Compound

Abstract

A compound applicable to various uses can be provided in the present application. In one embodiment, the compound can be included in a cross-linkable composition to serve as a crosslinking rate regulator. In another embodiment, the compound can be applied to a cross-linkable composition such that a membrane formed by the cross-linkable composition has excellent interfacial adhesion with another membrane, and also prevent the occurrence of leakage of the membrane formed by the cross-linkable composition.

Claims

1. A compound of the following Formula 1: ##STR00008## where A is a core including polyalkylene oxide units including a polyethylene oxide unit and a polypropylene oxide unit, wherein the core has a weight average molecular weight of 6,000 or more, and a ratio (P/E) of a number of moles (P) of the polypropylene oxide unit to a number of moles (E) of the polyethylene oxide unit in the core is in a range from 4 to 10, B is a chain represented by the following Formula 2, m is an integer of 1 or more, n is an integer of 0 or more, and the sum of m and n (m+n) is 3 or more, ##STR00009## where A.sub.1 to A.sub.3 each independently represent an alkylene group, Q.sub.1 and Q.sub.2 represent an aliphatic or aromatic divalent residue, L.sub.1 to L.sub.4 each independently represent a linker, x is an integer of 1 or more, y is an integer of 0 or more, and z is an integer of 1 or more, wherein the compound of Formula 1 has a weight average molecular weight in a range from 10,000 to 28,900.

2. The compound of claim 1, wherein the linker of Formula 2 is an oxygen atom, a sulfur atom, an alkylene group, an alkenylene group or an alkynylene group, or is represented by the following Formula 4 or 5: ##STR00010## where R.sub.1 and R.sub.2 each independently represent a hydrogen atom or an alkyl group.

3. The compound of claim 1, wherein B of Formula 1 is represented by the following Formula 6: ##STR00011## where A.sub.1 to A.sub.3 each independently represent an alkylene group, Q.sub.1 and Q.sub.2 represent an aliphatic or aromatic divalent residue, x is an integer of 1 or more, y is an integer of 0 or more, and z is an integer of 1 or more.

4. The compound of claim 1, wherein a hydroxyl value is 4 mgKOH/g or more.

5. A pressure-sensitive adhesive optical member for an image display device, comprising a pressure-sensitive adhesive layer which contains a pressure-sensitive adhesive composition formed on one or both surfaces of the pressure-sensitive adhesive optical member for an image display device, wherein the pressure-sensitive adhesive composition includes an ionic liquid and a polymer with a glass transition temperature of 0 C. or less as a base polymer, the polymer with a glass transition temperature of 0 C. or less is an acrylic polymer having a monomer which includes one or more (meth)acrylates with an alkyl group having 1 to 14 carbon atoms in an amount of 50 to 100 wt % as a main component, and has an acid value of 29 or less, and the pressure-sensitive adhesive composition further includes a compound of the following Formula 1: ##STR00012## where A is a core including polyalkylene oxide units including a polyethylene oxide unit and a polypropylene oxide unit, wherein the core has a weight average molecular weight of 6,000 or more, and a ratio (P/E) of a number of moles (P) of the polypropylene oxide unit to a number of moles (E) of the polyethylene oxide unit in the core is in a range from 4 to 10, B is a chain represented by the following Formula 2, m is an integer of 1 or more, n is an integer of 0 or more, and the sum of m and n (m+n) is 3 or more, ##STR00013## where A.sub.1 to A.sub.3 each independently represent an alkylene group, Q.sub.1 and Q.sub.2 represent an aliphatic or aromatic divalent residue, L.sub.1 to L.sub.4 each independently represent a linker, x is an integer of 1 or more, y is an integer of 0 or more, and z is an integer of 1 or more, wherein the compound of Formula 1 has a weight average molecular weight in a range from 10,000 to 28,900.

