TW201708484A - Curable resin composition for interlayer filling - Google Patents

Abstract

To provide an active energy ray-curable composition that has excellent wettability with plastics and glass, that induces no appearance change such as discoloration or deformation even in a high temperature and high humidity environment, and that is suitable for interlayer filling. The active energy ray-curable composition comprises a specific urethane (meth)acrylate (X), a monofunctional (meth)acrylate (Y), and a photopolymerization initiator (Z). A cured product layer is formed from the active energy ray-curable composition of the present invention, and the cured product layer 1 can be used, as shown in Fig.1, as a filler between transparent substrates 2, 3 of a liquid crystal television set, an electronic paper display, a personal computer, and a mobile phone display portion.

Description

Curable resin composition for interlayer filling

The present invention relates to an active energy ray-curable composition which can be used as an interlayer filler for a transparent substrate for a display such as a personal computer, a television or a mobile phone, and a laminate of a cured layer having the active energy ray-curable composition. body. This application was filed in Japan on April 6, 2015, and claims the priority of Japanese Patent Application No. 2015-078067, the contents of which are hereby incorporated herein.

Displays used in personal computers, car navigation, televisions, mobile phones, etc., are reflected by light from the backlight. The display includes a filter, and a transparent substrate such as a glass substrate such as a glass plate or a plastic substrate such as a plastic film can be used, thereby reducing the influence of light scattering or absorption of the transparent substrate. The amount of light that the light source outputs to the outside of the display. If the reduction is large, the screen becomes dark and the visibility is lowered. In order to improve the visibility, the antireflection property of the surface layer of the display or the amount of light from the light source is increased as a correspondence.

In one aspect, there is a method of converting an air layer between transparent substrates such as a glass substrate or a plastic substrate into a resin layer. By changing the air layer to the resin layer, light scattering in the interface between the air and the glass substrate or the plastic substrate can be prevented, so that the reduction in the amount of output light can be prevented.

In terms of the properties required for the resin used in the interlayer of the transparent substrate such as a glass substrate or a plastic substrate, in addition to the adhesion to the transparent substrate, high deformation resistance, and high flexibility, High transparency is also required, especially at a transmittance of more than 95% at 400 nm. Further, it is necessary to have resistance at a high temperature, and specifically, it is necessary to have no shape change or no color change at 95 °C. In view of the resin having such properties, the urethane skeleton urethane (meth) acrylate or a composition containing the same is proposed in the prior literature shown below.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 1041553

[Patent Document 2] Japanese Patent No. 2582575

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2002-069138

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2002-309185

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2003-155455

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2010-144000

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2010-254890

[Patent Document 8] Japanese Patent Laid-Open Publication No. 2010-254891

[Patent Document 9] Japanese Patent Laid-Open Publication No. 2010-265402

[Patent Document 10] Japanese Laid-Open Patent Publication No. 2011-116965

However, the urethane (meth) acrylates described in these prior documents, or compositions containing the same, have the following disadvantages : Since the urethane (meth) acrylate has high viscosity at the time of synthesis, it cannot be produced on a large scale; or since the reaction becomes uneven, the obtained urethane (meth) acrylate or These compositions become cloudy at low temperatures, and the transparency is lowered. The cured coating film undergoes a shape change at a high temperature. Therefore, there is still a disadvantage in that it is an interlayer filler for a transparent substrate for a display. In addition, as a representative of a substrate for a smart phone or a tablet, the substrate is required to be thinned, and the hardenability and shrinkage property of the active energy ray-curable composition used as the interlayer filler is further reduced. Further, with the widening of the use environment, durability at high temperatures is required, and in this case, adhesion retention between the interlayer filler after curing and the substrate is required.

Therefore, an object of the present invention is to provide an active energy ray-curable composition which does not have high viscosity when producing a component of an active energy ray-curable composition, and which has a small amount of by-product formation, and can produce a target component. Since the active energy ray-curable composition has low hardenability and shrinkage, it can be used as an interlayer filler even in the case of a thin substrate for a smart phone or a tablet computer. Further, an active energy ray-curable composition is provided, and the cured product of the active energy ray-curable composition exhibits high-temperature heat resistance in addition to high flexibility and high transparency, and is closely adhered to a substrate. High; and a laminate provided with a cured layer of the active energy ray-curable composition.

The present inventors have focused on the results of the review in order to achieve the above object, and found that the urethane (meth) acrylate (X) containing a polyolefin-based polyol having a specific polyolefin skeleton; monofunctional (methyl) Propylene The active energy ray-curable composition of the acid ester initiator (Y) and the photopolymerization initiator (Z) is useful as a curable resin composition for filling between layers of a glass substrate or a plastic substrate.

That is, the present invention provides an active energy ray-curable composition comprising: a urethane (meth) acrylate (X) which is a polyolefin-based polyol having a polyolefin skeleton (A) An aliphatic alcohol (B) having three or more hydroxyl groups and having a molecular weight of 100 or more and less than 800, and an aliphatic diisocyanate (C) are subjected to a urethanization reaction to form an amino group containing an isocyanate group. After the acid ester isocyanate prepolymer, the urethane isocyanate prepolymer, the (meth) acrylate having a hydroxyl group (D), and the alcohol having one hydroxyl group (E) are reacted, monofunctional ( a methyl acrylate (Y), and an active energy ray-curable composition of a photopolymerization initiator (Z); a polyolefin-based polyol (A) having a polyolefin skeleton selected from the group consisting of hydroxyl groups at both terminals At least one of the group of polybutadiene, polyisoprene, and the hydrogenated hydrogenated polyol, having a weight average molecular weight of 2,000 to 10,000; urethane (meth)acrylic acid The (meth)acrylonitrile group concentration of the ester (X) is 0.05 or more and less than 0.20 mol/kg.

Further, the concentration of the isocyanate group in the reaction liquid in the case where the above-mentioned isocyanate-containing urethane isocyanate prepolymer is formed, and the reaction is carried out until all of the hydroxyl groups in the reaction are subjected to urethane grouping. The residual isocyanate group concentration below is preferred.

In addition, in the present invention, it is also described in the selection of glass and plastic. A laminate of a first transparent substrate of a glue and a second transparent substrate selected from the group consisting of glass and plastic, and having a cured layer of the active energy ray-curable composition.

Furthermore, in the present invention, a laminate is also described which is formed by coating the active energy ray-curable composition of any of the above-mentioned transparent substrates on a first transparent substrate to form a resin layer, and then to make the second transparent The substrate is adhered to the resin layer, and then irradiated with an active energy ray to cure the active energy ray-curable composition to form a cured layer.

That is, the present invention relates to the following.

[1] An active energy ray-curable composition comprising: a urethane (meth) acrylate (X) which is a polyolefin-based polyol (A) having a polyolefin skeleton, having 3 The aliphatic alcohol (B) having more than one hydroxyl group and having a molecular weight of 100 or more and less than 800, and the aliphatic diisocyanate (C) are subjected to a urethanization reaction to form a urethane isocyanate containing an isocyanate group. After the polymer, the aforementioned urethane isocyanate prepolymer, the (meth) acrylate having a hydroxyl group (D), and the alcohol having one hydroxyl group (E) are reacted, monofunctional (methyl) An active energy ray-curable composition of an acrylate (Y) and a photopolymerization initiator (Z); wherein the polyolefin-based polyol (A) having a polyolefin skeleton is selected from the group consisting of hydroxyl groups having hydroxyl groups at both terminals At least one of butadiene, polyisoprene, and a group of such hydrogenated polyols, and having a weight average molecular weight of 2,000 to 10,000, urethane (meth) acrylate (X) (methyl) acrylonitrile The degree is 0.05 or more and less than 0.20 mol/kg.

[2] The active energy ray-curable composition according to [1], wherein the polyol (A) has a weight average molecular weight (Mw) of 2,000 to 6,000.

[3] The active energy ray-curable composition according to [1] or [2] wherein the alcohol (B) is selected from the group consisting of trimethylolpropane, pentaerythritol, glycerin, and the like. At least one of the groups.

[4] The active energy ray-curable composition according to any one of [1] to [3], wherein the total amount of the obtained urethane (meth) acrylate content (100 weight) is obtained. The amount of the alcohol (B) used is, for example, 0.01 to 3% by weight, preferably 0.1 to 1% by weight, more preferably 0.3 to 0.6% by weight.

[5] The active energy ray-curable composition according to any one of [1] to [4] wherein the diisocyanate (C) is selected from the group consisting of alicyclic diisocyanates, linear or branched chain fats. At least one of a group of a diisocyanate and a diisocyanate compound obtained by hydrogenating an aromatic isocyanate.

[6] The active energy ray-curable composition according to any one of [1] to [5] wherein (meth) acrylate (D) is 2-hydroxyethyl (meth) acrylate, (methyl) a (meth) acrylate having one (meth) acryl fluorenyl group and having a hydroxyl group; or pentaerythritol triacrylate, such as 2-hydroxy-n-propyl acrylate or 4-hydroxybutyl (meth) acrylate; A (meth) acrylate having two or more (meth) acrylonitrile groups and having a hydroxyl group.

