KR101909156B1 - Curable resin composition - Google Patents

Abstract

(식 중, R은 말단에 치환 또는 비치환된 스티렌기를 갖는 탄소수 1 내지4의 알킬기; 말단에 치환 또는 비치환된 스티렌옥시기를 갖는 탄소수 1 내지4의 알킬기; 또는 비닐기로 치환된 벤질옥시기를 말단에 갖는 탄소수 1 내지 4의 알킬기이고, 이때 상기 벤질옥시기는 치환되거나 비치환된 것이며, n은 4 내지 20의 정수임).TECHNICAL FIELD The present invention relates to a curable resin composition, and more particularly, a molded article produced from the silsesquioxane resin of the following formula (1) has a high heat resistance, transparency, impact resistance and low thermal expansion, To a curable resin composition which can be used.
[Chemical Formula 1]

(Wherein R represents an alkyl group having 1 to 4 carbon atoms having a styrene group or a terminally substituted or unsubstituted styrene group, an alkyl group having 1 to 4 carbon atoms having a styreneoxy group and a terminally substituted or unsubstituted benzyloxy group, Wherein the benzyloxy group is substituted or unsubstituted, and n is an integer of 4 to 20).

Description

[0001] CURABLE RESIN COMPOSITION [0002]

The present invention relates to a curable resin composition excellent in transparency, heat resistance and low thermal expansion.

Glass has transparency, heat resistance, dimensional stability, low thermal expansion, chemical stability, and is a structure that does not interfere with the field of vision by transmitting visible light and is used in a wide industrial field. However, since the specific gravity is over 2.5, it has a disadvantage that it is heavy and has a weak impact. Therefore, it has been studied to improve the above disadvantages according to the demand for downsizing of lightweight and thin.

In order to meet such a demand, transparent plastic is attracting attention as a substitute material for glass. PMMA, alicyclic polyolefin, epoxy resin, silicone resin and the like are known as transparent plastic, and PMMA and alicyclic polyolefin are called organic glass because of their excellent transparency and they are used for optical lenses and light guide plates ), Optical discs, and the like.

However, they have a disadvantage in that their use is limited in a process involving a thermal process of 150 to 200 DEG C or more because of a low heat distortion temperature.

A curable resin composition containing a polysilsesquioxane resin having high transparency and heat resistance and excellent dimensional stability has been proposed (Japanese Patent Laid-Open Publication No. 2006-89685, Korean Patent Laid-Open Publication No. 2011-105338). The polysilsesquioxane resin essentially contains a polymerizable functional group such as a vinyl group, an allyl group, an acrylic group or an epoxy group.

As described above, there are disadvantages in that the kinds of polymerizable functional groups are limited, and studies on various polymerizable functional groups that can exhibit the same or better effects as the proposed functional groups have been desired.

An object of the present invention is to provide a curable resin composition containing a silsesquioxane resin having a novel polymerizable functional group so as to have heat resistance, transparency, impact resistance and low thermal expansion equivalent to those of the conventional art.

In order to achieve the above object, the present invention provides a curable resin composition containing a silsesquioxane resin represented by the following general formula (1).

(Wherein R represents an alkyl group having 1 to 4 carbon atoms having a styrene group or a terminally substituted or unsubstituted styrene group, an alkyl group having 1 to 4 carbon atoms having a styreneoxy group and a terminally substituted or unsubstituted benzyloxy group, Wherein the benzyloxy group is substituted or unsubstituted, and n is an integer of 4 to 20).

Preferably, R is an alkyl group having 1 to 4 carbon atoms having an unsubstituted styrene group at the terminal; An alkyl group having 1 to 4 carbon atoms and having an unsubstituted styreneoxy group at the terminal; Or an alkyl group having 1 to 4 carbon atoms having a benzyloxy group substituted with a vinyl group, wherein the benzyloxy group is unsubstituted, and n may be an integer of 4 to 20.

More preferably, the formula (1) may be at least one selected from the group consisting of the following formulas (2) to (4).

(In the above Chemical Formulas 2 to 4, n is an integer of 4 to 20)

The curable resin composition may contain a silsesquioxane resin of formula (1) and an unsaturated compound capable of radical polymerization with the silsesquioxane resin.

The silsesquioxane resin and the unsaturated compound of Formula 1 may be contained in a weight ratio of 1:99 to 99: 1.

