JP2012097251A - Radiation-curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation-curable composition capable of showing excellent adhesiveness to various base materials by being cured quickly only by being irradiated in a short time with a small amount of a radiation, and forming a cured film having an excellent effect to corrosion prevention of a base material under a severe condition.SOLUTION: This radiation-curable composition contains at least (A) organopolysiloxane represented by general formula (1), (B) a phenyl ester derivative having an acrylic group, and (C) a radiosensitizer, wherein, R, Rand Rin the general formula (1) are each independently 1C-10C monovalent hydrocarbon group, X is a group containing an acrylic group or a methacrylic group wherein each X may be the same or different respectively, a and b are each independently a number of ≥0.1 and <0.9, and c and d are each independently a number of 0-0.8 (under the condition that c and d are not 0 at the same time) that satisfies a relation: a+b+c+d=1.

Description

  The present invention relates to a radiation curable composition having excellent anticorrosion properties such as electrodes in electrical / electronic parts or devices, and particularly suitable for sealing electrical / electronic parts, with low illuminance curability and small light quantity curability. The present invention relates to an excellent radiation curable composition, and an electric device and / or an electronic device using the composition.

  Organopolysiloxane compositions that cure by irradiation with radiation such as ultraviolet light are already known. For example, an organopolysiloxane composition comprising a vinyl functional group-containing organopolysiloxane and a photopolymerization initiator is excellent as a radiation-curable optical fiber coating agent (Patent Document 1). However, since this composition has low adhesion to the substrate, it could not be used as a general adhesive, or as an electrical / electronic-related coating agent or potting agent.

  Such a disadvantage is that at least a specific organopolysiloxane having a radiation-functional (meth) acryloyl group at both ends of the molecular chain, a photosensitizer, a tetraalkylsilane, or an organoorganism containing a partially hydrolyzed condensate thereof. Although it has been improved by the polysiloxane composition (Patent Document 2), it has not been able to adequately answer the recent demand for curing speed and the demand for lowering the illuminance during irradiation.

Japanese Patent Publication No. 4-25231 JP-A-11-302348

Therefore, the first object of the present invention is to cure quickly by simply irradiating a small amount of radiation for a short time, exhibit good adhesion to various substrates, and to prevent corrosion of substrates under severe conditions. An object of the present invention is to provide a radiation curable composition capable of forming a cured film having an excellent effect on the composition.
A second object of the present invention is to provide an electric device and / or an electronic device having excellent product reliability.

  The above objects of the present invention include at least (A) an organopolysiloxane represented by the following general formula (1), (B) a phenyl ester derivative having an acrylic group, and (C) a radiosensitizer. It was achieved by a radiation curable composition, and an electric device and / or an electronic device using the same.

但し、式中のＲ^１、Ｒ^２、及びＲ^３は、それぞれ独立に、炭素原子数１〜１０の１価の炭化水素基、Ｘはアクリル基又はメタクリル基を含有する基であり、各Ｘは、それぞれ同じであっても異なっていてもよい。又、ａ及びｂは、それぞれ独立に０．１以上０．９未満の数、ｃ及びｄはそれぞれ独立に０〜０．８（但し、ｃ、ｄは同時に０とはならない）であると共に、ａ＋ｂ＋ｃ＋ｄ＝１の関係を満たす数である。 General formula (1):

However, in the formula, R ¹ , R ² , and R ³ are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, X is a group containing an acrylic group or a methacryl group, and each X May be the same or different. A and b are each independently a number of 0.1 or more and less than 0.9; c and d are each independently 0 to 0.8 (provided that c and d are not 0 at the same time); It is a number that satisfies the relationship of a + b + c + d = 1.

The monovalent hydrocarbon group having 1 to 10 carbon atoms may be an aromatic hydrocarbon group. The blending ratio of the component (A), the component (B) and the component (C) is such that the component (B) is 0.1 to 10,000 parts by weight with respect to 100 parts by weight of the component (A) (C The component is preferably 0.1 to 100 parts by mass. The radiation curable composition of the present invention is preferably a radiation curable composition having a water vapor permeability after curing measured in accordance with JIS Z 0208 of 20 g / mm ² day or less.