6. An image display device, comprising the pressure-sensitive adhesive optical member of claim 5.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIGS. 1 to 4 show infrared (IR) spectrum results for compounds prepared in Preparation Examples 2 to 5.

EFFECT

(2) A compound applicable to various uses can be provided in the present application. In one embodiment, the compound can be included in a cross-linkable composition to serve as a crosslinking rate regulator. In another embodiment, the compound can be applied to a cross-linkable composition such that a membrane formed by the cross-linkable composition has excellent interfacial adhesion with another membrane, and also prevent the occurrence of leakage of the membrane formed by the cross-linkable composition.

EMBODIMENTS

(3) Hereinafter, the present invention will be explained in detail with reference to examples and comparative examples, but it is to be noted that the range of the pressure-sensitive adhesive composition is not limited to the following examples.

(4) 1. Infrared (IR) Spectrometry

(5) Conditions for measuring an IR spectrum applied in the present specification are as follows. The spectrum baseline is air during the measurement.

(6) <Measurement Conditions>

(7) Measuring instrument: Agilent Cary 660 FTIR Spectrometer

(8) ATR: PIKE Technologies 025-2018 Miracle ZnSe performance crystal plate

(9) Measurement wavelength: 400 to 4000 nm

(10) Measurement temperature: 25 C.

(11) 2. Evaluation of Molecular Weight

(12) A weight average molecular weight (Mn) was measured under the following conditions using GPC. In preparing calibration curves, the measuring results were converted using standard polystyrene in Agilent system.

(13) <Measurement Conditions>

(14) Measuring instrument: Agilent GPC (Agilent 1200 series, U.S.)

(15) Column: connected two PL Mixed B

(16) Column temperature: 40 C.

(17) eluent: tetrahydrofuran (THF)

(18) Flow rate: 1.0 mL/min

(19) Concentration: 1 mg/mL (100 L injection)

(20) 3. Measurement of Acid Value

(21) An acid value was measured using an automatic titration device (COM-550, manufactured by HIRANUMA SANGYO Co., Ltd.), and calculated by the following equation:
A={(YX)f5.611}/M

(22) A; an acid value

(23) Y; a titration amount (ml) of a sample solution

(24) X; a titration amount (ml) of a solution containing 50 g of a mixed solvent

(25) f; a factor of a titration solution

(26) M; a weight (g) of a polymer sample

(27) Measurement conditions were as follows.

(28) Sample solution: prepared by dissolving about 0.5 g of a polymer sample in 50 g of a mixed solvent (toluene/2-propanol/distilled water=50/49.5/0.5, weight ratio)

(29) Titration solution: 0.1N, 2-propanol-type potassium hydroxide solution (manufactured by Wako Junyaku Kogyo Co., Ltd., for test neutralization value of petroleum products)

(30) Electrode: glass electrode, GE-101, Comparative electrode: RE-201

(31) Measurement mode: for test neutralization value of petroleum products

(32) 4. Measurement of Octanol-Water Partition Coefficient

(33) The octanol-water partition coefficient (Log P) was calculated using COSMOtherm (version C30_1301, COSMOlogic) which is a commercial thermodynamic program. The surface charge distribution of each compound and the difference in chemical potential of water and octanol was calculated using the program, and thereby the partition coefficient (Log P) was obtained. In this process, the BP_TZVP_C30_1301 parameterization was applied.

(34) 5. Measurement of Cation-Water Binding Energy

(35) The binding energy was obtained by calculating the energy of each model and calculating the difference in energy in the case where water and a corresponding compound remain apart and in the case where they form a water-cation complex, using a commercial density functional theory (DFT) program called TURBOMOLE (version 6.5, manufactured by COSMOlogic GmbH & Co. KG). In this process, B-P functional, def-TZVP basis set, COSMO with epsilon=infinity was applied.