[7] The active energy ray-curable composition according to any one of [1] to [6] wherein the alcohol (E) is an aliphatic or alicyclic primary alcohol having a carbon number of 3 or more and a molecular weight of 70 To the extent of 400.

[8] Active energy ray hardenability as described in any one of [1] to [7] a composition in which the (meth) acrylate (Y) is used in a concentration of, for example, 20 to 60% by weight based on the total amount of the obtained urethane (meth) acrylate content (100% by weight). Preferably, it is 20 to 40% by weight.

[9] The active energy ray-curable composition according to any one of [1] to [8] wherein the reaction is carried out until the formation of the above-mentioned isocyanate-containing urethane isocyanate prepolymer The isocyanate group concentration in the reaction liquid is equal to or lower than the concentration of the isocyanate group remaining in the case where all of the hydroxyl groups providing the reaction are esterified with the urethane.

[10] A laminate having a first transparent substrate selected from the group consisting of glass and plastic and a second transparent substrate selected from the group consisting of glass and plastic, having any one of [1] to [9] A cured layer of the active energy ray-curable composition.

[11] A laminated body obtained by coating the active energy ray-curable composition according to any one of [1] to [9] on a first transparent substrate to form a resin layer to form a second transparent group. The material is adhered to the resin layer, and then irradiated with an active energy ray to cure the active energy ray-curable composition to form a cured layer.

When the active energy ray-curable composition of the present invention is produced as a component-containing urethane (meth) acrylate (X), it does not have high viscosity, and the generation of by-products is small, and it can be produced as The target urethane (meth) acrylate. As a result, in the active energy ray-curable composition of the present invention (before curing), the appearance of the resin due to white turbidity at a low temperature is not deteriorated. Further, the active energy ray-curable composition of the present invention has good wettability with a glass substrate or a plastic substrate, and has It has high flexibility and high heat resistance, and has low hardenability and shrinkage. Therefore, it can be used as an interlayer filler even in the case of a thin substrate for a smart phone or a tablet. Moreover, when the active energy ray-curable composition of the present invention is used as an interlayer filler, the adhesion between the cured product and the substrate is good. Further, the cured product of the active energy ray-curable composition of the present invention has high transparency, and is less likely to be deformed at a high temperature or deteriorated in hue.

Further, by incorporating the active energy ray-curable composition of the present invention between transparent substrates of displays for personal computers, car navigation, televisions, mobile phones (smart phones), tablets, and the like, air and air can be prevented. The light scattering in the interface of the transparent substrate and the layered body which is less likely to cause a hue change or a shape change in the heat resistance test are very useful in this point.

1‧‧‧hardened layer of active energy ray hardening composition

2‧‧‧Transparent substrate

3‧‧‧Transparent substrate

4‧‧‧矽 rubber

11‧‧‧Resin

21‧‧‧Microglass

31‧‧‧Resin

41‧‧‧ glass plate

[Fig. 1] is a schematic view showing an aspect of a laminate of the present invention.

[Fig. 2] is a schematic view showing an aspect of the glass laminate used in the present embodiment.

[Fig. 3] is a schematic view showing an aspect of the glass laminate used in the present embodiment. In the figure, (A) is a view in which the glass laminate is viewed from above, and (B) is a view in which the glass laminate is viewed from the lateral direction.

[Formation of the Invention]

<Amino acid ester (meth) acrylate (X) and a method for producing the same>

The urethane (meth) acrylate (X) used in the present invention can give a polyolefin-based polyol (A) having a specific polyolefin skeleton, a specific aliphatic alcohol (B), and an aliphatic group. The diisocyanate (C) is subjected to a urethanization reaction to form an aminocyanate isocyanate prepolymer containing an isocyanate group, and the aforementioned urethane isocyanate prepolymer having a hydroxyl group The acrylate (D) and the alcohol (E) having one hydroxyl group are reacted and produced. Further, in the method for producing a urethane (meth) acrylate (X) of the present invention, when a urethane isocyanate prepolymer containing an isocyanate group is formed, a monofunctional group may also be used ( Methyl) acrylate (Y) acts as a compatibilizing agent.

Further, the urethane (meth) acrylate (X) is abbreviated as "urethane (meth) acrylate (X)" or "(X)", and has a polyolefin skeleton. The polyolefin-based polyol (A) is abbreviated as "polyol (A)" or "(A)", and an aliphatic alcohol (B) having three or more hydroxyl groups and having a molecular weight of 100 or more and less than 800 is simply referred to as "alcohol ( B)" or "(B)", the aliphatic diisocyanate (C) is simply referred to as "diisocyanate (C)" or "(C)", and the (meth) acrylate (D) having a hydroxyl group is simply referred to as " (Meth)acrylate (D)" or "(D)", the alcohol (E) having one hydroxyl group is simply referred to as "alcohol (E)" or "(E)", and "isocyanate-containing" The urethane isocyanate prepolymer is abbreviated as "urethane isocyanate prepolymer", and the monofunctional (meth) acrylate (Y) is simply referred to as "(meth) acrylate (Y)" or "(Y)". Further, the photopolymerization initiator (Z) to be described later is simply referred to as "(Z)".

In the method for producing the urethane (meth) acrylate (X) of the present invention, for example, "make (A), (B), (C), (D), and (E) The method of carrying out the reaction together or the method of "polymerizing (C), (D) and (E), and the method of reacting the polymer with (A) and (B)" The effect of preventing an increase in viscosity and significantly improving the appearance of the resin, suppression of by-products, transparency of the cured product, heat resistance, and the like can be achieved.

Specifically, a urethane (meth) acrylate formed by "a method in which (A), (B), (C), (D), and (E) are mixed together to carry out a reaction" Since it becomes a high viscosity, stirring becomes difficult. Further, since the urethanization reaction proceeds unevenly, not only is the possibility of partial gelation high, but also the urethane (meth) acrylate which does not contain the polyol (A) in the skeleton. (by-product), which causes a decrease in transmittance and a decrease in flexibility. Moreover, since various urethane (meth)acrylates are produced, when used as an active energy ray-curable composition, quality management becomes difficult.

Further, in the case where "the (C), (D), and (E) are polymerized, and the method of reacting the polymer with (A) and (B) is carried out, a diisocyanate (C) is formed. A urethane (meth) acrylate (by-product) in which all of the isocyanate groups are reacted with a hydroxyl group of (meth) acrylate (D) or alcohol (E). Since the by-product does not contain the polyol (A) skeleton, the crystallinity is exhibited, the transmittance at 400 nm is lowered, and the possibility of gelation is also high.

The method (synthesis method) for forming a urethane isocyanate prepolymer in the method for producing a urethane (meth) acrylate (X) of the present invention includes the following methods 1 to 3 .

[Method 1] A method in which a polyol (A), an alcohol (B), and a diisocyanate (C) are mixed and reacted.

[Method 2] A method in which a polyol (A) and an alcohol (B) are dropped into a diisocyanate (C) and simultaneously reacted.

[Method 3] A method in which a diisocyanate (C) is dropped into a polyol (A) and an alcohol (B) while allowing a reaction.

Hereinafter, [Method 3] will be described, but in order to simplify the description, the alcohol (B) is not discussed.

In the case of [Method 3], since the diisocyanate (C) is dropped into a large amount of the polyol (A) and simultaneously reacted, the isocyanate groups on both sides of the diisocyanate (C) and the 2 mol multicomponent The hydroxyl group of the alcohol (A) is subjected to urethane formation, and the diol which is a hydroxyl group at both ends of the ACA type is patterned by a formula, and further reacted with 2 mol of the diisocyanate (C). A compound which is modeled as a CAACAC type and whose ends are isocyanate groups is formed, and the same reaction is repeated, and a compound which is patterned and written as a compound having the following structure may be produced in a large amount.

C-[AC] _n -AC (an integer greater than n=1)

When such a by-product is produced in a large amount, the urethane (meth) acrylate obtained by reacting the (meth) acrylate (D) with the alcohol (E) has a low density of acrylic acid, so that the cured product is cured. A sufficient crosslink density is not obtained.

Therefore, in order to obtain the target urethane isocyanate prepolymer in a good yield, it is particularly preferable to use [Method 1] and [Method 2].

In the case of [Method 1], the polyol (A) and the alcohol (B) are first added to the reactor, and after stirring until uniform, the diisocyanate (C) is added and adjusted to be uniform. By this means, the viscosity of the reaction liquid can be lowered. Then, to A method of starting the ureido formation by introducing a urethane catalyst after stirring, if necessary, is preferably carried out. After the urethane catalyst is introduced, the temperature may be raised as needed.

In the case where the polyol (A), the alcohol (B), and the isocyanate (C) are uniformly stirred, the urethane catalyst is introduced, and since the urethanization reaction proceeds unevenly, the obtained amine is obtained. The urethane prepolymer causes problems such as gelation. Further, there is a case where the reaction is terminated in a state where the unreacted diisocyanate (C) remains in the system. In this case, since the (meth) acrylate (D) and the alcohol (E) which are used in the subsequent reaction are reacted with the residual diisocyanate (C), the by-product thus obtained lowers the transmittance at 400 nm, so good.

