JP2016035055A - Active energy ray curable composition for optical component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray curable composition capable of providing a cured product having excellent scratch recoverability, adhesiveness with a plastic substrate and transparency upon curing.SOLUTION: There is provided an active energy ray curable composition for an optical component which comprises: a multi-functional (meth) acrylate (A) without having any one of an urethane group, au urea group, an allophanate group or a biuret group; and a photopolymerization initiator (C) and which contains, as (A), both a multi-functional (meth) acrylate (AS1) having a solubility parameter (SP value) value of 10.0 or more and a multi-functional (meth) acrylate (AS2) having a solubility parameter (SP value) value of less than 10.0, wherein a cured product cured with an active energy ray has a sea-island structure and the size of the island is 1 to 1000 nm.SELECTED DRAWING: None

Description

  The present invention relates to an active energy ray-curable composition for optical components, and a cured product and an optical component obtained from the cured product.

  Conventionally, optical lenses such as prism sheets and diffusion sheets used in liquid crystal displays, Fresnel lenses and lenticular lenses used in projection TVs are generally manufactured by injection molding of thermoplastic resin or hot press molding. there were. These manufacturing methods have a problem in that productivity is low because a long time is required for heating and cooling during manufacturing, and reproducibility of the fine structure is poor due to thermal contraction of the optical lens. In order to solve these problems, a method in which an active energy curable composition is poured into a mold in which a transparent resin base material is set on the inner surface of a mold and is irradiated with active energy rays to be cured.

In recent years, with the increase in brightness of displays, attempts have been made to improve the brightness of optical lenses. For this purpose, for example, techniques for molding lenses with a high refractive index with a high content of aromatic rings have been studied. (For example, Patent Document 1).
However, since the cured product of the high-refractive index type active energy ray-curable composition with a high aromatic ring content in Patent Document 1 becomes rigid, the fine shape of the optical lens after curing molding is deformed, It breaks and becomes a wound, and the wound does not recover to its original state over time. As a result, there is a problem that optical characteristics such as transmittance and luminance are deteriorated.
Moreover, when the optical lens which has a hard and fine uneven | corrugated shape contacts another member, there existed a problem of damaging another member.

As a technique to solve the problems that the cured product is hard and has a fine uneven shape, the structure is broken, and other members are damaged, the shape of the optical lens itself is devised, and the fineness of the optical lens is reduced. A method for making the shape difficult to break has been proposed (for example, Patent Document 2).
In addition, there is a method of reducing the deformation amount of the lens shape so that scratches can be easily recovered. For example, a method of reducing the friction coefficient of the lens surface by adding a slip agent such as silicone oil has been proposed ( For example, Patent Document 3).

JP 2008-094987 A JP 2006-309248 A Japanese Patent Application Laid-Open No. 07-070219

However, the method of Patent Document 2 has a problem that the ease of recovery of scratches (recoverability of scratches) on a lens having a fine uneven shape is insufficient.
In addition, the method of Patent Document 3 has a problem that although the recoverability of scratches is improved, the slip agent bleeds out, and the adhesion and the transparency of the optical lens are lowered.

  The present invention has been made in view of the above-mentioned problems, and an object of the present invention is active energy ray curing that provides a cured product excellent in scratch recovery, adhesion to a plastic substrate, and transparency during curing. It is to provide a sex composition.

The inventors of the present invention have reached the present invention as a result of studies to achieve the above object.
That is, the present invention is an active energy ray curable composition comprising a polyfunctional (meth) acrylate (A) having no urethane group, urea group, allophanate group or biuret group and a photopolymerization initiator (C). A composition comprising (A) a polyfunctional (meth) acrylate (AS1) having a solubility parameter (SP value) of 10.0 or more and a polyfunctional (meth) acrylate having an SP value of less than 10.0 ( AS2), a cured product obtained by curing with active energy rays has a sea-island structure, and the size of the islands is 1 to 1,000 nm. Cured product obtained by curing a curable composition with active energy rays; optical lens, sheet for optical lens, film, coating material for decorative film, light using this cured product Aiba coating material, a hard coat film or an antireflection film.

