TWI613226B - Active energy ray curable composition for interlayer filling - Google Patents

Abstract

The present invention provides an active energy ray-curable composition, which has excellent wettability with plastic and glass, and does not accompany the appearance change such as discoloration and deformation even under high temperature and high humidity, and is suitable for interlayer filling. This active energy ray-curable composition is characterized by including a urethane (methyl group) produced by subjecting a diol (X) having a specific hydrogenated polyolefin skeleton to a urethane reaction under specific conditions. ) Acrylate (A), monofunctional (meth) acrylate (B), and photopolymerization initiator (C).

Description

Active energy ray-curable composition for interlayer filling

The present invention relates to an active energy ray-curable composition that can be used as an interlayer filler for transparent substrates for displays in computers, televisions, and mobile phones, and a hardened material layer having the active energy ray-curable composition Laminated body.

Monitors used in computers, car navigation, televisions, mobile phones, etc., reflect images with light from the backlight. The display includes color filters, and uses various transparent substrates such as glass substrates such as glass plates or plastic substrates such as plastic films. Because of the light scattering or absorption of these transparent substrates, Effect, so the amount of light output by the light source to the outside of the display will be reduced. When the reduction is larger, the screen becomes darker and the visibility decreases. In order to improve visibility, the display surface layer is improved in anti-reflection, and the amount of light from a light source is increased.

As a part thereof, 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, it is possible to prevent light scattering at the interface between the air and the glass substrate or the plastic substrate, and therefore it is possible to prevent a decrease in the amount of light output.

The properties required for resins used as interlayers of transparent substrates such as glass substrates and plastic substrates require not only adhesion to transparent substrates, but also high deformation resistance, high flexibility, and high transparency. In particular, the transmittance at 400 nm is 95% or more. In addition, the resistance to high temperature needs to be specifically no change in shape or color tone at 95 ° C. Aiming at such properties of resins, It has been proposed to use a carbamate (meth) acrylate of a hydrogenated butadiene polyol or a composition containing the same.

Prior art literature Patent literature

Patent Document 1 Japanese Patent No. 1041553

Patent Document 2 Japanese Patent No. 2582575

Patent Document 3 Japanese Patent Laid-Open No. 2002-069138

Patent Document 4 Japanese Patent Laid-Open No. 2002-309185

Patent Document 5 Japanese Patent Laid-Open No. 2003-155455

Patent Document 6 JP 2010-144000

Patent Document 7 Japanese Patent Laid-Open No. 2010-254890

Patent Document 8 Japanese Patent Laid-Open No. 2010-254891

Patent Document 9 Japanese Patent Application Publication No. 2010-265402

Patent Document 10 Japanese Patent Application Laid-Open No. 2011-116965

However, the urethane (meth) acrylates described in the prior art, or the composition containing them, have the following disadvantages, and are not sufficient as interlayer fillers for transparent substrates for displays. Disadvantages are: it cannot be produced on a large scale with a high viscosity during the synthesis of urethane (meth) acrylate, and because the reaction becomes uneven, the urethane (meth) acrylate obtained Or these compositions may have reduced transparency due to turbidity at low temperatures; and the cured coating film may undergo shape changes at high temperatures.

Therefore, an object of the present invention is to provide an active energy ray-curable composition and a laminated body having a hardened material layer of the active energy ray-curable composition, wherein the active energy ray-curable composition is for producing the active substance. The energy ray-curable composition does not have high viscosity when the components are contained, and there is less generation of by-products. The target component can be produced, and the hardened system of the active energy ray-curable composition exhibits high flexibility and high transparency. And high temperature heat resistance.

In order to achieve the foregoing object, the inventors of the present case conducted careful investigations, and found that: a kind of urethane (meth) acrylate (A) obtained from a specific diol having a hydrogenated polyolefin skeleton under specific conditions, active energy The active energy ray-curable composition of the linearly curable monofunctional monomer (B) and the photopolymerization initiator (C) is a curable composition for an interlayer filler 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 (A), a monofunctional (meth) acrylate (B), and a photopolymerization agent. Initiator (C); wherein the urethane (meth) acrylate (A) is a diol (X) having a weight-average molecular weight of 2,000 to 10,000 having a hydrogenated polyolefin skeleton, and is selected from alicyclic A diisocyanate (Y) of at least one of the group consisting of a formula diisocyanate, a branched aliphatic diisocyanate, and a diisocyanate compound obtained by hydrogenating an aromatic isocyanate, and the monofunctional (methyl) Carbamate reaction is performed in the presence of acrylate (B) to form an isocyanate group-containing urethane isocyanate prepolymer, and then the urethane isocyanate prepolymer and the hydroxyl group-containing (form Group) acrylate (Z) is produced by reaction.

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

[In formula (1), a represents an integer of 70 to 250, and R ² represents a monovalent base represented by the following formula (2) (in formula (2), b represents an integer from 0 to 10),

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

The urethane isocyanate prepolymer is preferably an amine obtained by reacting all hydroxyl groups of the diol (X) having a weight average molecular weight of 2,000 to 10,000 with a hydrogenated polyolefin skeleton until the urethane is formed. Carbamate isocyanate prepolymer.

The active energy ray-curable composition preferably does not include a volatile organic solvent.

In the active energy ray-curable composition, the increase in APHA of the laminate before and after storage is preferably 25 or less when the laminate obtained by the following steps is stored at 95 ° C. for 500 hours. The step is to apply a 0.200 g of the active energy ray-curable composition to the center of the first glass substrate (1 mm, 5 cm square) to form a circular resin layer (4 cm diameter), and apply the resin layer on the resin layer. A second glass substrate (square with a thickness of 1 mm and 5 cm) was attached, and then the active energy ray was irradiated to harden the active energy ray-curable composition to form a cured material layer.

The present invention also provides a laminated body comprising a hardened material layer having the active energy ray hardening composition between a first transparent substrate selected from glass and plastic and a second transparent substrate selected from glass and plastic. .

The laminated body preferably forms a resin layer by coating the active energy ray-curable composition on a first transparent substrate, attaches a second transparent substrate to the resin layer, and then irradiates the active energy rays to make the The active energy ray-curable composition is hardened to form a hardened material layer.

The active energy ray-curable composition of the present invention does not have a high viscosity when producing the urethane (meth) acrylate (A) as a component, and also has fewer by-products to produce, and can be produced. The target urethane (meth) acrylate (A). As a result, the active energy ray-curable composition (before curing) of the present invention did not deteriorate the appearance of the resin due to turbidity at low temperatures. In addition, the active energy ray-curable composition of the present invention has good wettability with a glass substrate or a plastic substrate, and has high flexibility and high heat resistance. Moreover, the hardened | cured material of the active-energy-ray-curable composition of this invention is high in transparency, and even if it is high temperature, it does not deform | transform or the color tone deteriorates little.

In addition, I know that by filling the active energy ray-curable composition of the present invention between transparent substrates of displays used in computers, car navigation, televisions, and mobile phones, it is possible to prevent light at the interface between air and transparent substrates. Scattering, even a laminated body that is hard to cause a change in hue or shape in a heat resistance test.

[Form of Implementing Invention] <Method for producing a urethane (meth) acrylate (A) obtained from a diol having a hydrogenated polyolefin skeleton>

The urethane (meth) acrylate (A) used in the present invention is a diol (X) which can have a weight average molecular weight of 2,000 to 10,000 having a hydrogenated polyolefin skeleton, and is selected from the group consisting of alicyclic An isocyanate, an aliphatic diisocyanate having a branched chain, and a diisocyanate (Y) of at least one of the group consisting of a diisocyanate compound obtained by hydrogenating an aromatic isocyanate, and a monofunctional (meth) acrylate ( B) Carrying out a urethane reaction in the presence of an isocyanate group-containing urethane isocyanate prepolymer, and then combining the urethane isocyanate prepolymer with a hydroxyl-containing (meth) acrylic acid Esters (Z) are produced by reaction.

In addition, the urethane (meth) acrylate (A) may be simply referred to as "urethane (meth) acrylate (A)" or "(A)" hereinafter, The diol (X) having a weight average molecular weight of 2,000 to 10,000 of the polyolefin skeleton is abbreviated as "diol (X)" or "(X)", and will be selected from alicyclic diisocyanates and branched aliphatic diisocyanates. And at least one diisocyanate (Y) in the group consisting of diisocyanate compounds obtained by hydrogenating aromatic isocyanates, is referred to as "diisocyanate (Y)", "(Y)", and the hydroxyl group-containing ( The meth) acrylate (Z) is abbreviated as "(Z)".

