JP4301052B2 - Ultraviolet curable resin composition, cured product and laminate - Google Patents

Description

  The present invention relates to an ultraviolet curable resin composition. More specifically, the present invention relates to an ultraviolet curable resin composition having excellent adhesion to a substrate, in particular, excellent adhesion to a substrate comprising a methyl methacrylate-styrene copolymer, and further excellent in transparency and antistatic performance. .

Conventionally, from the viewpoint of ensuring the performance of information communication equipment and safety measures, a radiation-curable composition is used on the surface of the equipment to provide a scratch-resistant coating (hard coat) or an antistatic coating (charging) Forming a prevention film).
In order to impart an antireflection function to an optical article, a low refractive index layer or a multilayer structure (antireflection film) of a low refractive index layer and a high refractive index layer is formed on the surface of the optical article. ing.
In recent years, there has been remarkable development and versatility of information communication devices, and further improvements in performance and productivity of hard coats, antistatic films, antireflection films and the like have been demanded.

For example, in display panels, prevention of adhesion of dust due to static electricity and prevention of reflection on a screen have been demanded.
In response to these demands, various radiation curable materials have been proposed with a focus on high productivity and curing at room temperature.

  As such a resin composition, for example, a conductive oxide fine powder having a primary particle diameter of 100 nm or less, an easily dispersible low-boiling solvent of the conductive oxide fine powder, and a difficult dispersion of the conductive oxide fine powder There is a paint for forming a transparent conductive film containing a conductive low-boiling solvent and a binder resin (see, for example, Patent Document 1).

By the way, in a video display device, in order to protect the display screen from an external impact or the like, a transparent protective plate (front plate) may be installed on the front surface (viewer side) of the screen. An acrylic resin is used as the transparent base material of the front plate. However, it has been studied to impart antistatic properties to the front plate to prevent adhesion of dust and the like due to charging.
However, while maintaining excellent transparency and antistatic performance, the resin composition has excellent adhesion to acrylic resins, particularly methyl methacrylate-styrene copolymer (hereinafter sometimes referred to as MS resin). There was nothing.
JP 2001-131485 A

  The present invention has been made in view of the above-described problems, and an object of the present invention is to provide an ultraviolet curable resin composition that is excellent in adhesiveness with an MS resin and excellent in antistatic properties and transparency.

［式中、Ｒ ^１ は、Ｈ又はＣＨ _３ 、Ｒ ^２ は、炭素数２０以下の有機基である。］
２．さらに、（Ｄ）成分として、３官能以上のアクリレート化合物を含有する１に記載の紫外線硬化性樹脂組成物。
As a result of diligent research to solve this problem, the present inventor, as a component of the resin composition, when blended with a specific acrylate-like compound, transparency and antistatic performance are not impaired, and adhesion to the MS base material is improved. As a result, the present invention has been completed.
According to this invention, the following ultraviolet curable resin composition, its hardened | cured material, and a laminated body are provided.
1. The ultraviolet curable resin composition containing the following (A)-(C) component.
(A) 1 selected from the group consisting of antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), niobium oxide, fluorine-doped tin oxide (FTO) and zinc antimonate having an average particle size of 0.1 μm or less Seed or two or more kinds of metal oxide particles (B) Compound (C) photopolymerization initiator represented by the following formula (1)

[Wherein R ¹ is H or CH ₃ , and R ² is an organic group having 20 or less carbon atoms. ]
2. Furthermore, the ultraviolet curable resin composition of 1 containing a trifunctional or more than trifunctional acrylate compound as (D) component.

４．さらに、（Ｅ）成分として、有機溶剤を含有する１〜３のいずれかに記載の紫外線硬化性樹脂組成物。
５．前記組成物中の全アクリレートモノマー中に占める成分（Ｂ）の含有量が、１０重量％〜１００重量％である１〜４のいずれかに記載の紫外線硬化性樹脂組成物。
６．上記１〜５のいずれかに記載の紫外線硬化性樹脂組成物を硬化してなる硬化物。
７．基材上に６記載の硬化物の膜を形成した積層体。 3. The ultraviolet curable resin composition of 1 or 2 whose said (B) component is a compound of following formula (2) or Formula (3).

