JP2006188589A - Active energy ray-curable resin composition and cured film obtained from the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray-curable resin composition which can form a film excellent in transparency, flexibility and water vapor barrier properties and having extremely low heat shrinkage. <P>SOLUTION: The active energy ray-curable resin composition comprises a urethane acrylate oligomer (A) prepared by reacting a polycarbonate-diol having a hydroxyl value of 100-500 mg KOH/g and/or a polyalkyldiol having a hydroxyl value of 100-1,810 mg KOH/g (a1), an aliphatic diisocyanate (a2), and a hydroxy (meth)acrylate (a3) in a ratio of the hydroxyl group of the component (a1)/the isocyanate group of the component (a2) (equivalent ratio) of 0.6-0.9, and a monomer (B) having an aliphatic cyclic structure and/or an aromatic cyclic structure and one (meth)acryloyl group in a molecule, wherein the compositional ratio [(A)/(A+B)] is 0.3-0.6. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an active energy ray-curable resin composition that is cured by active energy rays such as ultraviolet rays and electron beams, and a cured film obtained from the composition. More specifically, the active energy ray-curable resin composition of the present invention is excellent in flexibility, transparency, and water vapor barrier properties, and can form a cured film having a very small heat shrinkage rate. Useful.

Conventionally, plastic films have been used in various applications from the viewpoints of article protection, design properties, and other functionalities. As a method for producing a plastic film, an extrusion method or a calender method in which a thermoplastic resin is heated and melted for molding is generally used. As another method, a solvent solution of the thermoplastic resin is cast to form a film. A casting method, a method of curing an active energy ray-curable resin to form a film, and the like are known.

In the case of the extrusion method or the calendering method, the dimensional accuracy in the thickness direction of the obtained film is usually about ± 5%, even if an expensive precision device is used, about ± 3%, and the target of within ± 1% is achieved. It is difficult. Moreover, since it manufactures, pulling in an extrusion direction, there also exists a fault that the birefringence of a film is large.

  According to the casting method, it is easy to obtain a film having a high dimensional accuracy and a small birefringence. However, there are drawbacks such as the problem of the recovered solvent at the time of manufacturing the film and the generation of voids (bubbles) in the manufactured film due to the residual solvent. Although it is possible to manufacture a film without voids by relaxing the manufacturing conditions and minimizing the influence of the residual solvent, there is a disadvantage that the productivity is inferior and the production cost is extremely high.

When using the active energy ray curing method, a solvent-free liquid active energy ray curable resin is applied to a smooth release film at a certain thickness, irradiated with an active energy ray, cured, and peeled off from the release film. A film is obtained. The film obtained by this production method has high dimensional accuracy and is excellent in birefringence, transparency and weather resistance. Further, this manufacturing method has advantages in terms of production such as energy saving and improvement of processing speed.

However, when a film obtained by the active energy ray curing method having the above-mentioned advantages is used as a protective film, generally, reliability under high temperature and high humidity is required. In such an environment, the protective film absorbs moisture and moisture easily migrates and penetrates into the object to be protected. In extreme cases, the protective film may swell and peel from the substrate.

By the way, there are cases where various protective films are adhered to a base material (object to be protected), but if the heat shrinkage rate of the film is large at the time of the heat adhesion, adhesion failure between the base material and the protective film occurs, yield and productivity. There is a drawback that the production cost is reduced or the production cost is extremely high. In addition, thermal degradation of the obtained product often occurs. Moreover, when the base material is not a smooth plate shape but is curved or has irregularities, a protective film with low flexibility cannot follow the base material shape and a crack may occur in the protective film.

As an active energy ray resin composition capable of providing a protective film with good water vapor barrier properties, a urethane oligomer obtained by reacting polycarbonate diol, organic diisocyanate and hydroxy (meth) acrylate, and a glass transition temperature of a homopolymer of 55 ° C. The composition which consists of the (meth) acrylate monomer which is the above is disclosed (refer patent document 1). Since the composition described in this document uses a polycarbonate oligomer component as a constituent component, the resulting cured film has good water vapor barrier properties and flexibility, and is used for active energy ray-curable optical fiber coating agents, etc. It is described as being suitable. However, although there is no teaching or suggestion regarding the heat shrinkage of the cured film in the document, according to the knowledge of the present applicant, although the cured film is excellent in water vapor barrier property and flexibility, Therefore, the protective film is not always satisfactory.