The content of such by-products is preferably less than 7% by weight based on the intended urethane isocyanate prepolymer. When it is 7 weight% or more, the transmittance at 400 nm will fall.

[Method 1] From the viewpoint that a high-viscosity polyol (A) or a sometimes solid alcohol (B) can be directly added to a reactor as it is, an amine-based formate can be produced in a one-pot manner. From the viewpoint of the ester (meth) acrylate (X), it is industrially excellent.

Further, in [Method 1], (meth) acrylate (Y) can be used as a compatibilizing agent. In this case, the polyol (A) and the alcohol (B) are supplied together with the (meth) acrylate (Y), added to the reactor, and stirred until uniform, and then the diisocyanate (C) is added and adjusted to be uniform. Thereby, the viscosity of the reaction liquid can be further lowered. Then, a method of starting the ureido formation by adding a urethane catalyst after stirring, if necessary, is preferably carried out. After the introduction of the urethane catalyst, it may also be ascending temperature.

In the case of [Method 2], a diisocyanate (C), a urethane catalyst, and optionally a part of (meth) acrylate (Y) are added to the reactor, and stirred until uniform. The mixture is heated as needed while stirring, and a uniform mixture of the polyol (A) and the alcohol (B) and the (meth) acrylate (Y) is dropped and reacted.

In [Method 2], a homogeneous mixture of a high-viscosity polyol (A) and sometimes a solid alcohol (B) and a (meth) acrylate (Y) is separately prepared and dropped into the reactor. However, although it takes a lot of work, it is preferable from the viewpoint of producing the following by-products as described in [Method 3]:

C-[AC] _n -AC (an integer of n=1 or more).

Further, in any method, it is preferred to carry out a reaction by synthesizing (forming) a urethane isocyanate prepolymer by reaction with a polyol (A), an alcohol (B) and a diisocyanate (C) until All of the hydroxyl groups in the reaction solution were allylated. That is, it is preferred that the reaction proceeds until the concentration of the isocyanate in the reaction liquid in the case where the urethane isocyanate prepolymer is formed becomes a residue remaining in the case where all of the hydroxyl groups supplied to the reaction are urethane-formed. The cyanate group concentration is below.

At the end of the reaction, the concentration of the isocyanate group in the reaction solution can be determined, which is equal to or less than the concentration of the isocyanate group when the hydroxyl group added in the system is all aurethane-modified, or the concentration of the isocyanate group is not Confirm with changes and so on.

From the above viewpoints, the molar ratio of the hydroxyl group (total amount) of the polyol (A) and the alcohol (B) to the isocyanate group of the diisocyanate (C) is not particularly limited, but is not more than 1 mole of the hydroxyl group. For example, 1.1 to 2.0 moles can be used. The isocyanate group is preferably from 1.1 to 1.4 moles, more preferably from 1.17 to 1.38 moles.

Further, when the urethane isocyanate prepolymer is reacted with (meth) acrylate (D) or alcohol (E) to synthesize the target urethane (meth) acrylate (X), When the unreacted isocyanate group in the reaction liquid remains in a large amount, there is a possibility that gelation or gelation of the coating film may occur.

In order to avoid such a deficiency, in the foregoing reaction, it is necessary to have a hydroxyl group of a (meth) acrylate (D) having a hydroxyl group with respect to the molar number of the isocyanate group of the urethane isocyanate prepolymer. The number of ears is excessive, and the reaction is carried out, and the reaction is continued until the residual isocyanate group concentration in the reaction liquid is 0.05% by weight or less. Further, in the foregoing reaction, the number of moles of the isocyanato group relative to the urethane isocyanate prepolymer is 1 mole, and the (meth) acrylate (D) having the hydroxyl group and the alcohol (E) The total number of moles of the hydroxyl groups can be set to 1.0 to 1.1 moles, preferably 1.0 to 1.05 moles.

<Polymerization inhibitor>

The reaction is preferably dibutylhydroxytoluene, hydroquinone, hydroquinone monomethyl ether, dibenzothiazide for the purpose of preventing polymerization. It is carried out in the presence of a polymerization inhibitor. The amount of the polymerization inhibitor added is preferably from 1 to 10,000 ppm by weight, more preferably from 100 to 1,000 ppm, based on the amount of the urethane (meth)acrylate (X) produced. 400~1000ppm. When the addition amount of the polymerization inhibitor is less than 1 ppm with respect to the urethane (meth) acrylate (X), a sufficient polymerization inhibitory effect cannot be obtained, and if it exceeds 10,000 ppm, the physical properties of the product are caused. The impact of adverse effects.

<environment>

In the method for producing the urethane (meth) acrylate (X) of the present invention, it is preferably carried out in a gas atmosphere containing molecular oxygen. The oxygen concentration is suitably selected in consideration of the safety surface.

<catalyst>

In the method for producing a urethane (meth) acrylate (X) of the present invention, in order to obtain a sufficient reaction rate, a catalyst can be used. As the catalyst, dibutyltin dilaurate, tin octylate, tin chloride or the like can be used. However, dibutyltin dilaurate is preferred from the viewpoint of the reaction rate. The amount of such catalyst added is usually from 1 to 3,000 ppm by weight, preferably from 50 to 1,000 ppm, based on the urethane (meth) acrylate (X) produced. When the amount of the catalyst added is less than 1 ppm, a sufficient reaction rate cannot be obtained. When the amount is more than 3,000 ppm, the light resistance is lowered, which adversely affects the physical properties of the product.

<solvent>

The production of the urethane (meth) acrylate (X) of the present invention 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 urethane (meth) acrylate (X) is produced. Further, in the active energy ray-curable composition of the present invention, the volatile organic solvent remaining in the composition may be removed by drying after application to a transparent substrate. Further, the volatile organic solvent means an organic solvent having a boiling point of not more than 200 °C.

The active energy ray-curable composition of the present invention may or may not contain urethane (meth) acrylate (X). The organic solvent used in the process. Further, in the curing system in a sealed state, it is preferable to adjust from the production of the urethane (meth) acrylate (X) to the adjustment of the active energy ray-curable composition, and no volatile organic matter is used at all. Solvent. In this case, it is preferred that the active energy ray-curable composition of the present invention does not contain a volatile organic solvent. Here, "not contained" means that the ratio of the total active energy ray-curable composition is 1% by weight or less, preferably 0.5% by weight or less, more preferably 0.1% by weight or less.

<reaction temperature>

In the method for producing the urethane (meth) acrylate (X) of the present invention, the reaction is preferably carried out at a temperature of 130 ° C or lower, more preferably 40 to 130 ° C. When the temperature is lower than 40 ° C, a practically sufficient reaction rate cannot be obtained. When the temperature is higher than 130 ° C, the double bond moiety is crosslinked by radical polymerization by heat to form a gel.

<Other reaction conditions>

As described above, in the production (formation) of a urethane isocyanate prepolymer containing an isocyanate group, it is preferred to carry out the reaction until the concentration of the isocyanate in the reaction liquid becomes the hydroxyl group of the supply reaction. The urethane isocyanate prepolymer is formed by the concentration of the isocyanate group remaining in the case of the esterification. Further, the residual isocyanate group concentration can be analyzed by gas chromatography, titration or the like.

The concentration of the isocyanate group in the reaction liquid when the urethane (meth) acrylate (X) is formed from the aforementioned urethane isocyanate prepolymer is usually carried out until the residual isocyanate group becomes 0.1. Below weight %. The residual isocyanate concentration can be carried out by gas chromatography, titration, or the like. analysis.

Further, in order to adjust the concentration of the (meth) acrylonitrile group of the urethane (meth) acrylate (X), one part of the terminal (meth) acrylonitrile group may be modified to an alkoxy group. By modifying to an alkoxy group, for example, the wettability with the substrate can be adjusted.

In the present invention, the (meth) acrylonitrile group concentration of the urethane (meth) acrylate (X) (hereinafter simply referred to as "(meth) propylene sulfhydryl group concentration)" can be calculated by the following formula: .

[calculation formula of [(meth) acrylonitrile concentration]

"(Methyl) propylene sulfhydryl concentration (mole / kg)" = "(meth) acrylate (D) weight (g)" × "(meth) acrylate (D) molecule (methyl) "Acryl sulfhydryl number" ÷ "Molecular weight of (meth) acrylate (D)" × 1,000 ÷ "weight of produced urethane (meth) acrylate (X) (g)"

Further, when the number of (meth)acrylonitrile groups of the (meth) acrylate (D) is, for example, 2-hydroxyethyl acrylate, the number of (meth) acrylonitrile groups is "1"; In the case of acrylate, the number of (meth)acrylonitrile groups is "3".

In the present invention, the (meth)acrylonitrile group concentration required is 0.05 or more and less than 0.20 mol/kg, preferably 0.06 to 0.16 mol/kg or less.