The curable resin composition according to the present invention can obtain a molded article having high heat resistance, transparency, impact resistance and low thermal expansion. The molded article can be used as a substrate for a liquid crystal display element, a substrate for a color filter, a substrate for an organic EL display element, a substrate for an electronic paper, a TFT substrate, a transparent substrate such as a solar cell substrate, a touch panel, , A polarizing film, a phase difference film, a lens sheet, an optical disk, an optical fiber, or various transporting machines, and a window glass for a house.

The present invention relates to a curable resin composition excellent in transparency, heat resistance and low thermal expansion.

Hereinafter, the present invention will be described in detail.

The curable resin composition of the present invention contains a silsesquioxane resin represented by the following formula (1).

 [Chemical Formula 1]

(Wherein R represents an alkyl group having 1 to 4 carbon atoms having a styrene group or a terminally substituted or unsubstituted styrene group, an alkyl group having 1 to 4 carbon atoms having a styreneoxy group and a terminally substituted or unsubstituted benzyloxy group, Wherein the benzyloxy group is substituted or unsubstituted, and n is an integer of 4 to 20).

Preferably, R is an alkyl group having 1 to 4 carbon atoms having an unsubstituted styrene group at the terminal; An alkyl group having 1 to 4 carbon atoms having an unsubstituted styreneoxy group at the terminal, or a benzyloxy group substituted with a vinyl group at the terminal thereof, and n is an integer of 4 to 20.

More preferably, the formula (1) is at least one selected from the group consisting of the following formulas (2) to (4).

(2)

(3)

[Chemical Formula 4]

(In the above Chemical Formulas 2 to 4, n is an integer of 4 to 20)

등과 같은 실록산 화합물을 극성 용매 및 알칼리성 촉매 존재하에서 가수분해 반응시키는 동시에 부분 축합시켜 얻어진 가수분해 생성물, 비극성 용매 및 알칼리성 촉매 존재하에서 재축합시켜 얻을 수 있다(일본특허공개 제2004-143449 참조)The silsesquioxane resin of Formula 1 may be synthesized or commercially available. As a synthesis method

, Etc., in the presence of a polar solvent and an alkaline catalyst, and at the same time partial condensation, in the presence of a hydrolysis product, a non-polar solvent and an alkaline catalyst (see Japanese Patent Application Laid-Open No. 2004-143449)

The curable resin composition of the present invention preferably contains the silsesquioxane resin of formula (1) and the silsesquioxane resin and an unsaturated compound capable of radical polymerization.

Examples of the unsaturated compound capable of radical polymerization with the silsesquioxane resin include a reactive oligomer such as a polymer having a repeating number of the structural unit of 2 to 20 or a reactive monomer having a low molecular weight and a low viscosity.

Specific examples of the reactive oligomer include epoxy acrylate, epoxylated acrylate, urethane acrylate, unsaturated polyester, polyester acrylate, polyether acrylate, vinyl acrylate, polyene / thiol, silicone acrylate, polybutadiene , Polystyrylethyl methacrylate, and the like.

Examples of the reactive monomer include styrene, vinyl acetate, divinylbenzene, N-vinylpyrrolidone, butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, Monofunctional monomers such as dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, phenoxyethyl acrylate, and trifluoroethyl methacrylate, or dicyclopentanyl diacrylate, tripropylene glycol diacrylate, 1,6- Hexanediol diacrylate, bisphenol A diglycidyl ether diacrylate, tetraethylene glycol diacrylate, hydroxypivalic acid neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, penta Polyfunctional monomers such as erythritol tetraacrylate, dipentaerythritol hexaacrylate and the like are used .

In addition, various reactive oligomers and monomers may be used, and these may be used alone or in combination of two or more.

The silsesquioxane resin of Formula 1 and the unsaturated compound may be contained in a weight ratio of 10:90 to 90:10 by weight, preferably 20:80 to 80:20 by weight. If the content of the silsesquioxane resin of the formula (1) is less than 10 parts by weight, the heat resistance improving ability may be insufficient. When the content exceeds 90 parts by weight, the viscosity may increase and the processability may be insufficient.

The curable resin composition may further contain a polymerization initiator. The polymerization initiator may be a photopolymerization initiator such as an alkyne phonon-based, acylphosphine oxide-based or titanocene-based initiator; Ketone peroxide type, peroxyketal type, hydroperoxide type, dialkyl peroxide type, diacyl peroxide type, peroxydicarbonate type, peroxy ester type and the like can be used.