(36) 6. Measurement of Durability

(37) A polarizing plate of examples or comparative examples was cut to a size of about 262 mmabout 465 mm (widthlength) to prepare a specimen of two sheets, and two sheets of the specimen thus prepared were attached to both surfaces of a glass substrate with the optical absorbing axes of each polarizing plate crossed, thereby preparing a sample. The pressure applied on attaching was about 5 Kg/cm.sup.2 and this work was performed in a clean room such that no bubbles or foreign material was introduced.

(38) Durability of the sample was evaluated by heat resistant durability and moisture-heat resistant durability. The moisture-heat resistant durability was evaluated after leaving the sample at a temperature of 60 C. and a relative humidity of 90% for about 500 hours, and the heat resistant durability was evaluated after leaving the sample at a temperature of 80 C. for 500 hours.

(39) The evaluation criteria of durability are as follows.

(40) <Evaluation Criteria>

(41) : No bubbles and peeling observed when evaluating heat resistant and moisture-heat resistant durability

(42) : A few bubbles and/or peeling observed when evaluating heat resistant and/or moisture-heat resistant durability

(43) X: Many bubbles and/or peeling observed when evaluating heat resistant and/or moisture-heat resistant durability

(44) 7. Measurement of Surface Resistance of Pressure-Sensitive Adhesive Layer

(45) The polarizing plate prepared in examples or comparative examples was left under room temperature conditions of 25 C. and 50% RH for 7 days and the surface resistance (initial surface resistance) was measured. The surface resistance was measured after removing a release film from the polarizing plate, and applying a voltage of 500 V for 1 minute under an environment of 23 C. and 50% RH using HIRESTA-UP (MCP-HT450; manufactured by Mitsubishi Chemical Corporation). The sample (pressure-sensitive adhesive polarizing plate) was left at 80 C. for 1,000 hours to measure the surface resistance of the sample in heat resistance conditions, and the sample (pressure-sensitive adhesive polarizing plate) was left at 60 C. and 90% RH for 1,000 hours to measure the surface resistance of the sample in hygrothermal resistance conditions. The samples left in heat resistance and hygrothermal resistance conditions as above were subjected to evaluation after leaving each specimen at room temperature for 24 hours.

(46) 8. Evaluation of Haze

(47) The haze was evaluated by observing the condition of a coating solution with the naked eye just after coating the pressure-sensitive adhesive composition prepared in examples or comparative examples. The evaluation was conducted according to the following criteria.

(48) <Evaluation Criteria>

(49) : No haze observed

(50) : Slight haze observed

(51) X: Severe haze observed

(52) 9. Evaluation of Peel Strength

(53) The pressure-sensitive adhesive polarizing plate prepared in examples or comparative examples was cut to a size of 25 mm120 mm (widthlength) and attached to a glass substrate by the medium of a pressure-sensitive adhesive layer.

(54) After 4 hours of attachment, the polarizing plate was gradually peeled from the glass substrate at a peeling angle of 180 degrees and a peeling speed of 300 mm/min to measure peel strength (initial peel strength). Furthermore, the polarizing plate was left at 50 C. for 4 hours after the attachment, and peel strength (50 C. peel strength) was measured in the same manner.

(55) 10. Evaluation of Substrate Adhesion

(56) The substrate adhesion (adhesion between a pressure-sensitive adhesive layer and a polarizing plate protective film (TAC film)) of the pressure-sensitive adhesive polarizing plate was evaluated by the following method. A strong adhesive tape was first attached onto a surface of a pressure-sensitive adhesive layer formed on one surface of the pressure-sensitive adhesive polarizing plate. The strong adhesive tape was peeled from the pressure-sensitive adhesive polarizing plate within 1 minute after lamination, an amount of the pressure-sensitive adhesive layer remaining on a surface of the polarizing plate after peeling was measured and classified based on the following criteria.

