KR20140099235A - Active energy ray-curable composition for interlayer filler - Google Patents

Abstract

The present invention provides an active energy ray curable composition which is excellent in wettability with plastics and glass and is suitable for interlayer filling without change in appearance such as discoloration and deformation under high temperature and high humidity. The active energy ray-curable composition comprises a urethane (meth) acrylate (A), a monofunctional (meth) acrylate (B), and a urea (meth) acrylate prepared by subjecting a diol (X) having a specific hydrogenated polyolefin skeleton to a urethane- And a polymerization initiator (C).

Description

TECHNICAL FIELD [0001] The present invention relates to an active energy ray curable composition for interlayer filling,

The present invention relates to an active energy ray curable composition which can be used as an intercalating agent for a transparent base material for displays such as a personal computer, a television, a mobile phone and the like, and a laminate having a cured layer of the active energy ray curable composition.

BACKGROUND ART [0002] A display used in a personal computer, car navigation system, television, cellular phone, or the like illuminates an image with light from a backlight. Various transparent substrates such as a glass substrate such as a glass plate and a plastic substrate such as a plastic film including a color filter are used for the display, and the amount of light output from the light source to the outside of the display due to the light scattering and absorption of these transparent substrates is reduced do. When the decrease width is large, the screen is darkened and the visibility is lowered. In order to enhance the visibility, the anti-reflection property of the display surface layer is enhanced or the light amount from the light source is strengthened.

As an example of such a method, there is a method of changing an air layer between a transparent substrate such as a glass substrate and a plastic substrate to a resin layer. It is possible to prevent the light scattering at the interface between the air and the glass base material or the plastic base material by changing the air layer to the resin layer.

As the performance required for a resin used in a layer of a transparent substrate such as a glass substrate or a plastic substrate, it is required that not only adhesiveness to a transparent substrate, but also high deformation resistance and high flexibility, high transparency, particularly transmittance at 400 nm is 95% Is required. Further, it is necessary that there is no change in resistance at high temperature, specifically, a change in shape at 95 DEG C, or no change in color. A urethane (meth) acrylate using a hydrogenated butadiene polyol and a composition containing the urethane (meth) acrylate have been proposed in the following prior art documents.

Japanese Patent No. 1041553 Japanese Patent No. 2582575 Japanese Patent Application Laid-Open No. 2002-069138 Japanese Patent Application Laid-Open No. 2002-309185 Japanese Patent Application Laid-Open No. 2003-155455 Japanese Patent Application Laid-Open No. 2010-144000 Japanese Patent Application Laid-Open No. 2010-254890 Japanese Patent Application Laid-Open No. 2010-254891 Japanese Patent Application Laid-Open No. 2010-265402 Japanese Patent Application Laid-Open No. 11-116965

However, the urethane (meth) acrylates and the compositions containing them described in these prior art documents have problems in that the viscosity is increased during the synthesis of urethane (meth) acrylate and thus the preparation can not be carried out at a large scale or the reaction becomes uneven, (Meth) acrylate and these compositions are opaque at low temperature to have low transparency or change shape under a high temperature of the cured coating film, which is insufficient as an interlayer filler for transparent substrates for displays.

Accordingly, an object of the present invention is to provide a method for producing an active energy ray-curable composition, which does not increase the viscosity when the component containing the active energy ray-curable composition is prepared, An object of the present invention is to provide an active energy ray curable composition in which the cargo exhibits high heat resistance in addition to high flexibility and high transparency and a laminate having a cured layer of the active energy ray curable composition.

The inventors of the present invention have made intensive studies in order to achieve the above object. As a result, they have found that a urethane (meth) acrylate (A), an active energy ray-curable monofunctional monomer (B) (C) is useful as a curable composition for an interlayer filler of a glass substrate or a plastic substrate.

That is, the present invention relates to a diisocyanate compound having a hydrogenated polyolefin skeleton and having a weight average molecular weight of 2,000 to 10,000, a diisocyanate compound obtained by hydrogenating an alicyclic diisocyanate having an alicyclic diisocyanate and a branched chain, (Meth) acrylate (B) in the presence of a monofunctional (meth) acrylate (B) to form an isocyanate group-containing urethane isocyanate prepolymer, and then reacting the urethane isocyanate prepolymer (Meth) acrylate (A), monofunctional (meth) acrylate (B) and photopolymerization initiator (C) prepared by reacting a hydroxyl group-containing (meth) acrylate Lt; / RTI >

The diol (X) having a hydrogenated polyolefin skeleton and having a weight average molecular weight of 2,000 to 10,000 is preferably a diol represented by the following formula (1).

Wherein a represents an integer of 70 to 250 and R ² represents a monovalent group represented by the following formula (2) (in the formula (2), b represents an integer of 0 to 10) ,

R ¹ and R ³ may be the same or different from each other and represent a monovalent group represented by the following formula (3) (in the formula (3), c represents an integer of 0 to 10)

The urethane isocyanate prepolymer is preferably a urethane isocyanate prepolymer obtained by reacting a hydroxyl group of a diol (X) having a hydrogenated polyolefin skeleton and having a weight average molecular weight of 2,000 to 10,000 until urethane is entirely obtained.

In addition, it is preferable that the active energy ray curable composition does not contain a volatile organic solvent.

Further, 0.200 g of the active energy ray curable composition was applied to the center of the first glass substrate (thickness 1 mm, 5 cm square) in the active energy ray curable composition to form a circular resin layer (4 cm diameter) (1 mm in thickness, 5 cm square) was attached to the surface of the first glass substrate, and then the active energy ray-curable composition was cured by irradiating with an active energy ray to form a cured layer. It is preferable that the increase in the APHA of the laminate before and after the storage at the time of storage is 25 or less.

The present invention also provides a laminate having a cured layer of the active energy ray-curable composition between a first transparent material selected from glass and plastic and a second transparent material selected from glass and plastic.

The laminate is obtained by applying the active energy ray-curable composition onto a first transparent substrate to form a resin layer, attaching a second transparent substrate on the resin layer, and thereafter irradiating an active energy ray, And then curing the curable composition to form a cured layer.

The active energy ray-curable composition of the present invention does not have a high viscosity when producing urethane (meth) acrylate (A), which is a contained component, and has a low byproductivity of by- A) can be produced. As a result, the active energy ray curable composition (before curing) of the present invention does not deteriorate the appearance of the resin due to opacity at low temperature. In addition, the active energy ray curable composition of the present invention has good wettability with a glass substrate or a plastic substrate, has high flexibility and high heat resistance. Further, the cured product of the active energy ray-curable composition of the present invention has high transparency and is less deformed or deteriorated in color even at a high temperature.

In addition, by filling the active energy ray-curable composition of the present invention between transparent substrates of displays used in personal computers, car navigation systems, televisions, mobile phones, etc., light scattering at the interface between air and transparent substrates can be prevented, It was found that a laminate which hardly caused color change or shape change during the heat resistance test was obtained.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a schematic view showing an embodiment of a laminate of the present invention. FIG.
2 is a schematic view showing an embodiment of a glass laminate (test piece A) used in the present embodiment.
3 is a schematic view showing a glass laminate used for evaluation of transparency of a cured product in this embodiment. (A) is a top view of the glass laminate, and (B) is a side view of the glass laminate.

<Process for producing urethane (meth) acrylate (A) obtained from a diol having a hydrogenated polyolefin skeleton>

The urethane (meth) acrylate (A) used in the present invention may be obtained by reacting a diol (X) having a hydrogenated polyolefin skeleton and a weight average molecular weight of 2,000 to 10,000 with alicyclic diisocyanate, aliphatic diisocyanate having a branched chain, and aromatic isocyanate Diisocyanate (Y) selected from the group consisting of a diisocyanate compound obtained by hydrogenating an isocyanate group is subjected to a urethanation reaction in the presence of a monofunctional (meth) acrylate (B) to obtain a urethane isocyanate prepolymer containing an isocyanate group , And then reacting the urethane isocyanate prepolymer with a hydroxyl group-containing (meth) acrylate (Z).

