LAMINATED RESIN FILM, METHOD FOR PRODUCING SAME, LAMINATED OPTICAL FILM, IMAGE DISPLAY DEVICE, AND ADHESION IMPROVEMENT-TREATED RESIN FILM

Abstract

A laminated resin film, comprising a first resin film, and a second resin film laminated on/over at least one surface of the first resin film to interpose an adhesive layer between the surface and the second resin film, wherein an adhesion surface of at least one of the first resin film and the second resin film comprises a compound represented by general formula (1):

##STR00001##

wherein X is a functional group containing a reactive group, and R.sup.1 and R.sup.2 each independently represent a hydrogen atom, or an aliphatic hydrocarbon group, aryl group or heterocyclic group that may have a substituent, and the compound represented by the general formula (1) is interposed at either one or both of a position between the first resin film and the adhesive layer, and a position between the second resin film and the adhesive layer.

Claims

1. A laminated resin film, comprising a first resin film, and a second resin film laminated on/over at least one surface of the first resin film to interpose an adhesive layer between the surface and the second resin film, wherein an adhesion surface of at least one of the first resin film and the second resin film comprises a compound represented by general formula (1): ##STR00014## wherein X is a functional group containing a reactive group, and R.sup.1 and R.sup.2 each independently represent a hydrogen atom, or an aliphatic hydrocarbon group, aryl group or heterocyclic group that may have a substituent, and the compound represented by the general formula (I) is interposed at either one or both of a position between the first resin film and the adhesive layer, and a position between the second resin film and the adhesive layer.

2. The laminated resin film according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (1): ##STR00015## wherein Y is an organic group, and X, R.sup.1 and R.sup.2 are the same as described above.

3. The laminated resin film according to claim 1, wherein the first resin film is a polarizer, and the second resin film is a transparent film.

4. The laminated resin film according to claim 1, wherein the compound represented by the general formula (1) is interposed at both of the position between the first resin film and the adhesive layer, and the position between the second resin film and the adhesive layer.

5. The laminated resin film according to claim 1, wherein the reactive group that the compound represented by the general formula (1) has is at least one reactive group selected from the group consisting of ,-unsaturated carbonyl, vinyl, vinyl ether, epoxy, oxetane, amino, aldehyde, mercapto, and halogen groups.

6. A method for producing a laminated resin film comprising a first resin film, and a second resin film laminated on/over at least one surface of the first resin film to interpose an adhesive layer between the surface and the second resin film, the method comprising: an adhesion improvement-treating step of causing a compound represented by general formula (1): ##STR00016## wherein X is a functional group containing a reactive group, and R.sup.1 and R.sup.2 each independently represent a hydrogen atom, or an aliphatic hydrocarbon group, aryl group or heterocyclic group that may have a substituent to adhere to an adhesion surface of at least one of the first resin film and the second resin film; an applying step of applying a curable resin composition to the adhesion surface of at least one of the first resin film and the second resin film; a bonding step of causing the first resin film and the second resin film to each other; and an adhering step of radiating an active energy ray to the resultant laminate from a first resin film side of the laminate, or a second resin film side of the laminate to cure the curable resin composition to yield the adhesive layer, and adhering the first resin film and the second resin film to adhere each other through the yielded adhesive layer.

7. The method for producing the laminated resin film according to claim 6, wherein the compound represented by the general formula (1) is a compound represented by general formula (1): ##STR00017## wherein Y is an organic group, and X, R.sup.1 and R.sup.2 are the same as described above.

8. A laminated optical film, wherein at least one laminated resin film as recited in claim 1 is laminated.

9. An image display device, using a laminated resin film as recited in claim 1.

10. An adhesion improvement-treated resin film, comprising: a resin film having surfaces each comprising at least a reactive functional group; and a compound comprised on/over at least one of the surfaces of the resin film, and represented by general formula (1): ##STR00018## wherein X is a functional group containing a reactive group, and R.sup.1 and R.sup.2 each independently represent a hydrogen atom, or an aliphatic hydrocarbon group, aryl group or heterocyclic group that may have a substituent.