Compared with the above-mentioned production method, for example, "the method of mixing (X), (Y), and (Z) and reacting them together" "reacting (Y) and (Z) to form an isocyanate-containing urethane After the isocyanate prepolymer, the method of reacting the prepolymer with (X) "and other conventional methods have achieved significant improvements in preventing viscosity increase, resin appearance, suppression of by-products, transparency of hardened materials, heat resistance, etc. effect.

Specifically, if manufactured by "the method of mixing (X), (Y), and (Z) together and reacting"), the urethane (meth) acrylate (A) will have a high viscosity, and will be stirred It becomes difficult, or the reaction proceeds unevenly. Not only does the probability of partial gelation become higher, but the by-product of the compound that does not have a diol (X) having a polyolefin skeleton in the skeleton increases, and transmission is caused. Decrease in rate and decrease in flexibility. In addition, since various complex compounds are generated irregularly, it is difficult to control the quality when the product is used as an active energy ray-curable resin composition.

In addition, when "the method of reacting (Y) and (Z) to form an isocyanate group-containing urethane isocyanate prepolymer, and then reacting the prepolymer with (X)", side reactions are generated. A compound in which all the isocyanate groups of the diisocyanate (Y) of the product react with the hydroxyl group-containing (meth) acrylate (Z). This by-product does not contain a diol (X) skeleton having a polyolefin skeleton, and exhibits crystallinity. The transmittance at 400 nm decreases, and the possibility of gelation becomes high.

Among the above-mentioned production methods, as a method for synthesizing a urethane isocyanate prepolymer, the following method may be mentioned.

[Method 1] A method in which a diol (X) and a diisocyanate (Y) are mixed together and reacted.

[Method 2] A method in which a diol (X) is dropped into a diisocyanate (Y) and reacted.

[Method 3] A method in which a diisocyanate (Y) is dropped into a diol (X) and reacted.

[Method 3] In the case of a large amount of diol (X), the diisocyanate (Y) is reacted while being dropped, and thus the diisocyanate (Y) is reacted. The isocyanate groups on both sides are urethanized with the hydroxyl group of 2 moles of diol (X), and there are cases where the XYX-type diols with hydroxyl groups at both ends are formed by schematic writing. Furthermore, when it reacts with 2 moles of diisocyanate (Y), it is schematically written as a compound of the YXYXY type whose both ends are isocyanate groups to generate a by-product. The same reaction is further repeated, and it is schematically written as A large number of compounds of the following structures are produced as by-products.

Y- [XY] _n -XY (n = 1 or more)

When such by-products are generated in large amounts, the urethane (meth) acrylates obtained by reacting with the hydroxyl-containing (meth) acrylates (Z) may have a low density of acrylic acid, and hardened products may not be obtained. To sufficient crosslink density.

Therefore, in order to obtain the target urethane isocyanate prepolymer in a good yield, [Method 1] and [Method 2] are particularly applicable.

[Method 1] Case:

In the reactor, first add the diol (X) and the monofunctional (meth) acrylate (B), stir until homogeneous, and then add the diisocyanate (Y) and make it uniform. By the foregoing, the viscosity of the reaction solution can be reduced. After that, the method of continuously stirring and raising the temperature as necessary, and then starting the urethanization with a urethanization catalyst is preferred. After the urethane catalyst is added, the temperature may be increased as necessary.

Before the diol (X) and the diisocyanate (Y) become uniform, if a urethane catalyst is introduced from the beginning, the diol (X) and the diisocyanate ( Y) Carbamate reaction will be carried out in a non-uniform state, the molecular weight or viscosity of the urethane prepolymer obtained will change, and it will react with unreacted diisocyanate (Y) If it is left in the system, it ends. In this case, since only by-products caused by the reaction between the hydroxyl-containing (meth) acrylate (Z) and the residual diisocyanate (Y) used later, the transmittance at 400 nm is reduced, It is therefore inappropriate.

The content of such a by-product is preferably less than 7% with respect to the urethane (meth) acrylate (A) obtained from a diol having a hydrogenated polyolefin skeleton as a target. Above 7%, it will cause a decrease in transmittance at 400nm.

[Method 1] From the viewpoint of directly adding a high-viscosity diol (X) to a reactor, and from the viewpoint of being able to produce a urethane (meth) acrylate (A) in one-pot , Which is excellent in industry.

[Method 2] Case:

In the reactor, add the diisocyanate (Y), the urethane catalyst, and optionally add a part of the monofunctional (meth) acrylate (B), and stir until uniform. While stirring, the temperature was raised as needed, and a uniform mixed solution of the diol (X) and the monofunctional (meth) acrylate (B) was added dropwise to the reaction while reacting.

[Method 2] The steps of separately preparing a homogeneous mixed solution of a high viscosity diol (X) and a monofunctional (meth) acrylate (B) and adding it to the reactor are complicated, but in [Method 3 It is preferable from the viewpoint that the formation of the following by-products described below is minimal.

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

Furthermore, no matter which method is used, when the urethane isocyanate prepolymer is synthesized by the reaction of the diol (X) and the diisocyanate (Y), all the hydroxyl groups of the diol (X) are reacted to the amine. Reasonable until carbamate miss you. The end point of the reaction is to measure the isocyanate group concentration (also referred to as "NCO group concentration") in the reaction solution, and it is possible to reduce the isocyanate group concentration to less than the isocyanate group concentration when all the hydroxyl groups added to the system are urethanized. It has been confirmed that the isocyanate group concentration does not change.

According to the foregoing viewpoint, the molar ratio of the diol (X) to the diisocyanate (Y) is not particularly limited. For example, with respect to 1 mol of the diol (X), 1.1 to 2.0 mol of the diisocyanate (Y) can be used. , Preferably 1.2 to 1.5 moles can be used.

Further, a urethane isocyanate prepolymer is reacted with a hydroxyl group-containing (meth) acrylate (Z) to synthesize a urethane (methyl group) obtained from a diol having a hydrogenated polyolefin skeleton as a target. In the case of acrylate (A), when a large amount of unreacted isocyanate groups remain in the reaction solution, there is a possibility that defects such as gelation and poor curing of the coating film may occur.

In order to avoid these defects, it is necessary to make the molar number of the hydroxyl group of the (meth) acrylate (Z) hydroxyl group relative to the molar number of the isocyanate group of the urethane isocyanate prepolymer in the aforementioned reaction. The reaction becomes excessive and the reaction is continued until the isocyanate group concentration remaining in the reaction solution reaches 0.1% by weight or less. Furthermore, in the aforementioned reaction, the molar number of hydroxyl groups of the (meth) acrylate (Z) containing hydroxyl groups may be relative to the molar number of isocyanate groups of 1 molar urethane isocyanate prepolymer. It is set to 1.005 ~ 1.1 moles, preferably 1.01 ~ 1.05 moles.

等聚合抑制劑的存在下進行。該等聚合抑制劑的添加量，相對於生成的胺基甲酸酯(甲基)丙烯酸酯(A)，較佳為1~10000ppm(重 量基準)較佳，更佳為100~1000ppm，最佳為400~1000ppm。當聚合抑制劑的添加量相對於胺基甲酸酯(甲基)丙烯酸酯(A)小於1ppm時，有時得不到足夠的聚合抑制效果，且超過10000ppm時，有可能會對生成物之各種物性造成不良影響。 For the purpose of preventing polymerization, the above reaction is preferably carried out in dibutylhydroxytoluene, hydroquinone, hydroquinone monomethyl ether, phenanthrene

It is carried out in the presence of a polymerization inhibitor. The addition amount of these polymerization inhibitors is preferably 1 to 10,000 ppm (weight basis), more preferably 100 to 1000 ppm, and most preferably, relative to the urethane (meth) acrylate (A) formed. It is 400 ~ 1000ppm. When the addition amount of the polymerization inhibitor is less than 1 ppm with respect to the urethane (meth) acrylate (A), a sufficient polymerization inhibitory effect may not be obtained, and when it exceeds 10,000 ppm, the product may be Various physical properties cause adverse effects.