The diol (X) having a weight average molecular weight of 2,000 to 10,000 and having a hydrogenated polyolefin skeleton is referred to as "urethane (meth) acrylate (A)" or " Is at least one member selected from the group consisting of "diol (X)" or "(X)", a diisocyanate compound obtained by hydrogenating alicyclic diisocyanate, branched aliphatic diisocyanate and aromatic isocyanate The diisocyanate (Y) is simply referred to as "diisocyanate (Y)" or "(Y)" and the hydroxy group-containing (meth) acrylate (Z) is simply referred to as "(Z)".

(Y) and (Z) are reacted to form an isocyanate group-containing urethane isocyanate prepolymer, and then reacting the components (A) and A method of reacting the prepolymer with the prepolymer (X) ", the effect of preventing the viscosity increase, the appearance of the resin, suppressing the by-products, transparency of the cured product, heat resistance and the like are remarkably improved.

Concretely, when "(X), (Y), (Z) are mixed and reacted in a batch", the urethane (meth) acrylate (A) has a high viscosity and becomes difficult to stir, As a result, not only the probability of partial gelation increases but also the amount of the compound having no polyol skeleton-containing diol (X) in the skeleton increases, resulting in lowering of transmittance and lowering of flexibility. In addition, since various complicated compounds are irregularly formed, quality control becomes difficult when the product is used as an active energy ray-curable resin composition.

Further, when "(Y) and (Z) are reacted to form an isocyanate group-containing urethane isocyanate prepolymer, and then the prepolymer is reacted with (X) Compounds in which all of the isocyanate groups have reacted with the hydroxyl group-containing (meth) acrylate (Z) are produced as byproducts. This by-product does not contain a diol (X) skeleton having a polyolefin skeleton, exhibits crystallinity, decreases the transmittance at 400 nm, and increases the possibility of gelation.

As a method of synthesizing the urethane isocyanate prepolymer in the above production method, the following method can be mentioned.

[Method 1] A method wherein the diol (X) and the diisocyanate (Y) are mixed and reacted in a batch.

[Method 2] A method in which diol (X) is added dropwise to diisocyanate (Y).

[Method 3] A method in which diisocyanate (Y) is added dropwise to diol (X).

In the case of [Method 3], since diisocyanate (Y) is added dropwise to a large amount of diol (X), the isocyanate groups on both sides of diisocyanate (Y) are urethane- The diol having hydroxyl groups at both terminals of the XYX type is produced as a byproduct and 2 moles of the diisocyanate (Y) is reacted with the diol. As a result, a compound wherein both ends of the YXYXY type are isocyanate groups are produced as byproducts The reaction is repeated, and when used in a typical manner, a large amount of a by-product of the following structure may be produced.

Y- [XY] _n -XY (n is an integer of 1 or more)

When a large amount of such by-products are produced as a by-product, urethane (meth) acrylate obtained by reacting the (meth) acrylate (Z) with a hydroxy group has a low acrylic density and therefore a sufficient crosslinking density can not be obtained.

Therefore, [Method 1] and [Method 2] are particularly preferably used in order to obtain a desired urethane isocyanate prepolymer in a good yield.

For Method 1:

First, the diol (X) and the monofunctional (meth) acrylate (B) are introduced into the reactor and stirred until homogeneous, and then the diisocyanate (Y) is added to make it uniform. Whereby the viscosity of the reaction liquid is suppressed to be low. Thereafter, when the temperature is elevated as required while stirring, a method of introducing the urethanation catalyst to initiate the urethanization is preferable. After the urethanization catalyst is charged, the temperature may be raised as required.

If the urethanization catalyst is charged from the beginning before the diol (X) and the diisocyanate (Y) are homogenized, the diol (X) and the diisocyanate (Y) The reaction proceeds, the molecular weight and viscosity of the resulting urethane prepolymer change, and the reaction may terminate in a state where unreacted diisocyanate (Y) remains in the system. In this case, by-products resulting from the reaction of the hydroxy group-containing (meth) acrylate (Z) and the remaining diisocyanate (Y) to be used later are generated, so that the transmittance is deteriorated at 400 nm.

The content of such by-products is preferably less than 7% with respect to the urethane (meth) acrylate (A) obtained from the diol having the objective hydrogenated polyolefin skeleton. If it is 7% or more, the transmittance at 400 nm is lowered.

[Method 1] is industrially superior in that a diol (X) having a high viscosity can be directly introduced into a reactor and a urethane (meth) acrylate (A) can be produced in one port.

[Method 2] In the case of [Method 2], diisocyanate (Y), a urethanization catalyst and, if necessary, a part of monofunctional (meth) acrylate (B) are added to the reactor and stirred until homogeneous. While stirring, the mixture is heated as required and allowed to react while dropping a homogeneous mixture of diol (X) and monofunctional (meth) acrylate (B).

[Method 2] takes a long time to separately prepare a homogeneous mixture of a high viscosity diol (X) and a monofunctional (meth) acrylate (B) and drop it into a reactor, Is preferred because of the smallest by-product.

Y- [XY] _n -XY (n is an integer of 1 or more)

In any of the methods, when the urethane isocyanate prepolymer is synthesized by the reaction of the diol (X) and the diisocyanate (Y), it is preferable to carry out the reaction until all of the hydroxyl groups of the diol (X) are urethane. The end point of the reaction is determined by measuring the isocyanate group concentration (sometimes referred to as &quot; NCO group concentration &quot;) in the reaction solution and the concentration of the isocyanate group when all of the hydroxyl groups introduced into the system are urethane- Or the like has not already been changed.

The molar ratio of the diol (X) to the diisocyanate (Y) is not particularly limited. For example, the diisocyanate (Y) may be used in an amount of 1.1 to 2.0 moles, preferably 1.2 to 1.5 moles, Can be used.

Further, when a urethane (meth) acrylate (A) obtained from a diol having a desired hydrogenated polyolefin skeleton is reacted with a urethane isocyanate prepolymer and a hydroxy group-containing (meth) acrylate (Z) If a large amount of the isocyanate group in the reaction remains, gelation may occur or the curing of the coating film may become defective.

In order to avoid these problems, the reaction is carried out in such a manner that the number of moles of the hydroxyl group of the hydroxyl group-containing (meth) acrylate (Z) is excessive relative to the number of moles of the isocyanate group of the urethane isocyanate prepolymer, and the residual isocyanate group concentration It is necessary to continue the reaction until it reaches 0.1% by weight or less. In the above reaction, the number of moles of the hydroxyl group of the hydroxyl group-containing (meth) acrylate (Z) relative to 1 mole of the isocyanate group of the urethane isocyanate prepolymer may be 1.005 to 1.1 mole, preferably 1.01 to 1.05 mole.

The reaction is preferably carried out in the presence of a polymerization inhibitor such as dibutylhydroxytoluene, hydroquinone, hydroquinone monomethyl ether or phenothiazine for the purpose of preventing polymerization. The amount of these polymerization inhibitors to be added is preferably 1 to 10000 ppm (by weight), more preferably 100 to 1000 ppm, and still more preferably 400 to 1000 ppm based on the urethane (meth) acrylate (A) to be produced. When the addition amount of the polymerization inhibitor is less than 1 ppm with respect to the urethane (meth) acrylate (A), a sufficient polymerization inhibiting effect may not be obtained. When the addition amount exceeds 10,000 ppm, there is a fear that various physical properties of the product are adversely affected.

For the same purpose, the present reaction is preferably carried out in a molecular oxygen-containing gas atmosphere. The oxygen concentration is appropriately selected in consideration of the safety aspect.

The present reaction may be carried out using a catalyst to obtain a sufficient reaction rate. As the catalyst, dibutyltin dilaurate, tin octylate, tin chloride and the like can be used, but dibutyltin dilaurate is preferable in terms of the reaction rate. The amount of these catalysts added is usually 1 to 3000 ppm (by weight), preferably 50 to 1000 ppm. If the addition amount of the catalyst is less than 1 ppm, a sufficient reaction rate may not be obtained. If the addition amount of the catalyst is more than 3000 ppm, there is a possibility that various physical properties of the product such as lowering of light resistance are adversely affected.