When the (meth) acrylonitrile group concentration is less than 0.05 mol/kg, even if the active energy ray is irradiated, the hardening becomes insufficient, and the cohesive force is lowered, and the initial adhesion to the substrate is lowered, so that it is poor. . In addition, when the (meth) acrylonitrile group concentration is 0.20 mol/kg or more, the heat resistance durability of the cured product is lowered, which is not preferable. If specific The reduction in heat resistance durability is described in the case where the cured product is tested at 95 ° C for 1,000 hours, causing an increase in the hardness of the coating film, a decrease in adhesion to the substrate, and a hardening shrinkage. The lack of shape change of the membrane.

In order to improve the heat resistance, the (meth) acrylonitrile group concentration of the urethane (meth) acrylate (X) is lowered, and although the hardening shrinkage is effectively reduced, the hardness of the coating film is lowered. The disadvantage of the adhesion to the substrate is lowered.

In the method of forming an alkoxy group by a part of the terminal (meth) acryl fluorenyl group, in addition to reacting the urethane isocyanate prepolymer with the (meth) acrylate (D), an amine may be mentioned. A method of reacting a carbamate isocyanate prepolymer with an alcohol (E), and the like.

Specifically, for example, the following methods can be mentioned.

(1) reacting a urethane isocyanate prepolymer with an alcohol (E), forming an alkoxy group at a desired ratio of a terminal of the urethane isocyanate prepolymer, and reacting it with (meth)acrylic acid The ester (D) is reacted, and the (meth) acrylonitrile group is introduced into the residual isocyanate group.

(2) reacting the urethane isocyanate prepolymer with the (meth) acrylate (D), and forming the terminal of the urethane isocyanate prepolymer at a desired ratio to form a (meth) acrylonitrile group A method in which an alkoxy group is introduced into a residual isocyanate group by reacting it with an alcohol (E).

(3) simultaneously reacting the urethane isocyanate prepolymer with (meth) acrylate (D) and alcohol (E), and introducing a desired ratio of alkoxy groups at the end of the urethane isocyanate prepolymer. And a method of (meth)acrylonitrile.

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

<Polyolefin-based polyol (A) having a polyolefin skeleton>

The polyolefin-based polyol (A) having a polyolefin skeleton is not particularly limited as long as it has a polyolefin skeleton and has two or more hydroxyl groups, but is preferably selected from those having a hydroxyl group at both terminals. At least one of butadiene, polyisoprene, and a group of such hydrogenated polyols, and a polyol having a weight average molecular weight of 2,000 to 10,000.

The weight average molecular weight (Mw) of the polyolefin-based polyol (A) having a polyolefin skeleton may be in the range of 2,000 to 10,000, preferably 2,000 to 6,000. Further, the weight average molecular weight (Mw) is a value measured by GPC and expressed in terms of polystyrene. When the Mw is less than 2,000, the resin Tg after the methacrylate (meth) acrylate is increased, the flexibility is lowered, the appearance of the resin is deteriorated, and the by-products are also increased. On the other hand, when the Mw exceeds 10,000, the crosslinking density becomes too small, the curability is deteriorated, and the shape change at a high temperature is caused. The crosslinking density can be improved by the addition of a polyfunctional (meth) acrylate. However, as will be described later, when a polyfunctional monomer is blended, it causes a defect in appearance under an environmental test.

For the polyol (A), commercially available products can be used, and examples thereof include "EPOL" manufactured by Idemitsu Kosan Co., Ltd., "GI-2000" manufactured by Japan Soda Co., "GI-3000", and "G-3000". "KRASOL HLBH P3000" and "KRASOL LBH-P2000" manufactured by Nagase Industrial Co., Ltd. In addition, the polyol (A) may be used in combination of two or more kinds depending on the purpose.

<Organic alcohol (B) having three or more hydroxyl groups and having a molecular weight of 100 or more and less than 800>

An aliphatic alcohol (B) having three or more hydroxyl groups, as long as the molecular weight is The aliphatic alcohol of 100 or more and less than 800 is not particularly limited. When the molecular weight is 800 or more, the compatibility with the polyol (A) is deteriorated, which is not preferable. Specific examples thereof include trimethylolpropane, pentaerythritol, glycerin, and modified compounds thereof. Further, examples of the above-mentioned modified compound include PPG-modified pentaerythritol or PPG-modified glycerin.

In the present invention, since the alcohol (B) has a plurality of (three or more) hydroxyl groups, the obtained urethane (meth) acrylate (A) becomes branched, and the crosslinking density is obtained. rise. When such a urethane (meth) acrylate is used, it is a methyl group (meth) acrylate which can adversely affect the weather resistance and heat resistance of the cured product. The concentration of the acrylonitrile group is lowered, so that the hardness of the coating film of the cured product can be maintained.

The amount of the alcohol (B) to be used is not particularly limited, but is, for example, 0.01 to 3% by weight, based on the total amount of the urethane (meth) acrylate-containing material (100% by weight) obtained, preferably 0.1 to 1% by weight, more preferably 0.3 to 0.6% by weight. In the case of less than 0.01% by weight, the heat resistance after heating of the obtained cured product containing the urethane (meth) acrylate (refer to the change in hardness of the coating film) is deteriorated. On the other hand, when it exceeds 3% by weight, the molecular weight in the synthesis becomes too large, which may cause gelation, which is not preferable.

For the alcohol (B), a commercially available product can be used. For example, "trimethylolpropane (TMP)" manufactured by Mitsubishi Gas Chemical Co., Ltd., and "Sannix HD-402 (a mixture of neopentyl alcohol) manufactured by Sanyo Chemical Co., Ltd. can be used. Propylene glycol modified substance), "Sannix HD-250 (polypropylene glycol modified product of glycerin)", etc., but not limited to this. Further, the alcohol (B) may be used in combination of two or more kinds depending on the purpose.

<aliphatic diisocyanate (C)>

The diisocyanate (C) may be selected from the group consisting of an alicyclic diisocyanate, a linear or branched chain aliphatic diisocyanate, and a diisocyanate compound obtained by hydrogenating an aromatic isocyanate. At least one of them. The alicyclic diisocyanate is not particularly limited, and examples thereof include isophorone diisocyanate. The aliphatic diisocyanate is not particularly limited, and examples thereof include a linear aliphatic diisocyanate such as hexamethylene diisocyanate; 2,2,4-trimethylhexamethylene diisocyanate; a branched chain aliphatic diisocyanate such as 4,4-trimethylhexamethylene diisocyanate. The diisocyanate compound obtained by hydrogenating the aromatic isocyanate is not particularly limited, and examples thereof include hydrogenated xylene diisocyanate and hydrogenated diphenylmethane diisocyanate.

As the diisocyanate (C), a commercially available product can be used. For example, "VESTANAT IPDI (isophorone diisocyanate)" and "TMDI (2,2,4-trimethylhexamethylene) manufactured by Evonik Co., Ltd.) can be used. "Dibasic isocyanate", "HDI (hexamethylene diisocyanate)" manufactured by Tosoh Corporation. Further, the diisocyanate (C) may be used in combination of two or more kinds depending on the purpose.

<(meth)acrylate (D) having a hydroxyl group>

The (meth) acrylate (D) having a hydroxyl group is not particularly limited, but, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxy-n-propyl (meth)acrylate, (methyl) can be used. a (meth) acrylate having one (meth) acrylonitrile group and having a hydroxyl group, such as 4-hydroxybutyl acrylate; or two or more (meth) groups such as pentaerythritol triacrylate A propylene group and a (meth) acrylate having a hydroxyl group. Furthermore, (meth) acrylate (D) Two or more types may be used in combination for the purpose.

<Alcohol with one hydroxyl group (E)>

The alcohol (E) having one hydroxyl group may, for example, be an aliphatic or alicyclic monohydric alcohol having 3 or more carbon atoms, and the molecular weight thereof is preferably in the range of 70 to 400. In the case where the carbon number of the alcohol is less than 3 or the molecular weight is less than 70, it is not preferable because it is volatilized in the synthesis of the urethane (meth) acrylate. Further, when the molecular weight exceeds 400, the reactivity with the isocyanate group is lowered and the synthesis time is prolonged, which is not preferable. Further, the alcohol having an aromatic ring is not preferable because the hue of the obtained urethane (meth) acrylate (X) may become high or the weather resistance may be deteriorated. Further, the alcohol may be used in combination of two or more kinds depending on the purpose.

Specific examples of the alcohol (E) include 1-butanol, 1-heptanol, 1-hexanol, n-octanol, 2-ethylhexanol, cyclohexylmethanol, octanol, and lauryl alcohol. Myristyl alcohol, cetyl alcohol (cetyl alcohol), stearyl alcohol or a mixture of these. Among them, 2-ethylhexanol is preferred from the viewpoints of boiling point, price, and ease of availability.

<monofunctional (meth) acrylate (Y)>

The active energy ray-curable composition of the present invention can reliably adjust the viscosity by producing a urethane (meth) acrylate by containing a monofunctional (meth) acrylate (Y). The Tg of the cured coating film is adjusted to further improve the viscosity, increase the appearance of the resin, suppress by-products, transparency of the cured product, heat resistance, and the like. Further, monofunctional (meth) acrylate means a (monofunctional) (meth) acrylate having one acryl fluorenyl group in the molecule.