Japanese Patent Publication No. 6-76468

  The present invention has been made in view of the above-described background art, and the purpose thereof is active energy ray curable, which can form a film having excellent transparency, flexibility, water vapor barrier properties and extremely low heat shrinkage. The object is to provide a resin composition.

As a result of intensive studies to solve the above problems, the present inventor has found that an active energy ray-curable resin composition comprising a specific urethane acrylate oligomer and a specific monomer is excellent in flexibility, water vapor barrier properties, and heating. The inventor has obtained the knowledge that a transparent cured film can be provided which simultaneously satisfies the physical properties of extremely low shrinkage. The present invention has been completed based on such findings.

That is, the present invention relates to a polycarbonate diol having a hydroxyl value in the range of 100 to 500 mgKOH / g and / or a polyalkyldiol (a1) having a hydroxyl value in the range of 100 to 1,810 mgKOH / g, an aliphatic diisocyanate (a2 ) And hydroxy (meth) acrylate (a3), such that the hydroxyl group of component (a1) / isocyanate group (equivalent ratio) of component (a2) are in a ratio of 0.6 to 0.9. It contains an acrylate oligomer (A), a monomer (B) having an aliphatic cyclic structure and / or aromatic cyclic structure and one (meth) acryloyl group in the molecule, and their blending ratio (mass) [( A) / ((A) + (B))] relates to an active energy ray-curable resin composition in the range of 0.3 to 0.6.The present invention also relates to a cured film obtained by irradiating the active energy ray-curable resin composition with an active energy ray and curing it.

The active energy ray-curable resin composition of the present invention having the above configuration can provide a cured film excellent in toughness and flexibility due to the urethane acrylate oligomer (A) [hereinafter referred to as the component (A)]. . Further, the monomer (B) [hereinafter referred to as the component (B)] has excellent compatibility with the component (A), and the component (A) is uniformly dissolved in the resin composition, so that it has excellent transparency. A cured film is obtained. Furthermore, due to the components (A) and (B), a cured film having excellent water vapor barrier properties and a low heat shrinkage rate can be obtained. Based on these characteristics of the active energy ray-curable resin composition of the present invention, problems with conventional protective films that have been a concern when applied to various substrates (plastic molded products, metals, wood, etc.) A point, for example, adhesion failure with a base material, generation | occurrence | production of the crack of a protective film, etc. can be eliminated ugly.

The component (A) in the active energy ray-curable resin composition of the present invention is a polycarbonate diol having a hydroxyl value in the range of 100 to 500 mgKOH / g and / or a hydroxyl value in the range of 100 to 1,810 mgKOH / g. Residual isocyanate groups in a urethane prepolymer obtained by reacting a certain polyalkyldiol [hereinafter referred to collectively as component (a1)] and aliphatic diisocyanate (a2) [hereinafter referred to as component (a2)] at a specific ratio And hydroxy (meth) acrylate (a3) [hereinafter referred to as component (a3)].

Among the components (a1), the polycarbonate diol specified above is a compound having a hydrocarbon chain linked by a carbonate bond and having a hydroxyl group at the terminal, and the hydroxyl value thereof is in the range of 100 to 500 mgKOH / g. Specific examples include diols in which 1.4-butanediol, 1,6-hexanediol, 3-methylpentanediol, cyclohexanedimethanol and the like are linked by a carbonate bond. When a hydroxyl value of less than 100 mgKOH / g is used, excellent water vapor barrier properties as in the present invention are not exhibited. When a hydroxyl value exceeding 500 mgKOH / g is used, the viscosity of the reaction product becomes extremely high during the urethanization reaction, the reaction does not proceed easily and the synthesis tends to be difficult, and it is difficult to obtain. There are many cases.

Among the components (a1), the polyalkyldiol specified above is a compound that is a hydrocarbon chain other than the terminal hydroxyl group, and has a hydroxyl value in the range of 100 to 1,810 mgKOH / g. Specifically, ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 2-methylpentanediol, 3-methylpentanediol, 1,9-nonanediol, butylethyl Examples thereof include low molecular weight diols such as propanediol and 1,12-dodecanediol, and diols having an aliphatic cyclic structure such as cyclohexanedimethanol and hydrogenated bisphenol A. When a hydroxyl group having a hydroxyl value of less than 100 mgKOH / g is used, the urethane acrylate has an aliphatic cyclic structure and / or an aromatic cyclic structure and one (meth) acryloyl group in the molecule which is an essential component in the present invention. There exists a tendency for compatibility with the monomer which has this to worsen, and a uniform liquid transparent composition and transparent cured | curing material cannot be obtained. When a hydroxyl value exceeding 1,810 mgKOH / g is used, the viscosity of the reaction product becomes extremely high during the urethanization reaction, the reaction does not proceed easily, and the synthesis tends to be difficult. Often difficult.