  Since the radiation-curable composition of the present invention is easily cured by irradiation with a small amount of energy, it is particularly useful as a protective coating agent for liquid crystal electrodes, organic EL electrodes, plasma display electrodes and the like that are easily affected by radiation such as ultraviolet rays. .

  Hereinafter, the present invention will be described in detail. In this specification, (meth) acryloyl ((meth) acryloyl), (meth) acryl, (meth) acrylate, etc., respectively, acryloyl and methacryloyl, acryl and methacryl, and acrylate and Used as a term encompassing methacrylate. “Me” means a methyl group, “Et” means an ethyl group, “Pr” means a propyl group, and “iPr” means an isopropyl group.

但し、式中のＲ^１、Ｒ^２、及びＲ^３は、それぞれ独立に、炭素原子数１〜１０の１価の炭化水素基、Ｘはアクリル基又はメタクリル基を含有する基であり、各Ｘは、それぞれ同じであっても異なっていてもよい。又、ａ及びｂは、それぞれ独立に０．１以上０．９未満の数、ｃ及びｄはそれぞれ独立に０〜０．８（但し、ｃ、ｄは同時に０にはならない）であると共に、ａ＋ｂ＋ｃ＋ｄ＝１の関係を満たす数である。 [(A) Organopolysiloxane]
The organopolysiloxane of the component (A) used in the present invention is represented by the following general formula (1) and is the main ingredient of the radiation curable composition of the present invention.

General formula (1):

However, in the formula, R ¹ , R ² , and R ³ are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, X is a group containing an acrylic group or a methacryl group, and each X May be the same or different. A and b are each independently a number of 0.1 or more and less than 0.9; c and d are each independently 0 to 0.8 (provided that c and d are not 0 at the same time); It is a number that satisfies the relationship of a + b + c + d = 1.

  Specific examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, and hexyl group. Alkyl groups such as heptyl group, 2-ethylhexyl group, octyl group and nonyl group; cycloalkyl groups such as cyclohexyl group and cycloheptyl group; vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group An aryl group such as a phenyl group and a tolyl group; an aralkyl group such as a benzyl group, a phenylethyl group and a 3-phenylpropyl group; and at least a part of hydrogen atoms bonded to carbon atoms of these groups A chloromethyl group, a cyanoethyl group, a 3,3,3-trifluoropropyl group, etc. substituted with a substituent such as a halogen atom or a cyano group. It is.

In the organopolysiloxane of the component (A) used in the present invention, it is particularly preferable that 30 mol% or more of the total R ¹ is a phenyl group, and 50 mol% or more is a phenyl group.

  X in the general formula (1) is a monovalent organic group containing an acryl group or a methacryl group. Specific examples thereof include the following formulas, but the present invention is not limited thereto.

_{CH 2 = CHCOOCH 2 -, CH} 2 = C (CH 3) COOCH 2 -, CH 2 = CHCOOC 2 H 4 -,
CH ₂ = CHCOOC ₃ H _6- , CH ₂ = C (CH ₃ ) COOC ₃ H _6- ,

In the present invention, among these, those containing an acrylic group are preferable, and CH ₂ ═CHCOOCH ₂ — and CH ₂ ═CHCOOC ₃ H ₆ — are particularly preferable.

但し、a、ｂ及びｃは、それぞれ一般式（１）のa、ｂ及びｃと同じであり、XはCH₂=CHCOOC₃H₆-である。
（A）成分のオルガノポリシロキサンの重量平均分子量は、好ましくは３００〜３００００、より好ましくは４００〜１００００、特に好ましくは５００〜５０００である。 Preferable specific examples of the organopolysiloxane represented by the general formula (1) include, for example, those represented by the following general formula (2).
General formula (2):

However, a, b and c, a respective general formulas (1), the same as b and c, X is CH ₂ = CHCOOC ₃ H ₆ - is.
The weight average molecular weight of the organopolysiloxane (A) is preferably 300 to 30000, more preferably 400 to 10000, and particularly preferably 500 to 5000.