  A cured product obtained by curing the active energy ray-curable composition for optical parts of the present invention with active energy rays is excellent in scratch recovery, adhesion to a plastic substrate, and transparency during curing.

  The active energy ray-curable composition for optical components of the present invention comprises a polyfunctional (meth) acrylate (A) having no urethane group, urea group, allophanate group or biuret group and a photopolymerization initiator (C ) And.

  The polyfunctional (meth) acrylate (A) in the present invention needs to have no urethane group, urea group, allophanate group or biuret group. If it is a polyfunctional (meth) acrylate containing these groups in the molecule, these groups are compatible with each other, and a sea-island structure cannot be formed.

  In the present invention, “(meth) acrylate” means “acrylate or methacrylate”, “(meth) acryloyl group” means “acryloyl group or methacryloyl group”, and the same description method is used hereinafter.

As the polyfunctional (meth) acrylate (A) in the present invention, a polyfunctional (meth) acrylate (AS1) having a solubility parameter (hereinafter abbreviated as “SP value”) of 10.0 or more and an SP value of 10 are used. It is necessary to contain both polyfunctional (meth) acrylates (AS2) that are less than 0.0.
From the viewpoint of scratch recovery, the combination of (AS1) having an SP value of 10.0 or more and (AS2) having an SP value of less than 10.0 is combined.
In addition, (AS1) and (AS2) may be used individually by 1 type, respectively, or may use 2 or more types together.

Here, the SP value is obtained by the following equation.
SP value = (ΔH / V) ^1/2
In the formula, ΔH represents the heat of molar evaporation (cal / mol), and V represents the molar volume (cm ³ / mol).
ΔH and V are the heat of molar evaporation (Δei) of the atomic group described in “POLYMER ENGINEERING AND SCIENCE, February, 1974, Vol. 14, No. 2, Robert F. Fedors. And the total (V) of molar volumes (Δvi) can be used.

The SP value of the polyfunctional (meth) acrylate (AS1) is usually 10.0 or more, and preferably 10.0 to 10.8.
When two or more types of polyfunctional (meth) acrylates (AS1) are contained, the SP value of the component (AS1) having the largest content is adopted.
The SP value of the polyfunctional (meth) acrylate (AS2) is usually less than 10.0, preferably 9.2 to 9.8.
Similarly, when two or more types of polyfunctional (meth) acrylates (AS2) are contained, the SP value of the component (AS2) having the largest content is adopted.

Examples of the polyfunctional (meth) acrylate (A) having no urethane group, urea group, allophanate group or biuret group include reactive monomers having two or more (meth) acryloyl groups. Examples include di (meth) acrylate, tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate.

Examples of the di (meth) acrylate include poly (oxyalkylene glycol) di (meth) acrylate, aliphatic or alicyclic dihydric alcohol di (meth) acrylate, and aromatic dihydric alcohol alkylene oxide (hereinafter referred to as alkylene oxide). AO ”may be abbreviated.) Di (meth) acrylates of adducts and the like.

  Examples of the di (meth) acrylate of polyoxyalkylene glycol include di (meth) acrylate of polyoxyethylene glycol, di (meth) acrylate of polyoxypropylene glycol, and di (meth) acrylate of polyoxytetramethylene glycol. .

  Examples of the di (meth) acrylate of an aliphatic or alicyclic dihydric alcohol include 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate. (Meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, and the like.

  Di (meth) acrylates of aromatic dihydric alcohol AO adducts include dihydric phenol compounds [monocyclic phenols (catechol, resorcinol, hydroquinone, etc.), condensed polycyclic phenols (dihydroxynaphthalene, etc.), bisphenol compounds (bisphenol A, -F, -S, etc.)] AO adduct di (meth) acrylate, for example, resorcinol ethylene oxide (hereinafter ethylene oxide may be abbreviated as “EO”) 4 mol adduct di (meta) ) Acrylate, propylene oxide of dihydroxynaphthalene (hereinafter, propylene oxide may be abbreviated as “PO”) 4 mol adduct di (meth) acrylate, bisphenol A EO 4 mol adduct di (meth) acrylate, Bisphenol A EO10 EO20 mole of di (meth) acrylate Le di (meth) acrylate and bisphenol A are exemplified.

