Curable composition

Abstract

The present application relates to a curable composition and a use thereof. The present application can provide a curable composition having excellent transparency, heat resistance and adhesion. Such a curable composition can be usefully used in direct bonding between a filler and an optical member of a display device.

Claims

1. A curable composition comprising 20 to 70 parts by weight of a polysiloxane-based urethane (meth) acrylate and 30 to 70 parts by weight of a non-reactive oligomer that has no (meth)acryl group, wherein said non-reactive oligomer is a non-reactive silicone oligomer or a non-reactive silicone modified urethane oligomer, and wherein said polysiloxane-based urethane (meth) acrylate is the reaction product of a hydroxyl group-containing polysiloxane, a polyfunctional isocyanate, and a hydroxyl group-containing (meth) acrylate.

2. The curable composition according to claim 1, wherein said hydroxyl group-containing polysiloxane is a compound represented by Formula 1 below: ##STR00006## wherein, R.sub.1 and R.sub.3 are each independently a hydrocarbon group or an organic group containing a hetero atom or an ether group, each of R.sub.2 is independently an alkyl group, a cycloalkyl group or a phenyl group, a is an integer of 10 or more, b and c are each independently an integer of 0 to 3, provided that the sum of b and c is 1 or more.

3. The curable composition according to claim 1, wherein said polysiloxane-based urethane (meth) acrylate comprises one which is bifunctional.

4. The curable composition according to claim 3, wherein said polysiloxane-based urethane (meth) acrylate further comprises one which is monofunctional or one which is trifunctional.

5. The curable composition according to claim 1, wherein said polysiloxane-based urethane (meth) acrylate has a weight average molecular weight (Mw) of 10,000 to 100,000.

6. The curable composition according to claim 1, wherein said non-reactive oligomer has a weight average molecular weight (Mw) of 10,000 to 50,000.

7. The curable composition according to claim 1, wherein said non-reactive silicone oligomer is a compound represented by Formula 2 below: ##STR00007## wherein, R.sub.4 and R.sub.6 are each independently a hydrocarbon group or an organic group containing a hetero atom or an ether group, each of R.sub.5 is independently an alkyl group, a cycloalkyl group or a phenyl group, and n is an integer of 10 or more.

8. The curable composition according to claim 1, wherein said non-reactive silicone modified urethane oligomer is the reaction product of a hydroxyl group-containing polysiloxane, a polyfunctional isocyanate, and an alkyl group or a hydroxyl group-containing monomer.

9. The curable composition according to claim 8, wherein said hydroxyl group-containing polysiloxane is a compound represented by Formula 1 below: ##STR00008## wherein, R.sub.1 and R.sub.3 are each independently a hydrocarbon group or an organic group containing a hetero atom, an ether group or a hydroxyl group, each of R.sub.2 is independently an alkyl group, a cycloalkyl group or a phenyl group, a is an integer of 10 or more, b and c are each independently an integer of 0 to 3, provided that the sum of b and c is 1 or more.

10. The curable composition according to claim 1, wherein said curable composition after curing has an elastic modulus at 1 Hz of 10,000 Pa to 100,000 Pa, a shear strength of 20 N/cm.sup.2 or more, and a haze of 1% or less.

11. The curable composition according to claim 1, wherein said curable composition has a viscosity at 1 Hz and 25 C. of 1,000 cp to 10,000 cp.

12. The curable composition according to claim 1, wherein said curable composition after curing and storage at 105 C. for 1000 hours has a yellow index value (Y.I) of 2.0 or less.

13. A filler for a display device comprising a cured product of a curable composition, wherein the curable composition comprising 20 to 70 parts by weight of a polysiloxane-based urethane (meth) acrylate and 30 to 70 parts by weight of a non-reactive oligomer that has no (meth)acryl group, wherein said non-reactive oligomer is a non-reactive silicone oligomer or a non-reactive silicone modified urethane oligomer.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIGS. 1 and 2 exemplarily show display devices to which a cured product of the curable composition of the present application is applied.

MODE FOR THE INVENTION

(2) Hereinafter, the curable composition of the present application will be described in more detail through Examples and Comparative Examples, but the scope of the present application is not limited by Examples as set forth below. In addition, the physical properties and characteristics of Examples and Comparative Examples are measured as follows.