For the same purpose, the present reaction is preferably carried out in a gaseous environment containing oxygen in a molecular state. The oxygen concentration can be appropriately selected in consideration of safety.

In order to obtain a sufficient reaction rate, this reaction can also be performed using a catalyst. As the catalyst, dibutyltin dilaurate, tin octoate, tin chloride, or the like can be used, but from the viewpoint of reaction speed, dibutyltin dilaurate is preferred. The addition amount of these catalysts is usually 1 to 3000 ppm (weight basis), and preferably 50 to 1000 ppm. When the amount of the catalyst added is less than 1 ppm, a sufficient reaction rate may not be obtained. When the amount of the catalyst added is more than 3000 ppm, the light resistance may be decreased, which may adversely affect various physical properties of the product.

The production of the urethane (meth) acrylate (A) can be performed 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 (A) is produced. In addition, after the volatile organic solvent remaining in the active energy ray-curable resin composition is applied to a transparent substrate, it can also be removed by drying. Furthermore, the volatile organic solvent refers to an organic solvent having a boiling point of not more than 200 ° C.

However, from the production of the urethane (meth) acrylate (A) to the blending of the active energy ray-curable resin composition, no volatile is used. The organic solvent is an active energy ray-curable resin composition that does not include a volatile organic solvent, but is preferably a hardened system in a closed state.

The active energy ray-curable composition of the present invention preferably does not include a volatile organic solvent. Here, "not included" means that the proportion of the entire active energy ray-curable composition is 1% by weight or less, but 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 less, and more preferably 40 to 130 ° C. When the temperature is lower than 40 ° C, a sufficient reaction rate cannot be obtained practically. When the temperature is higher than 130 ° C, the free radical polymerization caused by heat causes partial cross-linking of the double bonds and generates a gel.

The reaction usually proceeds until the residual isocyanate group becomes 0.1% by weight or less. The residual isocyanate group concentration is analyzed by gas chromatography, titration, or the like.

Furthermore, a part of the terminal (meth) acrylfluorenyl group may be denatured to an alkoxy group. By denaturing to an alkoxy group, for example, the wettability with the substrate can be adjusted.

When a part of the terminal (meth) acrylfluorenyl group is denatured into an alkoxy group, the denaturation ratio is: when the total number of moles of the (meth) acrylfluorenyl group and the alkoxy group is 100%, the alkoxy The ratio is 1 to 30 mole%, preferably 5 to 20 mole%, and most preferably 5 to 10 mole%. If the proportion of 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 reduced. Less desirable.

As a method for making a part of the terminal (meth) acrylfluorenyl group into an alkoxy group, a urethane isocyanate prepolymer and a hydroxyl group-containing A method of reacting a (meth) acrylate (Z) and further reacting a urethane isocyanate prepolymer with an alcohol, and the like.

Specific examples include the following methods.

(1) First, the urethane isocyanate prepolymer is reacted with a desired amount of alcohol, and the required ratio of the ends of the urethane isocyanate prepolymer is made to be an alkoxy group, and then the hydroxyl group is contained. A method of introducing a (meth) acrylic acid ester (Z) by introducing a (meth) acrylfluorenyl group into a residual isocyanate group.

(2) First react the urethane isocyanate prepolymer with the required amount of hydroxyl-containing (meth) acrylate (Z), and make the end of the urethane isocyanate prepolymer required A method of forming a (meth) acrylfluorenyl group by reacting an alcohol and introducing an alkoxy group to the remaining isocyanate group.

(3) In a urethane isocyanate prepolymer, a required amount of alcohol is simultaneously reacted with a hydroxyl-containing (meth) acrylate (Z), and introduced into a terminal of the urethane isocyanate prepolymer The required ratio of alkoxy to (meth) acrylfluorenyl.

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

In addition, in any of the above methods (1) to (4), in order to make the residual isocyanate group concentration in the reaction liquid 0.1% by weight or less, it is necessary for the terminal of the urethane isocyanate prepolymer. The molar number of the isocyanate group reacts so that the total molar number of the hydroxyl groups of the alcohol and / or the hydroxyl group-containing (meth) acrylate (Z) used for the reaction becomes excessive.

The usable alcohol is 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 carbon number of the alcohol is less than 3 or the molecular weight is less than 70, there is a possibility of volatilization in the synthesis of the urethane (meth) acrylate, so it is less desirable. Moreover, when molecular weight exceeds 400, reactivity with an isocyanate group will fall, and since synthesis time may become long, it is unpreferable. In addition, an alcohol having an aromatic ring is not preferable because the weather resistance of the urethane (meth) acrylate (A) obtained may be deteriorated. Furthermore, alcohol may be used in combination of two or more depending on the destination.

Specifically, preferred alcohols include 1-butanol, 1-heptanol, 1-hexanol, n-octanol, 2-ethylhexanol, cyclohexanemethanol, octanol, lauryl alcohol, Myristyl alcohol, cetanol, stearyl alcohol or a mixture of these. Among these, from the viewpoints of boiling point, price, and availability, 2-ethylhexanol is preferred.

<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, but is preferably 3,000 to 6,000. The weight average molecular weight (Mw) is a polystyrene-equivalent value measured by GPC. When the Mw is less than 2,000, the Tg of the urethane (meth) acrylated resin becomes high, and the flexibility decreases, the appearance of the resin deteriorates, and by-products increase. On the other hand, when Mw exceeds 10,000, the cross-linking density may become too small, and the hardenability may be deteriorated and the shape may be changed at high temperatures. The crosslink density can be increased by adding a polyfunctional (meth) acrylate, but as will be described later, when a polyfunctional monomer is blended, it will become a major cause of poor appearance in an environmental test. As the diol (X) having a hydrogenated polyolefin skeleton, for example, a compound having hydrogenated polydiene (polybutadiene, polyisoprene, etc.) having hydroxyl groups at both ends can be used.

Commercial products may be used for the diol (X) having a hydrogenated polyolefin skeleton, and examples thereof include "EPOLE" manufactured by Idemitsu Kosan Co., Ltd., "GI-2000" and "GI-3000" manufactured by Soda Corporation of Japan. It is not limited to this.

<Diisocyanate (Y)>

As the diisocyanate (Y), those which do not show crystallinity can be used from the viewpoints of the appearance of the resin and the transparency of the cured product. Specifically, it is selected from the group consisting of an alicyclic diisocyanate and a branched aliphatic group. At least one of a group consisting of a diisocyanate and a diisocyanate compound obtained by hydrogenating an aromatic isocyanate. The alicyclic diisocyanate is not particularly limited, and examples thereof include isophorone diisocyanate and the like. The aliphatic diisocyanate having a branched chain is not particularly limited, and examples thereof include 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate. Wait. The diisocyanate compound obtained by hydrogenating an aromatic isocyanate is not particularly limited, and examples thereof include hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and the like. On the other hand, when using a diisocyanate (Y) other than the above, especially when a crystallinity is used, a problem arises in resin appearance and transparency of a hardened | cured material.

<Hydroxy-containing (meth) acrylate (Z)>

The hydroxyl-containing (meth) acrylate (Z) is not particularly limited, and for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and (meth) acrylic acid can be used. 4-Hydroxybutyl ester.

<Monofunctional (meth) acrylate (B)>

The active energy ray-curable composition of the present invention includes a monofunctional (meth) acrylate (B) to produce a urethane (meth) acrylic acid. With respect to the acid ester, correcting the viscosity and adjusting the Tg of the cured coating film have the effects of improving the prevention of viscosity increase, resin appearance, suppression of by-products, transparency of the cured product, and heat resistance. The monofunctional (meth) acrylate (B) may be simply referred to as (B).

The use concentration of the monofunctional (meth) acrylate (B) is not particularly limited, but it is, for example, 20 to 60% by weight based on the entire urethane (meth) acrylate content obtained, and more preferably 20 ~ 40% by weight. If it is less than 20% by weight, the viscosity of the urethane (meth) acrylate obtained becomes high, handling becomes difficult, and gelation sometimes occurs. On the other hand, if it exceeds 60% by weight, the wettability with the transparent substrate may be deteriorated due to excessively low viscosity during coating, and the urethane (meth) acrylate may be deteriorated. Reduced flexibility and heat resistance.