The production of the urethane (meth) acrylate (A) can be carried out in the presence of a known volatile organic solvent. The volatile organic solvent can be distilled off under reduced pressure after the production of the urethane (meth) acrylate (A). The volatile organic solvent remaining in the active energy ray-curable resin composition may be applied to the transparent substrate and then removed by drying. The volatile organic solvent means an organic solvent whose boiling point does not exceed 200 占 폚.

However, an active energy ray-curable resin composition containing no volatile organic solvent is not used at all from the preparation of urethane (meth) acrylate (A) to the combination of active energy ray-curable resin composition It is preferable in a hardening system in a closed state.

The active energy ray curable composition of the present invention preferably does not contain a volatile organic solvent. As used herein, the term &quot; not contained &quot; means that the proportion occupied by the total amount of the active energy ray-curable composition is 1% by weight or less, preferably 0.5% by weight or less and more preferably 0.1% by weight or less.

The reaction is preferably carried out at a temperature of 130 ° C or lower, more preferably 40 ° C to 130 ° C. If the temperature is lower than 40 ° C, a sufficient reaction rate may not be obtained in practical use. If the temperature is higher than 130 ° C, double bonds may cross-link due to thermal radical polymerization, resulting in gelation.

The reaction is usually carried out until the remaining isocyanate group becomes 0.1% by weight or less. Residual isocyanate group concentration is analyzed by gas chromatography, titration and the like.

Further, a part of the terminal (meth) acryloyl group may be modified to an alkoxy group. By modifying the alkoxy group, for example, the wettability with the substrate can be adjusted.

When a part of the terminal (meth) acryloyl group is modified to an alkoxy group, the modification ratio is preferably from 1 to 30 mol%, more preferably from 1 to 30 mol%, when the sum of the number of moles of the (meth) acryloyl group and the alkoxy group is 100% , Preferably 5 to 20 mol%, and more preferably 5 to 10 mol%. If the modifying ratio of the alkoxy group is less than 1 mol%, the effect is small, and if it exceeds 30 mol%, the compatibility of the obtained product may be deteriorated and the reactivity may be lowered.

Examples of a method of using a part of the terminal (meth) acryloyl group as an alkoxy group include a method of reacting an urethane isocyanate prepolymer with an alcohol in addition to reacting a urethane isocyanate prepolymer with a hydroxyl group-containing (meth) acrylate (Z) have.

Specifically, for example, the following method can be used.

(Meth) acrylate is reacted with an isocyanate group remaining after reacting a urethane isocyanate prepolymer with a desired amount of an alcohol to obtain a desired proportion of the terminal of the urethane isocyanate prepolymer to an alkoxy group and then reacting the hydroxyl group-containing (meth) acrylate (Z) A method of introducing an acryloyl group.

(2) reacting the urethane isocyanate prepolymer with a desired amount of a hydroxyl group-containing (meth) acrylate (Z) to obtain a desired (meth) acryloyl group at the terminal of the urethane isocyanate prepolymer, A method for introducing an alkoxy group into an isocyanate group.

(3) a method in which a desired amount of an alcohol and a hydroxyl group-containing (meth) acrylate (Z) are simultaneously reacted with a urethane isocyanate prepolymer and a desired ratio of an alkoxy group and (meth) acryloyl group is introduced at the end of the urethane isocyanate prepolymer .

(4) A method of combining the above-mentioned methods (1) to (3).

In all of the above methods (1) to (4), in order to make the residual isocyanate group concentration in the reaction liquid to be 0.1% by weight or less, the alcohol and the alcohol which are added to the reaction with respect to the number of moles of the terminal isocyanate group of the urethane isocyanate prepolymer / (Hydroxyl group-containing (meth) acrylate (Z)) must be excessively reacted.

The alcohols that can be used are not particularly limited, and examples thereof include aliphatic or alicyclic primary alcohols having 3 or more carbon atoms, and the molecular weight thereof is preferably in the range of 70 to 400. When the number of carbon atoms in the alcohol is less than 3 or the molecular weight is less than 70, there is a risk of volatilization during the synthesis of urethane (meth) acrylate. On the other hand, if the molecular weight exceeds 400, the reactivity with the isocyanate group is lowered and the synthesis time may become longer. Further, the alcohol having an aromatic ring is not preferable because the weatherability of the resultant urethane (meth) acrylate (A) may be lowered. In addition, two or more kinds of alcohols may be used in combination depending on the purpose.

Specific examples of preferred alcohols include 1-butanol, 1-heptanol, 1-hexanol, normal octyl alcohol, 2-ethylhexyl alcohol, cyclohexanemethanol, capryl alcohol, lauryl alcohol, myristyl alcohol, Stearyl alcohol, and mixtures thereof. Among them, 2-ethylhexyl alcohol is preferable in view of boiling point, price, and availability.

&Lt; Diol (X) having a hydrogenated polyolefin skeleton >

The weight average molecular weight (Mw) of the diol (X) having a hydrogenated polyolefin skeleton may be in the range of 2,000 to 10,000, preferably 3,000 to 6,000. The weight average molecular weight (Mw) is a value in terms of polystyrene measured by GPC. When the Mw is less than 2,000, the resin Tg after urethane (meth) acrylation is increased, the flexibility is lowered, the appearance of the resin is deteriorated, and the by-products are also increased. On the other hand, if the Mw exceeds 10,000, the crosslinking density becomes too small to cause deterioration of the curability and change of shape under high temperature. The crosslinking density can be raised by the addition of a polyfunctional (meth) acrylate, but mixing of a polyfunctional monomer as described later causes a poor appearance under environmental testing. As the diol (X) having a hydrogenated polyolefin skeleton, for example, a compound obtained by hydrogenating a polyalkadiene (polybutadiene, polyisoprene, etc.) having a hydroxyl group at both terminals can be used.

As the diol (X) having a hydrogenated polyolefin skeleton, a commercially available product may be used. Examples thereof include "Epol" manufactured by Idemitsu Kosan Co., Ltd., "GI-2000" manufactured by Nippon Soda Co., Ltd. and "GI-3000" .

&Lt; Diisocyanate (Y) >

As the diisocyanate (Y), those which do not show crystallinity from the viewpoints of the appearance of the resin and transparency of the cured product are used. Specifically, aliphatic diisocyanates having alicyclic diisocyanates, branched chains, and aromatic isocyanates are hydrogenated And a diisocyanate compound to be obtained. Examples of the alicyclic diisocyanate include, but are not limited to, isophorone diisocyanate. The aliphatic diisocyanate having a branched chain is not particularly restricted but includes, for example, 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate. Examples of the diisocyanate compound obtained by hydrogenating the aromatic isocyanate compound include, but are not limited to, hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate. On the other hand, when a diisocyanate (Y) other than the above is used, which exhibits crystallinity, there is a problem in the transparency of the appearance of the resin and the cured product.

&Lt; Hydroxy group-containing (meth) acrylate (Z)

Examples of the hydroxyl group-containing (meth) acrylate (Z) include, but are not limited to, 2-hydroxyethyl (meth) acrylate, 2- hydroxypropyl (meth) acrylate, Rate can be used.

&Lt; Monofunctional (meth) acrylate (B) >

The active energy ray-curable composition of the present invention contains the monofunctional (meth) acrylate (B), so that the viscosity adjustment and the Tg of the cured coating film are precisely controlled in the production of urethane (meth) acrylate, The appearance of the resin, the suppression of by-products, the transparency of the cured product, the heat resistance, and the like are improved. The monofunctional (meth) acrylate (B) may be simply referred to as (B).

The concentration of the monofunctional (meth) acrylate (B) to be used is not particularly limited, but is 20 to 60% by weight, preferably 20 to 40% by weight, based on the total amount of the resultant urethane (meth) . If the amount is less than 20% by weight, the resulting urethane (meth) acrylate may have a high viscosity, which makes handling difficult and may cause gelation. On the other hand, if it is more than 60% by weight, the viscosity becomes too low to wetter the wettability with the transparent base material, and the flexibility and heat resistance of the urethane (meth) acrylate may be lowered.