The curable resin composition may contain an organic or inorganic filler, a plasticizer, a flame retardant, a heat stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a lubricant, an antistatic agent, a releasing agent, A nucleating agent, a coloring agent, a cross-linking agent, and a dispersing assistant.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

Synthetic example  1: Synthesis of Formula 2 (see Japanese Patent Application Laid-Open No. 2004-143449)

In a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 100 ml of 2-propanol and 4 g of a 10 wt% tetramethylammonium hydroxide aqueous solution were added with a basic catalyst. 30 ml of isopropyl alcohol (IPA) was added to the dropping funnel , And the reaction vessel was added dropwise with stirring at room temperature over 1 hour. When the dropwise addition was completed, the solution was further stirred at room temperature for 24 hours. After removal of IPA under reduced pressure, 150 ml of toluene was dissolved and dehydrated by passing anhydrous magnesium sulfate through a packed tube.

의 가수분해 산물 10g이 얻어지며, 이를 딘스탁(Dean-Stark)장치에 넣고, 톨루엔 50ml와 10중량%의 테트라메틸암모늄하이드록시드 수용액 2g을 추가한 후 130℃에서 물을 증류 제거하면서 5시간 동안 톨루엔을 환류 가열하여 재축합 반응을 수행하였다.In the above,

10 g of the hydrolyzate of hydrolyzed product was obtained. This was put into a Dean-Stark apparatus, and 50 ml of toluene and 2 g of a 10% by weight aqueous solution of tetramethylammonium hydroxide were added, and water was distilled off at 130 ° C for 5 hours Toluene was refluxed for reflux condensation.

의 실세스퀴옥산 수지를 8.2g 얻었다. 이때, 상기 n은 4 내지 20의 정수이며 이중 8 내지 12의 정수가 90중량% 이상인 혼합물 형태이다(LC/MS로 분석)
Thereafter, the reaction solution was neutralized with 10 wt% citric acid, washed with saturated saline, dehydrated by passing anhydrous magnesium sulfate through a packed tube, and concentrated to obtain a recondensed compound

Of silsesquioxane resin was obtained. Herein, n is an integer of 4 to 20, and is in the form of a mixture having an integer of 8 to 12 in an amount of 90 wt% or more (analyzed by LC / MS)

Synthetic example  2: Synthesis of Formula 3

대신에

을 이용하여

의 실세스퀴옥산 수지를 8.3g 얻었다. 이때, 상기 n은 4 내지 20의 정수이며 이중 8 내지 12의 정수가 90중량% 이상인 혼합물 형태이다(LC/MS로 분석)
The reaction was carried out in the same manner as in Synthesis Example 1,

Instead of

Using

Of silsesquioxane resin was obtained. Herein, n is an integer of 4 to 20, and is in the form of a mixture having an integer of 8 to 12 in an amount of 90 wt% or more (analyzed by LC / MS)

Synthetic example  3: Synthesis of formula 4

대신에

을 이용하여

의 실세스퀴옥산 수지를 8.1g 얻었다. 이때, 상기 n은 4 내지 20의 정수이며 이중 8 내지 12의 정수가 90중량% 이상인 혼합물 형태이다(LC/MS로 분석)
The reaction was carried out in the same manner as in Synthesis Example 1,

Instead of

Using

Of silsesquioxane resin was obtained. Herein, n is an integer of 4 to 20, and is in the form of a mixture having an integer of 8 to 12 in an amount of 90 wt% or more (analyzed by LC / MS)

compare Synthetic example  One

대신에 메타크릴옥시프로필트리메톡시실란을 사용하여

의 실세스퀴옥산 수지를 8.2g 얻었다. 이때, 상기 n은 4 내지 20의 정수이며 이중 8 내지 12의 정수가 90중량% 이상인 혼합물 형태이다(LC/MS로 분석)
The reaction was carried out in the same manner as in Synthesis Example 1,

Instead of using methacryloxypropyltrimethoxysilane

Of silsesquioxane resin was obtained. Herein, n is an integer of 4 to 20, and is in the form of a mixture having an integer of 8 to 12 in an amount of 90 wt% or more (analyzed by LC / MS)

Example  One

20중량부, 트리메틸올프로판트리아크릴레이트 30중량부, 디비닐벤젠 50중량부, 광중합 개시제로 1-하이드록시시클로헥실페닐케톤 3중량부를 혼합하고 탈포하여 액상의 경화성 수지 조성물을 얻었다. The silsesquioxane resin of Synthesis Example 1

20 parts by weight of trimethylolpropane triacrylate, 50 parts by weight of divinylbenzene and 3 parts by weight of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator were mixed and defoamed to obtain a liquid curable resin composition.