  Tri (meth) acrylates include trimethylolpropane AO adduct [trimethylolpropane EO 6 mol adduct, trimethylolpropane EO 9 mol adduct, trimethylolpropane EO 15 mol adduct, trimethylolpropane EO 20 mol adduct. , Trimethylolpropane PO9 mol adduct and glycerin EO6 mol and PO3 mol adduct etc.] each tri (meth) acrylate and pentaerythritol AO adduct [pentaerythritol EO6 mol adduct etc.] And (meth) acrylate.

  Tetra (meth) acrylates include pentaerythritol and pentaerythritol AO adducts [pentaerythritol EO 2 mol adduct, pentaerythritol EO 4 mol adduct, pentaerythritol EO 10 mol adduct, pentaerythritol EO 15 mol adduct and Tetra (meth) acrylates of pentaerythritol, etc.], tetra (meth) acrylates of AO adduct of ditrimethylolpropane, etc. [EO, 10 mol adduct of ditrimethylolpropane, etc.].

  Penta (meth) acrylates include dipentaerythritol and dipentaerythritol AO adducts [dipentaerythritol EO 2 mol adduct, dipentaerythritol EO 4 mol adduct, dipentaerythritol EO 10 mol adduct and dipentaerythritol. And pentamine (meth) acrylates, etc.].

  Hexa (meth) acrylates include dipentaerythritol and dipentaerythritol AO adducts [dipentaerythritol EO 2 mol adduct, dipentaerythritol EO 4 mol adduct, dipentaerythritol EO 10 mol adduct and dipentaerythritol. EO 15 mol adduct etc.] and dipentaerythritol lactone (γ-butyrolactone, γ-valerolactone, ε-caprolactone etc.) adduct [dipentaerythritol ε-caprolactone 3 mol adduct, dipentaerythritol ε-caprolactone 6 mol adduct and 12 mol adduct of ε-caprolactone of dipentaerythritol, etc.] and the like.

The number average molecular weight (hereinafter sometimes abbreviated as Mn) in the present invention can be measured, for example, under the following conditions using gel permeation chromatography (GPC).
[1] Apparatus: Gel permeation chromatography
“HLC-8120GPC”, manufactured by Tosoh Corp. [2] Column: “TSKgel GMHXL” x 2 + “TSKgel”
Multipore HXL-M ", manufactured by Tosoh Corporation [3] Eluent: THF
[4] Reference material: Standard polystyrene
(TSKstandard POLYSYRENE),
[5] Injection conditions manufactured by Tosoh Corporation: Sample concentration 0.25% by weight, column temperature 40 ° C.

SP value (AS1) and (SP _1), SP value difference between the _{(SP 2) (SP 1 -SP} 2) is preferably 0.4 to 1.2 in (AS2), 0.5 to 1.0 More preferably.
In this calculation, when two or more types (AS1) are contained, or when two or more types (AS2) are contained, as described above, the content of (AS1) is the largest (AS1). ) The SP value (SP ₁ ) of the component and the SP value (SP ₁₂ ) of the component (AS 2) having the largest content in (AS 2) are used to calculate | SP ₁ −SP ₂ |.

In addition, from the viewpoint of forming a sea-island structure at each of the high-crosslinking site and the low-crosslinking site, the molecular weight (M ₁ ) per (meth) acryloyl group of (AS1) and the (meth) acryloyl group of (AS2) It is particularly preferred that the absolute value | M ₁ −M ₂ | of the difference from the molecular weight (M ₂ ) is 90 or more.

Incidentally, in this calculation, when containing two or more kinds of (AS1) adopts the molecular weight of the highest (AS1) (meth) per acryloyl groups of component content of them as M _1, when containing two or more (AS2) adopts highest (AS2) component of (meth) molecular weight per acryloyl group content of them as _{M 2, |} M 1 -M ₂ | Is to be calculated.

  The polyfunctional (meth) acrylate (AS1) is preferably a 4- to 6-functional (meth) acrylate from the viewpoint of wound recovery, and dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and pentaerythritol tetra. More preferred is (meth) acrylate.