4). Furthermore, the ultraviolet curable resin composition in any one of 1-3 containing an organic solvent as (E) component.
5. The ultraviolet curable resin composition in any one of 1-4 whose content of the component (B) which occupies in all the acrylate monomers in the said composition is 10 to 100 weight%.
6). Hardened | cured material formed by hardening | curing the ultraviolet curable resin composition in any one of said 1-5.
7). A laminate in which the cured product film described in 6 is formed on a substrate.

  ADVANTAGE OF THE INVENTION According to this invention, the ultraviolet curable resin composition which is excellent in adhesiveness with acrylic resin, and has transparency and antistatic property can be provided.

［式中、Ｒ^１は、Ｈ又はＣＨ_３、Ｒ^２は、炭素数２０以下の有機基である。］ Hereinafter, the ultraviolet curable resin composition of this invention is demonstrated concretely.
The ultraviolet curable resin composition of this invention contains the following (A)-(C) component.
(A) Metal oxide particles having an average particle size of 0.1 μm or less (B) Compound (C) photopolymerization initiator represented by the following formula (1)

[Wherein R ¹ is H or CH ₃ , and R ² is an organic group having 20 or less carbon atoms. ]

The metal oxide particles (A) are preferably conductive particles, and more specifically, antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), niobium oxide, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.
The average particle diameter of the metal oxide particles is 0.1 μm or less. When the average particle diameter is larger than 0.1 μm, it is difficult to uniformly disperse the metal oxide particles in the ultraviolet curable resin composition. Moreover, it becomes easy for a metal oxide particle to settle, and it uses for storage stability. Furthermore, it causes an increase in turbidity (Haze value) and coloring of the coating film obtained by curing the resin composition.
The average particle diameter of the metal oxide particles is preferably 0.08 μm or less, and more preferably 0.001 to 0.05 μm.
In addition, the average particle diameter of a metal oxide particle is a number average value of the particle diameter measured with an electron microscope.

  Specific examples of metal oxide particles are: Mitsubishi Materials Corporation product name: T-1 (ITO), Mitsui Metals Corporation product name: Pastoran (ITO, ATO), Ishihara Sangyo Co., Ltd. Name: SN-100P (ATO), manufactured by CI Kasei Co., Ltd. Product name: Nanotech ITO, manufactured by Nissan Chemical Industries, Ltd. Product names: ATO, FTO, and the like.

  A commercial product in which oxide particles are dispersed in a solvent can also be used. Specifically, product name: MTC filler 12867 (ATO of water dispersion), MHI filler # 8954MS (ATO of methyl ethyl ketone dispersion), manufactured by Ishihara Sangyo Co., Ltd., trade name: SN-100D (water dispersion) SNS-10I (isopropyl alcohol dispersed ATO), SNS-10B (isobutanol dispersed ATO), SNS-10M (methyl ethyl ketone dispersed ATO), FSS-10M (isopropyl alcohol dispersed ATO), Nissan Chemical Industries Product name: Cellnax CX-Z401M (methanol-dispersed zinc antimonate), Cellnax CX-Z200IP (isopropyl alcohol-dispersed zinc antimonate), Mitsui Kinzoku Co., Ltd. Product name: Pastorlan type A (ITO ) Aqueous dispersion, methanol content Liquid, isopropyl alcohol dispersion, methyl ethyl ketone dispersion, mention may be made of toluene dispersion like.

  (A) The compounding quantity of a component is 1 to 50 weight% by making into 100 weight% the composition whole quantity except the organic solvent which is the (E) component mentioned later. Within this range, the cured product has excellent transparency and antistatic properties. Preferably it is 3 to 30 weight%, Most preferably, it is 5 to 15 weight%.

［式中、Ｒ^１は、Ｈ又はＣＨ_３、Ｒ^２は、炭素数２０以下の有機基である。］ (B) A component is a compound represented by following formula (1).