Such a monofunctional (meth) acrylate is not particularly limited, but monofunctional (meth) acrylate other than polyether acrylate (PO modified product, EO modified product, etc.) is preferable from the viewpoint of heat resistance, Acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, glycerin mono (meth) acrylate, glycidyl (meth) acrylate, dicyclopentenyl (meth) (meth) acrylate, isobutyl (meth) acrylate, isobornyl (meth) acrylate, octyl / decyl (meth) acrylate, (Meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, n- , 2- (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like. Of these, n-octyl acrylate, isobornyl , Octyl / decyl (meth) acrylate are particularly preferred.

The above-mentioned monofunctional (meth) acrylate may be a commercially available product. For example, a commercial product "β-CEA" (β-carboxyethyl acrylate manufactured by Daicel-Cytec Co., Ltd.), "IBOA" (Trade name: ODA-N, manufactured by Daicel-Cytec, octyl / decyl acrylate) available from Seitech Co., Ltd. are available on the market.

&Lt; Photopolymerization initiator (C) >

The photopolymerization initiator (C) of the present invention is not particularly limited, but also depends on the type of active energy ray and the type of urethane (meth) acrylate (A), but known photo radical polymerization initiators and photo cation polymerization initiators can be used But are not limited to, for example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-on, diethoxyacetophenone, 1- 2-methylpropan-1-one, 4- (2-hydroxyethoxy) -2-methylpropan- 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1, benzoin, benzoin methyl ether, benzoin ethyl Ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, , Acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6 -Trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, benzyl, camphorquinone and the like.

The amount of the photopolymerization initiator to be used is not particularly limited, but is, for example, 1 to 20 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the active energy ray curable resin composition. If the amount is less than 1 part by weight, there is a fear that the curing is defective. On the other hand, if the amount of the photo polymerization initiator is large, odor originating from the photo polymerization initiator may remain from the cured film after curing.

<Transparent substrate>

As the transparent substrate used in the present invention, a plastic substrate such as a transparent plastic film can be used in addition to a glass substrate such as a transparent glass plate.

As the plastic substrate, it is possible to use a conventional transparent material, and it is not particularly limited, and examples thereof include polyolefin resins such as polyethylene, ethylene-propylene copolymer and ethylene-vinyl acetate copolymer, polyethylene terephthalate, polyethylene naphthalate, Polyester resins such as butylene terephthalate, acrylic resins, polycarbonate resins and the like. Of these, a polycarbonate resin and an acrylic resin are particularly preferably used.

<Additives>

The active energy ray-curable composition of the present invention may contain various additives as required. Examples of such additives include fillers, salt pigments, leveling agents, ultraviolet absorbers, light stabilizers, antifoaming agents, dispersants, thixotropic agents and the like. The amount of these additives to be added is not particularly limited, but is, for example, 0 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the active energy ray curable composition.

&Lt; Coating and Curing Method for Transparent Substrate >

When the active energy ray curable composition of the present invention is applied to a transparent substrate (for example, a glass substrate such as a glass plate or a plastic substrate such as a plastic film), the coating method is not particularly limited and may be a spraying method, A spray coating method, a roll coating method, a bar coating method, and a gravure method. Among them, the roll coating method is most preferably used from the viewpoints of gravity, cost, workability, and the like. The coating may be a so-called inline coating method, which is performed in a manufacturing process of a plastic film or the like, or a so-called off-line coating method, in which a previously prepared transparent substrate is coated by a separate process. From the viewpoint of production efficiency, off-line coating is preferable.

The thickness of the coating film of the present invention is preferably 50 to 300 占 퐉, more preferably 50 to 200 占 퐉. When the layer thickness exceeds 300 탆, the amount of the resin composition to be applied becomes large, so that the cost may be increased or the uniformity of the film thickness may be lowered. When the thickness is less than 50 탆, the curability of the curable resin can not be exhibited.

&Lt; Heat resistance in color change >

The active energy ray curable composition of the present invention is prepared by applying 0.200 g of the active energy ray curable composition to the center of a first glass substrate (1 mm thick, 5 cm square) to form a circular (4 cm diameter) resin layer, , A second glass substrate (thickness: 1 mm, 5 cm square) was adhered to the active energy ray-curable composition, and then the active energy ray-curable composition was cured to form a cured layer, It is preferable that the increase in the APHA of the laminate before and after storage when stored is 25 or less, more preferably 20 or less, still more preferably 15 or less.

<Laminate>

The laminate of the present invention may be a laminate having a cured layer of the active energy ray-curable composition between a first transparent material selected from glass and plastic and a second transparent material selected from glass and plastic, It does not. Preferably, the active energy ray-curable composition is applied onto the first transparent substrate to form a resin layer, the second transparent substrate is adhered to the resin layer, and then the ultraviolet ray or electron beam The active energy ray curable composition can be cured in a very short time by irradiating an active energy ray to form a cured layer to obtain a laminate. Fig. 1 shows an embodiment of the laminate.

The increase in APHA of the laminate before and after storage at 95 ° C for 500 hours is not particularly limited, but is preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less .

The light source for ultraviolet irradiation is not particularly limited, but high-pressure mercury lamps, ultra-high pressure mercury lamps, carbon arc lamps, xenon lamps, metal halides, and the like are used. The irradiation time varies depending on the kind of the light source, the distance between the light source and the coated surface, and other conditions, but it is several tens of seconds long and usually several seconds. Normally, an irradiation source having a lamp output of about 80 to 300 W / cm is used. In the case of electron beam irradiation, it is preferable to use an electron beam having an energy in the range of 50 to 1000 keV and an irradiation dose of 2 to 5 Mrad. After the active energy ray irradiation, the curing may be promoted by heating as necessary.

<Examples>

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited at all by these examples.

&Lt; Measurement method of physical properties, test method, evaluation method >

Methods for measuring physical properties, test methods, and evaluation methods are described below.

(Weight average molecular weight)

The weight average molecular weight was determined on the basis of standard polystyrene by GPC (gel permeation and gas chromatography) under the following measurement conditions.

Equipment used: TOSO HLC-8220GPC

Pump: DP-8020

Detector: RI-8020

Types of columns: Super HZM-M, Super HZ4000, Super HZ3000, Super HZ2000

Solvent: tetrahydrofuran

Flow rate: 1 mL / min

Column pressure: 5.0 MPa

Column temperature: 40 DEG C

Sample injection amount: 10 μL

Sample concentration: 0.2 mg / mL

(Appearance test of resin composition before curing)

The appearance of the resin composition before curing was confirmed. The resin composition was stored at -30 占 폚 (minus 30 占 폚) for 1 hour, and the presence or absence of turbidity and coloration due to crystallization or the like was visually evaluated according to the following criteria.

Specifically, in the case where neither opacity nor coloring is visually observed, the result is "good" (clear), and "○" is described in the column of "resin outer appearance (-30 ° C.)" in Tables 1 and 2. On the other hand, when either whitening or coloring was observed by naked eyes, the result was defective (appearance defective), and &quot; x &quot; was written in the column of &quot; resin outer appearance (-30 캜) &quot;

(By-product content)

The content of by-products relative to the urethane (meth) acrylate (A) obtained from the diol having the hydrogenated polyolefin skeleton which is the object of the present invention is determined by the following equation based on the peak area of each component obtained by GPC analysis, Respectively.

Area of by-product peak = area of by-product peak + area of urethane (meth) acrylate (A) peak obtained from a diol having a hydrogenated polyolefin skeleton 占 100

Concretely, when the by-product content is less than 7%, the result is good, and "o" is described in the column of "by-product content" in Tables 1 and 2. On the other hand, when the content of the by-product is 7% or more, the result is "poor", and "x" is described in the column of "by-product content" in Tables 1 and 2.

(Evaluation of transparency of cured product)

As shown in Fig. 2, a square frame made of silicone rubber was formed on a micro-glass (dimension: 1.0 x 76 x 26 mm) (1.0 x 40 x 10 mm in number of accents) and 1.0 g of the active energy ray- Respectively. Heated at 70 DEG C, and irradiated with ultraviolet rays under the following conditions at the time when the surface became smooth.