The component (a2) is, for example, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, dicyclohexylmethane-2,4′-diisocyanate, ω, ω′-diisocyanate dimethyl. Aliphatic diisocyanates such as cyclohexane and lysine diisocyanate can be mentioned. When an aromatic diisocyanate is used, it is preferable to use an aliphatic diisocyanate because the weather resistance of the cured film tends to decrease.

The component (a3) is a compound having one hydroxyl group and one (meth) acryloyl group in the molecule. For example, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) An acrylate etc. are mentioned. When a compound having one hydroxyl group and two or more (meth) acryloyl groups in the molecule is used, since the flexibility of the resulting cured film tends to be lowered, it cannot be used as the component (a3). .

In order to produce the component (A), various conventionally known production methods can be employed. For example, the method (1) in which the components (a1), (a2) and (a3) are charged together and reacted simultaneously. A method of reacting the component (a1) and the component (a3) and then reacting the component (a2) (2), a method of reacting the component (a1) and the component (a2) and then reacting the component (a3) (3) and the like, and can be selected as appropriate, but the method (3) is preferable from the viewpoint of increasing the molecular weight of urethane acrylate and reducing the low molecular weight components. Hereinafter, the method (3) will be described in more detail. The component (a1) and the excess component (a2) are reacted in the presence of a known urethanization catalyst at about 60 to 90 ° C, preferably 70 to 85 ° C. In the reaction, an acrylic monomer that is inactive with respect to the component (a2) can be present as a diluent as necessary from the viewpoint of adjusting the viscosity during the reaction and preventing side reactions. The hydroxyl group of component (a1) / isocyanate group (equivalent ratio) of component (a2) is about 0.6 to 0.9, preferably 0.65 to 0.9. If the ratio is less than 0.6, the component (A) finally obtained contains a large amount of low molecular weight urethane (meth) acrylate, and the resulting cured film becomes brittle. Moreover, when the said ratio exceeds 0.9, the number of terminal isocyanate groups will reduce extremely and it will become difficult to obtain the target (A) component.

The component (a3) is then reacted with the urethane prepolymer obtained by reacting the component (a1) and the component (a2), and the reaction temperature is usually about 60 to 90 ° C, preferably 70 to 85 ° C. It is good. In the reaction, the proportion of the urethane prepolymer and the component (a3) used is determined in consideration of [residual isocyanate group of the urethane prepolymer / hydroxyl group of the component (a3)] (equivalent ratio). The range is 1.0 to 1.1, preferably 1.0 to 1.05. If the ratio is less than 1.0, unreacted isocyanate groups remain in the finally obtained component (A), and the resulting composition has poor stability such as thickening and gelation over time. Tend to be. Moreover, when the said ratio exceeds 1.1, an unreacted (a3) component will remain and the outstanding water vapor | steam barrier property in this invention is not expressed.

In addition, the use ratio with the component (a3) can also be shown as follows. That is, the hydroxyl group of component (a3) / isocyanate group (equivalent ratio) of component (a2) is in the range of 0.1 to 0.4, preferably 0.1 to 0.35. If the ratio is less than 0.1, unreacted isocyanate groups remain in the finally obtained component (A), and the resulting composition has poor stability such as thickening and gelation over time. Tend to be. Moreover, when the said ratio exceeds 0.4, an unreacted (a3) component will remain and the outstanding water vapor | steam barrier property in this invention is not expressed.

Furthermore, the mutual use ratio of the component (a1), the component (a2) and the component (a3) can be shown as follows. That is, [the hydroxyl group of component (a1) + the hydroxyl group of component (a3)] / isocyanate group (equivalent ratio) of component (a2) is in the range of 1.0 to 1.1, preferably 1.0 to 1.05. is there. If the ratio is less than 1.0, unreacted isocyanate groups remain in the finally obtained component (A), and the resulting composition has poor stability such as thickening and gelation over time. Tend to be. Moreover, when the said ratio exceeds 1.1, an unreacted (a3) component will remain and the outstanding water vapor | steam barrier property in this invention is not expressed.

The quantification of the residual isocyanate group can be measured, for example, according to JIS K1556, and the quantification of the number of hydroxyl equivalents can be measured, for example, according to JIS K1557.