  This (A) component organopolysiloxane has a (meth) acrylic group as a radiation-polymerizable group, so it can be easily irradiated with radiation such as ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and γ rays. Can be polymerized to cure the composition of the present invention. In addition, as organopolysiloxane of this (A) component, it can also be used individually by 1 type and can be used in combination of 2 or more type.

The organopolysiloxane of the component (A) can be prepared, for example, by hydrolyzing a corresponding alkoxysilane represented by the following formula.

本発明においては、これらの中でも特に２−ヒドロキシフェノキシプロピルアクリレートを使用することが好ましい。
本発明においては、（Ｂ）成分として、１種類の化合物を単独で使用することも、２種以上を組み合わせて使用することもできる。
又、(Ｂ)成分の使用量は、（Ａ）成分１００質量部に対して、０．１〜１０，０００質量部であることが好ましく、特に、１〜１，０００質量部であることが好ましい。 [(B) Phenyl ester derivative having acrylic group]
Although the phenyl ester derivative which has an acryl group used as (B) component by this invention is not specifically limited, For example, what is represented by a following formula is mentioned.

In the present invention, it is particularly preferable to use 2-hydroxyphenoxypropyl acrylate among these.
In the present invention, as the component (B), one type of compound can be used alone, or two or more types can be used in combination.
The amount of component (B) used is preferably 0.1 to 10,000 parts by weight, and more preferably 1 to 1,000 parts by weight with respect to 100 parts by weight of component (A). preferable.

[(C) Radiosensitizer]
The radiation sensitizer of the component (C) used in the present invention is not particularly limited, but it is preferable to use a benzoyl compound (or phenyl ketone compound) such as benzophenone, particularly 1-hydroxycyclohexyl. Α-position of carbonyl group such as phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, etc. It is preferable to use a benzoyl compound (or a phenyl ketone compound) having a hydroxy group on the carbon atom.

Other preferred radio sensitizers that can be used in the present invention include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bisacyl monoorganophosphine oxide, bis (2,6-dimethoxybenzoyl) -2 And 4,4, -trimethylpentylphosphine oxide, etc .; benzoin ether compounds such as isobutyl benzoin ether; ketal compounds such as acetophenone diethyl ketal; thioxanthone compounds; acetophenone compounds.
In the present invention, as the radiosensitizer for the component (C), only one kind can be used alone, or two or more kinds can be used in combination.

  The amount of component (C) used in the present invention is not particularly limited as long as it is an amount effective for curing the composition of the present invention, but is usually based on 100 parts by mass of component (A). 0.1 to 100 parts by mass, preferably 0.5 to 50 parts by mass, and more preferably 1.0 to 25 parts by mass.

[Other ingredients]
In addition to the above components (A) to (C), other components can be appropriately blended in the composition of the present invention as long as the objects and effects of the present invention are not impaired. For example, for the purpose of appropriately adjusting the shrinkage ratio during curing and the thermal expansion coefficient, mechanical strength, heat resistance, chemical resistance, flame resistance, thermal expansion coefficient, gas permeability, etc. of the resulting cured product Various additives may be blended.

  In the present invention, as the other components described above, for example, inorganic fillers such as fumed silica, silica airgel, quartz powder, glass fiber, iron oxide, titanium oxide, calcium carbonate, magnesium carbonate; hydroquinone, methoxyhydroquinone, A radical polymerization inhibitor (pot life extending agent) such as 2,6-di-tert-butyl-p-cresol may be blended.

  The radiation-curable composition of the present invention can be obtained by mixing the above components (A) to (C) and, if necessary, other blending components. By irradiating the obtained composition with radiation, the composition of the present invention is quickly cured and exhibits strong adhesiveness immediately after curing.