Such a monofunctional (meth) acrylate is not particularly limited, but from the viewpoint of heat resistance, a non-polyether-based acrylate (PO modified product, EO modified product, etc.) monofunctional (meth) Specific examples of the acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, glycerol mono (meth) acrylate, glycidyl (meth) acrylate, and (meth) acrylic acid. Dicyclopentenyl ester, n-butyl (meth) acrylate, β-carboxyethyl (meth) acrylate, isoamyl (meth) acrylate, oct / decyl (meth) acrylate, n-octyl acrylate , Isooctyl acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, ortho- (meth) acrylate Aliphatic ester, cyclohexyl (meth) acrylate, other alkyl (meth) acrylates, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid 4-Hydroxybutyl ester and the like are particularly preferred, n-octyl acrylate, isofluorenyl (meth) acrylate, and octyl / decyl (meth) acrylate.

The above-mentioned monofunctional (meth) acrylate may also be a commercially available product. For example, the product name "β-CEA" (made by Daicel-Cytec, acrylic-β-carboxyethyl ester) and the product name "IBOA" are commercially available. "(Manufactured by Daicel-Cytec, isopropyl acrylate), product name" ODA-N "(manufactured by Daicel-Cytec, octyl / decyl acrylate), and the like.

<Photopolymerization initiator (C)>

啉基丙烷-1、苯偶姻、苯偶姻甲醚、苯偶姻乙醚、苯偶姻異丙醚、苯偶姻正丁醚、苯偶姻苯醚、苄基二甲基縮酮、二苯甲酮、苄醯基安息香酸、苄醯基安息香酸甲酯、4-苯基二苯甲酮、羥基二苯甲酮、丙烯酸化二苯甲酮、4-苄醯基-4’-甲基二苯基硫化物、3,3’-二甲基-4-甲氧基二苯甲酮、噻吨酮(thioxanthone)、2-氯噻吨酮、2-甲基噻吨酮、2,4-二甲基噻吨酮、異丙基噻吨酮、2,4-二氯噻吨酮、2,4-二乙基噻吨酮、2,4-二異丙基噻吨酮、2,4,6-三甲基苄醯基二苯基膦氧化物、甲基苯基乙醛酸酯、二苯乙二酮、樟腦醌等。 The photopolymerization initiator (C) of the present invention also varies depending on the kind of active energy ray or the kind of the urethane (meth) acrylate (A). Although it is not particularly limited, a known one can be used. Although not specifically limited, a photoradical polymerization initiator or a photocationic polymerization initiator includes, for example, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan- 1-ketone, diethoxyacetophenone, 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-

Phenylpropane-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzyl dimethyl ketal, two Benzophenone, benzamidinebenzoic acid, methyl benzamidinebenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzylfluorenyl-4'-formaldehyde Diphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2, 4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2 , 4,6-trimethylbenzylfluorenyldiphenylphosphine oxide, methylphenylglyoxylate, diphenylethylenedione, camphorquinone and the like.

The use amount of the photopolymerization initiator is not particularly limited, and for example, it is 1 to 20 parts by weight, and preferably 1 to 5 parts by weight based on 100 parts by weight of the active energy ray-curable resin composition. If it is less than 1 part by weight, hardening may be caused. On the other hand, if the photopolymerization initiator is used in a large amount, an odor derived from the photopolymerization initiator from the cured coating film may remain.

<Transparent substrate>

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

As the plastic substrate, an existing transparent material can be used and is not particularly limited, and examples thereof include polyolefin resins such as polyethylene, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, and polyterephthalic acid. Polyester resins, acrylic resins, polycarbonate resins, etc., such as ethylene glycol, polyethylene naphthalate, and polybutylene terephthalate. Among them, polycarbonate resins and acrylic resins are suitably used.

<Additives>

Various additives may be blended into the active energy ray-curable composition of the present invention as necessary. Examples of such additives include fillers, dyes, leveling agents, ultraviolet absorbers, light stabilizers, defoamers, dispersants, and thixotropy imparting agents. The addition amount of these additives is not particularly limited, but it is, for example, 0 to 10 parts by weight, and preferably 0.05 to 5 parts by weight based on 100 parts by weight of the active energy ray-curable composition.

<Coating and hardening methods for transparent substrates>

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 a spray method may be used. , Airless spraying method, air spraying method, roll coating method, bar coating method, gravure printing method and the like. Among these, from the viewpoints of aesthetics, cost, and workability, a roll coating method is preferably used. Furthermore, the coating can be performed in a manufacturing step of a plastic film or the like, a so-called in-line coating method, or a transparent substrate that has been manufactured may be coated in another step, a so-called out-of-line coating method. From the viewpoint of production efficiency, outer coating is preferred.

The thickness of the coating film of the present invention is preferably 50 to 300 μm, and more preferably 50 to 200 μm. When the layer thickness exceeds 300 μm, the amount of the resin composition to be applied becomes excessive, so that the cost may increase, and the uniformity of the film thickness may decrease. Moreover, when it is less than 50 micrometers, the soft characteristic of a curable resin cannot be exhibited.

<Heat resistance of color change>

In the active energy ray-curable composition of the present invention, the increase in APHA of the laminate before and after storage is preferably 25 or less when the laminate obtained by the following steps is stored at 95 ° C for 500 hours. Preferably, it is 20 or less, and most preferably 15 or less. In this step, 0.200 g of the active energy ray-curable composition is applied to the center of the first glass substrate (1 mm, 5 cm square) to form a circle (4 cm diameter). A second glass substrate (1 mm, 5 cm square) with a thickness of 1 mm on the resin layer, and then irradiate the active energy ray to harden the active energy ray-curable composition to form a hardened material layer.

<Layered body>

The laminated body of the present invention only needs to have a hardened material layer of the active energy ray-curable composition between a first transparent substrate selected from glass and plastic and a second transparent substrate selected from glass and plastic, and No special limit set. Preferably, the active energy ray-curable composition is coated on the first transparent substrate to form a resin layer, and the second transparent substrate is adhered to the resin layer, and then the transparent substrate is interposed, for example, by irradiation. An active energy ray such as ultraviolet rays or an electron beam can harden the active energy ray-curable composition in an extremely short time, and form a cured material layer to obtain a laminated body. One aspect of the aforementioned laminated body is shown in FIG. 1.

The increase in APHA of the laminated body before and after storage when the laminated body is stored at 95 ° C. for 500 hours is not particularly limited, and is, for example, 25 or less, preferably 20 or less, and more preferably 15 or less.

The light source used for the ultraviolet irradiation is not particularly limited, and examples thereof include a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a xenon lamp, and a metal halide lamp. The irradiation time varies depending on the type of light source, the distance between the light source and the coating surface, and other conditions, but it is a few seconds at most, usually several seconds. Generally, an irradiation source with a lamp output of about 80 to 300 W / cm is used. In the case of electron beam irradiation, an electron beam having an energy in a range of 50 to 1000 KeV is used, and an irradiation amount of 2 to 5 Mrad is preferably set. After the active energy ray is irradiated, it can also be heated as necessary to try to promote hardening.

[Example]

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

<Measurement method, test method, and evaluation method of physical properties>

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

(Weight average molecular weight)

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

Equipment used: TOSO HLC-8220GPC

Pump: DP-8020

Detector: RI-8020

Type of column: Super HZM-M, Super HZ4000, Super HZ3000, Super HZ2000

Solvent: Tetrahydrofuran

Phase flow: 1mL / min

Pressure in the column: 5.0MPa

Column temperature: 40 ℃

Sample injection volume: 10 μL

Sample concentration: 0.2mg / 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 ° C (minus 30 ° C) for 1 hour, and the presence or absence of turbidity and coloring due to crystallization or the like was evaluated visually and based on the following criteria.

Specifically, when any turbidity or coloration cannot be identified by visual inspection, the result is clear, and "￮" is described in the column of "resin appearance (-30 ° C)" in Tables 1 and 2. On the other hand, when any of turbidity and coloring was visually recognized, the result was defective (exterior appearance), and "×" is described in the column of "resin appearance (-30 ° C)" in Tables 1 and 2.