11. An adhesion-improving composition, comprising a compound represented by general formula (1): ##STR00019## wherein X is a functional group containing a reactive group, and R.sup.1 and R.sup.2 each independently represent a hydrogen atom, or an aliphatic hydrocarbon group, aryl group or heterocyclic group that may have a substituent.

12. An image display device, using a laminated optical film as recited in claim 8.

Description

EXAMPLES

[0158] Hereinafter, working examples of the present invention will be described. However, embodiments of the invention are not limited thereto.

<Production of Each Polarizer>

[0159] A 45-m-thickness film of a polyvinyl alcohol having an average polymerization degree of 2400 and a saponification degree of 99.5% by mole was immersed in hot water of 30 C. temperature for 60 seconds to be swollen. Next, the film was immersed in an aqueous solution of iodine and potassium iodide (ratio by weight=0.5/8), the concentration thereof being 0.3%, and the film was dyed therewith while stretched into a length 3.5 times the original length. Thereafter, the film was stretched in an aqueous solution of a boric acid that had a temperature of 65 C. to give a total stretch ratio of 6. After the stretching, the film was dried in an oven of 40 C. temperature for 3 minutes. In this way, each polyvinyl alcohol-based polarizer (thickness: 18 m) was yielded.

<Transparent Protective Films>

[0160] Each protective film A: A biaxial kneader was used to mix 100 parts by weight of an imidated MS resin described in Production Example 1 in JF-A-2010-284840 with 0.62 parts by weight of a triazine-based ultraviolet absorbent (trade name: T 712, manufactured by Adeka Corp.) at 220 C. to produce resin pellets. The resultant resin pellets were dried at 100.5 kPa and 100 C. for 12 hours, and a uniaxial extruder was then used to extrude the pellets through a T die at a dice temperature of 270 C. to be shaped into the form of a film (thickness: 160 m). Furthermore, this film was stretched, into the transporting direction thereof in an atmosphere of 150 C. temperature (thickness: 80 m). Next, an adhesion-improving agent containing an aqueous urethane resin was applied onto the film, and then the film was stretched into a direction orthogonal to the film-transporting direction in an atmosphere of 150 C. temperature. In this way, each transparent protective film A of 40 m thickness was yielded.

[0161] Each protective film B: Each 60-m-thickness triacetylcellulose film (FUJTTACK TG6GUL, manufactured by Fujifilm Corp.) was used.

[0162] Each protective film C: Each 50-m-thickness cyclic olefin polymer film (COP) (ZB-12, manufactured by Zeon Corp.) was used.

<Active Energy Rays>

[0163] As active energy rays, visible rays (gallium sealed metal halide lamp) were used. Radiating device: Light HAMMER 10, manufactured by Fusion UV Systems, Inc. Bulb: V bulb. Peak irradiance: 1600 mW/cm.sup.2. Integrated radiated-light quantity: 1000/mJ/cm.sup.2 (wavelengths: 380 to 440 nm). The irradiance of the visible rays was measured, using a Sola-Check system manufactured by Solatell Ltd.

(Preparation of Curable Resin Composition)

[0164] A curable resin composition was prepared which included the following in this curable resin composition, the total proportion of which was 100% by weight: 10% by weight of hydroxyethylacrylamide (manufactured by Kojin Co., Ltd.); 30% by weight of acryloylmorpholine (manufactured by Kojin Co., Ltd.); 45% by weight of 1,9-nonanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.); 10% by weight of a product ARUFRON UP1190 (acrylic oligomer yielded by polymerizing (meth)acrylic monomers, this product being manufactured by Toagosei Co., Ltd.); 3% by weight, of a product. IRGACURE 907 (polymerization initiator, manufactured by the company BASF); and 2% by weight of a product KAYACURE DETX-S (polymerization initiator, manufactured by Nippon Kayaku Co., Ltd.