Further, as described above, the formation of urethane isocyanate is pre-formed. In the case of a polymer, (meth) acrylate (Y) can be used as a compatibilizing agent. By using (meth) acrylate (Y) as a compatibilizing agent, a raw material (for example, a polyol (A), an alcohol (B), and a diisocyanate (C)) can be melt|dissolved. Further, when the urethane isocyanate prepolymer is formed, the viscosity of the reaction liquid may increase. However, in this case, there is also a function as a so-called diluent for alleviating the viscosity. Further, in the case of a compatibilizing agent (diluent), it is used at the time of forming a urethane isocyanate prepolymer, since the (meth) acrylate (Y) can be omitted from being added to the urethane. The operation of the ester isocyanate prepolymer improves the work efficiency.

The concentration of the (meth) acrylate (Y) to be used is not particularly limited, but is, for example, 20 to 60% by weight based on the total amount of the urethane (meth) acrylate-containing material (100% by weight) obtained. %, preferably 20 to 40% by weight. When it is less than 20% by weight, the viscosity of the obtained urethane (meth) acrylate becomes high, and handling becomes difficult, and gelation may occur. On the other hand, when it is more than 60% by weight, the viscosity at the time of application is too low, and the wettability with the transparent substrate is deteriorated, and the flexibility and heat resistance of the urethane (meth)acrylate are lowered. .

The (meth) acrylate (Y) is not particularly limited, but from the viewpoint of heat resistance, it is preferably a single non-polyether acrylate (PO modified product, EO modified product, etc.). Specific examples of the functional (meth) acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, glycerol mono(meth)acrylate, and glycidyl (meth)acrylate. Dialkylpentene acrylate, n-butyl (meth)acrylate, β-carboxyethyl (meth)acrylate, isobornyl (meth)acrylate, octyl (meth)acrylate/decyl ester, positive Octyl (meth) acrylate, isooctyl acrylate, Isobutyl (meth) acrylate, butyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, (A) Base) cyclohexyl acrylate, other alkyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. However, n-octyl (meth)acrylate, isobornyl (meth)acrylate, and octyl (meth)acrylate/decyl ester are particularly preferred.

A commercially available product such as the product name "β-CEA" (manufactured by Daicel-Allnex, β-carboxyethyl acrylate) and the product name "IBOA" (Daicel-) can be used as the above-mentioned (meth) acrylate (Y). "Allenex", isobornyl acrylate), product name "ODA-N" (Daicel-Allnex, octyl acrylate/decyl acrylate), product name "NOA" (Osaka Organic Chemical Co., Ltd., compound name n-octyl acrylate) ) etc. can be purchased from the market. Further, (meth) acrylate (Y) may be used in combination of two or more kinds depending on the purpose.

<Photopolymerization initiator (Z)>

The photopolymerization initiator (Z) of the present invention may be different depending on the type of active energy ray and the type of urethane (meth) acrylate (X), and is not particularly limited. However, known photoradicals can be used. The polymerization initiator or the photocationic polymerization initiator is not particularly limited, and examples thereof include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and Ethoxyethyl benzene, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy- 2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)one, 2-methyl-1-[4-(methylthio) Phenyl]-2- Lolinylpropane-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzyl Methyl ketal, diphenyl ketone, benzhydrazinobenzoic acid, methyl benzalkonium benzoate, 4-phenyldiphenyl ketone, hydroxydiphenyl ketone, benzoated diphenyl ketone, 4-benzyl hydrazine -4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxydiphenyl ketone, thioxanthone, 2-chlorothiazepinone, 2-methylsulfide Xanthone, 2,4-dimethylthiazepinone, isopropyl thioxanthone, 2,4-dichlorothiazinone, 2,4-diethylthiaxanone, 2,4 -diisopropylthioxanthone, 2,4,6-trimethylbenzylnonyldiphenylphosphine oxide, methylphenyl glyoxylate, diphenylethylenedione (benzil), camphorquinone, etc. .

The amount of the photopolymerization initiator to be used is not particularly limited, and is, for example, 1 to 20 parts by weight, preferably 1 to 5 parts by weight, per 100 parts by weight of the active energy ray-curable composition. When it is less than 1 part by weight, there is a problem of causing hardening failure. Conversely, if the amount of the photopolymerization initiator used is too large, the odor of the photopolymerization initiator remains after the hardening of the coating film. In addition, the photopolymerization initiator (Z) may be used in combination of two or more kinds depending on the purpose.

<additive>

The active energy ray-curable composition of the present invention comprises, in addition to the aforementioned urethane (meth) acrylate (X), monofunctional (meth) acrylate (Y), and photopolymerization initiator (Z) In addition, various additives may be blended as needed. Examples of such an additive include a filler, a dye/pigment, a leveling agent, an ultraviolet absorber, a photostabilizer, an antifoaming agent, a dispersing agent, a shake imparting agent, and the like. The amount of the additive 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, per 100 parts by weight of the active energy ray-curable composition.

<Laminated body>

The laminate of the present invention is as long as it is selected from the group consisting of glass and plastic. The transparent substrate and the second transparent substrate selected from the group consisting of glass and plastic are not particularly limited as long as they have a layered body of the cured layer of the active energy ray-curable composition. Preferably, the active energy ray-curable composition is coated on the first transparent substrate to form a resin layer, and a second transparent substrate is attached to the resin layer, and then irradiated with ultraviolet rays, for example, through a transparent substrate. Or the active energy ray such as an electron beam hardens the active energy ray-curable composition in a very short time to form a cured layer, and a laminated body can be obtained. In Fig. 1, one aspect of the above laminated body is shown.

<Transparent substrate>

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

The plastic substrate may be any transparent material that is already present, and is not particularly limited, and examples thereof include polyolefin resins such as polyethylene, ethylene-propylene copolymer, and ethylene-vinyl acetate copolymer; A polyester resin such as polyethylene terephthalate, polyethylene naphthalate or polybutylene terephthalate; an acrylic resin; a polycarbonate resin. Among them, a polycarbonate resin or an acrylic resin is particularly preferred.

<Coating of transparent substrate ‧Injection ‧ Hardening method>

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. A blown method, an airless spray method, an air spray method, a roll coating method, a bar coating method, a gravure method, or the like can be used. Among them, from the viewpoints of aesthetics, cost, workability, and the like, it is preferred to use a roll coating method. Furthermore, coating can be used to make plastic thin The film or the like is carried out in a step, that is, a so-called in-line coating; the prepared transparent substrate can also be coated in other steps, that is, a so-called off-line coating method. From the viewpoint of production efficiency, an off-line coating method is preferred. Further, in order to prevent the occurrence of bubbles at the time of injection, it is preferable to use a cartridge.

The thickness of the coating film of the present invention is preferably 50 to 300 μm, more preferably 50 to 200 μm. When the layer thickness exceeds 300 μm, the amount of the resin composition to be applied increases, so that the cost becomes high or the uniformity of the film thickness is lowered. Moreover, in the case of less than 50 μm, the softness of the curable resin cannot be exhibited.

<irradiation>

The light source when the ultraviolet ray is irradiated is not particularly limited, and for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp or the like can be used. The irradiation time varies depending on the type of the light source, the distance between the light source and the coated surface, and other conditions, but the maximum length is several tens of seconds, usually several seconds. Generally, an illumination source of about 80 to 300 W/cm can be used for light output. 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 amount of 2 to 5 Mrad. After the active energy ray is irradiated, heating may be performed as needed to promote hardening.

[Examples]

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

<Method for measuring physical properties, test method, and evaluation method>

The measurement method, test method and evaluation method of physical properties are shown below Show.

(weight average molecular weight)

The weight average molecular weight was determined by a GPC (gel permeation chromatography) method under the following measurement conditions using standard polystyrene as a reference.

Use machine: TOSO HLC-8220GPC

Pump: DP-8020

Detector: RI-8020

Type of pipe column: Super HZM-M, Super HZ4000, Super Z3000, Super HZ2000

Solvent: tetrahydrofuran

Phase flow: 1mL/min

Pipe column pressure: 5.0MPa

Column temperature: 40 ° C

Sample injection amount: 10 μL

Sample concentration: 0.2 mg/mL

[Appearance test of resin composition before hardening (resin appearance)]

The appearance of the resin composition before hardening was confirmed. The resin composition was stored at -30 ° C (minus 30 ° C) for 1 hour, and the presence or absence of white turbidity or coloration caused by crystallization or the like was visually observed and evaluated by the following criteria.

Specifically, when it was not possible to visually recognize that there was any turbidity or coloring, the result was good (clarification), and it was described as "○" in the column of "resin appearance" in Table 1. On the other hand, when it was confirmed by visual observation that any of white turbidity and coloring was observed, the result was poor (lack of appearance), and it was described as "x" in the column of "resin appearance" in Table 1.