(By-product content)

The content of the by-products of the urethane (meth) acrylate (A) obtained from a diol having a hydrogenated polyolefin skeleton as a target of the present invention is based on the content of each component obtained by GPC analysis. The peak area was obtained by the following calculation formula, and evaluated based on the following criteria.

Content of by-products = peak area of by-products ÷ (peak area of by-products + peak area of urethane (meth) acrylate (A) obtained from diol having a hydrogenated polyolefin skeleton) × 100

Specifically, when the content of the by-product is less than 7%, the result is good, and "￮" is described in the column of "by-product content" in Tables 1 and 2. On the other hand, when the content of by-products was 7% or more, the result was unsatisfactory, and “×” is described in the “by-product content” column of Tables 1 and 2.

(Evaluation of the transparency of the hardened material)

As shown in FIG. 2, a square frame (internal size: 1.0 × 40 × 10mm) was made of silicone rubber on a micro glass (size: 1.0 × 76 × 26mm), and 1.0g of active energy rays was dropped into the frame. Hardening composition. The surface was smoothed by heating at 70 ° C, and ultraviolet irradiation was performed under the following conditions.

[UV irradiation conditions]

Irradiation intensity: 120W / cm

Irradiation distance: 10cm

Conveyor speed: 5m / min

Exposure times: 2 times

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

When the transmittance at 400 nm is 95% or more, the transmittance is good, and "￮" 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 poor, and "×" is described in the column of "Transparency (transmittance at 400 nm)" in Tables 1 and 2.

(Evaluation of heat resistance of hardened material)

The glass laminate (test piece A) shown in FIG. 3 was stored under the following heat-resistant conditions, and changes in APHA (hue) and shape of the test piece A were observed. 3 (A) is a view of the glass laminated body viewed from above, and FIG. 3 (B) is a view of the glass laminated body viewed from the side.

[Making of test piece A]

The glass laminated body (test piece A) shown in FIG. 3 was produced as follows. First, 0.200 g of an active energy ray-curable composition was accurately weighed and placed in the center of a glass plate (1 mm, 5 cm square). A glass plate of the same shape was further covered from above, and the resin layer was expanded into a circle (4 cm diameter) to obtain a glass laminate. Then, the glass surface of one surface of this glass laminated body was irradiated with ultraviolet rays under the following conditions using a high-pressure mercury lamp (manufactured by Eye Graphics) to obtain a glass laminated body (test piece A) having a cured resin composition layer.

(UV irradiation conditions)

Irradiation intensity: 120W / cm

Irradiation distance: 10cm

Conveyor speed: 5m / min

Exposure times: 8 times

[Storage under heat-resistant conditions]

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

[Determination of APHA]

The measurement of APHA was performed using a spectrophotometer (product name: Spectro Color Meter SE2000, manufactured by Nippon Denshoku Industries Co., Ltd.) to measure the APHA of the glass laminate before and after storage under heat-resistant conditions, and the evaluation was performed based on the following criteria.

When the increase in APHA before and after storage under heat-resistant conditions is less than 15, the heat resistance is extremely good from the viewpoint of hue, and the "Hue Change" column in the heat resistance of Tables 1 and 2 states "◎". In addition, when the increase in APHA before and after storage under heat-resistant conditions is 15 or more and less than 50, the heat resistance is good from the viewpoint of color tone, and belongs to the "color change" column of the heat resistance of Tables 1 and 2. Bit records "￮". On the other hand, when the increase in APHA before and after storage under heat-resistant conditions is 50 or more, from the viewpoint of color tone, the heat resistance is poor, and belongs to the "color change" column of the heat resistance of Tables 1 and 2. Write "×".

[Measurement of shape]

The presence or absence of shape change (warpage) in Test A after storage under heat-resistant conditions was visually measured, and evaluated on the basis of the following criteria.

Specifically, when the shape change (warping) cannot be recognized visually, the result is good, and "￮" is described in the "shape change" column of "heat resistance" of Tables 1 and 2. On the other hand, when the shape change (warping) was visually recognized, the result was bad, and "×" was described in the "shape change" column of "heat resistance" in Tables 1 and 2.

<Synthesis example>

Synthesis examples and examples of urethane (meth) acrylate are described below.

(Determination of isocyanate group concentration)

The isocyanate group concentration was measured as follows. The measurement was performed in a 100 mL glass flask and stirred with a stirrer.

(Determination of blank test value)

15mL of THF was added with 15mL of dibutylamine in THF (0.1N), and 3 drops of bromophenol blue (1% methanol dilution) was added to make the color blue, and the equivalent concentration was 0.1N. Aqueous HCl solution was titrated. See titer discoloration aqueous HCl point of time as V _b (mL).

(Determination of measured isocyanate group concentration)

A sample of W _s (g) was weighed, dissolved in 15 mL of THF, and 15 mL of a solution of dibutylamine in THF (0.1 N) was added. After confirming that the solution had been dissolved, 3 drops of bromophenol blue (1% methanol dilution) was added to make it blue, and then titration was performed with a 0.1N equivalent HCl aqueous solution. The titration of the aqueous HCl solution at the point where discoloration was seen was taken as V _s (mL).

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

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

(Polyolefin skeleton-containing diol (X) used in Synthesis Example and Comparative Synthesis Example)

"EPOLE" (manufactured by Idemitsu Kosan Co., Ltd.); hydroxy-terminated polyolefin (hydroxyl value 0.92 mol / kg, bromine value 5.9 g / 100 g, non-volatile matter 99.5% by weight or more, estimated weight average molecular weight 2174), "NISSO PB GI -1000 "(manufactured by Soda Co., Ltd.); hydrogenated 1,2-polybutadiene glycol (hydroxyl value 67.2 mgKOH / g, iodine value 11.2 g / 100 g, estimated weight average molecular weight 1670), "NISSO PB GI-2000" (manufactured by Soda Co., Ltd.); hydrogenated 1,2-polybutadiene glycol (hydroxyl value 48.3 mgKOH / g, iodine value 9.0 g / 100g, hydrogenation rate 97.6%, estimated weight average molecular weight 2323 ), "NISSO PB GI-3000" (manufactured by Soda Co., Ltd.); hydrogenated 1,2-polybutadiene glycol (hydroxyl value 28.3mgKOH / g, iodine value 15.6g / 100g, volatile matter 0.11%, estimated weight (Molecular weight 3965)

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

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

"HDI" (compound name hexamethylene diisocyanate); product name "HDI" (manufactured by POLYURETHANE, Japan)

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

(Monofunctional (meth) acrylate (B) used in Synthesis Example and Comparative Synthesis Example)

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

(Hydroxy-containing (meth) acrylate (Z) used in Synthesis Example and Comparative Synthesis Example)

"HEA"; 2-hydroxyethyl acrylate (manufactured by Japan Catalyst Corporation)

(Alcohol used in Synthesis Examples and Comparative Synthesis Examples)

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

The synthesis examples and comparative synthesis examples are described below, but unless otherwise specified, the concentration labels "ppm", "wt%", and "wt%" refer to the obtained urethane (meth) acrylate. Concentration of the entire contents.

<Synthesis example 1 / A-1>

The molar ratio of GI-3000, IPDI, and HEA was set to 2: 3: 2.02, and ODA-N was used as the monofunctional (meth) acrylate (B).

The actual addition amount and reaction conditions are described below.

A separable flask equipped with a thermometer and a stirring device was filled with 215 g of GI-3000 (manufactured by Soda Co., Ltd.), 800 ppm of dibutylhydroxytoluene (BHT), and 103 g (30% by weight) of oct / decyl acrylate ( ODA-N). After the internal temperature was set to 50 ° C., the mixture was stirred for 1 hour to homogenize the system, and then 18 g of isophorone diisocyanate was charged. After stirring at the reaction temperature for 1 hour, 300 ppm of dibutyltin dilaurate was added, and the mixture was further stirred at 50 ° C for 3 hours.

The completion of the reaction is based on the isocyanate group concentration in the reaction solution being equal to or lower than the isocyanate group concentration (hereinafter referred to as the "theoretical end point isocyanate group concentration") remaining when all of the hydroxyl groups provided for the reaction are homourethanated. Confirmed (the same applies to other synthesis examples).

In this example, after confirming that the isocyanate group concentration in the reaction liquid is equal to or lower than the theoretical end-point isocyanate group concentration (0.67% by weight), the process proceeds to the next operation.