[UV irradiation condition]

Irradiation intensity: 120 W / cm

Survey distance: 10cm

Conveyor speed: 5m / min

Number of investigations: 2

The transmittance was measured using a spectrophotometer (product name: VISIBLE SPECTROPHOTO METER, manufactured by Shimadzu Corporation) with only a microglass as a reference, and evaluated by the following criteria.

When the transmittance at 400 nm is not less than 95%, the transmittance is good and &quot;? &Quot; is described in the column of "Transparency (transmittance at 400 nm)" in Tables 1 and 2. On the other hand, when the transmittance at 400 nm is less than 95%, the transmittance is considered to be defective and &quot; x &quot; is described in the column of "Transparency (transmittance at 400 nm)" in Tables 1 and 2.

(Evaluation of Heat Resistance of Cured Product)

The glass laminate (specimen A) shown in Fig. 3 was stored under the following heat-resistant conditions, and the change of the APHA (color) and the shape of the specimen A was observed. 3 (A) is a top view of the glass laminate, and FIG. 3 (B) is a side view of the glass laminate.

[Preparation of test piece A]

The glass laminate (specimen A) shown in Fig. 3 was prepared as follows. First, 0.200 g of the active energy ray curable composition was precisely weighed and placed in the center of a glass plate (1 mm thick, 5 cm square). Further, a copper glass plate was placed thereon, and the resin layer was widened to a circular shape (4 cm in diameter) to obtain a glass laminate. Thereafter, ultraviolet irradiation was conducted from one side of the glass surface of the glass laminate using a high-pressure mercury lamp (manufactured by Igraphics Co., Ltd.) under the following conditions to obtain a glass laminate (test piece A) having a cured resin composition layer.

(Ultraviolet irradiation condition)

Irradiation intensity: 120 W / cm

Survey distance: 10cm

Conveyor speed: 5m / min

Number of investigations: 8

[Storage under heat-resistant conditions]

A test plate (glass laminate, after curing) was stored for 500 hours at a temperature of 95 캜 using a small environmental tester (product name: SH-641, manufactured by Espec Corp.).

[Measurement of APHA]

The APHA of the glass laminate before and after storage under heat-resistant conditions was measured using a spectroscopic colorimeter (product name: Spectro Color Meter SE2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.) and evaluated according to the following criteria .

When the increase in APHA before and after storage under a heat-resistant condition is less than 15, "⊚" is described in the column of "color change" of "heat resistance" in Tables 1 and 2 because heat resistance is very good from the viewpoint of color. In the case where the increase in APHA before and after storage under heat-resistant conditions is 15 or more and less than 50, "○" is described in the column of "color change" of "heat resistance" in Tables 1 and 2 because heat resistance is good from the viewpoint of color. On the other hand, when the increase in APHA before and after storage under heat-resistant conditions is 50 or more, heat resistance is poor from the viewpoint of hue, and "x" is described in the column of "color change" of "heat resistance" in Tables 1 and 2.

[Measurement of shape]

The presence or absence of the shape change (warpage) of the test piece A after storage under heat-resistant conditions was visually measured and evaluated according to the following criteria.

Specifically, when the shape change (warpage) can not be seen by the naked eye, the result is "good" and "○" is shown in the column of "shape change" of "heat resistance" in Tables 1 and 2. On the other hand, when a shape change (warpage) is observed by the naked eye, the result is defective, and &quot; x &quot; is described in the column of &quot; shape change &quot;

<Synthesis Example>

Examples of the synthesis and examples of urethane (meth) acrylate are described below.

(Measurement of isocyanate group concentration)

The isocyanate group concentration was measured as follows. Further, the measurement was carried out in a 100 mL glass flask under stirring with a stirrer.

(Measurement of Blank Value)

To 15 mL of THF was added 15 mL of a THF solution of dibutylamine (0.1 N), and further 3 drops of bromophenol blue (1% methanol diluent) were added thereto to give a blue color. Thereafter, an aqueous HCl solution Respectively. The appropriate amount of aqueous HCl solution at the point of discoloration was defined as V _b (mL).

(Measurement of actual isocyanate group concentration)

The sample was weighed in W _s (g), dissolved in 15 mL of THF and 15 mL of a THF solution of dibutylamine (0.1 N) was added. After confirming that the solution had been solubilized, 3 drops of bromophenol blue (1% methanol diluent) were added to the solution to give a blue color, and the solution was titrated with a 0.1 N aqueous HCl solution. The appropriate amount of aqueous HCl solution at the time point of discoloration was defined as V _s (mL).

The isocyanate group concentration in the sample was calculated by the following equation.

An isocyanate group content _{(wt%) = (V b -V s} ) × 1.005 × 0.42 ÷ W s

(Synthesis Example, Diol (X) Containing Polyolefin Skeleton Used in Comparative Synthesis Example)

"Epol" (manufactured by Idemitsu Kosan Co., Ltd.); (Hydroxyl value of 0.92 mol / kg, bromine value of 5.9 g / 100 g, nonvolatile content of 99.5% by weight or more, estimated weight average molecular weight: 2174), hydroxyl group-terminated polyolefin

&Quot; NISSO PB GI-1000 &quot; (manufactured by Nippon Soda Co., Ltd.); Hydrogenated 1,2-polybutadiene glycol (hydroxyl value of 67.2 mg KOH / g, iodine value of 11.2 g / 100 g, estimated weight average molecular weight of 1670)

"NISSO PB GI-2000" (manufactured by Nippon Soda Co., Ltd.); Hydrogenated 1,2-polybutadiene glycol (hydroxyl value of 48.3 mgKOH / g, iodine value of 9.0 g / 100 g, hydrogenation rate of 97.6%, estimated weight average molecular weight of 2323)

"NISSO PB GI-3000" (manufactured by Nippon Soda Co., Ltd.); Hydrogenated 1,2-polybutadiene glycol (hydroxyl value of 28.3 mg KOH / g, iodine of 15.6 g / 100 g, volatile content of 0.11%, estimated weight average molecular weight of 3965)

(Synthesis Example, Diisocyanate (Y) used in Comparative Synthesis Example)

&Quot; IPDI &quot; (compound name isophorone diisocyanate); Quot; VESTANAT IPDI &quot; (manufactured by Evonix)

"HDI" (compound name: hexamethylene diisocyanate); HDI &quot; (manufactured by Nippon Polyurethane Industry Co., Ltd.)

&Quot; TMHDI &quot; (compound name 2,2,4-trimethylhexamethylene diisocyanate); TMDI &quot; (manufactured by Evonix)

(Synthesis example, monofunctional (meth) acrylate (B) used in Comparative Synthesis Example)

"ODA-N"; Octyl / decyl acrylate (manufactured by Daicel-Cytec)

(Synthesis Example, hydroxyl group-containing (meth) acrylate (Z) used in Comparative Synthesis Example)

"HEA"; 2-hydroxyethyl acrylate (manufactured by Nippon Shokubai Co., Ltd.)

(Synthesis example, alcohol used in comparative synthesis example)

&Quot; 2-EH &quot;; 2-ethylhexyl alcohol (manufactured by Sankyo Chemical Co., Ltd.)

The "ppm", "% by weight", and "% by weight" of the concentration indications are concentrations of the entire urethane (meth) acrylate-containing material to be obtained, unless otherwise specified .

&Lt; Synthesis Example 1 / A-1 &

ODA-N was used as monofunctional (meth) acrylate (B) by reacting GI-3000, IPDI and HEA at a molar ratio of 2: 3: 2.02. The actual doses and reaction conditions are described below.

215 g of GI-3000 (manufactured by Nippon Soda Co., Ltd.), 103 g (30% by weight) of dibutylhydroxytoluene (BHT) and octyl / decyl acrylate (ODA-N) of 800 ppm were placed in a separable flask equipped with a stirrer, Lt; / RTI &gt; The inner temperature was adjusted to 50 DEG C and the mixture was stirred for 1 hour. After the inside of the system was homogenized, 18 g of isophorone diisocyanate was added. After stirring at the reaction temperature for 1 hour, 300 ppm of dibutyltin dilaurate was added and the mixture was further stirred at 50 DEG C for 3 hours.