[Evaluation of transparency of cured product (transparency)]

As shown in Fig. 2, a square frame (internal size: 1.0 × 40 × 10 mm) was made of enamel rubber on a microglass (size: 1.0 × 76 × 26 mm), and 1.0 g of active energy was dropped into the frame. A radiation hardening composition. When the temperature was raised at 70 ° C, when the surface became smooth, ultraviolet irradiation was performed under the following conditions.

(UV irradiation conditions)

Irradiation intensity: 120W/cm

Irradiation distance: 10cm

Conveyor speed: 5m/min

Number of exposures: 2 times

Using a spectrophotometer (product name: UV-VISIBLE SPECTROPHOTO METER, manufactured by Shimadzu Corporation), the transmittance was measured using only the microglass as a control, and the evaluation was performed based on the following criteria.

When the transmittance at 400 nm is 95% or more, the transmittance is considered to be good, and it is described as "○" in the column of "transparency (transmittance of 400 nm)". On the other hand, when the transmittance at 400 nm is less than 95%, the transmittance is regarded as defective, and is described as "x" in the column of "transparency (transmittance of 400 nm)" in Table 1.

[Evaluation of heat resistance of hardened material (hue change)]

The glass laminate (test piece A) shown in Fig. 3 was stored under the following heat-resistant conditions, and the change in APHA (hue) and shape of the test piece A was observed. Further, Fig. 3(A) is a plan view of the glass laminate from above, and Fig. 4(B) is a view of the glass laminate viewed from the lateral direction.

(production of test piece A)

The glass laminate (test piece A) shown in Fig. 3 was produced in the following manner. First, at the center of the glass plate (thickness 1mm, four sides 5cm), A 0.200 g active energy ray hardening composition was placed and placed correctly. Further, a glass plate of the same shape was covered thereon, and the resin layer was developed in a circular shape (diameter: 4 cm) to obtain a glass laminate. Then, a glass laminate (test piece A) having a cured layer of a resin composition was obtained by ultraviolet irradiation using a high-pressure mercury lamp (manufactured by Eye Graphics Co., Ltd.) from the glass surface of the glass laminate.

(UV irradiation conditions)

Irradiation intensity: 120W/cm

Irradiation distance: 10cm

Conveyor speed: 5m/min

Number of exposures: 8 times (4 times on each side)

(preservation under heat-resistant conditions)

The test plate (glass laminate, after hardening) was stored for 1,000 hours at a temperature of 95 ° C using a small environmental tester (product name: SH-641, manufactured by ESPEC).

(Measurement of APHA)

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

In the case where the increase in APHA before and after storage under heat-resistant conditions is less than 15, it is considered to be extremely excellent in heat resistance from the viewpoint of hue, and is described as "in the hue change" column of "heat resistance" in Table 1. ◎". Moreover, in the case where the increase in APHA before and after storage under heat-resistant conditions is 15 or more and less than 50, from the viewpoint of hue, heat resistance is regarded as It is good, and it is described as "○" in the "hue change" column of "heat resistance" in Table 1. On the other hand, when the increase in APHA before and after storage under heat-resistant conditions is 50 or more, it is considered to be poor in heat resistance from the viewpoint of hue, and is described in the "hue change" column of "heat resistance" in Table 1. It is "X".

[Evaluation of heat resistance of cured product (shape change)]

The presence or absence of a shape change of the test piece A after storage under heat-resistant conditions was visually observed and evaluated by the following criteria.

Specifically, in the case where it is impossible to visually recognize the shape change (any shape change such as bending, wrinkles, or shift of the pattern), the result is regarded as good, and the shape change of "heat resistance" in Table 1 is considered. The column is marked as "○". On the other hand, when the shape is changed by visual observation, the result is regarded as a defect, and it is described as "x" in the "shape change" column of "heat resistance" in Table 1.

[Evaluation of heat resistance of cured product (change in hardness of coating film)]

On a glass (size: 2 × 100 × 200 mm) plate, a square frame (internal size: 7 × 40 × 40 mm) was made of enamel rubber, and in this frame, a preheated active energy ray hardening composition was prepared. Slowly put in a way that does not produce bubbles as much as possible. Further, when the bubbles were noticeable, the bubbles were eliminated by being placed in an oven at 80 °C. Then, the film was heated at 80 ° C, and when the surface was smooth, ultraviolet irradiation was carried out under the following conditions, and the coating film was turned over, and ultraviolet rays were irradiated under the same conditions to obtain a test piece B (tablet computer).

(UV irradiation conditions)

Irradiation intensity: 120W/cm

Irradiation distance: 10cm

Conveyor speed: 3.5m/min

Number of exposures: 5 times

The A hardness was measured in accordance with JIS K 6253 using an automatic constant pressure loader (GS-610, manufactured by Technoc Co., Ltd.). Further, the load at the time of measurement was set to 500 g, and the load reduction speed was set to 9 mm/s. Then, the test piece B was stored at a temperature of 95 ° C for 1,000 hours. If the value of the hardness before and after storage is less than ±20%, it is described as "○" in the "Change in film hardness" of "Heat resistance". On the other hand, if the value of the hardness of the coating film is ±20% or more, it is described as "x". Further, the aforementioned "hardness value" can be calculated by dividing the hardness of the test piece B after storage by the hardness of the test piece B before storage.

<Synthesis Example>

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

(Measurement of isocyanate concentration)

The isocyanate group concentration was measured in the following manner. Further, the measurement was carried out in a 100 mL glass flask and stirred with a stirrer.

(Measurement of blank value)

In 15 mL of THF, 15 mL of dibutylamine in THF (0.1 N) was added, and 3 drops of bromophenol blue (1% methanol dilution) were further added. After coloring to blue, the equivalent concentration was 0.1 N HCl. Aqueous solution titration. The titration amount of the aqueous HCl solution at the time of discoloration was set as V _b (mL).

(Measurement of measured isocyanate concentration)

The scale was sampled with W _s (g), dissolved in 15 mL of THF, and 15 mL of a solution of dibutylamine in THF (0.1 N) was added. After confirming the solution, 3 drops of bromophenol blue (1% methanol diluent) was added to be colored blue, and then titrated with an aqueous solution of 0.1 N in an equivalent concentration. The titration amount of the aqueous HCl solution at the time of visible discoloration was set as V _s (mL).

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

Isocyanate group concentration (% by weight) = (V _b - V _s ) × 1.005 × 0.42 ÷ W _s

The following are descriptions of (A) to (E), (Y), and (Z) used in the synthesis examples and comparative synthesis examples.

[Polyol (A)]

"P3000" (Compound name hydrogenated polybutadiene diol, hydroxyl value 0.56 Phth meq / g (in terms of decanoic anhydride), non-volatile 99.98%, estimated weight average molecular weight 3571); product name "KRASOL HLBH P3000" (Japan Caoda Corporation)

"P2000" (compound name polybutadiene diol, hydroxyl value 49.71 mgKOH/g, estimated weight average molecular weight 2257); product name "KRASOL LBH P2000" (made by Nippon Soda Co., Ltd.)

"Epol" (compound name hydroxyl terminated liquid polyolefin: hydrogenated polyisoprene polyol having hydroxyl group at the end, hydroxyl group price 0.92 mol / kg, bromine price 5.9 g / 100 g, nonvolatile matter 99.5 weight % or more, estimated weight average molecular weight 2174); product name "Epol" (made by Idemitsu Kosan Co., Ltd.)

"GI-2000" (compound name hydrogenated 1,2-polybutadiene diol, hydroxyl value 48.3 mgKOH/g, iodine value 9.0 g/100 g, hydrogenation rate 97.6%, estimated weight average molecular weight 2323); product name "NISSO" PB GI-2000" (made by Japan Soda Corporation)

"GI-3000" (compound name hydrogenated 1,2-polybutadiene diol, hydroxy The base price is 28.3 mgKOH/g, the iodine value is 15.6 g/100 g, the volatile matter is 0.11%, and the weight average molecular weight is estimated to be 3965); the product name is "NISSO PB GI-3000" (manufactured by Nippon Soda Co., Ltd.)

"G-3000" (compound name 1,2-polybutadiene diol, hydroxyl value 31.0 mgKOH/g, estimated weight average molecular weight 3619); product name "NISSO PB G-3000" (made by Nippon Soda Co., Ltd.)

"PP4000" (compound name: polypropylene glycol, hydroxyl value: 26.9 mgKOH/g, estimated weight average molecular weight: 4171); product name "Newpol PP4000" (manufactured by Sanyo Chemical Industries, Ltd.)

[alcohol (B)]

"TMP" (compound name trimethylolpropane, trifunctional alcohol, molecular weight 134, white solid); product name "trimethylolpropane (TMP)" (Mitsubishi Gas Chemical Co., Ltd.)

"HD-402" (a compound name PPG modified pentaerythritol, a trifunctional alcohol, a hydroxyl group price of 561 mgKOH/g, a molecular weight of 400); and a product name "Sannix HD-402" (manufactured by Mitsubishi Gas Chemical Co., Ltd.)

"GP-250" (compound name PPG modified glycerin, trifunctional alcohol, hydroxyl value 672 mgKOH/g, molecular weight 250); product name "Sannix GP-250" (Mitsubishi Gas Chemical Co., Ltd.)