The GPC measurement of the component (A) synthesized by the above method, the weight average molecular weight in terms of polystyrene is in the range of 10,000 to 50,000, preferably 10,000 to 30,000. When the weight average molecular weight is less than 10,000, the low heat shrinkage rate in the present invention is not exhibited. When the weight average molecular weight is 50,000 or more, the viscosity of the resulting resin composition becomes very high, and when the film is produced, coating unevenness and undulation occur, and the desired film having a high dimensional accuracy with a certain film thickness. It becomes difficult to obtain.

The component (B) is a compound having an aliphatic cyclic structure and / or an aromatic cyclic structure and having one (meth) acryloyl group in the molecule, and is other than the component (A). Specifically, one (meth) acryloyl group added to a monocyclic hydrocarbon such as cyclohexane or benzene, or one (meth) acryloyl group added to a polycyclic hydrocarbon condensed with two or more rings There are various types such as those obtained by adding a (meth) acryloyl group to a bridged cyclic hydrocarbon. More specifically, cyclohexyl (meth) acrylate, EO-modified phenol (meth) acrylate, EO-modified nonylphenol (meth) acrylate, EO-modified cumylphenol (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) Examples include acrylate and dicyclopentanyl (meth) acrylate. In addition, when a monomer having neither an aliphatic cyclic structure nor an aromatic cyclic structure chain is used in place of the component (B), the resulting cured film has excellent water vapor barrier properties as in the present invention. Or low heat shrinkage. In addition, when a compound having two or more (meth) acryloyl groups in the molecule is used instead of the component (B), the resulting cured film is brittle and inflexible. Such a low heat shrinkage rate is not exhibited.

[(A) / ((A) + (B))] is about 0.3 to 0.6, preferably 0.4 to 0, in the use ratio (mass) of the component (A) and the component (B). To be 5. If it is less than 0.3, the curability at the time of film creation is poor, a large amount of active energy rays must be irradiated, the productivity deteriorates, and the flexibility of the resulting film tends to be insufficient. is there. When the blending amount exceeds 0.6, the viscosity of the resulting resin composition becomes very high, making it difficult to produce a film with a constant film thickness and high dimensional accuracy, Water vapor barrier properties tend to be insufficient.

The viscosity of the resin composition of the present invention is usually 1,000 to 30,000 mPa · s / 25 ° C., preferably 2,000 to 20,000 mPa · s / 25 ° C. If the viscosity is too high, coating unevenness and undulation will occur when the film is produced, and it will be difficult to obtain a film with a desired constant film thickness and high dimensional accuracy. On the other hand, even if it is too low, it is difficult to control the film thickness, and it may be impossible to form a target film with a certain thickness and high dimensional accuracy.

The active energy ray-curable resin composition of the present invention is cured by irradiating active energy rays after being applied to a release film or a plastic substrate. Examples of active energy rays include electron beams, ultraviolet rays, and visible rays. In the case of curing with ultraviolet light or visible light, a photopolymerization initiator is blended in the composition, but the photopolymerization initiator is not particularly limited and various known ones can be used. Specifically, methyl benzoylbenzoate, benzoin, benzyldimethyl ketal, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-methyl-1- [4- (methylthio) phenyl] 2-morpholino-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2,4-diethylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide , Camphorquinone, anthracene, benzyl, phenylmethylglyoxylate and the like. These photopolymerization initiators can be used alone or in combination. The optimum amount of the photopolymerization initiator for curing the resin composition of the present invention with ultraviolet rays or visible rays is preferably about 0.01 to 10%, particularly preferably 0.5 to 5% in the entire composition. . The upper limit of the blending is preferably in this range from the viewpoints of the curing characteristics, mechanical characteristics, optical characteristics, handling, etc. of the composition, and the lower limit of the blending is preferably in this range from the viewpoint of preventing the curing rate from being lowered.

  In order to further improve the curing rate of the active energy ray-curable resin composition of the present invention, the photopolymerization initiator and the photosensitizer may be used in combination. Specific examples of the photosensitizer include triethanolamine, diethanolamine, methyldiethanolamine, triisopropanolamine, 4,4′-diethylaminobenzophenone, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and benzoic acid. -2-dimethylaminoethyl, diethylaminoethyl (meth) acrylate, tributylphosphine and the like can be mentioned, and these can be used alone or in combination. The optimum amount of the photosensitizer for curing the resin composition of the present invention with ultraviolet rays or visible rays is preferably about 0.01 to 10%, particularly preferably 0.5 to 5% in the entire composition. . The upper limit of the blending is preferably within this range from the viewpoints of the curing characteristics, mechanical characteristics, optical characteristics, handling, etc. of the composition, and the lower limit of the blending indicates the amount at which the addition effect is manifested.