  As the polyfunctional (meth) acrylate (AS2), a bifunctional to hexafunctional (meth) acrylate is preferable from the viewpoint of scratch recovery.

The polyfunctional (meth) acrylate (AS2) preferably contains at least one (meth) acrylate having 6 to 40 oxyalkylene groups from the viewpoint of scratch recovery.
For example, poly (oxyethylene glycol) di (meth) acrylate, bisphenol A EO 10 mol di (meth) acrylate, bisphenol A EO 20 mol di (meth) acrylate, trimethylolpropane EO 9 mol adduct, trimethylolpropane More preferred are tri (meth) acrylate of EO 15 mol adduct and tetra (meth) acrylate of EO 35 mol adduct of pentaerythritol.

As the photopolymerization initiator (C) in the present invention, phosphine oxide compound (C1), benzoylformate compound (C2), thioxanthone compound (C3), oxime ester compound (C4), hydroxybenzoyl compound (C5), benzophenone compound (C6), ketal compound (C7), 1,3α aminoalkylphenone compound (C8) and the like.
(C) may be used alone or in combination of two or more.

  Examples of the phosphine oxide compound (C1) include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Examples of the benzoylformate compound (C2) include methylbenzoylformate.

  Examples of the thioxanthone compound (C3) include isopropylthioxanthone.

  Examples of the oxime ester compound (C4) include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] and ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl]-, 1 (0-acetyloxime)) and the like.

  Examples of the hydroxybenzoyl compound (C5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -Benzyl] phenyl} -2-methyl-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, benzoin alkyl ether and the like.

  Examples of the benzophenone compound (C6) include benzophenone.

  Examples of the ketal compound (C7) include benzyldimethyl ketal.

  As the 1,3α aminoalkylphenone compound (C8), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopro-butanone-1,2- (dimethylamino) -2-[(4-methyl Phenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone and the like.

Among the photopolymerization initiators (C), those having an absorption wavelength at 400 nm or more are preferred, and those having an absorption wavelength at 400 to 450 nm are more preferred.
Of these photopolymerization initiators (C), the phosphine oxide compound (C1) is preferable from the viewpoint of curability in the visible light region of 400 nm or more and coloring of the cured product, and more preferably bis (2 , 4,6-trimethylbenzoyl) -phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  The content of the photopolymerization initiator (C) is preferably 0.5 to 10% by weight, more preferably 0.8 to 9% by weight, particularly preferably 1 to 8 based on the weight of (A). % By weight. When it is 0.5% by weight or more, the photocuring reactivity is good, and when it is 10% by weight or less, the scratch recovery property of a cured product cured by irradiation with active energy rays is not lowered, which is preferable.

  The active energy ray-curable composition of the present invention preferably further contains a polysiloxane (D) having an oxyalkylene group from the viewpoint of scratch recovery.

The polysiloxane (D) having an oxyalkylene group is preferably compatible with the polymerizable monomer (A). This compatibility index can be expressed by an SP value, and the SP value of (D) is preferably 8.0 to 9.0, and more preferably 8.1 to 8.8.
(D) may be used individually by 1 type, or may use 2 or more types together.

(D) preferably has 2 to 100 oxyalkylene groups. A polysiloxane containing two or more oxyalkylene groups has good compatibility with other raw materials constituting the active energy ray-curable composition, and a polysiloxane having 100 or less oxyalkylene groups is a cured product. The dynamic friction coefficient is preferably reduced.

Examples of (D) include AO-modified polydialkylsiloxane, polydialkylsiloxane (D1) modified with AO at the end, polydialkylsiloxane (D2) modified with AO at the side chain, and two or more of these A mixture is mentioned. In addition, (D1) and (D2) may be further modified with (meth) acryloyl.

  Examples of the polydialkylsiloxane (D1) modified with AO at the end include polydimethylsiloxane modified with EO at the end, polydimethylsiloxane modified with EO and PO at the end, and polydiethylsiloxane modified with EO at the end And these (meth) acrylates.