Examples 1 to 18, and Comparative Examples 1 to 5

(Preparation of Adhesion-Improving Composition (A) for Forming Each Adhesion-Improving Layer)

[0165] An adhesion-improving composition (A) used in each of Examples 1 to 18 and Comparative Examples 1 to 5 was yielded by mixing individual components with each other in accordance with a blend table described in Table 1. Compounds blended into the adhesion-improving composition (A) are as follows:

[0166] 3-Acrylamidephenylboric acid (compound represented by the general formula (1) (manufactured by Junsei Chemical Co., Ltd.),

[0167] 3-Methacrylamidephenylboric acid (compound represented by the general formula (1): (manufactured by Junsei Chemical Co., Ltd.),

[0168] 4-Methacrylamidephenylboric acid (compound represented by the general formula (1)): (manufactured by Junsei chemical Co., Ltd.),

[0169] 4-Vinylphenylboric acid (compound represented by the general formula (1): (manufactured by Junsei chemical Co., Ltd.),

[0170] OLFIN EXP4200 (leveling agent): (manufactured by Nissin Chemical Industry Co., Ltd.),

[0171] ARON A-104 (binder component): acrylic resin (solid content: 40%) (manufactured by Toagosei Co., Ltd.), and

[0172] JC-25 (binder component): polyvinyl, alcohol resin (manufactured by Japan VAM & Poval Co., Ltd.).

(Production of Polarizing Film)

[0173] The composition (A) used in each of Examples 1 to 18 and Comparative Examples 1 to 5, which is described in one of Tables 1 to 3, was applied onto both surfaces of any one of the above-mentioned polarizers, using a wire bar (manufactured by a company limited Dai-Ichi Rika; No. 2). The resultant was wind-dried at 60 C. for one minute to remove the solvent therein to produce an adhesion-improving-layer-attached polarizer. Next, the above-mentioned curable resin, composition was applied onto an adhesion surface of any one of the transparent protective films A, and onto an adhesion, surface of any one of the transparent protective films B, so as to give each thickness of 0.7 m, using an MCD coater (manufactured by FUJI KIKAI KOGYO Co., Ltd) (cell shape: honeycomb, the number of gravure lines: 1000 lines/inch, and rotating speed: 140% of the line speed). A rolling device was then used to bond these protective films onto both surfaces of the above-mentioned polarizer, respectively. Thereafter, from an active energy ray radiating device, the above-mentioned visible rays were radiated onto both surfaces of the workpiece from the bonded transparent protective film sides (both sides) thereof to cure the active energy ray curable adhesive. Thereafter, the workpiece was dried by hot wind at 70 C. for 3 minutes to yield a polarizing film having, on both sides thereof, the transparent protective films, respectively. The line speed for the bonding was 25 m/min.

[0174] About the polarizing film yielded in each of the working examples and the comparative examples, evaluations described below were made. Results of the evaluations are shown in Tables 1 to 4.

<Adhering Strength Test>

[0175] The polarizing film yielded in each of the examples was cat into pieces each having a size of 200 mm in a direction in parallel with the stretched direction of the polarizer, and 20 mm in an direction orthogonal thereto. A utility knife was cut into between one of the transparent protective films and the polarizer of one of the pieces, and into between the other side transparent protective film and the polarizer of another of the pieces. Each of the resultant polarizing films was bonded to a glass plate. A machine Tensilon was used to peel off the transparent protective film and the polarizer from each other into 90-degree directions at a peel rate of 10 m/min. The peel strength thereof was measured. Moreover, after the peeling, an infrared absorption spectrum of each of the resultant peel surfaces was measured, using an ATR method. The peel interface was then evaluated in accordance with the following criterion:

[0176] A: cohesive fracture of the one or the other transparent protective film,

[0177] B: interfacial fracture between the transparent protective film and the adhesive layer,

[0178] C: interfacial fracture between the adhesive layer and the polarizer, or

[0179] D: cohesive fracture of the polarizer.