Moreover, the active energy ray-curable resin composition of the present invention includes, in addition to the above-mentioned various components, a surface smoothing agent, a surfactant, an ultraviolet absorber, an inorganic filler, a silane coupling agent, colloidal silica, an adhesion improver, Additives such as antifoaming agents, wetting agents, rust inhibitors and storage stabilizers can be appropriately blended.

The active energy ray-curable resin composition of the present invention is applied to the surface of various base materials (plastic molded product films, sheets, etc.) and polymerized and cured. As the coating method, various known methods can be employed without any particular limitation. The coating amount of the curable resin composition is not particularly limited and can be appropriately determined according to the use, but is usually an amount that provides a cured film thickness of about 0.01 to 100 mm. When the film thickness is less than 0.01 mm, the cured film tends to be brittle and insufficient in flexibility. Moreover, when a film thickness exceeds 100 mm, there exists a tendency for a crack etc. to generate | occur | produce in a cured film.

In the case of curing with ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp is used as a light source, and the amount of light and the arrangement of the light source are adjusted as necessary. It is preferable to cure at a conveyance speed of 5 to 60 m / min for one lamp having a light quantity of 160 W / cm. On the other hand, when curing with an electron beam, it is preferable to use an electron beam accelerator having energy of 100 to 500 eV.

It is particularly preferred that the cured product obtained by curing the resin composition of the present invention with active energy rays has the following physical properties. One is that the heat shrinkage rate of a cured film having a thickness of 100 μm obtained by curing the resin composition when heated at 120 ° C. for 1 hour is 1.5% or less, preferably 1% or less. By using a resin composition that gives a film satisfying these physical properties, when various protective films are formed, excellent adhesion to a substrate, heat resistance, and the like are given. If the heat shrinkage rate exceeds 1.5%, adhesion failure with the substrate, cracking of the protective film, etc. may be caused.

Further, the moisture permeability of the cured film is 100 g / m ² · day or less, preferably 70 g / m ² · day or less. By using a resin composition that provides a film satisfying these physical properties, when various protective films are formed, excellent durability under high temperature and high humidity is provided. When the moisture permeability exceeds 100 g / m ² · day, the protective film absorbs moisture in the environment and moisture easily migrates and penetrates into the object to be protected. In extreme cases, the protective film swells and becomes a base material. May peel off.

Furthermore, the elongation of the cured film is in the range of 10 to 300%, preferably 50 to 200%. By using a resin composition that gives a film satisfying these physical properties, when various protective films are formed, excellent adhesion to a substrate, shape following property, and the like are given. If the elongation is less than 10%, poor adhesion to the substrate, cracking of the protective film, etc. may be caused.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Hereinafter, “parts” and “%” are based on mass unless otherwise specified.

(Synthesis of active energy ray-curable resin composition)
Example 1
In a reaction apparatus equipped with a thermometer, a stirrer, and a condenser tube, 76.30 parts of polycarbonate diol (manufactured by Daicel Chemical Industries, trade name “Placcel CD205PL”, hydroxyl value 224 mgKOH / g), dicyclopentanyl acrylate (Hitachi) 200 parts by Kasei Kogyo Co., Ltd., trade name “Fancryl FA-513A”), 0.2 part hydroquinone monomethyl ether (trade name “MQ” by Kawaguchi Chemical Industries, Ltd.) as a polymerization inhibitor, isophorone diisocyanate (Degussa, trade name “VESTANAT IPDI”) was charged with 67.85 parts, heated to 80 ° C. with stirring, and incubated for 1 hour, then octylate (API Corporation, trade name “STANOCTO”). 0.08 part was added, and it heat-retained at 80 degreeC continuously for 1 hour. Subsequently, the internal temperature was reduced to 70 ° C. or less, 38.15 parts of polycarbonate diol was added, the temperature was raised to 80 ° C. with stirring, and the mixture was kept for 1 hour, and then hydroxyethyl acrylate (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.) "HEA") 17.70 parts was added. The mixture was allowed to react at 80 ° C. for 0.5 hours with stirring, 0.08 part of tin octylate was added, and the mixture was further reacted at 80 ° C. for 1.5 hours and sampled. The sample was measured by the infrared absorption spectrum method, and it was confirmed that the absorption of the isocyanate group having a wavelength of 2250 cm ⁻¹ disappeared. To 400 parts of the obtained urethane acrylate oligomer / monomer composition, 0.2 part of hydroquinone monomethyl ether and 100 parts of EO-modified paracumylphenol acrylate (trade name “Aronix M-110” manufactured by Toagosei Co., Ltd.) are added and mixed. Then, an active energy ray-curable resin composition was obtained. The weight average molecular weight of the urethane oligomer component in the composition is GPC (apparatus: manufactured by Tosoh Corp., trade name “HLC-8020”, column: manufactured by Tosoh Corp., trade names “G5000HXL”, “G4000HXL”. ”,“ G3000HXL ”,“ G2000HXL ”) and the measured value was 11,800. The viscosity (25 ° C.) of the composition was measured using an E-type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd.), and the measured value was 7,050 mPa · s.