Examples of the radiation used in the present invention include ultraviolet rays, far infrared rays, electron beams, X-rays, γ rays, and the like, but it is preferable to use ultraviolet rays from the viewpoint of ease of handling and ease of handling of the apparatus. Examples of the ultraviolet light source include a UVLED lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, and a xenon lamp. The irradiation amount of ultraviolet rays (peak wavelength: 320 to 390 nm) is, for example, 100 to 2,400 mJ / cm ² , preferably 200 to 800 mJ / cm ² with respect to a sheet obtained by molding the composition of the present invention to a thickness of 2 mm. ² .

The cured product obtained by the composition of the present invention is useful not only as a protective film for electrodes such as flat panel displays and plasma displays, but also as a protective film or sealant for various electric / electronic parts, Even under severe conditions, it has a very excellent anticorrosion effect.
Hereinafter, the present invention will be described in more detail with reference to synthesis examples, examples and the like, but the present invention is not limited thereto. In the following description, “part” represents mass part, and “%” represents mass%.

ＸはCH₂=CHCOOC₃H₆-である。
また、Ｌ＝０．７１、Ｍ＝０．２４、Ｎ＝０．０５であった。 [Synthesis Example 1]
In a 2 L separable flask with a cock at the bottom, phenyltrimethoxysilane 295 g (1.5 mol), dimethyldimethoxysilane 60.1 g (0.5 mol), 3-acryloxypropyltrimethoxysilane 23.4 g (0.1 mol), toluene After adding 270 g and 156 g of IPA (isopropyl alcohol) and stirring at room temperature, 156 g of water and 17.2 g of 25% aqueous tetramethylammonium hydroxide solution were added. After stirring at room temperature for 3 hours, 200 g of a 10% aqueous sodium dihydrogen phosphate solution was added for neutralization. The organic phase was separated, washed with water, and evaporated under reduced pressure to obtain a product represented by the following formula.
The obtained organopolysiloxane had a styrene-equivalent weight average molecular weight of 1612 as measured by GPC.

X is CH ₂ = CHCOOC ₃ H _6- .
L = 0.71, M = 0.24, and N = 0.05.

但し、ＸはCH₂=CHCOOC₃H₆-である。
また、Ｌ＝０．３３、Ｍ＝０．４２、Ｎ＝０．２２及びＯ＝０．０３であった。 [Synthesis Example 2]
In a 5 L separable flask with a cock at the bottom, 237.9 g (1.2 mol) of phenyltrimethoxysilane, 244.36 g (1.5 mol) of diphenyldimethoxysilane, 174.6 g (0.8 mol) of 3-acryloxypropylmethyldimethoxysilane, After adding 23.4 g (0.1 mol) of 3-acryloxypropyltrimethoxysilane, 800 g of toluene and 400 g of IPA and stirring at room temperature, 400 g of water and 37.8 g of 25% tetramethylammonium hydroxide aqueous solution were added. After stirring at room temperature for 3 hours, 500 g of a 10% aqueous sodium dihydrogen phosphate solution was added for neutralization. The organic phase was separated, washed with water, and evaporated under reduced pressure to obtain a product represented by the following formula.
The resulting organopolysiloxane had a styrene-converted weight average molecular weight of 1145 as measured by GPC.

However, X is CH ₂ = CHCOOC ₃ H ₆ - is.
L = 0.33, M = 0.42, N = 0.22, and O = 0.03.

The following components (A) to (C) were mixed to obtain a radiation curable composition of the present invention.
(A) Reaction product obtained in Synthesis Example 1: 50 parts by mass (B) 2-hydroxyphenoxypropyl acrylate (KAYARAD R-128 manufactured by Nippon Kayaku Co., Ltd.): 50 parts by mass (C) Radiosensitizer ( IRGACURE 907 manufactured by Toyotsu Plachem Co., Ltd. 2.5 parts by mass The composition obtained was poured into a mold having a depth of 1 mm, a width of 120 mm and a length of 170 mm, and a conveyor furnace equipped with two metal halide mercury lamps (illuminance: 40 W / cm ² ) For 2 seconds (energy amount: 200 mJ) to obtain a cured product.