[0180] In this criterion, A and D each mean that the adhering strength is not less than the cohesive strength of the film so that the adhering strength is very good. In the meantime, B and C each mean that the transparent-protective-film/adhesive-layer (adhesive-layer/polarizer) interface is insufficient in adhering strength (or poor in adhering strength). Considering these matters, when the polarizing film falls under A or D, the adhering strength is judged to be good (circular mark); when the polarizing film falls under A and B (simultaneous generation of cohesive fracture of the transparent protective film and interfacial fracture between the transparent protective film and the adhesive layer) or under A and C (simultaneous generation of cohesive fracture of the transparent protective film and interfacial fracture between the adhesive layer and the polarizer), the adhering strength is judged to be acceptable (triangular mark); or when the polarizing film falls under B or C, the adhering strength is judged to foe bad (cross mark).

<Cold Water Immersion Peeling Test>

[0181] The polarizing film yielded in each of the examples was cut into pieces each having a size of 200 mm in a direction in parallel with the stretched direction of the polarizer, and 20 mm in a direction orthogonal thereto. The polarizing films were immersed in pure water of 23 C. temperature for 24 hours, and then taken out. The polarizing films were wiped with a dried cloth, and then a utility knife was cut into between one of the transparent protective films and the polarizer of one of the pieces, and into between the other side transparent protective film and the polarizer of another of the pieces. Each of the resultant polarizing films was bonded to a glass plate. A machine Tensilon was used to peel off the transparent protective film and the polarizer from each other into 90-degree directions at a peel rate of 10 m/min. The peel strength thereof was measured. Moreover, after the peeling, an infrared absorption spectrum of each of the resultant peel surfaces was measured, using an ATR method. The peel interface was then evaluated in accordance with the same criterion as in the adhering strength test. This evaluation was made within one minute after the time when the polarizing film was taken out from the pure water.

<Severe Cold Water Immersion Peeling Test>

[0182] The polarizing film yielded in each of the examples was cut into pieces each having a size of 200 mm in a direction in parallel with the stretched direction of the polarizer, and 20 mm in an direction orthogonal thereto. The polarizing films were immersed in pure water of 23 C. temperature for 48 hours, and then taken out. The polarizing films were wiped with a dried cloth, and then a utility knife was cut into between one of the transparent protective films and the polarizer of one of the pieces, and into between the other side transparent protective film and the polarizer of another of the pieces. Each of the resultant polarizing films was bonded to a glass plate. A machine Tensilon was used to peel off the transparent protective film and the polarizer from each other into 90-degree directions at a peel rate of 10 m/min. The peel strength thereof was measured. Moreover, after the peeling, an infrared absorption spectrum of each of the resultant peel surfaces was measured, using an ATR method. The peel interface was then evaluated in accordance with the same criterion as in the adhering strength test. This evaluation was made within one minute after the time when the polarizing film was taken out from the pure water.

TABLE-US-00001 TABLE 1 Comparative Examples Examples 1 2 3 4 5 1 2 3 Adhesion- Boron Boric acid 0.1 improving compounds 3-Acrylamidephenylboric 2 composition (A) acid 3-Methacrylamidephenyl- 1 boric acid 4-Methacrylamidephenyl- 1 boric acid 4-Vinylphenylboric acid Levelling OLFIN EXP 4200 0.1 0.1 agent Binder ARON A-104 5 components JC-25 2 Solvents Water 78 75 Isopropyl alcohol 99.9 20 20 97.9 97.9 98 Wire bar count 2 2 2 2 2 2 Dried treated-layer thickness [nm] 5 100 100 55 55 100 Adhesion- Formation Formation Only on Only on Only on Only on Only on Only on improving- of no of no polar- polar- polar- polar- polar- polar- layer-formation adhesion- adhesion- izer izer izer izer izer izer surface improving improving side side side side side side layer layer Water content in % 20 17 15 15 15 15 15 15 polarizer Adhering strength Peel strength 0.7N 0.3N 0.3N 0.4N 0.3N 2.7N 3N 2.8N (protective film A) Decision x(C) x(C) x(C) x(C) x(C) (A) (A) (A) Adhering strength Peel strength 0.5N 0.4N 0.3N 0.3N 0.4N 2.9N 2.6N 2.5N (protective film B) Decision x(C) x(C) x(C) x(C) x(C) (A) (A) (A) Cold water immersion Peel strength 0.2N 0.2N 0.2N 0.1N 0.2N 2.2N 1.5N 1.8N peeling test Decision x(C) x(C) x(C) x(C) x(C) (A) (A) (A) (protective film A) Cold water immersion Peel strength 0.2N 0.2N 0.3N 0.1N 0.2N 2.3N 1.5N 1.9N peeling test Decision x(C) x(C) x(C) x(C) x(C) (A) 0(A) (A) (protective film B) Severe cold water Peel strength 0.2N 0.2N 0.1N 0.2N 0.2N 2.0N 1.2N 1.5N immersion peeling test Decision x(C) x(C) x(C) x(C) x(C) (A) (A .Math. C) (A) (protective film A) Severe cold water Peel strength 0.2N 0.2N 0.2N 0.2N 0.2N 1.8N 1.0N 1.5N immersion peeling test Decision x(C) x(C) x(C) x(C) x(C) (A) (A .Math. C) (A) (protective film B)