(57) <Evaluation Criteria>

(58) : Pressure-sensitive adhesive layer remained on 90% or more of the total area of the polarizing plate

(59) : Pressure-sensitive adhesive layer remained on 50% or more and less than 90% of the total area of the polarizing plate

(60) X: Pressure-sensitive adhesive layer remained on less than 50% of the total area of the polarizing plate

(61) 11. Release Peel Strength at Room Temperature

(62) The pressure-sensitive adhesive polarizing plate prepared in examples or comparative examples was cut to a size of 50 mm120 mm (widthlength). Thereafter, a surface of the cut pressure-sensitive adhesive polarizing plate with no pressure-sensitive adhesive layer was attached to a glass substrate using a double-sided tape. Then, a release film on the pressure-sensitive adhesive layer was peeled at a peeling angle of 180 degrees and a peeling speed of 300 mm/min to measure peel strength (initial peel strength).

Preparation Example 1. Preparation of Acrylic Pressure-Sensitive Adhesive Resin Solution

(63) In a 1 L reactor with nitrogen gas refluxed and a cooling device installed to easily regulate a temperature, n-butyl acrylate (BA) and acrylic acid (AA) were introduced in a weight ratio (BA:AA) of 94:6, and ethyl acetate was also introduced therein as a solvent. Subsequently, oxygen was removed by purging with nitrogen gas for 1 hour, and a reaction initiator (AIBN: azobisisobutyronitrile) was introduced and reacted for about 8 hours. Then, the reactants were diluted with ethyl acetate to prepare an acrylic pressure-sensitive adhesive resin solution having an acid value in a range of about 32 to 34 and a weight average molecular weight of about 1,800,000.

Preparation Example 2. Preparation of Compound (A) of Formula 1

(64) In a reactor with nitrogen gas refluxed and a heater, a cooling device and a thermometer installed to easily regulate a temperature, polyethylene glycol (PEG) with a weight average molecular weight of about 400 and isophorone diisocyanate (IPDI) were introduced in a weight ratio (PEG:IPDI) of about 5:2.8, and a temperature was slowly raised up to about 50 C. and maintained. In such a state, a mixture was uniformly mixed and reacted for about 1 hour. The reaction time was determined by an IR spectrum, and the reaction was continued until an area of an NCO peak found at 2,270 cm.sup.1 in an IR spectrum before reaction decreased to 50%.

(65) Subsequently, the reactants were reacted with a polyol to prepare a compound (A) of Formula 1. In the above description, a polyol compound (HP-3753, manufactured by KPX CHEMICAL CO., LTD.) with a weight average molecular weight of approximately 7,000, which is a triol compound with three terminal hydroxyl groups including a polypropylene oxide unit at 85 wt % and a polyethylene oxide unit at 15 wt %, was used as the polyol.

(66) The polyol compound, the reactants and catalyst (dibutyltin dilaurate) were mixed in a weight ratio (polyol compound:reactants:catalyst) of 92.1:7.8:0.003, and the mixture was gradually added dropwise into a reactor with a temperature maintained to about 60 C. and further reacted, thereby preparing the compound (A) of Formula 1. The reaction was continued until an NCO peak completely disappeared in an IR spectrum.

(67) The compound (A) thus prepared had a molecular weight (Mw) of about 15,200 and a hydroxyl value (OHv) of about 11.2 mgKOH/g. The IR spectrum of the prepared compound is shown in FIG. 1.

Preparation Example 3. Preparation of Compound (B) of Formula 1

(68) In a reactor with nitrogen gas refluxed and a heater, a cooling device and a thermometer installed to easily regulate a temperature, polyethylene glycol (PEG) with a weight average molecular weight of about 400 and isophorone diisocyanate (IPDI) were introduced in a weight ratio (PEG:IPDI) of about 13.6:7.6, and a temperature was slowly raised up to about 50 C. and maintained. In such a state, a mixture was uniformly mixed and reacted for about 1 hour. The reaction time was determined by an IR spectrum, and the reaction was continued until an area of an NCO peak found at 2,270 cm.sup.1 in an IR spectrum before reaction decreased to 50%.