[Wherein R ¹ is H or CH ₃ , and R ² is an organic group having 20 or less carbon atoms. ]

By this (B) component, the adhesiveness with MS base material can be provided to the composition of this invention, and the transparency and favorable surface-resistance value of a cured coating film can be made compatible.
In Formula (1), when R ² is an organic group having more than 20 carbon atoms, the strength of the cured coating film obtained by ultraviolet curing is significantly reduced. Preferably, the number of carbon atoms in ^{R 2} is 10 or less. Specific examples of R ² include —CH ₂ —, — (CH ₂ CH ₂ O) _n —, —CH ₂ CHOH—CH ₂ O—, and the like. Here, n is 1/2 of the number of carbon atoms in ^{R 2.}
Among the compounds represented by the formula (1), the film strength after curing is also good, and it is easy to apply with an optimum film thickness, and therefore, those represented by the following formulas (2) and (3) Particularly preferred.

  To illustrate specific examples of the compound of formula (1), Osaka Organic Chemical Co., Ltd. Trade name: Biscote # 160, manufactured by Kyoeisha Chemical Co., Ltd. Trade name: Epoxy ester M-600A, manufactured by Toagosei Co., Ltd. Aronix M-5700, Aronix M-102, manufactured by Shin-Nakamura Chemical Co., Ltd. Product name: NK ester AMP-20G, NK ester AMP-60G, manufactured by Kyoeisha Chemical Co., Ltd. Product name: Light acrylate PO-A Can do.

  Component (B) is blended in an amount of 10 to 100% by weight, preferably 20 to 80% by weight, based on the total amount of acrylate monomers (B component, D component and other acrylate monomers) contained in the composition. Preferably it is 30 to 70% by weight.

Component (C) is a photopolymerization initiator and preferably contains a photoradical initiator. A photo-radical initiator is defined as a compound that can generate a photocuring (crosslinking) radical substance from the component (B) or the component (D) described below by irradiating energy rays such as light. The
Examples of the photo radical initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 1-hydroxycyclohexyl phenyl ketone. More preferred.

  Illustrative examples of photoradical initiators include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one: Irgacure 907, 1-hydroxycyclohexyl phenyl ketone: Irgacure 184 (both Ciba Specialty Chemicals Co., Ltd.).

  In addition to the photo radical initiator, a photo acid generator can also be used. As the photoacid generator, for example, those described in JP-A No. 2001-296401 can be preferably used.

The blending amount of the component (C) is not particularly limited, but is preferably set to a value within the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the polymerizable component. When the amount of the photo radical initiator used is less than 0.1 parts by weight, the crosslinking component may be insufficiently cured. On the other hand, when the amount used exceeds 20 parts by weight, the storage stability of the ultraviolet curable resin composition may be lowered. More preferably, the value is in the range of 0.5 to 10 parts by weight with respect to 100 parts by weight of the crosslinking component.
In addition, a polymeric component means the (B) component mentioned above and the (D) component demonstrated below.

The resin composition of the present invention preferably contains a trifunctional or higher acrylate compound, specifically, a compound containing at least three (meth) acryloyl groups in the molecule as the component (D). Thereby, the reactivity of an ultraviolet curable resin composition can be improved.
Among the compounds containing a tri- or higher functional (meth) acryloyl group, dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and trimethylolpropane triacrylate are particularly preferable.

Since these polyfunctional (meth) acrylate compounds are particularly excellent in photocurability, the coating film after curing of the composition has sufficient hardness. In addition, the compatibility with the component (B) is also particularly excellent.
In addition, when only the bifunctional or less acrylate is used, the obtained cured coating film may not exhibit sufficient hardness.

  Specific examples of the component (D) include Nippon Kayaku Co., Ltd. product name: KAYARAD DPHA, Kayaku Sartomer Co., Ltd. Product name: SR399E, Toagosei Co., Ltd. Product name: Aronix M-305, Toago Product name: Aronix M-450, etc. manufactured by Synthesizer Co., Ltd. can be mentioned.