"PCL308" (compound name polycaprolactone modified alcohol, trifunctional alcohol, hydroxyl value 193 mgKOH/g, molecular weight 870); product name "Placcel PCL308" (made by Daicel Co., Ltd.)

[diisocyanate (C)]

"IPDI" (compound name isophorone diisocyanate); product name "VESTANAT IPDI" (Evonik)

"HDI" (compound name hexamethylene diisocyanate); product name "HDI" (made by Japan Polyurethane Co., Ltd.)

"TMDI" (compound name 2,2,4-trimethylhexamethylene diisocyanate); product name "TMDI" (manufactured by Evonik)

[(Meth)acrylate (D)]

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

[alcohol (E)]

"2-EH"; 2-ethylhexanol (manufactured by Sankyo Chemical Co., Ltd.)

[(Meth)acrylate (Y)]

"NOA" (compound name n-octyl acrylate); product name "NOAA" (made by Osaka Organic Chemical Co., Ltd.)

[Photopolymerization initiator (Z)]

Irg184 (compound name 1-hydroxycyclohexyl phenyl ketone); product name "Irg184" (manufactured by BASF Japan Co., Ltd.)

In the following, although the synthesis example and the comparative synthesis example are described, the "ppm", "% by weight", and "% by weight" of the concentration mark are all based on (theoretical) all of the amino carboxylic acid obtained unless otherwise specified. The concentration of the ester (meth) acrylate content.

<Synthesis Example 1/X-1>

In a separable flask equipped with a thermometer and a stirring device, 269.1 g of P3000 as a polyol (A), 1.5 g of TMP as an alcohol (B), 800 ppm of dibutylhydroxytoluene (BHT), and 128.5 g were added. This is NOA (30% by weight) of (meth) acrylate (Y). The internal temperature was set to 70 ° C and stirred for 1 hour to homogenize the system, and then cooled again to 50 ° C. 24.7 g of IPDI as diisocyanate (C) was added. After homogenizing the system, 300 ppm of dibutyltin dilaurate (DBTDL) was added. After stirring at the reaction temperature for 1 hour, the temperature was raised to 70 ° C, and then the reaction was continued.

Further, the completion of the reaction is carried out by the concentration of the isocyanate group remaining in the reaction solution in which the hydroxyl group of the reaction solution is all-formated by the urethane (hereinafter referred to as "the theoretical terminal isocyanate group". Concentration") is confirmed below.

In this example, after confirming that the isocyanate group concentration in the reaction liquid was equal to or less than the theoretical end point isocyanate group concentration (0.37% by weight), the operation was shifted to the following.

Then, 2.4 g of 2-EH as the alcohol (E) was charged. After further stirring at 70 ° C for 2 hours, 2.2 g of 2-hydroxyethyl acrylate as (meth) acrylate (D) was added, and it was confirmed that the isocyanate group concentration was 0.05% by weight or less, and the reaction was terminated to obtain activity. Energy ray-curable urethane (meth) acrylate-containing material (X-1).

Further, the molar ratios of HLBH-P3000, TMP, IPDI, HEA, and 2-EH used in the above reaction were 4.0:0.6:5.9:1.02:1.0.

<Synthesis Example 2/X-2>

In addition to 245.7 g of Epol as the polyol (A), 33.1 g of IPDI as the diisocyanate (C), and 122.1 g of NOA (30% by weight) as the (meth) acrylate (Y), Synthesis Example 1 was carried out in the same manner to obtain an active energy ray-curable urethane (meth) acrylate-containing material (X-2).

Further, the molar ratios of Epol, TMP, IPDI, HEA, and 2-EH used in the above reaction were 6.0:0.6:7.9:1.02:1.0.

<Synthesis Example 3/X-3>

In addition to 262.6 g of GI-2000 as the polyol (A), 33.1 g of IPDI as the diisocyanate (C), and 129.3 g of NOA (30% by weight) as the (meth) acrylate (Y) In the same manner as in Synthesis Example 1, an active energy ray-curable urethane (meth) acrylate-containing material (X-3) was obtained.

Further, the molar ratios of GI2000, TMP, IPDI, HEA, and 2-EH used in the above reaction were 6.0:0.6:7.9:1.02:1.0.

<Synthesis Example 4/X-4>

In the same manner as in Synthesis Example 1, except that 298.8 g of GI-3000 as the polyol (A) and 141.3 g of NOA (30% by weight) as the (meth) acrylate (Y) were used, the active energy was obtained. The radiation-curable urethane (meth) acrylate-containing material (X-4).

Furthermore, the molar ratios of GI3000, TMP, IPDI, HEA, and 2-EH are 4.0:0.6:5.9:1.02:1.0.

<Synthesis Example 5/X-5>

Active energy ray hardening was carried out in the same manner as in Synthesis Example 1, except that 272.7 g of G3000 as the polyol (A) and 130.1 g of NOA (30% by weight) as the (meth) acrylate (Y) were used. The urethane (meth) acrylate contains (X-5).

Further, the molar ratios of G3000, TMP, IPDI, HEA, and 2-EH used in the above reaction were 4.0:0.6:5.9:1.02:1.0.

<Synthesis Example 6/X-6>

In addition to using 170.1 g of P2000 as polyol (A) and 86.1 g of NOA (30% by weight) as (meth) acrylate (Y), and synthesis In the same manner as in Example 1, an active energy ray-curable urethane (meth) acrylate-containing material (X-6) was obtained.

Further, the molar ratios of P2000, TMP, IPDI, HEA, and 2-EH used in the above reaction were 4.0:0.6:5.9:1.02:1.0.

<Synthesis Example 7/X-7>

In addition to using 148.0 g of P3000 as the polyol (A), 0.75 g of TMP as the alcohol (B), 15.3 g of IPDI as the diisocyanate (C), and 3.17 g as the (meth) acrylate (D). In the same manner as in Synthesis Example 1, except that 0.12 g of the above-mentioned HEA and 1.32 g were used as the 2-EH of the alcohol (E), and 48.2 g of NOA (20% by weight) as the (meth) acrylate (Y) was used. An active energy ray-curable urethane (meth) acrylate-containing material (X-7) was obtained.

Further, the molar ratios of P3000, TMP, IPDI, HEA, and 2-EH used in the above reaction were 2.2:0.3:3.65:1.47:0.55.

<Synthesis Example 8/X-8>

Active energy ray hardening was carried out in the same manner as in Synthesis Example 1, except that 19.1 g of HDI as the diisocyanate (C) and 126.1 g of NOA (30% by weight) as the (meth) acrylate (Y) were used. The urethane (meth) acrylate contains (X-8).

Further, the molar ratios of P3000, TMP, HDI, HEA, and 2-EH used in the above reaction were 4.0:0.6:5.9:1.02:1.0.

<Synthesis Example 9/X-9>

Active energy ray hardening was carried out in the same manner as in Synthesis Example 1 except that 23.4 g of TMDI as the diisocyanate (C) and 128.0 g of NOA (30% by weight) as the (meth) acrylate (Y) were used. Amine Carbamate (meth) acrylate containing (X9).

Further, the molar ratios of P3000, TMP, TMDI, HEA, and 2-EH used in the above reaction were 4.0:0.6:5.9:1.02:1.0.

<Synthesis Example 10/X-10>

In addition to 298.8 g of GI-3000 as the polyol (A), 2.24 g of HD402 as the alcohol (B), 23.4 g of IPDI as the diisocyanate (C), and 141.0 g of (meth) acrylate ( In the same manner as in Synthesis Example 1, except for NOA (30% by weight) of Y), an active energy ray-curable urethane (meth) acrylate-containing material (X-10) was obtained.

Further, the molar ratios of GI-3000, HD402, IPDI, HEA, and 2-EH used in the above reaction were 4.0:0.3:5.6:1.02:1.0.

<Synthesis Example 11/X-11>

In addition to 298.8 g of GI-3000 as the polyol (A), 1.40 g of GP250 as the alcohol (B), 22.8 g of IPDI as the diisocyanate (C), and 140.4 g of (meth) acrylate ( In the same manner as in Synthesis Example 1, except for NOA (30% by weight) of Y), an active energy ray-curable urethane (meth) acrylate-containing material (X-11) was obtained.

Further, the molar ratios of GI-3000, GP250, IPDI, HEA, and 2-EH used in the above reaction were 4.0:0.3:5.45:1.02:1.0.

<Synthesis Example 12/X-12>

In addition to 298.8 g of GI-3000 as the polyol (A), 2.50 g of TMP as the alcohol (B), 27.2 g of IPDI as the diisocyanate (C), and 142.8 g of (meth) acrylate ( In the same manner as in Synthesis Example 1, except for NOA (30% by weight) of Y), an active energy ray-curable urethane (meth) acrylate-containing material (X-12) was obtained.

Further, the molar ratios of GI-3000, TMP, IPDI, HEA, and 2-EH used in the above reaction were 4.0:1.0:6.5:1.02:1.0.

