzophenone, 3,3 '
Benzophenones such as -dimethyl-4-methoxybenzophenone; thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and isopropylthioxanthone;
There are photopolymerization initiators such as 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, and benzyl.

One or more photopolymerization initiators can be used. The amount of the photopolymerization initiator is from 0 to 1
0 parts by weight. A photopolymerization sensitizer may be used in combination with these photopolymerization initiators in order to adjust curability. Representative examples of known photosensitizers include triethanolamine, methyldiethanolamine, triisopropanolamine, 4,4′-diethylaminobenzophenone, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid. -N-butoxyethyl, isoamyl 4-dimethylaminobenzoate and the like.

The composition of the present invention has the inherent properties of the composition,
In particular, as long as the photocuring properties are not impaired, as desired.
A surfactant, a leveling agent, an antifoaming agent, a diluent for adjusting viscosity, a coupling agent, a fragrance, a flame retardant, and other additives can be contained in an amount of 0 to 10 parts by weight. Further, a coloring agent such as a pigment, a dye, or a metal fine powder may be contained in an amount of 0 to 60 parts by weight.

As a method of irradiating the composition of the present invention with light to cure it, an ultraviolet ray generator equipped with a low-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, an arc lamp or the like is used.
It can be carried out in the atmosphere or in an inert gas such as nitrogen. Also, an electron beam generator or a cobalt beam generator can be used. In this case, the composition of the present invention can be polymerized and cured without using a photopolymerization initiator.

The composition of the present invention is cured by actinic radiation and has a transparency, toughness, scratch resistance, water resistance, low curing shrinkage, low temperature press moldability and cured shape memory. give. For this reason, a surface protective sheet or a surface protective film for the purpose of preventing scratches, a film or a sheet having excellent optical properties, a film or a sheet having high flexibility, a film or a sheet which can be formed at a low temperature, a film having a shape memory property, Sheets can be made by curing the composition of the present invention. Further, it can be suitably used as a paint for providing a coating film having each of these characteristics, an adhesive for providing an adhesive layer, and a casting material for producing a cast product.

In order to produce a sheet or a film using the composition of the present invention, for example, the composition can be cast on a mirror-finished drum or an endless belt made of metal and cured as described above.

In order to produce a casting using the composition of the present invention, the composition of the present invention is filled into a mold of an arbitrary shape made of a material transparent to light, and then the surroundings of the mold are filled. A method of irradiating light from above to cure the internal composition can be used. Further, the composition of the present invention can also be used as a stereolithography material for curing with laser light controlled by a computer.

In order to form a cured film on a substrate using the composition of the present invention, the composition of the present invention can be applied to the substrate by using any coating method. In this application step, any method such as a spray method, a dipping method, a flow coating method, a roll coating method, a bar coating method, a curtain flow coating method, a spin coating method, and a screen printing method can be used. Immediately after the composition is applied to the substrate or after setting for several minutes after application, light is applied to the coating layer to form a cured film.

[0056]

Example ( Reference Example 1) "Placcel CD-210PL" (Daicel Chemical Co., Ltd.)
Polycarbonate diol, molecular weight 2000, 27 g of component (1)), 18 g of isophorone diisocyanate (component (3)), 5 g of 1,4-butanediol (component (2)) and 0.0 g of dibutyltin dilaurate.
2 g was mixed in a flask having a capacity of 300 cc and stirred while heating the contents of the flask to 50 ° C. with a mantle heater. Heat generation occurred gradually, and the transparency of the liquid mixture increased. The temperature was raised to 80 ° C. in about 30 minutes.

Next, 50 g of isobornyl acrylate (component (b)) and Shikko 7000B (Nippon Synthetic Chemical Co., Ltd.)
Made, polyester urethane acrylate) 100g
Was blended in the above blended solution, mixed uniformly, and reacted for 24 hours while heating to 50 ° C. As a result of infrared spectrum measurement of this reaction solution, -NC observed at 2250 cm ^-1 was observed.
It was confirmed that the absorption of O (isocyanate group) had disappeared. At this stage, the component (a) was generated.

