KR20120035118A - Radiation-curable composition - Google Patents

Abstract

PURPOSE: A radiation-curable composition is provided to be easily cured by small light amount radiating, thereby having good adhesion to various substrates, and to form a cured layer having excellent effect to a substrate under severe condition. CONSTITUTION: A radiation-curable composition comprises organopolysiloxane in chemical formula 1, phenylester derivative having an acryl group, and a radiation sensitizer. In chemical formula 1, R^1, R^2 and R^3 is respectively C1-10 monovalent hydrocarbon, X is a group containing an acryl group or an methacryl group, each X can be same or different, a and b is respectively a number from 0.1-0.9, and c and d is respectively 0-0.8, satisfying a+b+c+d=1, but not 0 at the same time.

Description

Radiation curable composition {RADIATION-CURABLE COMPOSITION}

TECHNICAL FIELD The present invention relates to a radiation curable composition having excellent anticorrosive properties such as an electrode in an electrical / electronic component or an apparatus, and particularly excellent in low light curing and extinction amount curability, which is preferable for sealing electrical / electronic components. A curable composition and an electrical device and / or an electronic device made using the composition.

Organopolysiloxane compositions which are cured by irradiation with radiation such as ultraviolet rays are already known. For example, the organopolysiloxane composition containing a vinyl functional group containing organopolysiloxane and a photoinitiator is excellent as a coating agent for radiation curable optical fibers (patent document 1). However, since the composition has low adhesiveness to the substrate, it was not possible to use it as a general adhesive or as an electrical / electronic coating or potting agent.

This drawback comprises organopolysiloxane compositions comprising a specific organopolysiloxane, a photosensitizer, a tetraalkylsilane or a partial hydrolysis condensate thereof, at least on both ends of the molecular chain, having a radiofunctional (meth) acryloyl group. Although it improved by the document 2), it was not able to fully satisfy the request | requirement of the hardening rate in recent years, or the request of the low illumination of the irradiation at the time of hardening.

Japanese Patent Publication Hei 4-25231 Japanese Patent Publication No. 11-302348

Accordingly, the first object of the present invention is to cure rapidly by only irradiating a small amount of radiation for a short time to form a cured film having not only good adhesion to various substrates but also excellent effects on the manner of the substrate under severe conditions. It is providing the radiation curable composition which can be used.

A second object of the present invention is to provide an electrical device and / or an electronic device having excellent reliability of a product.

 The above-mentioned various objects of the invention comprise at least (A) an organopolysiloxane represented by the following formula (1), (B) a phenyl ester derivative having an acrylic group, and (C) a radiation sensitizer. And electrical and / or electronic devices using the same.

Wherein 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 acryl group or methacryl group, and each X may be the same or different. It may be. A and b are each independently a number of 0.1 or more and less than 0.9, and c and d are each independently 0 to 0.8 (where c and d are not 0 at the same time), and a + b + c + A number satisfying the relationship of d = 1.

The monovalent hydrocarbon group having 1 to 10 carbon atoms may be an aromatic hydrocarbon group. Moreover, the compounding ratio of the said (A) component, (B) component, and (C) component is 0.1-10000 mass parts of (B) component with respect to 100 mass parts of (A) component, and (C) component is 0.1- It is preferable that it is 100 mass parts. It is preferable that the radiation curable composition of this invention is a radiation curable composition whose water vapor transmittance after hardening measured based on JISZ0220 will be 20 g / mm <^2> or less.

Since the radiation curable composition of this invention hardens easily by little energy irradiation, it is especially useful as a protective coating agent, such as a liquid crystal electrode, an organic EL electrode, and a plasma display electrode which are easy to be influenced by radiation, such as an ultraviolet-ray.

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

[(A) organopolysiloxane]

The organopolysiloxane of (A) component used by this invention is represented by following General formula (1), and is a subject of the radiation curable composition of this invention.

<Formula 1>

Wherein 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 acryl group or methacryl group, and each X may be the same or different. It may be. A and b are each independently a number of 0.1 or more and less than 0.9, and c and d are each independently 0 to 0.8 (where c and d are not 0 at the same time), and a + b + c + A number satisfying the relationship of d = 1.

Specific examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, Alkyl groups such as heptyl, 2-ethylhexyl, octyl and nonyl; Cycloalkyl groups such as cyclohexyl group and cycloheptyl group; Alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group and hexenyl group; Aryl groups, such as a phenyl group and a tolyl group; Aralkyl groups such as benzyl, phenylethyl and 3-phenylpropyl; And a chloromethyl group, cyanoethyl group, 3,3,3-trifluoropropyl group in which at least a part of the hydrogen atoms bonded to the carbon atoms of these groups is substituted with a substituent such as a halogen atom and a cyano group.

In the organopolysiloxane of (A) component used by this invention, it is especially preferable that 30 mol% or more of all R <^1> is a phenyl group, and it is more preferable that 50 mol% or more is a phenyl group.

X in 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 preferable to contain an acrylic, in particular _{CH 2 = CHCOOCH 2 -, CH} 2 = CHCOOC 3 H 6 - is preferable.