Measurement Example 1: Modulus Measurement

(3) The curable compositions of Examples and Comparative Examples were applied between the release-treated films, and then irradiated with ultraviolet having a wavelength band of 150 nm to 450 nm at a light intensity of about 4000 mJ/cm.sup.2 using a metal halide UV lamp (D-bulb) and cured so as to have a thickness of 1 mm after curing. The cured products were tailored to prepare circular samples having a diameter of 8 mm and a thickness of 1 mm, and then storage elastic modulus (G) at 1 Hz was measured using an ARES-G2 Rheometer from TA instruments. Measuring temperature: 25 C. Measuring strain: 5%, Measurement mode: frequency sweep mode

Measurement Example 2: Viscosity Measurement

(4) For the curable compositions of Examples and Comparative Examples, viscosity at 1 Hz was measured using an ARES-G2 Rheometer from TA instruments. Measuring temperature: 25 C. Measuring strain: 10% Measurement mode: frequency sweep mode

Measurement Example 3: Elongation Measurement

(5) The curable compositions of Examples and Comparative Examples were applied between the release-treated films and then cured under the same conditions as in the modulus measurement. Samples with a thickness of 1 mm were tailored into a size of 1.5 cm5 cm and elongation was measured using TA-XT2 plus from Texture Technology, while pulling the joint portion up and down at a speed of 4.8 mm/min.

Measurement Example 4: Shear Strength Measurement

(6) The curable compositions of Examples and Comparative Examples were applied to washed soda lime glasses (1T), covered with glasses, and cured under the same conditions as in the modulus measurement. The cured products were tailored to have a diameter of 1.5 cm and a thickness of 200 m and circular samples were prepared, and then shear strength was measured using TA-XT 2 plus from Texture Technology, while pulling the joint portion up and down at a speed of 12.7 mm/min.

Measurement Example 5: Haze Measurement

(7) The curable compositions of Examples and Comparative Examples were applied to soda lime glasses (1T) and cured under the same conditions as in the modulus measurement. The cured products were tailored to have a diameter of 5 cm and a thickness of 200 m and circular samples were prepared, and then haze was measured in accordance with ASTM standard using NDH-5000 Haze meter from Nippon Denshoku.

Measurement Example 6: Y.I (Yellow Index) Measurement

(8) After samples were prepared in the same manner as in the haze measurement, they were left at 105 C. for 1000 hours, and then Yellow Index (Y.I) was measured in accordance to ASTM standard using a COH400 transmittance meter from Nippon Denshoku.

Measurement Example 7: Evaluation of Adhesion Durability

(9) The curable compositions of Examples and Comparative Examples were applied between glasses and cured under the same conditions as in the modulus measurement. The cured products were tailored to have a diameter of 1.5 cm and a thickness of 200 m and circular samples were prepared, and then they were left at 105 C. for 1000 hours. The adhesive strength was measured using TA-XT2 plus from Texture Technology, while pulling the joint portion up and down at a speed of 12.7 mm/min. By comparing with the adhesive strengths before and after heat treatment, adhesion durability was determined according to the following evaluation criteria.

(10) <Evaluation Criteria of Adhesion Durability> O: no change in adhesive strength : decrease of adhesive strength X: the cured product melts and flows down

Production Example 1: Preparation of Monofunctional Silicone Oligomer (A1)

(11) Apparatus

(12) Thermometer, stirrer, water-cooled condenser, nitrogen gas

(13) Preparation Method

(14) 350 g of polydimethylsiloxane diol of Formula A (Silaplane FM-4411, Chisso), 112 g of isophorone diisocyanate (isocyanate group content 37.8%) and 1 g of dibutyltin dilaurate were reacted in a flask at 60 C. for 5 hours. Next, 9.8 g of hydroxyethyl acrylate and 15.6 g of lauryl alcohol were added in drops and the reaction was continued as such, and the reaction was terminated when the isocyanate group disappeared.

(15) ##STR00004##

Production Example 2: Preparation of Bifunctional Silicone Oligomer (A2)

(16) Apparatus

(17) Thermometer, stirrer, water-cooled condenser, nitrogen gas

(18) Preparation Method

(19) 350 g of polydimethylsiloxane diol of Formula A (Silaplane FM-4411, Chisso), 102.7 g of isophorone diisocyanate (isocyanate group content 37.8%) and 1 g of dibutyltin dilaurate were reacted in a flask at 60 C. for 5 hours. Next, 4.9 g of hydroxyethyl acrylate, 6.1 g of hydroxybutyl acrylate and 7.4 g of lauryl alcohol were added in drops, and the reaction was continued as such, and the reaction was terminated when the isocyanate group disappeared.

Production Example 3: Preparation of Trifunctional Silicone Oligomer (A3)

(20) Apparatus

(21) Thermometer, stirrer, water-cooled condenser, nitrogen gas

(22) Preparation Method

(23) 350 g of polydimethylsiloxane diol of Formula A (Silaplane FM-4411, Chisso), 276.7 g of isophorone diisocyanate-isocyanurate (isocyanate group content 17.0%) and 1 g of dibutyltin dilaurate were reacted in a flask at 60 C. For 5 hours. Next, 50.7 g of hydroxyethyl acrylate was added in drops and the reaction was continued as such, and the reaction was terminated when the isocyanate group disappeared.