The obtained resin composition was applied to a PET film having a silicone-treated release film formed thereon so as to have a thickness of 100 占 퐉 with air and then cured at a total exposure dose of 4000 mJ / cm2 using a 40 W / cm high pressure mercury lamp, And peeled off to obtain a molded article.

Example  2

30중량부, 트리메틸올프로판트리아크릴레이트 70중량부, 광중합 개시제로 1-하이드록시시클로헥실페닐케톤 3중량부를 사용하여 성형체를 얻었다.
The procedure of Example 1 was repeated except that the compound of Synthesis Example 1

, 70 parts by weight of trimethylolpropane triacrylate, and 3 parts by weight of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator.

Example  3

대신에 합성예 2의

를 사용하여 성형체를 얻었다.
The procedure of Example 2 was repeated except that the compound of Synthesis Example 1

Instead of Synthesis Example 2

To obtain a molded article.

Example  4

대신에 합성예 3 의

를 사용하여 성형체를 얻었다.
The procedure of Example 2 was repeated except that the compound of Synthesis Example 1

Instead of Synthesis Example 3

To obtain a molded article.

Comparative Example  One

A molded product was obtained in the same manner as in Example 1 except that the silsesquioxane resin of Comparative Synthesis Example 1 was used instead of the silsesquioxane resin of Synthesis Example 1.

Experimental Example

The physical properties of the molded articles obtained in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1 below.

1. Glass transition temperature

Using a DSC measuring instrument (TA company Q1000), the molding compound (3 mg) was measured under an N ₂ atmosphere at a heating rate of 10 ° C / min.

2. Thermal expansion coefficient

Based on the thermomechanical analysis (TMA) method using a thermomechanical analyzer (Bruker AXS product TMA4030SA), the change in the thermal expansion at 150 占 폚 at 50 占 폚 was measured at a rate of 5 占 폚 / min.

3. Light Transmittance

The light transmittance spectrum of light of 400 to 800 nm of the molded article was measured using a spectrophotometer (U4000 manufactured by Hitachi Seisakusho Co., Ltd.) at an extracellular time, and the transmittance of light with a wavelength of 550 nm was represented as a typical value.

division Glass transition temperature (캜) Thermal Expansion Coefficient (ppm / k) Light transmittance (%) Example 1 330 35 90 Example 2 320 40 91 Example 3 315 41 91 Example 4 327 37 90 Comparative Example 1 310 50 90

As shown in Table 2, the curable resin compositions of Examples 1 to 4 containing the silsesquioxane resin of Chemical Formula 1 according to the present invention had a low coefficient of thermal expansion while maintaining a glass transition temperature and a light transmittance equal to or higher than those of Comparative Example 1 .

Claims (5)

A silsesquioxane resin represented by the following formula (1); And an unsaturated compound capable of radical polymerization with the silsesquioxane resin,
Wherein the silsesquioxane resin and the unsaturated compound of Formula 1 are contained in a weight ratio of 10:90 to 90:10.
[Chemical Formula 1]

(Wherein R represents an alkyl group having 1 to 4 carbon atoms having a styrene group or a terminally substituted or unsubstituted styrene group, an alkyl group having 1 to 4 carbon atoms having a styreneoxy group and a terminally substituted or unsubstituted benzyloxy group, And n is an integer of 4 to 20).
[2] The compound according to claim 1, wherein R is an alkyl group having 1 to 4 carbon atoms and having a styrene group at the terminal thereof; An alkyl group having 1 to 4 carbon atoms and having an unsubstituted styreneoxy group at the terminal; Or an alkyl group having 1 to 4 carbon atoms having a benzyloxy group substituted with a vinyl group at the terminal thereof, and n is an integer of 4 to 20;
The curable resin composition according to claim 2, wherein the formula (1) is at least one selected from the group consisting of the following formulas (2) to (4)
(2)

(3)

[Chemical Formula 4]

(In the above Chemical Formulas 2 to 4, n is an integer of 4 to 20)
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