(69) Subsequently, the reactants were reacted with a polyol to prepare a compound (A) of Formula 1. In the above description, a polyol compound (HP-3753, manufactured by KPX CHEMICAL CO., LTD.) with a weight average molecular weight of approximately 7,000, which is a triol compound with three terminal hydroxyl groups including a polypropylene oxide unit at 85 wt % and a polyethylene oxide unit at 15 wt %, was used as the polyol.

(70) The polyol compound, the reactants and catalyst (dibutyltin dilaurate) were mixed in a weight ratio (polyol compound:reactants:catalyst) of 78.9:21.2:0.009, and the mixture was gradually added dropwise into a reactor with a temperature maintained to about 60 C. and further reacted, thereby preparing the compound (B) of Formula 1. The reaction was continued until an NCO peak completely disappeared in an IR spectrum.

(71) The compound (B) thus prepared had a molecular weight (Mw) of about 28,900 and a hydroxyl value (OHv) of about 5.61 mgKOH/g. The IR spectrum of the prepared compound is shown in FIG. 2.

Preparation Example 4. Preparation of Compound (D) of Formula 1

(72) In a reactor with nitrogen gas refluxed and a heater, a cooling device and a thermometer installed to easily regulate a temperature, polyethylene glycol (PEG) with a weight average molecular weight of about 400 and isophorone diisocyanate (IPDI) were introduced in a weight ratio (PEG:IPDI) of about 17.3:9.7, and a temperature was slowly raised up to about 50 C. and maintained. In such a state, a mixture was uniformly mixed and reacted for about 1 hour. The reaction time was determined by an IR spectrum, and the reaction was continued until an area of an NCO peak found at 2,270 cm.sup.1 in an IR spectrum before reaction decreased to 50%.

(73) Subsequently, the reactants were reacted with a polyol. In the above description, a polyol compound (GP-5000, manufactured by KPX CHEMICAL CO., LTD.) with a weight average molecular weight of approximately 5,000, which is a triol compound with three terminal hydroxyl groups including a polypropylene oxide unit, was used as the polyol.

(74) The polyol compound, the reactants and catalyst (dibutyltin dilaurate) were mixed in a weight ratio (polyol compound:reactants:catalyst) of 73.1:27:0.011, and the mixture was gradually added dropwise into a reactor with a temperature maintained to about 60 C. and further reacted, thereby preparing the compound (D) of Formula 1. The reaction was continued until an NCO peak completely disappeared in an IR spectrum.

(75) The compound (D) thus prepared had a molecular weight (Mw) of about 13,500 and a hydroxyl value (OHv) of about 12.2 mgKOH/g. The IR spectrum of the prepared compound is shown in FIG. 3.

Preparation Example 5. Preparation of Compound (E) of Formula 1

(76) In a reactor with nitrogen gas refluxed and a heater, a cooling device and a thermometer installed to easily regulate a temperature, polyethylene glycol (PEG) with a weight average molecular weight of about 2000 and isophorone diisocyanate (IPDI) were introduced in a weight ratio (PEG:IPDI) of about 17.3:9.7, and a temperature was slowly raised up to about 45 C. and maintained. In such a state, a mixture was uniformly mixed and reacted for about 1 hour. The reaction time was determined by an IR spectrum, and the reaction was continued until an area of an NCO peak found at 2,270 cm.sup.1 in an IR spectrum before reaction decreased to 50%.

(77) Subsequently, the reactant was reacted with a polyol. In the above description, a polyol compound (GP-5000, manufactured by KPX CHEMICAL CO., LTD.) with a weight average molecular weight of approximately 5,000, which is a triol compound with three terminal hydroxyl groups including a polypropylene oxide unit, was used as the polyol.