Next, Irgacure 184 (manufactured by Ciba Geigy) as a photoinitiator was added to the reaction solution, and the mixture was stirred and uniformly mixed. This mixed solution was degassed using a vacuum dryer, and subjected to a silicon release treatment to a thickness of 50 μm.
Is cast between two PET (polyethylene terephthalate) films, and the thickness of the liquid is 20 using an applicator.
It was adjusted to 0 μm and immediately irradiated with 1000 mJ / cm ² using a high pressure mercury lamp to obtain a cured film.

Using this cured film, the following items were tested. Tensile properties: The cured product was measured for tensile strength and elongation according to JIS-K-6301. Toughness: The value of (tensile strength of cured product x elongation) / 1000 was calculated and used as an index of toughness. Transparency: The transparency of the cured product was visually confirmed.

Press formability: A film is sandwiched between upper and lower molds of male and female with a height of 5 mm and having irregularities, a pressure of 10 kg / cm ² is applied by a hydraulic press machine, and press molding is performed in an atmosphere of 25 ° C. for 10 minutes. Was performed. Then, the degree of deformation and cracking along the shape of the mold were examined. Shape memory: A rectangular sample having a width of 1 cm and a length of 10 cm was bent at approximately 5 cm by 180 ° to form a creased sample. This sample was immersed in warm water at 70 ° C. for 10 seconds, and the degree of restoration of the fold was observed.

[0061] (Comparative Example 1) except that the isobornyl acrylate Reference Example 1 was changed to phenoxyethyl acrylate was performed in the same manner as in Reference Example 1.

Comparative Example 2 100 g of Shikko 7000B (a polyester urethane acrylate manufactured by Nippon Synthetic Chemical Co., Ltd.), 50 g of isobornyl acrylate, and "Irgacure 184"
1.5 g was placed in a beaker having a capacity of 300 cc,
The solution in the beaker was stirred and mixed under an atmosphere. Next, the mixed solution was degassed using a vacuum dryer. Subsequent operations were performed in the same manner as in Reference Example 1. Hereinafter, the composition tables and measurement results of the present reference example and comparative example are shown.

[0063]

[Table 2]

[0064]

[Table 3]

As can be seen from these results, the present invention
In Reference Example 1, the toughness of the cured product was significantly improved,
Transparency is maintained, press molding is easy, and
It had the function of storing the shape. On the other hand, in Comparative Example 1, the cured product has low tensile elongation, low press moldability, and no shape memory effect. Further, in Comparative Example 2, the elongation of the cured product was extremely low.

Example 1 "Placcel CD-210PL" (manufactured by Daicel Chemical Co., Ltd., polycarbonate diol, hydroxyl value 112 KOHmg /
g) 78.6 g, isophorone diisocyanate 52.2
g, 14.4 g of 1,4-butanediol and 145.2 g of t-butyl methacrylate were placed in a 1-liter flask and stirred for 30 minutes to form a uniform liquid state. Next, 0.145 g of dibutyltin dilaurate (a urethanization catalyst) was added, and stirring was continued. Ten minutes later, the temperature of the solution was raised to 80 ° C. due to the heat of the reaction. When the stirring was continued for 1 hour, a white sticky liquid state was obtained.

Next, separately, "Fluxel CD-210
PL "(polycarbonate diol), 1 mol of isophorone diisocyanate, and 2 mol of 2-hydroxyethyl acrylate were reacted in t-butyl methacrylate at a concentration of 65% by weight, and 257.4 g of a polycarbonate urethane acrylate was added. Mixed.
As a result, the white color disappeared, and a colorless and transparent viscous liquid was obtained.

This solution was further kept at 80 ° C., and occasionally sampled to measure an infrared absorption spectrum.
After confirming that the absorption of the isocyanate group at 2250 cm ^-1 disappeared, the urethanization reaction was completed. It took 36 hours.