TABLE-US-00002 TABLE 2 Examples 4 5 6 7 8 9 10 11 Adhesion- Boron Boric acid improving compounds 3-Acrylamidephenylboric 1 0.1 1 1 1 1 1 1 composition (A) acid 3-Methacrylamidephenyl- boric acid 4-Methacrylamidephenyl- boric acid 4-Vinylphenylboric acid Levelling OLFIN EXP 4200 0.1 0.1 0.1 agent Binder ARON A-104 1 1 1 components JC-25 Solvents Water Isopropyl alcohol 99 99.9 99 99 99 97.9 97.9 97.9 Wire bar count 2 2 2 2 2 2 2 2 Dried treated-layer thickness [nm] 50 5 50 50 50 105 105 105 Adhesion- Only on Only on Only on Only on Only on Only on Only on Only on improving- polar- polar- polar- polar- polar- polar- polar- polar- layer-formation izer izer izer izer izer izer izer izer surface side side side side side side side side Water content in % 15 15 13 10 5 13 20 18 polarizer Adhering strength Peel strength 2.7N 3N 2.9N 2.8N 2.8N 3N 1.0N 2.1N (protective film A) Decision (A) (A) (A) (A) (A) (A) (A .Math. C) (A) Adhering strength Peel strength 2.9N 2.6N 3.0N 3.1N 3.1N 2.6N 0.8N 2.5N (protective film B) Decision (A) (A) (A) (A) (A) (A) (A .Math. C) (A) Cold water immersion Peel strength 2.2N 1.7N 2.1N 2.2N 2.0N 2.2N 0.7N 1.2N peeling test Decision (A) (A) (A) (A) (A) (A) (A .Math. C) (A .Math. C) (protective film A) Cold water immersion Peel strength 2.3N 1.8N 2.1N 2.4N 2.3N 1.8N 0.6N 1.1N peeling test Decision (A) (A) (A) (A) (A) (A) (A .Math. C) (A .Math. C) (protective film B) Severe cold water Peel strength 2.0N 1.5N 1.8N 2.0N 2.0N 1.7N 0.5N 0.4N immersion peeling test Decision (A) (A) (A) (A) (A) (A) (A .Math. C) (A .Math. C) (protective film A) Severe cold water Peel strength 1.8N 1.6N 2.1N 2.0N 2.1N 1.6N 0.5N 0.6N immersion peeling test Decision (A) (A) (A) (A) (A) (A) (A .Math. C) (A .Math. C) (protective film B)