As a preferable specific example of the organopolysiloxane represented by the said General formula (1), what is shown by following General formula (2) is mentioned, for example.

Provided that a, b and c are the same as a, b and c in Formula 1, respectively, and X is CH ₂ = CHCOOC ₃ H _6- .

The weight average molecular weight of the organopolysiloxane of (A) component becomes like this. Preferably it is 300-30000, More preferably, it is 400-10000, Especially preferably, it is 500-5000.

Since the organopolysiloxane of this (A) component has a (meth) acryl group as a radiation polymerizable group, it superposes | polymerizes easily by irradiating radiation, such as an ultraviolet-ray, an ultraviolet-ray, an electron beam, X-rays, (gamma) rays, and of this invention, The composition can be cured. As the organopolysiloxane of the component (A), one type may be used alone, or two or more types may be used in combination.

The organopolysiloxane of the said (A) component can be manufactured by hydrolyzing the corresponding alkoxysilanes shown by following formula, for example.

[(B) Phenyl Ester Derivative Having Acrylic Group]

Although the phenyl ester derivative which has an acryl group used as (B) component in this invention is not specifically limited, For example, what is represented by following Formula is mentioned.

In this invention, it is preferable to use 2-hydroxyphenoxy propyl especially among these.

In the present invention, as the component (B), one type of compound may be used alone, or two or more types may be used in combination.

Moreover, it is preferable that it is 0.1-10,000 mass parts with respect to 100 mass parts of (A) component, and, as for the usage-amount of (B) component, it is especially preferable that it is 1-1,000 mass parts.

[(C) Radiation Sensitizers]

Although the radiation sensitizer of (C) component used by this invention is not specifically limited, It is preferable to use benzoyl compounds (or phenyl ketone compound), such as benzophenone, Especially 1-hydroxycyclohexyl phenyl ketone, Of the α-position of the carbonyl group, such as 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one Preference is given to using benzoyl compounds (or phenylketone compounds) having hydroxy groups on the carbon atoms.

Other preferred radiation sensitizers that may be used in the present invention include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bisacyl monoorganophosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4 Organophosphine oxide compounds such as -trimethylpentylphosphine oxide; Benzoin ether compounds such as isobutyl benzoin ether; Ketal compounds such as acetophenonediethyl ketal; Thioxanthone type compound; Acetophenone type compound etc. are mentioned.

In this invention, only 1 type may be used as a radiation sensitizer of (C) component, and it may be used in combination of 2 or more type.

The usage-amount of (C) component in this invention may be an amount effective for hardening of the composition of this invention, although it does not restrict | limit especially, Usually, it is 0.1-100 mass parts with respect to 100 mass parts of said (A) component, Preferably Preferably it is 0.5-50 mass parts, More preferably, it is 1.0-25 mass parts.

[Other Blended Ingredients]

In addition to said (A)-(C) component, the composition of this invention can mix | blend another component suitably as long as it does not impair the objective and effect of this invention. For example, various additives may be blended for the purpose of appropriately adjusting the shrinkage rate at the time of curing and the coefficient of thermal expansion, mechanical strength, heat resistance, chemical resistance, flame retardancy, coefficient of thermal expansion, gas permeability, and the like of the resulting cured product.

In the present invention, as the above-mentioned other compounding components, for example, inorganic fillers such as aerosol silica, silica airgel, quartz powder, glass fiber, iron oxide, titanium oxide, calcium carbonate and magnesium carbonate; You may mix | blend radical polymerization inhibitors (availability time extension), such as hydroquinone, methoxy hydroquinone, and 2, 6- di-tert- butyl- p-cresol.

The radiation curable composition of this invention is obtained by mixing the said (A)-(C) component and other compounding components as needed. By irradiating the obtained composition with radiation, the composition of the present invention cures rapidly and expresses strong adhesiveness immediately after curing.

Examples of the radiation used in the present invention include ultraviolet rays, far infrared rays, electron beams, X-rays, gamma rays, and the like. However, ultraviolet rays are preferably used from the viewpoint of the simplicity and ease of handling of the device. As a light source of an ultraviolet-ray, a UV LED lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a xenon lamp etc. are mentioned, for example. 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, for the sheet formed by molding the composition of the present invention to a thickness of 2 mm. to be.

The hardened | cured material obtained by the composition of this invention is useful not only as a protective film of electrodes, such as a flat panel display and a plasma display, but also as a protective film or sealing agent of various electrical and electronic components, etc., and is a very excellent system under severe conditions. Has an effect.

Hereinafter, although this invention is further described by a synthesis example, an Example, etc., this invention is not limited by these. In addition, "part" below means a mass part and "%" shall represent mass%.

Synthesis Example 1

In a separable flask with a coke attached to the bottom of 2 L, 295 g (1.5 mol) of phenyltrimethoxysilane, 60.1 g (0.5 mol) of dimethyldimethoxysilane, and 23.4 g (0.1) of 3-acryloxypropyltrimethoxysilane Mole), 270 g of toluene and 156 g of IPA (isopropyl alcohol) were added, and after stirring at room temperature, 156 g of water and 17.2 g of 25% aqueous tetramethylammonium hydroxide solution were added. After stirring for 3 hours at room temperature, 200 g of 10% aqueous sodium dihydrogenphosphate solution was added to neutralize. The organic phase was separated and washed with water and distilled off under reduced pressure to obtain a product represented by the following formula.