Example 2
In Example 1, instead of the dicyclopentanyl acrylate, 200 parts of isobornyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name “IBXA”) was used, and the reaction was performed in the same manner. An energy ray curable resin composition was obtained.

Example 3
In the same reactor as used in Example 1, 95.40 parts of the polycarbonate diol, 200 parts of the dicyclopentanyl acrylate, 50 parts of the EO-modified paracumylphenol acrylate, the hydroquinone monomethyl ether as a polymerization inhibitor 0.2 part and 84.80 parts of the isophorone diisocyanate were added, the temperature was raised to 80 ° C. with stirring, and the temperature was kept for 1 hour, and then 0.1 part of the tin octylate was added, and then kept at 80 ° C. for 1 hour. did. Subsequently, the internal temperature was reduced to 70 ° C. or less, 47.70 parts of polycarbonate diol was added, the temperature was raised to 80 ° C. with stirring, and the temperature was kept for 1 hour, and then 22.10 parts of the hydroxyethyl acrylate was added. The mixture was allowed to react at 80 ° C. for 0.5 hours with stirring, 0.1 part of tin octylate was added, and the mixture was further reacted at 80 ° C. for 1.5 hours and sampled. The sample was measured by the infrared absorption spectrum method, and it was confirmed that the absorption of the isocyanate group having a wavelength of 2250 cm ⁻¹ disappeared. To 500 parts of the obtained urethane acrylate oligomer / monomer composition, 0.2 part of hydroquinone monomethyl ether was added and mixed to obtain an active energy ray-curable resin composition.

Example 4
In the same reaction apparatus as used in Example 1, 60.57 parts of 1,12-dodecanediol (manufactured by Ube Industries, trade name “1,12-dodecanediol”, hydroxyl value 555 mgKOH / g), 250 parts of cyclopentanyl acrylate, 0.2 part of the hydroquinone monomethyl ether as a polymerization inhibitor, and 125.89 parts of trimethylhexamethylene diisocyanate (manufactured by Degussa, trade name “VESTANATM TMDI”) are charged to 80 ° C. with stirring. After raising the temperature and keeping the temperature for 1 hour, 0.1 part of the tin octylate was added, and the temperature was kept at 80 ° C. for 1 hour. Subsequently, the internal temperature was reduced to 70 ° C. or less, 40.38 parts of 1,12-dodecanediol was added, the temperature was raised to 80 ° C. with stirring, and the mixture was kept for 1 hour, and then 23.15 parts of the hydroxyethyl acrylate was added. . The mixture was allowed to react at 80 ° C. for 0.5 hours with stirring, 0.1 part of tin octylate was added, and the mixture was further reacted at 80 ° C. for 1.5 hours and sampled. The sample was measured by the infrared absorption spectrum method, and it was confirmed that the absorption of the isocyanate group having a wavelength of 2250 cm ⁻¹ disappeared. To 500 parts of the obtained urethane acrylate oligomer / monomer composition, 0.2 part of hydroquinone monomethyl ether was added and mixed to obtain an active energy ray-curable resin composition.

Example 5
20 parts of the EO-modified paracumylphenol acrylate was added to and mixed with 80 parts of the active energy ray-curable resin composition obtained in Example 4 to obtain an active energy ray-curable resin composition.