Then, the reaction temperature was raised to 70 ° C, and 7 g of hydroxyethyl acrylate was charged. The mixture was further stirred at 70 ° C for 3 hours. The isocyanate group concentration was confirmed to be 0.1% by weight or less, and the reaction was completed to obtain an active energy ray-curable urethane (meth) acrylate-containing material (A-1).

<Synthesis example 2 / A-2>

The mole ratios of GI-3000, IPDI, and HEA were changed to 3: 4: 2.02, and the same operations as in Synthesis Example 1 were repeated. The actual addition amount and reaction conditions are described below.

A separable flask equipped with a thermometer and a stirring device was charged with 230 g of GI-3000 (manufactured by Soda Co., Ltd.), 800 ppm of dibutylhydroxytoluene (BHT), and 107 g (30% by weight) of oct / decyl acrylate ( ODA-N). After the internal temperature was set to 50 ° C., the mixture was stirred for 1 hour to homogenize the system, and then 17 g of isophorone diisocyanate was charged. After stirring at the reaction temperature for 1 hour, 300 ppm of dibutyltin dilaurate was added, and the mixture was further stirred at 50 ° C for 3 hours.

In this example, after confirming that the isocyanate group concentration in the reaction liquid is equal to or lower than the theoretical end-point isocyanate group concentration (0.45 wt%), the process proceeds to the next operation.

Then, the reaction temperature was raised to 70 ° C, and hydroxyethyl acrylate (4 g) was charged. The mixture was further stirred at 70 ° C for 3 hours. The isocyanate group concentration was confirmed to be 0.1% by weight or less, and the reaction was completed to obtain an active energy ray-curable urethane (meth) acrylate-containing material (A-2).

<Synthesis example 3 / A-3>

The molar ratios of GI-3000, IPDI, and HEA were changed to 3: 4: 2.02, and the use concentration of the monofunctional (meth) acrylate (B) was reduced to 20% by weight. In addition, the same procedures were repeated as in Synthesis Example 1. The same operation. The actual addition amount and reaction conditions are described below.

A separable flask equipped with a thermometer and a stirring device was filled with 256 g of GI-3000 (manufactured by Soda Co., Ltd.), 800 ppm of dibutyl hydroxytoluene (BHT), and 70 g (20 wt. ODA-N). After the internal temperature was set to 50 ° C., the mixture was stirred for 1 hour to homogenize the system, and then 19 g of isophorone diisocyanate was charged. After stirring at the reaction temperature for 1 hour, 300 ppm of dibutyltin dilaurate was added, and the mixture was further stirred at 50 ° C for 3 hours.

In this example, after confirming that the isocyanate group concentration in the reaction liquid is equal to or lower than the theoretical end-point isocyanate group concentration (0.52% by weight), the process proceeds to the next operation.

Then, the reaction temperature was raised to 70 ° C, and hydroxyethyl acrylate (5 g) was charged. The mixture was further stirred at 70 ° C for 3 hours. The isocyanate group concentration was confirmed to be 0.1% by weight or less, and the reaction was completed to obtain an active energy ray-curable urethane (meth) acrylate-containing material (A-3).

<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 addition amount and reaction conditions are described below.

A separable flask equipped with a thermometer and a stirring device was filled with 225 g of GI-3000 (manufactured by Soda Co., Ltd.), 800 ppm of dibutylhydroxytoluene (BHT), and 107 g (30% by weight) of isopropyl acrylate (IBOA ). After the internal temperature was set to 50 ° C., the mixture was stirred for 1 hour to homogenize the system, and then 19 g of isophorone diisocyanate was charged. After stirring at the reaction temperature for 1 hour, 300 ppm of dibutyltin dilaurate was added, and the mixture was further stirred at 50 ° C for 3 hours.

In this example, after confirming that the isocyanate group concentration in the reaction liquid is equal to or lower than the theoretical end-point isocyanate group concentration (0.67% by weight), the process proceeds to the next operation.

Then, the reaction temperature was raised to 70 ° C, and 7 g of hydroxyethyl acrylate was charged. The mixture was further stirred at 70 ° C for 3 hours. The isocyanate group concentration was confirmed to be 0.1% by weight or less, and the reaction was completed to obtain an active energy ray-curable urethane (meth) acrylate-containing material (A-4).

<Synthesis example 5 / A-5>

The molar ratios of GI-3000, IPDI, and HEA were changed to 3: 4: 2.02, and the monofunctional (meth) acrylate (B) was changed to IOA (concentration: 20% by weight). In addition, it was repeated and synthesized. Example 1 Same operation. The actual addition amount and reaction conditions are described below.

A separable flask equipped with a thermometer and a stirring device was filled with 227 g of GI-3000 (manufactured by Soda Co., Ltd.), 800 ppm of dibutylhydroxytoluene (BHT), and 63 g (20% by weight) of isooctyl acrylate (IOA ). After the internal temperature was set to 50 ° C., the mixture was stirred for 1 hour to homogenize the system, and then 18 g of isophorone diisocyanate was charged. After stirring at the reaction temperature for 1 hour, 300 ppm of dibutyltin dilaurate was added, and the mixture was further stirred at 50 ° C for 3 hours.

In this example, after confirming that the isocyanate group concentration in the reaction liquid is equal to or lower than the theoretical end-point isocyanate group concentration (0.45 wt%), the process proceeds to the next operation.

Then, the reaction temperature was raised to 70 ° C, and 5 g of hydroxyethyl acrylate was charged. The mixture was further stirred at 70 ° C for 3 hours. The isocyanate group concentration was confirmed to be 0.1% by weight or less, and the reaction was completed to obtain an active energy ray-curable urethane (meth) acrylate-containing material (A-5).

<Synthesis example 6 / A-6>

Using "EPOLE" and "GI-3000" as the diol (X) with a hydrogenated polyolefin skeleton, the molar ratios of EPOLE, GI-3000, IPDI, and HEA were adjusted to 1: 1: 3: 2.02, and The functional (meth) acrylate (B) was changed to IBOA, and the same operation as in Synthesis Example 1 was repeated. The actual addition amount and reaction conditions are described below.

A separable flask equipped with a thermometer and a stirring device was filled with 78 g of EPOLE (manufactured by Idemitsu Kosan Co., Ltd.), 141 g of GI-3000 (manufactured by Soda Co., Ltd.), 800 ppm of dibutylhydroxytoluene (BHT), 107 g (30 Isopropyl acrylate (IBOA). After the internal temperature was adjusted to 50 ° C. and stirred for 2 hours to homogenize the system, 24 g of isophorone diisocyanate was charged. After stirring at the reaction temperature for 1 hour, 300 ppm of dibutyltin dilaurate was added, and the mixture was further stirred at 50 ° C for 3 hours.

In this example, after confirming that the isocyanate group concentration in the reaction liquid is equal to or lower than the theoretical end-point isocyanate group concentration (0.85 wt%), the process proceeds to the next operation.

Then, the reaction temperature was raised to 70 ° C, and 9 g of hydroxyethyl acrylate was charged. The mixture was further stirred at 70 ° C for 3 hours. The isocyanate group concentration was confirmed to be 0.1% by weight or less, and the reaction was completed to obtain an active energy ray-curable urethane (meth) acrylate-containing material (A-6).

<Synthesis example 7 / A-7>

Using TMHDI instead of IPDI as the diisocyanate (Y), the same operation as in Synthesis Example 1 was performed. The actual addition amount and reaction conditions are described below.

A separable flask equipped with a thermometer and a stirring device was filled with 226 g of GI-3000 (manufactured by Soda Co., Ltd.), 800 ppm of dibutylhydroxytoluene (BHT), and 107 g (30% by weight) of oct / decyl acrylate ( ODA-N). After the internal temperature was set to 50 ° C., the mixture was stirred for 1 hour to homogenize the system, and then 18 g of trimethylhexamethylene diisocyanate (TMHDI) was charged. After stirring at the reaction temperature for 1 hour, 300 ppm of dibutyltin dilaurate was added, and the mixture was further stirred at 50 ° C for 2 hours.

In this example, after confirming that the isocyanate group concentration in the reaction liquid is equal to or lower than the theoretical end-point isocyanate group concentration (0.68% by weight), the process proceeds to the next operation.