  Examples of the commercially available product (D1) include “X-22-4952” and “X-22-4272” manufactured by Shin-Etsu Chemical Co., Ltd. and “BYK-333” manufactured by Big Chemie Japan Co., Ltd.

  The polydialkylsiloxane (D2) modified with AO in the side chain includes polydimethylsiloxane modified with PO in the side chain, polydimethylsiloxane modified with EO and butylene oxide in the side chain, and EO and PO in the side chain. And polydimethylsiloxane modified with (meth) acrylate and the like.

  Examples of the commercially available product (D2) include “KF-352A” and “KF-355A” manufactured by Shin-Etsu Chemical Co., Ltd. and “BYK-349” manufactured by Big Chemie Japan Co., Ltd.

  Of the polysiloxanes (D) having an oxyalkylene group, (D2) is preferable from the viewpoint of scratch recovery, and more preferably polydimethylsiloxane whose side chain is modified with EO and PO.

  A preferable range of Mn in (D) is 300 to 50,000. When the Mn of (D) is 300 or more, the adhesion to the plastic substrate is good. Moreover, if it is 50,000 or less, the compatibility with the resin is good, which is preferable.

  The content of (D) is preferably 0.05 to 10% by weight, more preferably 0.1 to 5% by weight, based on the weight of (A). When the content is 0.05% by weight or more, scratch recovery of the cured product is better, and the original performance of the cured product can be exhibited. Moreover, the adhesiveness to a plastic film is more favorable as it is 10 weight% or less.

The active energy ray-curable composition for optical components of the present invention may contain an antistatic agent (E).
Examples of the antistatic agent (E) include a tertiary amine salt compound (E1) having no cyclic structure, a cyclic amidine salt compound (E2), and an organic lithium salt compound (E3).
(E) may be used individually by 1 type, or may use 2 or more types together.

  The tertiary amine salt compound (E1) having no cyclic structure includes a salt of triethylamine and dodecylbenzenesulfonic acid, a salt of dimethylstearylamine and paratoluenesulfonic acid, a salt of dimethylaminoethyl acrylate and dodecylbenzenesulfonic acid, and the like. Can be mentioned.

  As the cyclic amidine salt compound (E2), a salt of dodecylbenzenesulfonic acid and 1,8-diazabicyclo (5,4,0) -undecene-7, a salt of dodecylbenzenesulfonic acid and 1-methyl-3-ethylimidazole, and And a salt of benzoic acid and 1,5-diazabicyclo (4,3,0) -nonene-5.

  Examples of the organic lithium salt compound (E3) include p-toluenesulfonic acid lithium salt, trifluoromethanesulfonic acid lithium salt, and trifluoromethanesulfonylimide lithium salt.

  When the antistatic agent (E) is contained, the content is preferably 0.05 to 5% by weight based on the weight of (A).

The active energy ray-curable composition for optical components of the present invention may contain various additives as necessary within a range not impairing the effects of the present invention.
Additives include plasticizers, organic solvents, dispersants, antifoaming agents, thixotropic agents (thickeners), slip agents, antioxidants, hindered amine light stabilizers and ultraviolet absorbers.
Examples of the organic solvent include methyl ethyl ketone, ethyl acetate, methyl isobutyl ketone, isopropanol, toluene and methanol.

  Although the manufacturing method of the molded object using the active energy ray curable composition for optical components of this invention is not specifically limited, For example, it can apply and shape | mold by the following method. That is, the composition of the present invention is preliminarily temperature-controlled at 20 to 50 ° C. to obtain a mold (mold temperature is usually 20 to 50 ° C., preferably 25 to 40 ° C.) from which a molded body shape (for example, optical lens shape) is obtained. Using a dispenser, etc., apply (or fill) the cured film to a thickness of 50 to 150 μm, and apply pressure on the transparent substrate (including the transparent film) to prevent air from entering the coating. Furthermore, after irradiating active energy rays, which will be described later, from the transparent substrate to cure the coating film, it is released from the mold to obtain a molded body (lens sheet).