(78) The polyol compound, the reactants and catalyst (dibutyltin dilaurate) were mixed in a weight ratio (polyol compound:reactants:catalyst) of 73.1:27:0.011, and the mixture was gradually added dropwise into a reactor with a temperature maintained to about 60 C. and further reacted, thereby preparing the compound (E) of Formula 1. The reaction was continued until an NCO peak completely disappeared in an IR spectrum.

(79) The compound (E) thus prepared had a molecular weight (Mw) of about 20,200 and a hydroxyl value (OHv) of about 8.27 mgKOH/g. The IR spectrum of the prepared compound is shown in FIG. 4.

Example 1

(80) As an ionic compound, an ionic compound having methyl tributyl ammonium as a cation and trifluoromethanesulfonyl imide as an anion (octanol-water partition coefficient: about 5.65, cation-water binding energy: 0.45 Kcal/mol) was used. The ionic compound, the acrylic pressure-sensitive adhesive resin of Preparation Example 1, a crosslinking agent, the compound (A) of Preparation Example 2 and an isocyanate compound were mixed to prepare a cross-linkable composition. In the above description, an epoxy crosslinking agent (T-743L, manufactured by Nippon Soken Inc.) was used as the crosslinking agent, a compound (T-760B) prepared by addition polymerization of tolylene diisocyanate and trimethylolpropane was applied as the isocyanate compound. Based on 100 parts by weight of the solid content of the acrylic pressure-sensitive adhesive resin solution, 0.0052 parts by weight of the crosslinking agent, about 0.0793 parts by weight of the compound (A) of Preparation Example 2, about 4 parts by weight of the ionic compound and about 2 parts by weight of the isocyanate compound were mixed. The cross-linkable composition thus prepared was applied onto the release-treated surface of a release-treated poly(ethyleneterephthalate) (PET, MRF-38, manufactured by Mitsubishi Chemical Corporation) film and dried under suitable conditions to form a pressure-sensitive adhesive layer. The pressure-sensitive adhesive layer thus formed was laminated onto one surface of an iodine-based polarizing plate having a triacetyl cellulose (TAC)-based protective film attached to both surfaces thereof, thereby preparing a pressure-sensitive adhesive polarizing plate. The pressure-sensitive adhesive polarizing plate had a structure in which a pressure-sensitive adhesive layer and a release film were sequentially formed on a TAC film of one surface of a polarizing plate (TAC film/iodine-based polarizer/TAC film).

Example 2

(81) A cross-linkable composition, a pressure-sensitive adhesive layer and a pressure-sensitive adhesive polarizing plate were prepared in the same manner as in Example 1 except that the compound (B) of Preparation Example 3 was used instead of the compound (A) of Preparation Example 2.

Example 3

(82) A cross-linkable composition, a pressure-sensitive adhesive layer and a pressure-sensitive adhesive polarizing plate were prepared in the same manner as in Example 1 except that the compound (D) of Preparation Example 4 was used instead of the compound (A) of Preparation Example 2.

Example 4

(83) A cross-linkable composition, a pressure-sensitive adhesive layer and a pressure-sensitive adhesive polarizing plate were prepared in the same manner as in Example 1 except that the compound (E) of Preparation Example 5 was used instead of the compound (A) of Preparation Example 2.

Comparative Example 1

(84) A cross-linkable composition, a pressure-sensitive adhesive layer and a pressure-sensitive adhesive polarizing plate were prepared in the same manner as in Example 1 except that the compound (A) of Preparation Example 2 was not used.

(85) The results of the examples and comparative examples are summarized in the following Table 1.

(86) TABLE-US-00001 TABLE 1 Comparative Example Example 1 2 3 4 1 Substrate X adhesion Haze Peel 700 700 500 580 450 strength at room temperature (gf/25 mm) 50 C. peel 1,200 1,200 1,200 1,300 1,000 strength Surface 5.3 5.2 5.3 5.5 5.1 resistance (10.sup.10 /) Release 9.7 9.8 11 9.8 13 peel strength at room temperature (gf/25 mm) Durability