Then, the reaction temperature was raised to 70 ° C, and 7 g of 2-hydroxyethyl acrylate was charged. The mixture was further stirred at 70 ° C for 3 hours. The isocyanate group concentration was confirmed to be 0.1% by weight or less, and the reaction was completed to obtain an active energy ray-curable urethane (meth) acrylate-containing material (A-7).

<Synthesis example 8 / A-8>

"EPOLE" was used instead of GI-3000 as the diol (X) having a hydrogenated polyolefin skeleton, and the same operation as in Synthesis Example 1 was performed. The actual addition amount and reaction conditions are described below.

A separable flask equipped with a thermometer and a stirring device was filled with 199 g of EPOLE (manufactured by Idemitsu Kosan Co., Ltd.), 800 ppm of dibutylhydroxytoluene (BHT), and 103 g (30% by weight) of oct / decyl acrylate (ODA -N). After the internal temperature was set to 50 ° C., the mixture was stirred for 1 hour to homogenize the system, and then 30 g of isophorone diisocyanate was charged. After stirring at the reaction temperature for 1 hour, 300 ppm of dibutyltin dilaurate was added, and the mixture was further stirred at 50 ° C for 2 hours.

In this example, after confirming that the isocyanate group concentration in the reaction liquid is equal to or lower than the theoretical end-point isocyanate group concentration (1.15 wt%), the process proceeds to the next operation.

Then, the reaction temperature was raised to 70 ° C, and 2-hydroxyethyl acrylate (11 g) was charged. The mixture was further stirred at 70 ° C for 3 hours. The isocyanate group concentration was confirmed to be 0.1% by weight or less, and the reaction was completed to obtain an active energy ray-curable urethane (meth) acrylate-containing material (A-8).

<Synthesis example 9 / A-9>

During the synthesis of the urethane isocyanate prepolymer, GI-3000 was dropped into IPDI and reacted, and the same operation as in Synthesis Example 1 was repeated. The MoA ratio of HEA was set to 2: 3: 2.02, and ODA-N was used as the monofunctional (meth) acrylate (B). The actual addition amount and reaction conditions are described below.

A separable flask equipped with a thermometer and a stirring device was filled with isophorone diisocyanate (18 g), 800 ppm dibutylhydroxytoluene (BHT), octyl / decyl acrylate (ODA-N) (43 g), and 300 ppm Dibutyltin dilaurate. While stirring the inside of the system to be uniform, the internal temperature was raised to 50 ° C. ODA-N was distributed to 43g to enable IPDI to be stirred.

Stirring was continued, and while maintaining the temperature at 50 ° C, 215 g of GI-3000 (manufactured by Soda Co., Ltd.) was uniformly dissolved in 60 g of an octyl / decyl acrylate (ODA-N) mixed solution over 30 minutes. At this time, the total weight of octyl / decyl acrylate (ODA-N) charged in the system was 103 g (30% by weight). Then, it stirred at 50 degreeC for 3 hours.

In this example, after confirming that the isocyanate group concentration in the reaction liquid is equal to or lower than the theoretical end-point isocyanate group concentration (0.67% by weight), the process proceeds to the next operation.

Then, the reaction temperature was raised to 70 ° C, and 11 g of 2-hydroxyethyl acrylate was charged. The mixture was further stirred at 70 ° C for 3 hours. The isocyanate group concentration was confirmed to be 0.1% by weight or less, and the reaction was completed to obtain an active energy ray-curable urethane (meth) acrylate-containing material (A-9).

<Synthesis example 10 / A-10>

The molar ratios of GI-3000, IPDI, and HEA were changed to 3: 4: 1.82, and 0.2 mol parts of 2-ethylhexanol (2-EH) was further used. The molar ratio of HEA to 2-EH is 90:10. The actual addition amount and reaction conditions are described below.

A separable flask equipped with a thermometer and a stirring device was filled with 273 g of GI-3000 (manufactured by Soda Co., Ltd.), 800 ppm of dibutylhydroxytoluene (BHT), and 75 g (20% by weight) of oct / decyl acrylate ( ODA-N). The internal temperature was adjusted to 50 ° C., and the mixture was stirred for 1 hour to homogenize the system, and then 21 g of isophorone diisocyanate was charged. After stirring at the reaction temperature for 1 hour, 300 ppm of dibutyltin dilaurate was added, and the mixture was further stirred at 50 ° C for 3 hours.

After confirming that the isocyanate group concentration in the reaction liquid is equal to or lower than the theoretical end-point isocyanate group concentration (0.57 wt%), the process proceeds to the next operation.

Then, the reaction temperature was raised to 70 ° C, and 0.6 g of 2-ethylhexanol (2-EH) (manufactured by Sankyo Chemical Co., Ltd.) was charged and reacted for 1 hour. Thereafter, 5.1 g of hydroxyethyl acrylate was charged and stirred at 70 ° C. for 3 hours. The isocyanate group concentration was confirmed to be 0.1% by weight or less, and the reaction was completed to obtain an active energy ray-curable urethane (meth) acrylate-containing material (A-10). The 10 mol% of the terminal of the urethane (meth) acrylate is 2-ethylhexanol, and the 90 mol% is added to hydroxyethyl acrylate.

<Comparative Synthesis Example 1 / CA-1>

HDI was used as the diisocyanate (Y), and the same operation as in Synthesis Example 1 was repeated. Molar ratios of GI-3000, HDI, and HEA were adjusted to 2: 3: 2.02. The actual addition amount and reaction conditions are described below.

A separable flask equipped with a thermometer and a stirring device was filled with 320 g of GI-3000 (manufactured by Soda Co., Ltd.), 800 ppm of dibutylhydroxytoluene (BHT), and 150 g (30% by weight) of oct / decyl acrylate ( ODA-N). The internal temperature was adjusted to 50 ° C., and the mixture was stirred for 1 hour to homogenize the system, and then 20 g of hexamethylene diisocyanate (HDI) was charged. After stirring at the reaction temperature for 1 hour, 300 ppm of dibutyltin dilaurate was added, and the mixture was further stirred at 50 ° C for 3 hours.

In this example, after confirming that the isocyanate group concentration in the reaction liquid is equal to or lower than the theoretical end-point isocyanate group concentration (0.69% by weight), the process proceeds to the next operation.

Then, the reaction temperature was raised to 70 ° C, and 10 g of hydroxyethyl acrylate was charged. The mixture was further stirred at 70 ° C for 3 hours. The isocyanate group concentration was confirmed to be 0.1% by weight or less, and the reaction was completed to obtain an active energy ray-curable urethane (meth) acrylate-containing material (CA-1).

<Comparative Synthesis Example 2 / CA-2>

GI-1000 was used as the diol (X) having a hydrogenated polyolefin skeleton, and the same operation as in Synthesis Example 1 was repeated. Molar ratios of GI-1000, IPDI, and HEA were adjusted to 2: 3: 2.02.

The actual addition amount and reaction conditions are described below.

A separable flask equipped with a thermometer and a stirring device was filled with 276 g of GI-1000 (manufactured by Soda Co., Ltd.), 800 ppm of dibutylhydroxytoluene (BHT), and 150 g (30% by weight) of octyl / decyl acrylate ( ODA-N). After the internal temperature was set to 50 ° C., the mixture was stirred for 1 hour to homogenize the system, and then 55 g of isophorone diisocyanate (IPDI) was charged. After stirring at the reaction temperature for 1 hour, 300 ppm of dibutyltin dilaurate was added, and the mixture was further stirred at 50 ° C for 3 hours.

In this example, after confirming that the isocyanate group concentration in the reaction liquid is equal to or lower than the theoretical end-point isocyanate group concentration (1.42% by weight), the process proceeds to the next operation.

Then, the reaction temperature was raised to 70 ° C, and 19 g of hydroxyethyl acrylate was charged. The mixture was further stirred at 70 ° C for 3 hours. The isocyanate group concentration was confirmed to be 0.1% by weight or less, and the reaction was completed to obtain an active energy ray-curable urethane (meth) acrylate-containing material (CA-2).

<Comparative Synthesis Example 3 / CA-3>

The monofunctional (meth) acrylate (B) was not used, and the same operation as in Synthesis Example 1 was repeated. Molar ratios of GI-3000, IPDI, and HEA were adjusted to 2: 3: 2.02. The actual addition amount and reaction conditions are described below.