Although the addition amount of (D) component is not specifically limited, For example, it is preferable to set it as the value within the range of 1-10,000 weight part per 100 weight part of (A) component. When the addition amount is less than 0.1 parts by weight, the reactivity of the ultraviolet curable composition may be reduced. On the other hand, when the addition amount exceeds 5,000 parts by weight, the antistatic performance of the ultraviolet curable composition is decreased. May decrease.
Since the balance of reactivity, antistatic performance and transparency of the ultraviolet curable composition becomes better, the addition amount of the component (D) is in the range of 30 to 3000 parts by weight per 100 parts by weight of the component (A). More preferably, the value is more preferably in the range of 100 to 1400 parts by weight.

  It is preferable to add an organic solvent as the component (E) to the resin composition of the present invention. Thereby, while improving the storage stability of an ultraviolet curable resin composition, the coating film formed by apply | coating and hardening a resin composition can be made into uniform thickness.

As the organic solvent, an alcohol solvent alone or a mixed solvent composed of an alcohol solvent and a ketone solvent can be preferably used.
The alcohol solvent improves the particle dispersion stability of the component (A) and also improves the coating properties (such as the transparency of the coating film).
If only the ketone solvent is used, the particle dispersibility of the component (A) may be reduced, and the component (A) may settle. Moreover, when a ketone solvent erodes a base material at the time of coating, coating property and the external appearance of a coating film may fall. However, if it is a mixed solvent of an alcohol solvent and a ketone solvent, the adhesion to the MS substrate can be further improved.

  Specific examples of the component (E) include methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, methyl amyl ketone, methanol, ethanol, t-butanol, isopropanol, n-butanol, propylene glycol monomethyl ether and the like alone or in combination of two or more. Can be mentioned.

  The amount of component (E) is preferably set to a value in the range of 1 to 10,000 parts by weight per 100 parts by weight of components (A), (B), (C), and (D). It is preferable to set the value within the range of ˜5,000 parts by weight, and further 40 to 1,000 parts by weight.

  In addition to the above components (A) to (E), the resin composition of the present invention includes a monofunctional or bifunctional acrylate compound other than the component (B) as long as the objects and effects of the present invention are not impaired. , Thermal acid generator, photosensitizer, polymerization inhibitor, polymerization initiator, leveling agent, wettability improver, surfactant, plasticizer, UV absorber, antioxidant, antistatic agent, silane coupling It is also preferable to further contain additives such as an agent, an inorganic filler, a pigment, and a dye.

  The resin composition of the present invention can be prepared by a generally used method. For example, the method which throws the said component into the container which has a stirrer, and mixes each component uniformly can be mentioned.

The resin composition of the present invention is used, for example, by applying (coating) to a substrate (application member) and curing.
The type of the base material is not particularly limited, and examples include base materials made of glass, polycarbonate resin, polyester resin, acrylic resin, triacetyl acetate resin (TAC), norbornene resin, and the like. Can do. In particular, the present invention exhibits extremely excellent adhesion to a methyl methacrylate-styrene copolymer, which is a kind of acrylic resin.

  As the coating method, for example, a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, an ink jet method, or the like can be used.

A cured product (film) can be formed by irradiating the substrate coated with the resin composition with ultraviolet rays. In this case, it is preferable to use an ultraviolet irradiation device (metal halide lamp or the like) and set light irradiation conditions of 0.001 to 10 J / cm ² .

Hereinafter, the present invention will be described more specifically with reference to examples.
Example 1
[Preparation of UV curable composition]
In a container shielded from ultraviolet rays, as component (B), 43.0 parts of 2-hydroxy-3-phenoxypropyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: epoxy ester M-600A), as component (C) , 1-hydroxy-cyclohexyl phenyl ketone (Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 184) 3.0 parts, (D) component, dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., (Product name: KAYARAD DPHA) 43.0 parts, (E) As the component (E), 64.3 parts of methanol and 60.0 parts of propylene glycol monomethyl ether were stirred at room temperature for 2 hours to obtain a uniform solution.
Thereafter, as component (A), antimony-containing tin oxide dispersion (manufactured by Ishihara Sangyo Co., Ltd., SN-100P, dispersant: Adeka Pluronic TR701 (Asahi Denka Kogyo Co., Ltd.), dispersion solvent: methanol, antimony-containing tin oxide 36.6 parts) (content: 29.1% by weight, average particle size: 20 nm, dispersant content 0.9% by weight) is added and stirred for 1 hour to obtain a UV curable resin composition that is a uniform solution. It was.
The solid content and the inorganic content in the solid content of this composition were measured and found to be 40% by weight and 10.6% by weight, respectively.