Comparative Example 1
In the same reactor as used in Example 1, polyester diol (manufactured by Asahi Denka Kogyo Co., Ltd., trade name “Adeka New Ace YG-108”, hydroxyl value 125 mg KOH / g) 117.76 parts, the isoboronyl acrylate 250 parts, 0.2 part of the hydroquinone monomethyl ether as a polymerization inhibitor, and 58.18 parts of the isophorone diisocyanate were charged, the temperature was raised to 80 ° C. with stirring, the temperature was kept for 1 hour, and then the tin octylate 0.1 Then, the mixture was kept at 80 ° C. for 1 hour. Subsequently, the internal temperature was reduced to 70 ° C. or less, 58.88 parts of the polyester diol was added, the temperature was raised to 80 ° C. with stirring, and the mixture was kept for 1 hour, and then 15.18 parts of the hydroxyethyl acrylate was added. The reaction was allowed to proceed for 1.5 hours at 80 ° C. with stirring, and sampling was performed. The sample was measured by the infrared absorption spectrum method, and it was confirmed that the absorption of the isocyanate group having a wavelength of 2250 cm ⁻¹ disappeared. To 500 parts of the obtained urethane acrylate oligomer / monomer composition, 0.37 part of hydroquinone monomethyl ether was added and mixed to obtain an active energy ray-curable resin composition.

Comparative Example 2
In the same reactor as used in Example 1, 106.20 parts of the polycarbonate diol, 250 parts of the isobornyl acrylate, 0.2 part of the hydroquinone monomethyl ether as a polymerization inhibitor, and 94.47 parts of the isophorone diisocyanate. The mixture was heated to 80 ° C. with stirring, and kept for 1 hour, and then 0.1 part of the tin octylate was added, and then kept at 80 ° C. for 1 hour. Subsequently, the internal temperature was set to 70 ° C. or lower, and 49.29 parts of the hydroxyethyl acrylate was added. The reaction was continued at 80 ° C. for 0.5 hours with stirring, 0.1 part of tin octylate was added, and the reaction was further carried out at 80 ° C. for 1.5 hours, and sampling was performed. The sample was measured by the infrared absorption spectrum method, and it was confirmed that the absorption of the isocyanate group having a wavelength of 2250 cm ⁻¹ disappeared. To 500 parts of the obtained urethane acrylate oligomer / monomer composition, 0.2 part of hydroquinone monomethyl ether was added and mixed to obtain an active energy ray-curable resin composition.

Comparative Example 3
In the same reaction apparatus as used in Example 1, polycarbonate diol (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Nipporan 980R”, hydroxyl value 56 mg KOH / g) 186.8 parts, 250 parts of the above isobornyl acrylate, polymerization 0.2 parts of the hydroquinone monomethyl ether as an inhibitor and 41.5 parts of the isophorone diisocyanate were charged, heated to 80 ° C. with stirring, and kept for 1 hour, and then added with 0.1 parts of the tin octylate, Subsequently, the mixture was kept at 80 ° C. for 1 hour. Subsequently, the internal temperature was set to 70 ° C. or lower, and 21.67 parts of the hydroxyethyl acrylate was added. The reaction was allowed to proceed for 1.5 hours at 80 ° C. with stirring and sampled. The sample was measured by the infrared absorption spectrum method, and it was confirmed that the absorption of the isocyanate group having a wavelength of 2250 cm ⁻¹ disappeared. To 500 parts of the obtained urethane acrylate oligomer / monomer composition, 0.2 part of hydroquinone monomethyl ether was added and mixed to obtain an active energy ray-curable resin composition.

Comparative Example 4
In the same reaction apparatus as used in Example 1, polycarbonate diol (Placcel CD205PL manufactured by Daicel Chemical Industries, Ltd.) 133.53 parts, 150 parts of isobornyl acrylate, and hydroquinone monomethyl ether 0.2 as a polymerization inhibitor And 118.73 parts of the isophorone diisocyanate were added, the temperature was raised to 80 ° C. with stirring, and the temperature was kept for 1 hour. Then, 0.14 part of the tin octylate was added, and the temperature was kept at 80 ° C. for 1 hour. Subsequently, the internal temperature was reduced to 70 ° C. or less, 66.76 parts of polycarbonate diol was added, the temperature was raised to 80 ° C. with stirring, and the temperature was kept for 1 hour, and then 30.98 parts of hydroxyethyl acrylate was added. The mixture was allowed to react with stirring at 80 ° C. for 0.5 hours, 0.1 part of tin octylate was added, and the mixture was further reacted at 80 ° C. for 1.5 hours and sampled. The sample was measured by the infrared absorption spectrum method, and it was confirmed that the absorption of the isocyanate group having a wavelength of 2250 cm ⁻¹ disappeared. To 500 parts of the obtained urethane acrylate oligomer / monomer composition, 0.2 part of hydroquinone monomethyl ether was added and mixed to obtain an active energy ray-curable resin composition.