A separable flask equipped with a thermometer and a stirring device was filled with 320 g of GI-3000 (manufactured by Soda Co., Ltd.) and 800 ppm of dibutylhydroxytoluene (BHT). The internal temperature was adjusted to 50 ° C., and the mixture was stirred for 1 hour to homogenize the system, and then 20 g of isophorone diisocyanate (IPDI) was charged. After stirring at the reaction temperature for 1 hour, 300 ppm of dibutyltin dilaurate was added. Since the viscosity has been increased, although it is desired to change the reaction temperature in the system to 70 ° C and reduce the viscosity, the resin is entangled with the stirring wing to achieve gelation, so the synthesis reaction cannot be continued.

<Comparative Synthesis Example 4 / CA-4>

In addition to the synthesis of the urethane (meth) acrylate (A) to "react (Y) and (Z) and form an isocyanate group-containing urethane isocyanate prepolymer, The same procedure as in Synthesis Example 1 was repeated except for the order of "method of reacting polymer with (X)". The actual addition amount and reaction conditions are described below.

A separable flask equipped with a thermometer and a stirring device was filled with IBOA (150 g, 30% by weight), 27 g of isophorone diisocyanate (IPDI), 9 g of 2-hydroxyethyl acrylate, and 800 ppm of dibutyl Hydroxytoluene (BHT), 100 ppm dibutyltin dilaurate. The internal temperature was adjusted to 70 ° C. and stirred for 1 hour.

In this example, after confirming that the isocyanate group concentration in the reaction liquid is equal to or lower than the theoretical end-point isocyanate group concentration (4.75% by weight), the process proceeds to the next operation.

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

<Preparation of active energy ray-curable composition>

The total amount of the components described in Tables 1 and 2 was adjusted to about 15 g in a 20 mL brown bottle, and the active energy ray-curable composition used in the examples was prepared.

In addition, Irg184 (made by Ciba Specialty Chemicals) was used as a photopolymerization initiator.

<Test result>

Each of the aforementioned tests and evaluations was performed with the active energy ray-curable composition blended in Tables 1 and 2. As described above, the results of the tests and evaluations are described in Tables 1 and 2.

As shown in Table 1 and Examples, the present invention includes reacting isophorone diisocyanate or trimethylhexamethylene diisocyanate with a diol having a hydrogenated polyolefin skeleton, and then reacting a hydroxyl-containing Urethane (meth) acrylate hardened composition obtained by the reaction of methacrylic acid ester, by filling the space between the films, preventing air and the film boundary Surface light scattering. Moreover, it turns out that it has the performance which is hard to cause a change of a hue or a shape in a heat resistance test. In contrast, as shown in Table 2 and Comparative Examples, crystalline hexamethylene diisocyanate was used as the diisocyanate (Y) (Comparative Examples 1, 2), and the one having a smaller weight average molecular weight was used as the diol (X). (Comparative Example 3) When the reaction during the synthesis of the urethane (meth) acrylate was not performed in the correct order (Comparative Example 4), it can be seen that the appearance of the resin before curing is turbid at low temperatures, and the resin is damaged and hardened The transparency of the object is damaged, or it has the disadvantages of showing a change in shape in a heat resistance test.

[Industrial availability]

According to the active energy ray-curable composition of the present invention, when the urethane (meth) acrylate (A) is contained as a component, the viscosity is not increased, and the generation of by-products is small. The target urethane (meth) acrylate (A) can be produced. As a result, the appearance of the resin is not deteriorated due to turbidity at a low temperature. Furthermore, the active energy ray-curable composition of the present invention, It has good wettability with glass substrates or plastic substrates, and has high flexibility and high heat resistance. Furthermore, the cured product of the active energy ray-curable composition of the present invention has high transparency and can be used even at high temperatures. Since it has less deformation or color tone degradation, it is especially used as a filler between transparent substrates for displays used in computers, car navigation, televisions, and mobile phones.

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

2, 3‧‧‧ transparent substrate

4‧‧‧ Silicone

11‧‧‧ resin

21‧‧‧ glass plate

[Fig. 1] A schematic view showing one aspect of a laminated body of the present invention.

FIG. 2 is a schematic view showing a state of a glass laminate (test piece A) used in this example.

FIG. 3 is a schematic view of a glass laminate showing the evaluation of the transparency of a cured product used in this example. (A) is the figure which looked at the glass laminated body from the top, (B) is the figure which looked at the glass laminated body from the side.

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

2, 3‧‧‧ transparent substrate

Claims (8)

An active energy ray-curable composition comprising a urethane (meth) acrylate (A), a monofunctional (meth) acrylate (B), and a photopolymerization initiator (C); The urethane (meth) acrylate (A) is a diol (X) having a weight-average molecular weight of 3,000 to 10,000 having a hydrogenated polyolefin skeleton, and is selected from the group consisting of an alicyclic diisocyanate, A chain of an aliphatic diisocyanate and at least one diisocyanate (Y) from the group consisting of diisocyanate compounds obtained by hydrogenating aromatic isocyanates are present in the monofunctional (meth) acrylate (B) Carbamate reaction is carried out to form an isocyanate group-containing urethane isocyanate prepolymer, and then the urethane isocyanate prepolymer and the hydroxyl group-containing (meth) acrylate (Z) are formed. It is produced by reaction, and the monofunctional (meth) acrylate (B) contains at least one selected from the group consisting of n-octyl acrylate and isomethacrylate (meth) acrylate. For example, the active energy ray-curable composition according to item 1 of the application, wherein the diol (X) having a weight average molecular weight of 3,000 to 10,000 having a hydrogenated polyolefin skeleton is a diol represented by the following formula (1);

[In formula (1), a represents an integer of 70 to 250, and R ² represents a monovalent base represented by the following formula (2) (in formula (2), b represents an integer from 0 to 10),

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

For example, the active energy ray-curable composition of the scope of application for patents 1 or 2, wherein the urethane isocyanate prepolymer is a hydroxyl group of a diol (X) having a hydrogenated polyolefin skeleton with a weight average molecular weight of 3,000 to 10,000 The urethane isocyanate prepolymer obtained by all the reactions until urethane formation. For example, the active energy ray-curable composition of item 1 or 2 of the patent application scope does not include a volatile organic solvent. For example, the active energy ray-curable composition of item 1 or 2 of the patent application scope, in which the laminated body obtained by the following steps is stored at 95 ° C for 500 hours before and after the APHA of the laminated body is stored. The increase is 25 or less, where the step is to apply 0.200 g of the active energy ray-curable composition to the center of the first glass substrate of a 5 cm square with a thickness of 1 mm to form a circular resin layer with a diameter of 4 cm. On the layer, a second glass substrate of 5 cm square with a thickness of 1 mm was attached, and then the active energy ray was irradiated to harden the active energy ray-curable composition to form a hardened material layer. A laminated body comprising an active energy ray as in any one of claims 1 to 5 between a first transparent substrate selected from glass and plastic and a second transparent substrate selected from glass and plastic Sclerosing composition Layer of hardened material. For example, the laminated body according to item 6 of the patent application scope is formed by coating a resin layer on the first transparent substrate with the active energy ray-hardenable composition according to any one of the application scopes 1 to 5, and then A second transparent substrate is adhered to the resin layer, and then the active energy ray is irradiated to harden the active energy ray-curable composition to form a cured material layer. An active energy ray-curable composition for use as an interlayer filling. The active energy ray-curable composition includes a urethane (meth) acrylate (A), a monofunctional (meth) acrylate ( B), and a photopolymerization initiator (C); wherein the urethane (meth) acrylate (A) is a diol (X having a weight average molecular weight of a hydrogenated polyolefin skeleton of 2,000 to 10,000) ), And a diisocyanate (Y) selected from the group consisting of an alicyclic diisocyanate, a branched aliphatic diisocyanate, and a diisocyanate compound obtained by hydrogenating an aromatic isocyanate, in A urethane reaction is performed in the presence of a monofunctional (meth) acrylate (B) to form an urethane isocyanate prepolymer containing an isocyanate group, and then the urethane isocyanate prepolymer is formed. It is produced by reacting with a hydroxyl-containing (meth) acrylate (Z).