When the reaction was completed, it was confirmed that the isocyanate group concentration in the reaction liquid became equal to or lower than the residual isocyanate group concentration (hereinafter referred to as &quot; theoretical end isocyanate group concentration &quot;) when all the hydroxyl groups provided to the reaction were urethane (The other synthetic examples are the same).

In this example, after confirming that the concentration of the isocyanate group in the reaction liquid was the theoretical end-point isocyanate group concentration (0.67 wt%) or less, the operation was shifted to the next operation.

Thereafter, the reaction temperature was raised to 70 DEG C, and 7 g of hydroxyethyl acrylate was added. Followed by stirring at 70 占 폚 for 3 hours. The reaction was terminated by confirming that the concentration of the isocyanate group was 0.1 wt% or less to obtain an active energy ray-curable urethane (meth) acrylate-containing material (A-1).

&Lt; Synthesis Example 2 / A-2 &

The procedure of Synthesis Example 1 was repeated except that the molar ratio of GI-3000, IPDI and HEA was changed to 3: 4: 2.02. The actual doses and reaction conditions are described below.

230 g of GI-3000 (manufactured by Nippon Soda Co., Ltd.), 107 g (30% by weight) of dibutylhydroxytoluene (BHT) and octyl / decyl acrylate (ODA-N) of 800 ppm were placed in a separable flask equipped with a stirrer, . The internal temperature was adjusted to 50 캜 and stirred for 1 hour. After homogenizing the system, 17 g of isophorone diisocyanate was added. After stirring at the reaction temperature for 1 hour, 300 ppm of dibutyltin dilaurate was added and the mixture was further stirred at 50 캜 for 3 hours.

In this example, after confirming that the isocyanate group concentration in the reaction liquid was the theoretical end-point isocyanate group concentration (0.45 wt%) or less, the operation was shifted to the next operation.

Thereafter, the reaction temperature was raised to 70 캜, and hydroxyethyl acrylate (4 g) was added. Followed by stirring at 70 占 폚 for 3 hours. The reaction was terminated by confirming that the isocyanate group concentration was 0.1 wt% or less, and an active energy ray-curable urethane (meth) acrylate-containing material (A-2) was obtained.

&Lt; Synthesis Example 3 / A-3 >

The procedure of Synthesis Example 1 was repeated except that the molar ratio of GI-3000, IPDI and HEA was changed to 3: 4: 2.02 and the used concentration of monofunctional (meth) acrylate (B) was reduced to 20 wt% . The actual doses and reaction conditions are described below.

(20% by weight) of octyl / decyl acrylate (ODA-N), 256 g of GI-3000 (manufactured by Nippon Soda Co., Ltd.), 800 ppm of dibutylhydroxytoluene (BHT) . The internal temperature was adjusted to 50 캜 and stirred for 1 hour. After the inside of the system was homogenized, 19 g of isophorone diisocyanate was added. After stirring at the reaction temperature for 1 hour, 300 ppm of dibutyltin dilaurate was added and the mixture was further stirred at 50 캜 for 3 hours.

In this example, after confirming that the concentration of the isocyanate group in the reaction liquid was not higher than the theoretical end-point isocyanate group concentration (0.52 wt%), the operation was shifted to the next operation.

Thereafter, the reaction temperature was raised to 70 캜, and hydroxyethyl acrylate (5 g) was added. Followed by stirring at 70 占 폚 for 3 hours. The reaction was terminated by confirming that the concentration of the isocyanate group was 0.1 wt% or less to obtain an active energy ray-curable urethane (meth) acrylate-containing material (A-3).

&Lt; Synthesis Example 4 / A-4 &

The same operation as in Synthesis Example 1 was repeated except that the monofunctional (meth) acrylate (B) was changed to IBOA. The actual doses and reaction conditions are described below.

225 g of GI-3000 (manufactured by Nippon Soda Co., Ltd.), 107 g (30% by weight) of dibutylhydroxytoluene (BHT) and isobornyl acrylate (IBOA) of 800 ppm were charged in a separable flask equipped with a stirrer, . The internal temperature was adjusted to 50 캜 and stirred for 1 hour. After the inside of the system was homogenized, 19 g of isophorone diisocyanate was added. After stirring at the reaction temperature for 1 hour, 300 ppm of dibutyltin dilaurate was added and the mixture was further stirred at 50 캜 for 3 hours.

In this example, after confirming that the concentration of the isocyanate group in the reaction liquid was the theoretical end-point isocyanate group concentration (0.67 wt%) or less, the operation was shifted to the next operation.

Thereafter, the reaction temperature was raised to 70 캜, and 7 g of hydroxyethyl acrylate was added. Followed by stirring at 70 占 폚 for 3 hours. The reaction was terminated by confirming that the concentration of the isocyanate group was 0.1 wt% or less to obtain an active energy ray-curable urethane (meth) acrylate-containing material (A-4).

&Lt; Synthesis Example 5 / A-5 >

Except that the molar ratio of GI-3000, IPDI and HEA was changed to 3: 4: 2.02 and the monofunctional (meth) acrylate (B) was changed to IOA (concentration 20% by weight) . The actual doses and reaction conditions are described below.

227 g of GI-3000 (manufactured by Nippon Soda Co., Ltd.), dibutylhydroxytoluene (BHT) of 800 ppm and 63 g (20% by weight) of isooctyl acrylate (IOA) were charged in a separable flask equipped with a thermometer and a stirring device. The inner temperature was adjusted to 50 DEG C and the mixture was stirred for 1 hour. After the inside of the system was homogenized, 18 g of isophorone diisocyanate was added. After stirring at the reaction temperature for 1 hour, 300 ppm of dibutyltin dilaurate was added and the mixture was further stirred at 50 캜 for 3 hours.

In this example, after confirming that the isocyanate group concentration in the reaction liquid was the theoretical end-point isocyanate group concentration (0.45 wt%) or less, the operation was shifted to the next operation.

Thereafter, the reaction temperature was raised to 70 DEG C, and 5 g of hydroxyethyl acrylate was added. Followed by stirring at 70 占 폚 for 3 hours. The reaction was terminated by confirming that the isocyanate group concentration was 0.1 wt% or less, and an active energy ray-curable urethane (meth) acrylate-containing product (A-5) was obtained.

&Lt; Synthesis Example 6 / A-6 >

The molar ratio of epol, GI-3000, IPDI, and HEA was adjusted to 1: 1: 3: 2.02 by using "Epol" and "GI-3000" as the diol (X) having a hydrogenated polyolefin skeleton, ) The procedure of Synthesis Example 1 was repeated except that the acrylate (B) was changed to IBOA. The actual doses and reaction conditions are described below.

(BHT) and isobornyl acrylate (IBOA) were added to a separable flask equipped with a reflux condenser, a thermometer and a stirrer in the same manner as in Example 1, except that 78 g of Eptol (manufactured by Idemitsu Kosan Co., Ltd.), 141 g of GI-3000 (manufactured by Nippon Soda Co., (30% by weight). The internal temperature was adjusted to 50 캜, and the mixture was stirred for 2 hours. After homogenizing the system, 24 g of isophorone diisocyanate was added. After stirring at the reaction temperature for 1 hour, 300 ppm of dibutyltin dilaurate was added and the mixture was further stirred at 50 캜 for 3 hours.

In this example, after confirming that the concentration of the isocyanate group in the reaction liquid was the theoretical end-point isocyanate group concentration (0.85 wt%) or less, the operation was shifted to the next operation.

Thereafter, the reaction temperature was raised to 70 DEG C, and 9 g of hydroxyethyl acrylate was added. Followed by stirring at 70 占 폚 for 3 hours. The reaction was terminated by confirming that the isocyanate group concentration was 0.1 wt% or less to obtain an active energy ray-curable urethane (meth) acrylate-containing material (A-6).