Comparative Example 5
The active energy ray-curable resin composition was obtained by adding and mixing 64.3 parts of the isobornyl acrylate to 35.7 parts of the active energy ray-curable resin composition obtained in Comparative Example 4.

Tables 1 and 2 show the composition of each component, the weight average molecular weight of the urethane oligomer component, and the viscosity of the composition of the active energy ray-curable resin composition obtained in each of the above examples.

In Table 1 and Table 2,
(A) Component-1: Urethane acrylate oligomer obtained in Examples 1 and 2 (A) Component-2: Urethane acrylate oligomer and other oligomers obtained in Example 3-1: Urethane acrylate oligomer and other oligomers obtained in Comparative Example 1 -2: Urethane acrylate oligomer and other oligomers obtained in Comparative Example 2-3: Urethane acrylate oligomer (B) component obtained in Comparative Example 3-1: Dicyclopentanyl acrylate (manufactured by Hitachi Chemical Co., Ltd., trade name " Funkrill FA-513A ")
(B) Component-2: Isobornyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name “IBXA”)
(B) Component-3: EO-modified paracumylphenol acrylate (trade name “Aronix M-110” manufactured by Toagosei Co., Ltd.)
Other monomer-1: dicyclopentadiene diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name “light acrylate DCP-A”)
Respectively.

(Method for creating cured sheet)
The various active energy ray-curable resin compositions obtained above are applied to a release film (base material) made of a smooth PET film, and then, from above the application surface, an electron current of 150 keV and an irradiation dose of 30 kGly. Then, a transparent cured sheet was formed on the release film by irradiating with an electron beam. The thickness of the cured sheet obtained by peeling from the release film was 100 μm.

(Performance evaluation of active energy ray-curable resin composition and cured sheet)
About various physical properties, it measured based on the following method and evaluated from the said measurement result.
(1) Moisture permeability of cured sheet: compliant with JIS Z0208 (cup method, 40 ° C. × 90% RH)
(2) Elongation of cured sheet: Conforms to JIS K7127 (Tensile speed: 200 mm / min)
(3) Heat shrinkage rate of the cured sheet: A 150 mm mark was inserted, and the length between the marks was measured. Then, it was left to stand in 120 degreeC oven for 1 hour, and the length between marked lines was measured again. The rate of change before and after heating was calculated.
The measured values obtained above are shown in Tables 3 and 4.

※加熱収縮が大きすぎて硬化シートが極度にカールし測定不可能

* Measurement is impossible due to excessive curling of the cured sheet due to excessive heat shrinkage

Claims (9)

Polycarbonate diol having a hydroxyl value in the range of 100 to 500 mg KOH / g and / or polyalkyl diol (a1) having a hydroxyl value in the range of 100 to 1,810 mg KOH / g, aliphatic diisocyanate (a2), and hydroxy ( Urethane acrylate oligomer (A) obtained by reacting (meth) acrylate (a3) such that hydroxyl group of component (a1) / isocyanate group (equivalent ratio) of component (a2) is in a ratio of 0.6 to 0.9. And a monomer (B) having an aliphatic cyclic structure and / or an aromatic cyclic structure and one (meth) acryloyl group in the molecule, and their blending ratio (mass) [(A) / (( A) + (B))] is in the range of 0.3 to 0.6. The active energy ray-curable resin composition according to claim 1, wherein the hydroxyl group of the component (a3) / the isocyanate group (equivalent ratio) of the component (a2) is 0.1 to 0.4. The hydroxyl group of the component (a1) + the hydroxyl group of the component (a3) / the isocyanate group (equivalent ratio) of the component (a2) is 1.0 to 1.1. Resin composition. The active energy ray-curable resin composition according to claim 1, wherein the component (A) has a weight average molecular weight (GPC measurement, polystyrene conversion) in the range of 10,000 to 50,000. The active energy ray-curable resin composition according to claim 1, wherein the viscosity at 25 ° C. is in the range of 1,000 to 30,000 mPa · s. A cured film obtained by irradiating the active energy ray-curable resin composition according to any one of claims 1 to 5 with an active energy ray and curing it. The cured film according to claim 6, wherein the heat shrinkage ratio (thickness: 100 μm) when heated at 120 ° C. for 1 hour is 1.5% or less. The cured film according to claim 6 or 7, wherein the moisture permeability (thickness: 100 µm) is 100 g / m ² · day or less. The cured film according to any one of claims 6 to 8, wherein the elongation (thickness: 100 µm) is in the range of 10 to 300%.