<Synthesis Example 13/X-13>

In the active energy ray-curable urethane (meth) acrylate (X)-containing material (X-1), 128.5 g of NOA is further added so that the NOA concentration is 60%, and active energy ray hardening is performed. The urethane (meth) acrylate contains (X-13).

<Synthesis Example 14/X-14>

In addition to 242.5 g of GI-2000 as the polyol (A), 8.7 g of GP250 as the alcohol (B), 40.2 g of TMDI as the diisocyanate (C), and 4.12 g as the (meth) acrylate ( In the same manner as in Synthesis Example 1, except that HEA of D) and 4.46 g were used as (2-EH of alcohol (E) and 200 g of NOA (40% by weight) of (meth) acrylate (Y). Active energy ray-curable urethane (meth) acrylate-containing material (X-14).

Further, the molar ratios of GI-2000, GP250, TMDI, HEA, and 2-EH used in the above reaction were 3.0:1.0:5.5:1.02:1.0.

<Comparative Synthesis Example 1/CA-1>

In addition to 148.0 g of P3000 as the polyol (A), 13.4 g of IPDI as the diisocyanate (C), 3.17 g of HEA as the (meth) acrylate, and 1.32 g (the alcohol (E) 2 -EH, 71.1 g of NOA (30% by weight) of (meth) acrylate (Y), and the same procedure as in Synthesis Example 1 except that the alcohol (B) was not used, and an active energy ray-curable amine group was obtained. Formate (meth) acrylate containing (CA-1).

Furthermore, P3000, IPDI, HEA, 2-EH used in the above reaction The molar ratio is 2.2:3.2:1.47:0.55.

<Comparative Synthesis Example 2/CA-2>

In addition to 148.0 g of P3000 as the polyol (A), 0.75 g of TMP as the alcohol (B), 15.3 g of IPDI as the diisocyanate (C), and 3.93 g of the (meth) acrylate (D) In the same manner as in Synthesis Example 1, the reaction was carried out in the same manner as in Synthesis Example 1 except that the amount of the above-mentioned HEA and 0.48 g (2-EH of the alcohol (E) and 72.2 g of the NO (30% by weight) of the (meth) acrylate (Y) was obtained. Energy ray-curable urethane (meth) acrylate-containing material (CA-2).

Further, the molar ratios of P3000, TMP, IPDI, HEA, and 2-EH used in the above reaction were 2.2:0.3:3.65:1.82:0.2.

<Comparative Synthesis Example 3/CA-3>

In addition to using 1.62 g of PCL308 as the alcohol (B), 21.6 g of IPDI as the diisocyanate (C), and 127.2 g of NOA (30% by weight) as the (meth) acrylate (Y), In the same manner as in Example 1, an active energy ray-curable urethane (meth) acrylate-containing material (CA-3) was obtained.

Further, the molar ratios of P3000, PCL308, IPDI, HEA, and 2-EH used in the above reaction were 4.0:0.1:5.15:1.02:1.0.

<Comparative Synthesis Example 4/CA-4>

In addition to 314.3 g of PP4000 as polyol (A), 1.50 g of TMP as alcohol (B), 24.7 g of IPDI as diisocyanate (C), and 4.36 g of (meth) acrylate (D) The active energy ray-curable amine group was obtained in the same manner as in Synthesis Example 1 except that NOA (30% by weight) of (meth) acrylate (Y) was used as the NOA (30% by weight) of the (meth) acrylate (Y). Formate (meth) acrylate containing (CA-4).

Further, the molar ratios of PP4000, TMP, IPDI, and HEA used in the above reaction were 4.0:0.6:5.9:2.02.

<Comparative Synthesis Example 5/CA-5>

In addition to 273.2 g of PP4000 as polyol (A), 1.30 g of TMP as alcohol (B), 21.4 g of IPDI as diisocyanate (C), and 1.90 g of (meth) acrylate (D) In the same manner as in Synthesis Example 1, except that 2.10 g of 2EH as the alcohol (E) and 128.5 g of NOA (30% by weight) as the (meth) acrylate (Y) were used, the active energy was obtained. Radiation-curable urethane (meth) acrylate-containing material (CA-5).

Further, the molar ratios of PP4000, TMP, IPDI, HEA, and 2-EH used in the above reaction were 4.0:0.6:5.9:1.02:1.0.

(modulation of active energy ray hardening composition)

Addition to 100 parts by weight of active energy ray-curable urethane (meth) acrylate containing materials (X-1) to (X-14), (CA-1) to (CA-5) 3 parts by weight of Irg 184 as a photopolymerization initiator was used as an active energy ray-curable composition.

<test result>

Each of the above tests and evaluations was carried out for the active energy ray-curable composition formed according to the blending ratio described in Table 1. As described above, the results of the tests and evaluations are shown in Table 1. In addition, in Table 1, the active energy ray-curable composition is simply referred to as "pre-curing composition".

As shown in the examples, the active energy ray-curable composition containing the urethane (meth) acrylate (X) of the present invention has a good appearance before curing, and can be prevented by filling between the films. Light scattering at the interface between air and film. Further, it is understood that the cured product has a colorless phase change or a shape change and a change in the hardness of the coating film even if it is applied to high heat for a long period of time.

On the other hand, as shown in Comparative Example 1, the active energy ray-curable composition in the case where the alcohol (B) was not used was changed in the heat resistance (tablet) test, and the change in the hardness of the coating film was large. Further, as shown in Comparative Example 2, when the (meth)acryl oxime group concentration in the urethane (meth) acrylate was set to 0.2 mol/kg, heat shrinkage due to hardening shrinkage (tablet computer) In the test, the change in the hardness of the coating film becomes large. Further, as shown in Comparative Example 3, when PCL308 was used as the alcohol (B), compatibility with other components was deteriorated, and white turbidity was caused, and it was not possible to use it as an active energy ray-curable composition. Further, as shown in Comparative Examples 4 and 5, it was found that when polypropylene glycol having excellent transparency was used as the polyol, the cured product was liquidized in the heat resistance test.

[Industrial availability]

When the active energy ray-curable composition of the present invention is produced as a component-containing urethane (meth) acrylate (X), it does not have high viscosity and produces little by-products, and can be produced as The target urethane (meth) acrylate (X). As a result, in the active energy ray-curable composition of the present invention (before curing), the appearance of the resin due to white turbidity at a low temperature is not deteriorated. Moreover, the active energy ray-curable composition of the present invention has good wettability with a glass substrate or a plastic substrate. Good, high flexibility, high heat resistance, and low hardenability, so it can be used as an interlayer filler even in the case of thin substrates for smart phones or tablets. Moreover, when the active energy ray-curable composition of the present invention is used as an interlayer filler, the adhesion between the cured product and the substrate is good. Further, the cured product of the active energy ray-curable composition of the present invention has high transparency, and even at a high temperature, deformation or hue deterioration is small. Further, the active energy ray-curable composition of the present invention can be prevented from being trapped in the air by filling a transparent substrate between a display used in a personal computer, a car navigation, a television, a mobile phone (smartphone), a tablet computer, or the like. Light scattering at the interface of the transparent substrate is also useful from the viewpoint of obtaining a laminate having a color change or a shape change which is less likely to cause a heat resistance test.

1‧‧‧hardened layer of active energy ray hardening composition

2‧‧‧Transparent substrate

3‧‧‧Transparent substrate

Claims (4)

An active energy ray-curable composition comprising a urethane (meth) acrylate (X) having a polyolefin-based polyol (A) having a polyolefin skeleton and having three or more An aliphatic alcohol (B) having a hydroxyl group and a molecular weight of 100 or more and less than 800, and an aliphatic diisocyanate (C) are subjected to a urethanization reaction to form a urethane isocyanate prepolymer containing an isocyanate group. Thereafter, the urethane isocyanate prepolymer, the (meth) acrylate having a hydroxyl group (D), and the alcohol (E) having one hydroxyl group are obtained by reacting a monofunctional (meth) acrylate ( Y), and an active energy ray-curable composition of the photopolymerization initiator (Z); wherein the polyolefin-based polyol (A) having a polyolefin skeleton is selected from polybutadiene having a hydroxyl group at both terminals And at least one of the group of polyisoprene and the hydrogenated hydrogenated polyol having a weight average molecular weight of 2,000 to 10,000; and a urethane (meth) acrylate (X) The (meth)acrylonitrile group concentration is 0.05 or more and less than 0.20 mol/kg. The active energy ray-curable composition of claim 1, wherein the reaction is carried out until the isocyanate concentration in the reaction liquid forming the isocyanate-containing urethane isocyanate prepolymer becomes a supply reaction The concentration of the isocyanate group remaining in the case where all of the hydroxyl groups are urethane-formed is equal to or less. A laminate comprising a first transparent substrate selected from the group consisting of glass and plastic and a second transparent substrate selected from the group consisting of glass and plastic, having a cured product of the active energy ray-curable composition of claim 1 or 2. Floor. A laminated body formed by coating an active energy ray-curable composition according to any one of claims 1 or 2 on a first transparent substrate to form a resin layer, and attaching a second transparent substrate to the resin layer The active energy ray is then irradiated to cure the active energy ray curable composition to form a cured layer.