&Lt; Synthesis Example 7 / A-7 >

The procedure of Synthesis Example 1 was repeated except that TMHDI was used instead of IPDI as the diisocyanate (Y). The actual doses and reaction conditions are described below.

(30% by weight) of GI-3000 (manufactured by Nippon Soda Co., Ltd.), 800 ppm of dibutylhydroxytoluene (BHT), and octyl / decyl acrylate (ODA-N) in a separable flask equipped with a stirrer, ). The inner temperature was adjusted to 50 占 폚 and the mixture was stirred for 1 hour. After the inside of the system was homogenized, 18 g of trimethylhexamethylene diisocyanate (TMHDI) was added. After stirring at the reaction temperature for 1 hour, 300 ppm of dibutyltin dilaurate was added and the mixture was further stirred at 50 캜 for 2 hours.

In this example, after confirming that the concentration of the isocyanate group in the reaction liquid was not higher than the theoretical end-point isocyanate group concentration (0.68 wt%), the operation was shifted to the next operation.

Thereafter, the reaction temperature was raised to 70 캜, and 7 g of 2-hydroxyethyl acrylate was added. Followed by stirring at 70 占 폚 for 3 hours. It was confirmed that the isocyanate group concentration was 0.1 wt% or less, and the reaction was terminated to obtain an active energy ray-curable urethane (meth) acrylate-containing material (A-7).

&Lt; Synthesis Example 8 / A-8 >

The procedure of Synthesis Example 1 was repeated except that &quot; epol &quot; was used instead of GI-3000 as the diol (X) having a hydrogenated polyolefin skeleton. The actual doses and reaction conditions are described below.

(30 wt%) of dibutylhydroxytoluene (BHT) and octyl / decyl acrylate (ODA-N) of 800ppm were charged in a separable flask equipped with a thermometer and a stirrer, Respectively. The internal temperature was adjusted to 50 캜 and stirred for 1 hour. After homogenizing the system, 30 g of isophorone diisocyanate was added. After stirring at the reaction temperature for 1 hour, 300 ppm of dibutyltin dilaurate was added and the mixture was further stirred at 50 캜 for 2 hours.

In this example, after confirming that the isocyanate group concentration in the reaction liquid was not higher than the theoretical end-point isocyanate group concentration (1.15 wt%), the operation was shifted to the next operation.

Thereafter, the reaction temperature was raised to 70 캜 and 2-hydroxyethyl acrylate (11 g) was added. Followed by stirring at 70 占 폚 for 3 hours. The reaction was terminated by confirming that the concentration of the isocyanate group was 0.1 wt% or less to obtain an active energy ray-curable urethane (meth) acrylate-containing material (A-8).

&Lt; Synthesis Example 9 / A-9 &

The procedure of Synthesis Example 1 was repeated except that GI-3000 was added dropwise in IPDI during the synthesis of the urethane isocyanate prepolymer. HEA molar ratio was 2: 3: 2.02, and ODA-N was used as monofunctional (meth) acrylate (B). The actual doses and reaction conditions are described below.

(18 g), 800 ppm of dibutylhydroxytoluene (BHT), octyl / decyl acrylate (ODA-N) (43 g) and 300 ppm of dibutyltin di (meth) acrylate were added to a separable flask equipped with a stirrer, Laurate. The inside temperature was raised to 50 캜 while uniformly stirring the system. The distribution of ODA-N is 43 g in order to allow IPDI to be stirred.

Stirring was continued, and a mixed solution obtained by uniformly dissolving 215 g of GI-3000 (manufactured by Nippon Soda Co., Ltd.) in 60 g of octyl / decyl acrylate (ODA-N) was added dropwise over 30 minutes while maintaining the temperature at 50 占 폚. At this time, the total weight of octyl / decyl acrylate (ODA-N) charged into the system was 103 g (30 wt%). Thereafter, the mixture was further stirred at 50 DEG C for 3 hours.

In this example, after confirming that the concentration of the isocyanate group in the reaction liquid was the theoretical end-point isocyanate group concentration (0.67 wt%) or less, the operation was shifted to the next operation.

Thereafter, the reaction temperature was raised to 70 DEG C and 11 g of 2-hydroxyethyl acrylate was added. Followed by stirring at 70 占 폚 for 3 hours. It was confirmed that the concentration of the isocyanate group was 0.1 wt% or less, and the reaction was terminated to obtain an active energy ray-curable urethane (meth) acrylate-containing material (A-9).

&Lt; Synthesis Example 10 / A-10 >

The molar ratio of GI-3000, IPDI and HEA was changed to 3: 4: 1.82, and 2-ethylhexyl alcohol (2-EH) of 0.2 molar fraction was further used. The molar ratio of HEA to 2-EH is 90:10. The actual doses and reaction conditions are described below.

273 g of GI-3000 (manufactured by Nippon Soda Co., Ltd.), 75 g (20 wt%) of dibutylhydroxytoluene (BHT) and octyl / decyl acrylate (ODA-N) in an amount of 800 ppm were placed in a separable flask equipped with a thermometer and a stirrer. Lt; / RTI &gt; The internal temperature was adjusted to 50 캜, and the mixture was stirred for 1 hour. After homogenizing the system, 21 g of isophorone diisocyanate was added. After stirring at the reaction temperature for 1 hour, 300 ppm of dibutyltin dilaurate was added and the mixture was further stirred at 50 DEG C for 3 hours.

After confirming that the isocyanate group concentration in the reaction liquid was not higher than the theoretical end-point isocyanate group concentration (0.57% by weight), the operation was shifted to the next operation.

Thereafter, the reaction temperature was raised to 70 캜, and 0.6 g of 2-ethylhexyl alcohol (2-EH) (manufactured by Sankyo Chemical Co., Ltd.) was added thereto and reacted for 1 hour. Then, 5.1 g of hydroxyethyl acrylate was added, and the mixture was stirred at 70 캜 for 3 hours. The reaction was terminated by confirming that the isocyanate group concentration was 0.1 wt% or less, and an active energy ray-curable urethane (meth) acrylate-containing product (A-10) was obtained. 10 mol% of the terminal of the urethane (meth) acrylate is 2-ethylhexyl alcohol, and 90 mol% is hydroxyethyl acrylate.

&Lt; Comparative Synthesis Example 1 / CA-1 >

The same procedure as in Synthesis Example 1 was repeated except that HDI was used as the diisocyanate (Y). The molar ratio of GI-3000, HDI, and HEA was adjusted to 2: 3: 2.02. The actual doses and reaction conditions are described below.

320 g of GI-3000 (manufactured by Nippon Soda Co., Ltd.), 150 g (30% by weight) of dibutylhydroxytoluene (BHT) and octyl / decyl acrylate (ODA-N) of 800 ppm were placed in a separable flask equipped with a stirrer, Lt; / RTI &gt; The internal temperature was adjusted to 50 캜 and stirred for 1 hour. After homogenizing the system, 20 g of hexamethylene diisocyanate (HDI) was added. After stirring at the reaction temperature for 1 hour, 300 ppm of dibutyltin dilaurate was added and the mixture was further stirred at 50 DEG C for 3 hours.

In this example, after confirming that the isocyanate group concentration in the reaction liquid was the theoretical end-point isocyanate group concentration (0.69 wt%) or less, the operation was shifted to the next operation.

Thereafter, the reaction temperature was raised to 70 캜, and 10 g of hydroxyethyl acrylate was added. Followed by stirring at 70 占 폚 for 3 hours. The reaction was terminated by confirming that the concentration of the isocyanate group was 0.1 wt% or less to obtain an active energy ray-curable urethane (meth) acrylate-containing material (CA-1).

&Lt; Comparative Synthesis Example 2 / CA-2 >

The procedure of Synthesis Example 1 was repeated except that GI-1000 was used as the diol (X) having a hydrogenated polyolefin skeleton. The molar ratio was adjusted to 2: 3: 2.02 with GI-1000, IPDI and HEA.

The actual doses and reaction conditions are described below.