The following components (A) to (C) were mixed to obtain a radiation curable composition of the present invention.
(A) Reaction product obtained in Synthesis Example 2: 99 parts by mass (B) 2-hydroxyphenoxypropyl acrylate (KAYARAD R-128 manufactured by Nippon Kayaku Co., Ltd.): 1 part by mass (C) Radiosensitizer ( IRGACURE 907 manufactured by Toyotsu Plachem Co., Ltd. 2.5 parts by mass The composition obtained was poured into a mold having a depth of 1 mm, a width of 120 mm and a length of 170 mm, and a conveyor furnace equipped with two metal halide mercury lamps (illuminance: 40 W / cm ² ) For 2 seconds (energy amount: 200 mJ) to obtain a cured product.

The following components (A) to (C) were mixed to obtain a radiation curable composition of the present invention.
(A) Reaction product obtained in Synthesis Example 1: 10 parts by mass (B) 2-hydroxyphenoxypropyl acrylate (KAYARAD R-128 manufactured by Nippon Kayaku Co., Ltd.): 90 parts by mass (C) Radiosensitizer ( IRGACURE 907 manufactured by Toyotsu Plachem Co., Ltd. 2.5 parts by mass The composition obtained was poured into a mold having a depth of 1 mm, a width of 120 mm and a length of 170 mm, and a conveyor furnace equipped with two metal halide mercury lamps (illuminance: 40 W / cm ² ) For 2 seconds (energy amount: 200 mJ) to obtain a cured product.

<Various performance evaluation>
-Physical property About the hardened | cured material obtained in Examples 1-3, the hardness was measured with the spring type A type tester based on JISK6301, and the water-vapor-permeation rate was measured based on JISZ0208. The results are shown in Table 1.

[Comparative Example 1]
A composition was prepared in the same manner as in Example 1 except that the organopolysiloxane of component (A) used in Example 1 was changed to urethane acrylate (UX-4101 manufactured by Nippon Kayaku Co., Ltd.). The test was conducted in the same manner. The results are shown in Table 1.

  As is clear from the results in Table 1, it was confirmed that the radiation curable composition of the present invention was not only sufficiently cured with a small irradiation energy, but also the water vapor permeability of the obtained cured product was sufficiently small. .

  Since the radiation curable composition of the present invention is easily cured by irradiation with a small amount of energy, it is not only used as a protective coating agent for liquid crystal electrodes, organic EL electrodes, and plasma display electrodes that are easily affected by radiation such as ultraviolet rays, but also various It is extremely useful industrially as a coating agent for protecting electrical and electronic parts.

Claims (5)

It contains at least (A) an organopolysiloxane represented by the following general formula (1), (B) a phenyl ester derivative having an acrylic group, and (C) a radiosensitizer. Radiation curable compositions;

However, R ¹ , R ² , and R ³ in the general formula (1) are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, and X is a group containing an acryl group or a methacryl group. Each X may be the same or different. A and b are each independently a number of 0.1 or more and less than 0.9; c and d are each independently 0 to 0.8 (provided that c and d are not 0 at the same time); It is a number that satisfies the relationship of a + b + c + d = 1. The radiation-curable composition according to claim ¹ , wherein at least one of R ¹ , R ² , and R ³ is an aromatic hydrocarbon group having 6 to 10 carbon atoms.   The blending ratio of the component (A), the component (B) and the component (C) is 0.1 to 10,000 parts by weight of the component (B) with respect to 100 parts by weight of the component (A), and the component (C) The radiation-curable composition according to claim 1 or 2, wherein is 0.1 to 100 parts by mass. The radiation-curable composition according to any one of claims 1 to 3, wherein the water vapor permeability after curing measured in accordance with JIS Z 0208 is 20 g / mm ² day or less.   An electric device and / or an electronic device sealed with a cured resin, wherein the cured resin is obtained by curing the radiation curable composition according to any one of claims 1 to 4. An electrical device and / or an electronic device, characterized in that