  Examples of the transparent substrate (including a transparent film) include those made of a resin such as methyl methacrylate (co) polymer, polyethylene terephthalate, polycarbonate, polytriacetylcellulose, and polycycloolefin.

  The active energy rays in the present invention include ultraviolet rays, electron beams, X-rays, infrared rays and visible rays. Of these active energy rays, ultraviolet rays and electron beams are preferable from the viewpoints of curability and resin deterioration.

When the active energy ray-curable composition for optical components of the present invention is cured with ultraviolet rays, various ultraviolet irradiation devices [for example, ultraviolet irradiation devices [model number “VPS / I600”, manufactured by Fusion UV Systems Co., Ltd.] are used. it can. Examples of the lamp to be used include a high-pressure mercury lamp and a metal halide lamp. The irradiation amount of ultraviolet rays (mJ / cm ² ) is preferably 10 to 10,000, more preferably 100 to 5,000, from the viewpoint of the curability of the composition and the flexibility of the cured product.

The cured product obtained by curing the active energy ray-curable composition for optical components of the present invention with active energy rays has a sea-island structure.
Here, with the sea-island structure in the present invention, the cured product is phase-separated,
1438234397656_0
Target
1438234397656_1
In
1438234397656_2
Of the phase (sea phase)
1438234397656_3
1438234397656_4
A number of other closed phases
1438234397656_5
(Island phase)
1438234397656_6
I mean. And the layered separation in which two different types of phases are regularly arranged alternately is excluded.

This sea-island structure is composed of a polyfunctional (meth) acrylate (AS1) having a solubility parameter (SP value) of 10.0 or more and a polyfunctional (meth) acrylate (AS2) having an SP value of less than 10.0 at the time of curing. It is formed by separating.
By forming this sea-island structure, when scratches are applied to the cured product, stress relaxation occurs in the sea part, and further, a restoration effect occurs in the island part, and the generated scratches recover and disappear after a few seconds. The effect of disappearing is obtained.

In the cured product of the present invention, the size of the island of sea-island structure is an average value obtained by measuring the portion of the diameter (in the case of an ellipse, the major axis is adopted), and is usually 1 to 1,000 nm, and is a scratch recovery property. From the viewpoint of transparency, 10 nm to 500 nm is preferable. If the island size is less than 1 nm, the scratch recovery is poor, and if it is greater than 1000 nm, the transparency is poor.

The island in the cured product is formed by curing a curable composition containing two or more polyfunctional (meth) acrylates (A), and the SP value of the polyfunctional (meth) acrylate (A) By adjusting the molecular weight per one active energy ray polymerizable group, the size of the island can be set within a preferable range.

The size of the island in the cured product in the present invention is measured with an atomic force microscope (hereinafter abbreviated as AFM),
The island portion in the present invention is a portion where the phase shift measured by AFM is 0 to 50%. The phase shift measured by the AFM is performed by tapping the surface of the cured product with a cantilever and measuring the phase shift of the cantilever. The phase shift is small in the hard resin portion, and the phase shift is large in the soft portion.
When the phase shift measurement result is image-processed, the island portion of the sea-island structure defined above is represented as an island having a certain size. The detection limit value of the island size that can be measured by this measurement method is around 1 nm.

Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these. Hereinafter, unless otherwise specified, “%” represents “% by weight” and “parts” represents “parts by weight”.

Examples 1 to 10 and Comparative Examples 1 to 3
According to each component and compounding amount of Table 1, it mix | blends collectively, and it stirs and mixes with a disperser until it becomes uniform, The active energy ray-curable composition of Examples 1-10 and Comparative Examples 1-3 was obtained. .