276 g of GI-1000 (manufactured by Nippon Soda Co., Ltd.), 150 g of dibutylhydroxytoluene (BHT) and octyl / decyl acrylate (ODA-N) (30% by weight) were added to a separable flask equipped with a stirrer, Lt; / RTI &gt; The internal temperature was adjusted to 50 占 폚 and stirred for 1 hour. After homogenizing the system, 55 g of isophorone diisocyanate (IPDI) was added. After stirring at the reaction temperature for 1 hour, 300 ppm of dibutyltin dilaurate was added and the mixture was further stirred at 50 DEG C for 3 hours.

In this example, after confirming that the concentration of the isocyanate group in the reaction liquid was not higher than the theoretical end-point isocyanate group concentration (1.42 wt%), the operation was shifted to the next operation.

Thereafter, the reaction temperature was raised to 70 DEG C, and 19 g of hydroxyethyl acrylate was added. Followed by stirring at 70 占 폚 for 3 hours. The reaction was terminated by confirming that the concentration of the isocyanate group was 0.1 wt% or less to obtain an active energy ray-curable urethane (meth) acrylate-containing material (CA-2).

&Lt; Comparative Synthesis Example 3 / CA-3 >

The same operation as in Synthesis Example 1 was repeated except that monofunctional (meth) acrylate (B) was not used. The molar ratio of GI-3000, IPDI and HEA was adjusted to 2: 3: 2.02. The actual doses and reaction conditions are described below.

320 g of GI-3000 (manufactured by Nippon Soda Co., Ltd.) and 800 ppm of dibutylhydroxytoluene (BHT) were charged in a separable flask equipped with a thermometer and a stirrer. The internal temperature was adjusted to 50 占 폚 and the mixture was stirred for 1 hour. After the inside of the system was homogenized, 20 g of isophorone diisocyanate (IPDI) was added. After stirring at the reaction temperature for 1 hour, 300 ppm of dibutyltin dilaurate was added. It was attempted to decrease the viscosity by changing the reaction temperature in the system to 70 캜. However, since the resin was entangled in the stirring wing to reach the gelation, the synthesis reaction could not be continued.

&Lt; Comparative Synthesis Example 4 / CA-4 >

A method of reacting (Y) and (Z) to form a urethane isocyanate prepolymer containing an isocyanate group and then reacting the prepolymer with (X), wherein the synthesis of urethane (meth) acrylate The procedure of Synthesis Example 1 was repeated except that the procedure of Example 1 was repeated. The actual doses and reaction conditions are described below.

(150 g, 30% by weight), isophorone diisocyanate (IPDI), 9 g of 2-hydroxyethyl acrylate, 800 ppm of dibutylhydroxytoluene (BHT), And filled with 100 ppm of dibutyltin dilaurate. The inner temperature was adjusted to 70 占 폚, and the mixture was stirred for 1 hour.

In this example, after confirming that the concentration of the isocyanate group in the reaction liquid was not higher than the theoretical end-point isocyanate group concentration (4.75 wt%), the operation was shifted to the next operation.

Thereafter, 315 g of GI-3000 (manufactured by Nippon Soda Co., Ltd.) and 200 ppm of dibutyltin dilaurate were added and reacted for 2 hours. The reaction was terminated by confirming that the concentration of the isocyanate group was 0.1 wt% or less to obtain an active energy ray-curable urethane (meth) acrylate-containing material (CA-4).

&Lt; Preparation of active energy ray curable composition >

The components described in Tables 1 and 2 were uniformly blended in 20 mL of a brown bottle so that the total amount was about 15 g to prepare an active energy ray curable composition used in the examples.

Irg184 (manufactured by Ciba Specialty Chemicals) was used as a photopolymerization initiator.

<Test Results>

The above-mentioned respective tests and evaluations were carried out on the active energy ray-curable compositions according to the formulations shown in Tables 1 and 2. The results of the test and evaluation as described above are shown in Tables 1 and 2.

As shown in Table 1 and Example, urethane (meth) acrylate obtained by reacting isophorone diisocyanate or trimethylhexamethylene diisocyanate and then hydroxyl group-containing (meth) acrylate with a diol having a hydrogenated polyolefin skeleton of the present invention The curable composition containing can prevent light scattering at the air and film interface by filling between films. In addition, it was found that there was a performance which is hard to cause color change or shape change during the heat resistance test. On the other hand, as shown in Table 2 and Comparative Examples, hexamethylene diisocyanate showing crystallinity as diisocyanate (Y) was used (Comparative Examples 1 and 2), diol (X) Example 3) In the case where the reaction during the synthesis of urethane (meth) acrylate was not carried out in an appropriate order (Comparative Example 4), the appearance of the resin such as that the composition before curing was opaque at low temperature was damaged and the transparency of the cured product was impaired And also shows defects such as a change in shape during the heat resistance test.

&Lt; Industrial applicability >

According to the active energy ray-curable composition of the present invention, the viscosity of the urethane (meth) acrylate (A), which is a contained component, is not increased and the byproducts of the by- (A) can be produced. As a result, there is no deterioration of the appearance of the resin due to opacity at low temperature. Further, the active energy ray-curable composition of the present invention is excellent in wettability with glass substrates or plastic substrates, The cured product of the active energy ray curable composition of the present invention has a high transparency and is less deformed or deteriorated in color even at a high temperature. Therefore, the cured product of the active energy ray curable composition of the present invention has transparency and transparency of the display used for personal computers, car navigation systems, It is useful as a filler between substrates.

1: Cure layer of active energy ray curable composition
2, 3: transparent substrate
4: Silicone rubber
11: Resin
21: Glass plate

Claims (7)

(X) having a hydrogenated polyolefin skeleton and having a weight average molecular weight of 2,000 to 10,000, aliphatic diisocyanate having an alicyclic diisocyanate and a branched chain, and diisocyanate compound obtained by hydrogenating an aromatic isocyanate (Meth) acrylate (B) in the presence of at least one diisocyanate (Y) to form an isocyanate group-containing urethane isocyanate prepolymer, and then reacting the urethane isocyanate prepolymer and the hydroxyl group- (Meth) acrylate (A), a monofunctional (meth) acrylate (B), and a photopolymerization initiator (C) prepared by reacting an acrylate (Z) The active energy ray-curable composition according to claim 1, wherein the diol (X) having a hydrogenated polyolefin skeleton and having a weight average molecular weight of 2,000 to 10,000 is a diol represented by the following formula (1).

Wherein a represents an integer of 70 to 250 and R ² represents a monovalent group represented by the following formula (2) (in the formula (2), b represents an integer of 0 to 10) ,

R ¹ and R ³ may be the same or different from each other and represent a monovalent group represented by the following formula (3) (in the formula (3), c represents an integer of 0 to 10)

The urethane isocyanate prepolymer of claim 1 or 2, wherein the urethane isocyanate prepolymer has a hydrogenated polyolefin skeleton and has a weight average molecular weight ranging from 2,000 to 10,000, wherein the urethane isocyanate prepolymer is reacted until all of the hydroxyl groups of the diol (X) Ray curable composition. The active energy ray-curable composition according to any one of claims 1 to 3, which is free from volatile organic solvents. The method according to any one of claims 1 to 4, wherein 0.200 g of the active energy ray curable composition is applied to the center of the first glass substrate (1 mm thick, 5 cm square) to form a circular (4 cm diameter) resin layer , A second glass substrate (1 mm in thickness, 5 cm in thickness) is attached to the resin layer, and then an active energy ray is irradiated to cure the active energy ray-curable composition to form a cured layer, Wherein the increase in APHA of the laminate before and after storage for 500 hours under the condition of 25% or less is 25 or less. A laminate having a cured layer of the active energy ray-curable composition according to any one of claims 1 to 5 between a first transparent material selected from glass and plastic and a second transparent material selected from glass and plastic. 7. The method of manufacturing a light emitting device according to claim 6, wherein the laminate is formed by applying the active energy ray-curable composition according to any one of claims 1 to 5 on a first transparent substrate to form a resin layer, And then curing the active energy ray-curable composition by irradiating an active energy ray to form a cured layer.

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