[Preparation of cured film]
The composition obtained above was applied onto a methyl methacrylate-styrene copolymer substrate (3 mm thickness) using a DIP coater at a pulling rate of 500 mm / min, dried at room temperature for 15 minutes, Formed.
Subsequently, the coating film was UV-cured under a light irradiation condition of 1 J / cm ² using a metal halide lamp in the atmosphere to obtain a cured film. The film thickness of the cured film was 3 μm.
Table 1 shows the evaluation results of the composition and the cured film of the resin composition of Example 1, the cured film, and the resin compositions prepared in Example 2-4 and Comparative Example 1-4 shown below.

The evaluation was performed by the following method.
(1) Transparency / turbidity Using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.), the transparency and turbidity were measured according to JIS K7105.
The transparency was evaluated as follows: ○: transmittance 90% or more, Δ: transmittance 80% or more and less than 90%, ×: transmittance 80% or less.
(2) Surface resistance (Ω / □)
Using a high resistance meter (Agilent Technology Co., Ltd. Agilent 4339B) and Resistivity Cell 16008B (Agilent Technology Co., Ltd.), the measurement was performed under the condition of an applied voltage of 100V.
(3) Adhesiveness Using a crosscut guide, a cross-cut peel test was performed according to JIS K5600-5-6.
Evaluation: A: No peeling (100/100), B: Partial peeling (99/100 to 90/100), Δ: Peeling (89/100 to 50/100), X: Peeling (49/100 or less) It was.

Examples 2 and 3
A resin composition and a cured film were prepared and evaluated in the same manner as in Example 1 except that the blending amounts of the component (B) and the component (D) were changed as shown in Table 1.

Example 4
A resin composition and a cured film were prepared and evaluated in the same manner as in Example 1 except that benzyl acrylate (Biscoat # 160, Osaka Organic Chemical Co., Ltd.) was used as the component (B).

Comparative Example 1-4
A resin composition and a cured film were prepared and evaluated in the same manner as in Example 1 except that the formulation shown in Table 1 was used.
From the above results, it was confirmed that the resin composition of the present invention was excellent in adhesion to the MS base material, and also had good antistatic properties and transparency.

The ultraviolet curable resin composition of the present invention has, for example, scratches (scratches) on plastic optical parts, touch panels, film-type liquid crystal elements, plastic cases, plastic containers, floor materials as building interior materials, wall materials, artificial marble, etc. ) Hard coating material for prevention and contamination prevention; High refractive index film for antireflection film; Adhesive and sealing material for various base materials; Binder material for printing ink.
In particular, since the resin composition of the present invention exhibits excellent adhesion to the MS substrate, it can be suitably used for an optical substrate using the MS substrate, such as a front panel of a projection television.

Claims (7)

The ultraviolet curable resin composition containing the following (A)-(C) component.
(A) 1 selected from the group consisting of antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), niobium oxide, fluorine-doped tin oxide (FTO) and zinc antimonate having an average particle size of 0.1 μm or less Seed or two or more kinds of metal oxide particles (B) Compound (C) photopolymerization initiator represented by the following formula (1)

[Wherein R ¹ is H or CH ₃ , and R ² is an organic group having 20 or less carbon atoms. ]
Furthermore, the ultraviolet curable resin composition of Claim 1 which contains an acrylate compound more than trifunctional as (D) component. The ultraviolet curable resin composition according to claim 1 or 2 , wherein the component (B) is a compound of the following formula (2) or formula (3).

  Furthermore, the ultraviolet curable resin composition as described in any one of Claims 1-3 which contains the organic solvent as (E) component.   The ultraviolet curable resin composition according to any one of claims 1 to 4, wherein the content of the component (B) in the total acrylate monomer in the composition is 10% by weight to 100% by weight.   Hardened | cured material formed by hardening | curing the ultraviolet curable resin composition as described in any one of Claims 1-5. The laminated body which formed the film | membrane of the hardened | cured material of Claim 6 on the base material.