In addition, the symbol of the compound described in Table 1 represents the following compounds.
(AS1-1): Dipentaerythritol hexaacrylate [trade name “Kayarad DPHA”, manufactured by Nippon Kayaku Co., Ltd.]
(AS1-2): Pentaerythritol tetraacrylate [trade name “Neomer EA-300”, manufactured by Sanyo Chemical Industries, Ltd.]
(AS1-3): Tetraacrylate of pentaerythritol EO 4 mol adduct [trade name “SR-494”, manufactured by Arkema Co., Ltd.]
(AS1-4): Hexaacrylate of ε-caprolactone 12 mol adduct of dipentaerythritol [trade name “Kayarad DPCA-120”, manufactured by Nippon Kayaku Co., Ltd.]
(AS2-1): Polyethylene glycol diacrylate [trade name “light acrylate 14EG-A”, manufactured by Kyoeisha Chemical Co., Ltd.]
(AS2-2): triacrylate of trimethylolpropane EO 9 mol adduct [trade name “SR-502”, manufactured by Arkema Co., Ltd.]
(AS2-3): Triacrylate of trimethylolpropane EO 15 mol adduct [trade name “SR-9035”, manufactured by Arkema Co., Ltd.]
(AS2-4): Diacrylate of EO 20 mol adduct of bisphenol A [trade name “New Frontier BPE-20G”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.]
(AS2-5): Tetraacrylate of EO35 mol adduct of pentaerythritol [trade name “NK Ester ATM-35E”, manufactured by Shin-Nakamura Chemical Co., Ltd.] In addition, each SP of the polymerizable monomer (A) Values and molecular weights per active energy ray polymerizable group are shown in Table 1.

(C-1): 2,4,6-trimethylbenzoyldiphenylphosphine oxide [trade name “Lucirin TPO”, manufactured by BASF Corporation]
(C-2): Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide [trade name “Irgacure 819”, manufactured by BASF Corporation]
(C-3): 1-hydroxycyclohexyl phenyl ketone [trade name “Irgacure 184”, manufactured by BASF Corporation]
(C-4): 2-Hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one [trade name “Irgacure 127 ", Manufactured by BASF]

(D-1): Polyether-modified polydimethylsiloxane [trade name “BYK-333”, manufactured by Big Chemie Japan Co., Ltd., SP value 8.7]
(D-2): Polyether-modified polydimethylsiloxane [trade name “BYK-349”, manufactured by Big Chemie Japan, SP value 8.4]
(D-3): polyether and acryloyl-modified polydimethylsiloxane [trade name “BYK-UV3500”, manufactured by Big Chemie Japan, SP value 8.5]

(E-1): Lithium salt of trifluoromethanesulfonylimide [trade name “Sanconol A600-50R”, manufactured by Sanko Chemical Co., Ltd.]

The size of islands in the sea-island structure of the cured product of the active energy ray-curable composition of the present invention, scratch recovery, adhesion, and transparency of the cured product were measured by the following methods.
The results are shown in Table 1.

<Create test piece>
After coating the active energy ray-curable composition on one side of the glass plate with an applicator so that the thickness is 100 μm, a polyester film with a thickness of 100 μm is stuck to the resin side, and the roller is rolled from above to extrude air. It was. From the polyester film side, ultraviolet rays were irradiated at 1000 mJ / cm ² by an ultraviolet irradiation device [model number “VPS / I600”, manufactured by Fusion UV Systems Co., Ltd., the same applies hereinafter] and cured. The cured product adhered to the PET film was peeled off from the glass plate to prepare a test piece.

<Measurement method of island size in sea-island structure of cured product>
The average size indicating the island portion was measured under the following conditions.
(1) Specimen adjustment method The test piece is cut to a size that can be placed on the sample stage, and fixed to the sample stage with double-sided tape.
(2) Measuring condition measuring device: AFM “SPI4000”, manufactured by Hitachi High-Tech Science Co., Ltd.]
Cantilever type: OMCL-AC160TS-C2
Measurement unit: E-sweep
Measurement mode: Dynamic force mode Scanning mode: Phase image (3) Method of measuring average size showing island portion 30 islands that are randomly shown in the phase image measured by AFM are selected and each island is selected. The diameter of the portion at (in the case of an ellipse, the major axis is adopted) was measured and the average value thereof was calculated. In addition, all the hardened | cured material of Comparative Examples 1-3 did not have a sea island structure.