TABLE-US-00003 TABLE 3 Examples 12 13 14 15 16 17 18 Adhesion- Boron Boric acid improving compounds 3-Acrylamidephenylboric composition (A) acid 3-Methacrylamidephenyl- boric acid 4-Methacrylamidephenyl- boric acid 4-Vinylphenylboric acid 0.01 1 1 0.05 1 1 1 Levelling OLFIN EXP 4200 0.1 agent Binder ARON A-104 2.5 2.5 components JC-25 1 Solvents Water 78 76.5 76.5 Isopropyl alcohol 99.99 99 99 99.8 20 20 20 Wire bar count 2 2 10 2 2 2 2 Dried treated-layer thickness [nm] 0.5 50 250 5 100 100 100 Adhesion- Only on Only on Only on Only on Only on Only on Only on improving- polar- polar- polar- polar- polar- polar- polar- layer-formation izer izer izer izer izer izer izer surface side side side side side side side Water content in % 15 15 15 15 15 15 15 polarizer Adhering strength Peel strength 2.5N 2.8N 2.3N 2.4N 2.6N 2.6N 2.5N (protective film A) Decision (A) (A) (A) (A) (A) (A) (A) Adhering strength Peel strength 2.9N 2.8N 2.9N 3.0N 2.9N 3.0N 3.0N (protective film B) Decision (A) (A) (A) (A) (A) (A) (A) Cold water immersion Peel strength 2.2N 2.9N 1.7N 2.1N 2.2N 2.3N 2.2N peeling test Decision (A) (A) (A) (A) (A) (A) (A) (protective film A) Cold water immersion Peel strength 1.9N 2.3N 1.3N 2.0N 2.3N 2.5N 2.5N peeling test Decision (A) (A) (A) (A) (A) (A) (A) (protective film B)

Example 19, and Comparative Examples 6 to 8

[0183] An adhesion-improving composition (A) used in each of Example 19 and Comparative Examples 6 to 8 was yielded by mixing individual components with each other in accordance with a blend table described in Table 4.

(Production of Polarizing Film)

[0184] The composition (A) used in each of Example 19 and Comparative Examples 6 to 8, which is described in Table 4, was applied onto both surfaces of any one of the above-mentioned polarizers, using a wire bar (manufactured by a company limited Dai-Ichi Rika; No. 2), The resultant was wind-dried at 60 C. for one minute to remove the solvent therein to produce an adhesion-improving-layer-attached polarizer. Next, each of two of the transparent protective films C was subjected to corona treatment, and the corona-treated surface of the film was coated with the composition (A) used in used in each of Example 19 and Comparative Examples 6 to 8, which is described in Table 3. The resultants were then dried at 60 C. for one minute to remove the solvent therein. In this way, adhesion-improving-layer-attached protective films C were produced. The above-mentioned curable resin composition was applied onto adhesion surfaces of the adhesion-improving-layer-attached polarizer and each of the adhesion-improving-layer-attached protective films C, so as to give each thickness of 0.7 m, using an MCB coater (manufactured by FUJI KIKAI KOGYO Co., Ltd) (cell shape: honeycomb, the number of gravure lines: 1000 lines/inch, and rotating speed: 140% of line speed). A rolling device was then used to cause the protective films to bond onto both surfaces of the polarizer, respectively. Thereafter, from an active energy ray radiating device, the above-mentioned visible rays were radiated onto both surfaces of the workpiece from the bonded transparent protective film sides (both sides) thereof to cure the active energy ray curable adhesive. Thereafter, the workpiece was dried by hot wind at 70 C. for 3 minutes to yield a polarizing film having, on both sides thereof, the transparent protective films, respectively. The line speed for the bonding was 25 m/min.

TABLE-US-00004 TABLE 4 Examples Comparative Examples 19 6 7 8 Adhesion- Boron compounds improving composition 4-Vinylphenylboric acid 0.01 0.01 0.01 (A) Isopropyl alcohol 99.99 99.99 99.99 Wire bar count 2 2 2 Dried treated-layer thickness [nm] 0.5 0.5 0.5 Adhesion-improving layer applied surface On both of polarizer Only on substrate side Only on polariser side None side and substrate side Adhering strength Peel strength 2.1N 2.1N 1.8N 1.8N (protective film C) Decision (A) (A) (A) (A) Cold water immersion Peel strength 1.4N 0.2N 0.2N 0.2N peeling test Decision (A) X(C) X(B) X(C) (protective film C)