The styrene conversion weight average molecular weight by GPC measurement of the obtained organopolysiloxane was 1612.

X is CH ₂ = CHCOOC ₃ H _6- .

Moreover, L = 0.71, M = 0.24, and N = 0.05.

Synthesis Example 2

In a separable flask with a coke attached to the bottom of 5 liters, 237.9 g (1.2 mol) of phenyltrimethoxysilane, 244.36 g (1.5 mol) of diphenyldimethoxysilane, and 174.6 g of 3-acryloxypropylmethyldimethoxysilane ( 0.8 mole), 23.4 g (0.1 mole) of 3-acryloxypropyltrimethoxysilane, 800 g of toluene and 400 g of IPA were added and stirred at room temperature, followed by 400 g of water and 25% aqueous tetramethylammonium hydroxide solution 37.8 g was added. After stirring for 3 hours at room temperature, 500 g of 10% aqueous sodium dihydrogen phosphate solution was added to neutralize. The organic phase was separated and washed with water and distilled off under reduced pressure to obtain a product represented by the following formula.

The styrene reduced weight average molecular weight by GPC measurement of the obtained organopolysiloxane was 1145.

With the proviso that X is CH ₂ = CHCOOC ₃ H _6- .

Moreover, L = 0.33, M = 0.42, N = 0.22 and O = 0.03.

Example 1

The following (A)-(C) component were mixed and the radiation curable composition of this invention was obtained.

(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) 2.5 parts by mass of a radiation sensitizer (IRGACURE 907, manufactured by Toyota Pram Chem Co., Ltd.)

The obtained composition was introduced into a mold having a depth of 1 mm, a width of 120 mm, and a length of 170 mm, and irradiated with ultraviolet rays for 2 seconds in a conveyor (roughness: 40 W / cm 2) equipped with a metal halide mercury lamp, etc. (energy amount: 200 mJ) hardened | cured material was obtained.

[Example 2]

The following (A)-(C) component were mixed and the radiation curable composition of this invention was obtained.

(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) 2.5 parts by mass of a radiation sensitizer (Irgacure 907, manufactured by Toyota Frachem Co., Ltd.)

The obtained composition was introduced into a mold having a depth of 1 mm, a width of 120 mm, and a length of 170 mm, and irradiated with ultraviolet rays for 2 seconds in a conveyor (roughness: 40 W / cm 2) equipped with a metal halide mercury lamp, etc. (energy amount: 200 mJ) hardened | cured material was obtained.

Example 3

The following (A)-(C) component were mixed and the radiation curable composition of this invention was obtained.

(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) 2.5 parts by mass of a radiation sensitizer (Irgacure 907, manufactured by Toyota Frachem Co., Ltd.)

The obtained composition was introduced into a mold having a depth of 1 mm, a width of 120 mm, and a length of 170 mm, and irradiated with ultraviolet rays for 2 seconds in a conveyor (roughness: 40 W / cm 2) equipped with a metal halide mercury lamp, etc. (energy amount: 200 mJ) hardened | cured material was obtained.

<Various performance evaluation>

?Properties

About the hardened | cured material obtained in Examples 1-3, the hardness was measured with the spring type A test machine based on JISK6301, and the water vapor transmission rate was measured based on JISZ0208. The results are shown in Table 1 below.

Comparative Example 1

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

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

Since the radiation curable composition of the present invention is easily cured by little energy irradiation, it is not only a protective coating agent for liquid crystal electrodes, organic EL electrodes, and plasma display electrodes susceptible to radiation such as ultraviolet rays, but also for various electrical and electronic components. It is very useful industrially as a protective coating.

Claims (5)

A radiation curable composition comprising at least (A) an organopolysiloxane represented by the following formula (1), (B) a phenyl ester derivative having an acrylic group, and (C) a radiation sensitizer.
<Formula 1>

(However, in formula (1) 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 methacryl group, each X is the same or different And a and b are each independently a number of 0.1 or more and less than 0.9, and c and d are each independently 0 to 0.8 (where c and d do not become 0 at the same time), and a + b + c satisfies the relationship of + d = 1) The compound of claim 1, wherein R ¹ , R ^2, and R ³ Radiation curable composition whose at least one is a C6-C10 aromatic hydrocarbon group. The compounding ratio of the said (A) component, (B) component, and (C) component is 0.1-10000 mass parts of (B) component with respect to 100 mass parts of (A) component, (C) Radiation curable composition whose component is 0.1-100 mass parts. The radiation curable composition according to claim 1, wherein the water vapor transmission rate after curing measured according to JIS Z 0208 is 20 g / mm ² day or less. An electrical device and / or an electronic device sealed by a cured resin, wherein the cured resin is a resin cured product obtained by curing the radiation curable composition according to any one of claims 1 to 4. And / or an electronic device.