Production Example 4: Non-Reactive Silicone Oligomer (B1)

(24) Monohydroxylpolysiloxane (FM-0411, Chisso) of Formula B below was prepared as the non-reactive silicone oligomer (B1).

(25) ##STR00005##

Production Example 5: Non-Reactive Silicone Modified Acrylate Oligomer (B2)

(26) Apparatus

(27) Thermometer, stirrer, water-cooled condenser, nitrogen gas

(28) Preparation Method

(29) 350 g of polydimethylsiloxane diol of Formula A (Silaplane FM-4411, Chisso), 124.4 g of isophorone diisocyanate (isocyanate group content 37.8%) and 1 g of dibutyltin dilaurate were reacted in a flask at 60 C. for 5 hours. Next, 52.2 g of lauryl alcohol was added in drops and the reaction was continued as such, and the reaction was terminated when the isocyanate group disappeared.

Production Example 6: Non-Reactive Silicone Modified Acrylate Oligomer (B3)

(30) Apparatus

(31) Thermometer, stirrer, water-cooled condenser, nitrogen gas

(32) Preparation Method

(33) 350 g of polydimethylsiloxane diol of formula A (Silaplane FM-4411, Chisso), 112 g of isophorone diisocyanate (isocyanate group content: 37.8%) and 1 g of dibutyltin dilaurate were reacted in a flask at 60 C. for 5 hours. Next, 31.2 g of lauryl alcohol was added in drops and the reaction was continued as such, and the reaction was terminated when the isocyanate group disappeared.

Example 1

(34) Preparation of Curable Composition

(35) The curable composition of Example 1 was prepared by mixing a curable oligomer and a diluent to be 100 parts by weight and compounding an initiator (C1), a silane coupling agent (C2) and an antioxidant (C3) in a ratio of Table 1.

Examples 2 to 6 and Comparative Examples 1 to 6

(36) The curable compositions were prepared in the same manner as in Example 1, except that on preparing the curable compositions, compounding ingredients and compositions were adjusted as shown in Table 1 below.

(37) TABLE-US-00001 TABLE 1 Unit Example Comparative Example (parts by weight) 1 2 3 4 5 6 1 2 3 4 5 6 Curable A1 50 20 20 20 10 10 10 oligomer A2 10 30 20 20 20 20 70 30 10 10 30 A3 10 A4 30 Diluent B1 40 70 70 60 20 70 80 B2 60 B3 60 80 B4 70 B5 70 Additive C1 5 5 5 5 5 5 5 5 5 5 5 5 C2 5 5 5 5 5 5 5 5 5 5 5 5 C3 1 1 1 1 1 1 1 1 1 1 1 1 A1: monofunctional silicone oligomer (Mw: 10,000) A2: bifunctional silicone oligomer (Mw: 70,000) A3: trifunctional silicone oligomer (Mw: 10,000) A4: polyfunctional urethane acrylate oligomer (CN9014NS, Sartomer) B1: non-reactive silicone oligomer (Mw: 10,000) B2: non-reactive silicone modified urethane oligomer (Mw: 10,000) B3: non-reactive silicone modified urethane oligomer (Mw: 40,000) B4: non-reactive PDMS (Silicon rubber, C6-530, Dow Corning (Mw: 200,000) B5: lauryl acrylate C1: initiator (Irgacure 184, BASF) C2: silane coupling agent (KBM-403, Shin-Etsu) C3: antioxidant (Irganox 1010, BASF)

(38) The evaluation results of physical properties of Examples and Comparative Examples were described in Tables 2 and 3 below.

(39) TABLE-US-00002 TABLE 2 Example 1 2 3 4 5 6 Modulus 1.3 3.1 3.9 2.8 2.9 2.7 (10.sup.4 Pa) Viscosity 5.7 4.4 3.3 3.9 4.7 5.1 (10.sup.3 cp) Elongation (%) 100 150 100 200 400 450 Shear strength 24 32 36 28 32 39 (N/cm.sup.2) Haze (%) 0.31 0.23 0.24 0.27 0.25 0.23 Y.I 1.5 1.2 1.0 1.4 1.3 1.4 Adhesion durability

(40) TABLE-US-00003 TABLE 3 Comparative Example 1 2 3 4 5 6 Modulus 10.5 0.75 3.2 0.8 0.72 3.9 (10.sup.4 Pa) Viscosity 13.5 1.0 8.9 2.7 3.6 15 (10.sup.3 cp) Elongation (%) 50 50 100 150 150 400 Shear strength 44 29 30 12 10 38 (N/cm.sup.2) Haze (%) 0.30 0.25 0.26 0.29 0.27 3.50 Y.I 3.0 2.5 2.6 1.7 1.6 2.4 Adhesion X X durability

DESCRIPTION OF SYMBOLS

(41) 10: spacer, 20: touch panel, 30: display panel, 40: cured product of curable composition