To this reaction solution, 32.4 g of 2-hydroxyethyl methacrylate, 10.2 g of an equimolar adduct of 2-hydroxyethyl methacrylate and isophorone diisocyanate, 4.8 g of a fluorine-based release agent, and Irgacure 184 (Ciba-Geigy, 1-hydroxy-
Cyclohexyl-phenyl-ketone) (4.8 g) was added, and the mixture was stirred at 50 ° C. for 3 hours to form a uniform solution.

This liquid was cast on a glass plate having a thickness of 3 mm, a PET film having a thickness of 50 μm was coated on the liquid, and the thickness of the liquid layer was adjusted to 250 μm with an applicator. Next, using a high-pressure mercury lamp, this was irradiated with ultraviolet rays of 1000 mJ / cm ² to obtain a cured film.

The tensile strength of this cured film is 405 kg
/ Cm ^2, elongation at break was 310%, 50% elongation modulus ^{101kg / cm 2/25 ℃,} 29kg / c
m ^2/50 ℃, was 9kg / cm ^2/80 ℃. Therefore, the “toughness” is 125.55. This cured film was excellent in transparency. When the cured film was measured for shape memory in the same manner as above,
It had excellent shape memory.

[0072]

As described above, in addition to good transparency, it is possible to form a cured product having a higher degree of toughness and furthermore a shape memory property. An energy ray-curable resin composition can be provided.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 290/00-290/14 C08F 299/00-299/08 C08F 2/00-2/60 C08L 1/00-101 / 16 C08G 18/00-18/87

Claims (6)

(57) [Claims] (1) a thermoplastic polyurethane elastomer, (b) t-butyl methacrylate, benzyl methacrylate
From N- (meth) acryloylmorpholine
Active energy ray curing, characterized by containing one or more monofunctional monomers selected from the group consisting of: and (c) a urethane (meth) acrylate oligomer which is compatible with the thermoplastic polyurethane elastomer (a) after curing. Mold resin composition. 2. The active energy ray-curable resin composition according to claim 1, which is a solventless type. 3. The thermoplastic polyurethane elastomer, the monofunctional monomer and the urethane (meth)
0 to 20 parts of a photopolymerization initiator, 0 to 20 parts of a photosensitizer, based on 100 parts by weight of the mixture comprising the acrylate oligomer
The active energy ray-curable resin composition according to claim 1 or 2, further comprising 0 to 10 parts of a thermosetting component, 0 to 10 parts of an additive, and 0 to 60 parts of a coloring agent. 4. The method for producing an active energy ray-curable resin composition according to claim 1, wherein (1) a molecular weight of 50.
The thermoplastic polyurethane elastomer is produced by addition-polymerizing a polyol having a terminal active hydrogen of 0 to 4000, (2) a low-molecular glycol or low-molecular diamine having a molecular weight of 490 or less, and (3) an organic diisocyanate. A method for producing an active energy ray-curable resin composition, comprising dissolving a plastic polyurethane elastomer together with the urethane (meth) acrylate oligomer in the monofunctional monomer. 5. The method for producing the active energy ray-curable resin composition according to claim 1, wherein (1) a molecular weight of 50.
A polyol having a terminal active hydrogen of 0 or more and 4000 or less, (2) a low-molecular glycol or low-molecular diamine having a molecular weight of 490 or less, and (3) an organic diisocyanate.
The thermoplastic polyurethane elastomer is produced by addition polymerization in the monofunctional monomer, and the thermoplastic polyurethane elastomer is dissolved in the monofunctional monomer, and the urethane (meth) acrylate oligomer is converted into the monofunctional monomer. A method for producing an active energy ray-curable resin composition, characterized by being dissolved in a monomer. 6. (a) a thermoplastic polyurethane elastomer, (b) t-butyl methacrylate, benzyl methacrylate
From N- (meth) acryloylmorpholine
An active energy ray-curable resin composition containing one or more monofunctional monomers selected from the group consisting of: and (c) a urethane (meth) acrylate oligomer which is compatible with the thermoplastic polyurethane elastomer (a) after curing. Molded and cured product of active energy ray-curable resin produced by irradiating active energy rays.