<Evaluation of wound recoverability>
(1) A stainless steel mold is prepared in which the groove depth is 50 μm, the pitch width is 20 μm, and parallel lines are cut to give a fine uneven process.
(2) An active energy ray-curable composition was applied to one side of this mold with an applicator so that the thickness was 100 μm, and then a polyester film with a thickness of 100 μm [trade name “Cosmo Shine A4300” Toyobo Co., Ltd. )] Was bonded to the resin side, and the roller was rolled from above to extrude air. An ultraviolet ray was irradiated from the polyester film side by an ultraviolet ray irradiating device at 1000 mJ / cm ² , and cured to prepare a cured film.
(3) The surface of the cured film was scratched with a pencil fitted with a chrome cap according to JIS K 5600-5-4.
(4) After leaving for 10 minutes, the scratch was visually observed and judged.

○: Scratch has completely disappeared △: Part of the scratch remains x: All the scratch remains

<Evaluation of adhesion>
The test piece was allowed to stand for 24 hours in an environment of 23 ° C. and 50% relative humidity, and then cut in a 1 mm width with a cutter knife in accordance with JIS K5600-5-6 (10 × 10) The cellophane adhesive tape was affixed on the grid and peeled by 90 degrees, and the peeled state of the cured product from the PET film was visually observed and evaluated.

Judgment was made according to the following criteria.
○: 90 or more of 100 grids remain on the substrate without peeling off.
(Triangle | delta): 10-89 out of 100 grids remain in a base material, without peeling.
X: Nine or less of 100 grids remain on the substrate without peeling off.

<Evaluation of transparency of cured product>
The test piece was measured for haze (%) using a haze meter [trade name “haze-garddual”, manufactured by BYK Gardner Co., Ltd.] in accordance with JIS-K7136.

Since the cured product of the present invention obtained by curing the optical component active energy ray-curable composition of the present invention is excellent in scratch recovery, substrate adhesion, and transparency, it can be used as an optical member or electrical / electronic member. Is also useful. Optical parts using the cured product of the present invention include plastic lenses (prism lenses, lenticular lenses, micro lenses, Fresnel lenses, viewing angle improvement lenses, etc.), optical compensation films, retardation films, prisms, optical fibers, flexible prints. It is useful as a solder resist for wiring, a plating resist, an interlayer insulating film for multilayer printed wiring boards, and a photosensitive optical waveguide.

Claims (8)

  An active energy ray-curable composition containing a polyfunctional (meth) acrylate (A) having no urethane group, urea group, allophanate group or biuret group and a photopolymerization initiator (C), As (A), both a polyfunctional (meth) acrylate (AS1) having a solubility parameter (SP value) of 10.0 or more and a polyfunctional (meth) acrylate (AS2) having an SP value of less than 10.0 are contained. An active energy ray-curable composition for optical parts, wherein a cured product obtained by curing with active energy rays has a sea-island structure, and the size of the islands is 1 to 1,000 nm. SP value of the polyfunctional (meth) acrylate (AS1) (SP ₁₎ and the multi-SP value of (meth) acrylate (AS2) the difference between (SP _{2) (SP} 1 -SP ₂₎ is 0.3 to 1. The active energy ray-curable composition according to claim 1, which is 2. The molecular weight (M ₁ ) per (meth) acryloyl group of the polyfunctional (meth) acrylate (AS1) and the molecular weight (M ₂ ) per (meth) acryloyl group of the polyfunctional (meth) acrylate (AS2) 3. The active energy ray-curable composition according to claim ₁ , wherein the absolute value | M ₁ −M ₂ | of the difference between the _two is 90 or more.   4. The active energy ray-curable composition according to claim 1, wherein the polyfunctional (meth) acrylate (AS1) is a 4 to 6 functional (meth) acrylate.   The active energy ray-curable composition according to any one of claims 1 to 4, wherein the polyfunctional (meth) acrylate (AS2) comprises (meth) acrylate having 6 to 40 oxyalkylene groups.   Furthermore, the active energy ray curable composition of any one of Claims 1-5 containing the polysiloxane (D) which has an oxyalkylene group.   Hardened | cured material which hardened the active energy ray curable composition in any one of Claims 1-6.   An optical lens, a sheet for an optical lens, a film, a coating material for a decorative film, a coating material for an optical fiber, a hard coat film, or an antireflection film, using the cured product according to claim 7.