CURABLE COMPOSITION, CURED PRODUCT THEREOF, AND CURING METHOD THEREFOR

Abstract

Provided are: a curable composition having excellent photolithographic properties and resin elution properties; a cured product of the curable composition; and a curing method of the curable composition. The curable composition is characterized by including: (A) at least one selected from the group consisting of a water-soluble polyfunctional (meth)acrylates and water-soluble polyfunctional (meth)acrylamides; and (B) a photosensitive group-containing water-soluble polymer. The water-soluble polyfunctional (meth)acrylates are preferably compounds represented by Formula (I) below, and the water-soluble polyfunctional (meth)acrylamides are preferably compounds represented by Formula (II) below. In Formulae (I) and (II), R.sup.1 represents a hydrogen atom, a methyl group, or a halogen atom; X.sup.1 represents an alkylene group having 1 to 6 carbon atoms that is optionally substituted with a hydroxy group; A represents an n-valent organic group; R.sup.11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; m represents a number of 1 to 30; n represents a number of 2 to 12; and t represents a number of 2 to 12.

##STR00001##

Claims

1. A curable composition comprising: (A) at least one selected from the group consisting of water-soluble polyfunctional (meth)acrylates and water-soluble polyfunctional (meth)acrylamides; and (B) a photosensitive group-containing water-soluble polymer.

2. The curable composition according to claim 1, wherein the water-soluble polyfunctional (meth)acrylates are represented by the following Formula (I): ##STR00032## where R.sup.1 represents a hydrogen atom, a methyl group, or a halogen atom; X.sup.1 represents an alkylene group having 1 to 6 carbon atoms that is optionally substituted with a hydroxy group; A represents an n-valent organic group; m represents a number of 1 to 30; and n represents a number of 2 to 12.

3. The curable composition according to claim 1, wherein the water-soluble polyfunctional (meth)acrylamides are represented by the following Formula (II): ##STR00033## where R.sup.11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; t represents a number of 2 to 12; and le and A have the same meanings as in the Formula (I).

4. The curable composition according to claim 1, wherein the (B) photosensitive group-containing water-soluble polymer is a water-soluble polymer comprising a structural unit represented by the following Formula (III) or (IV): ##STR00034## where Y represents a divalent organic group; and Q represents a photosensitive group.

5. The curable composition according to claim 4, wherein the (B) photosensitive group-containing water-soluble polymer is a water-soluble polymer comprising a structural unit represented by the following Formula (V): ##STR00035## where An.sup.q represents a q-valent anion; q represents 1 or 2; and p represents a coefficient that maintains a neutral charge.

6. The curable composition according to claim 4, wherein, in the Formulae (III) and (IV), Q is a vinyl group, an allyl group, a styryl group, a cinnamyl group, a cinnamoyl group, a cinnamylidene group, a cinnamylideneacetyl group, a chalcone group, a coumarin group, an isocoumarin group, a 2,5-dimethoxystilbene group, a maleimide group, an -phenylmaleimide group, a 2-pyrone group, an azide group, a thymine group, a quinone group, a maleimide group, a uracil group, a pyrimidine group, a stilbazolium group, a styrylpyridinium group, a styrylquinolium group, an epoxy group, an oxetane group, a vinyl ether group, an allyl ether group, an acetylacetone structure, or a -diketone structure.

7. The curable composition according to claim 1, wherein the (B) photosensitive group-containing water-soluble polymer is a polyvinyl alcohol derivative obtained by introducing a (meth)acrylate or (meth)acrylamide structure to a polyvinyl alcohol.

8. The curable composition according to claim 1, further comprising a radical initiator.

9. A cured product obtained by curing the curable composition according to claim 1.

10. A curing method comprising curing the curable composition according to claim 1 with an active energy ray.

11. The curable composition according to claim 2, wherein the water-soluble polyfunctional (meth)acrylamides are represented by the following Formula (II): ##STR00036## where R.sup.11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; t represents a number of 2 to 12; and R.sup.1 and A have the same meanings as in the Formula (I).

12. The curable composition according to claim 2, wherein the (B) photosensitive group-containing water-soluble polymer is a water-soluble polymer comprising a structural unit represented by the following Formula (III) or (IV): ##STR00037## where Y represents a divalent organic group; and Q represents a photosensitive group.

13. The curable composition according to claim 3, wherein the (B) photosensitive group-containing water-soluble polymer is a water-soluble polymer comprising a structural unit represented by the following Formula (III) or (IV): ##STR00038## where Y represents a divalent organic group; and Q represents a photosensitive group.

14. The curable composition according to claim 2, wherein the (B) photosensitive group-containing water-soluble polymer is a polyvinyl alcohol derivative obtained by introducing a (meth)acrylate or (meth)acrylamide structure to a polyvinyl alcohol.

15. The curable composition according to claim 2, further comprising a radical initiator.

16. The curable composition according to claim 3, further comprising a radical initiator.

17. The curable composition according to claim 4, further comprising a radical initiator.

18. The curable composition according to claim 5, further comprising a radical initiator.

19. The curable composition according to claim 6, further comprising a radical initiator.

20. The curable composition according to claim 7, further comprising a radical initiator.

Description

EXAMPLES

[0097] The curable composition of present invention will now be described in more detail by way of Examples and Comparative Examples.

Examples 1 to 14 and Comparative Examples 1 to 6

[0098] Components are mixed in accordance with the respective formulations shown in [Table 1] to [Table 3] and subsequently stirred for 1 hour at room temperature, after which the resultants were each filtered through a 1-m filter to obtain curable compositions of Examples and Comparative Examples. It is noted here that, in Examples and Comparative Examples, the term part(s) means part(s) by mass. The added amounts of PV-1 to PV-4 and PV-1 to PV-3 shown in [Table 1] to [Table 3] indicate the ratios (% by mass) of the respective components other than solvent. Further, PV-1 to PV-3 were each prepared by the following procedure.

Production Example

Preparation of Aqueous Water-Soluble Polymer Solutions PV-1 to PV-3

[0099] First, to 90.0 g of ion-exchanged water being stirred at room temperature, 10.0 g of each of the below-described comparative water-soluble polymers (B-1, B-2 and B-3) was slowly added. The resultants were each stirred at room temperature for 1 hour and subsequently heated until the inner temperature reached 85 to 90 C., after which stirring was continued at this temperature for 2 hours. After confirming that each comparative water-soluble polymer was dissolved, the resulting solutions were each cooled to room temperature. Thereafter, the thus prepared aqueous solutions were each filtered through a 1-m filter.

[0100] B-1: GOHSENOL.sup. NL-05, manufactured by The Nippon Synthetic Chemical Industry Co., Ltd.

[0101] B-2: G-Polymer OKS-1083, manufactured by The Nippon Synthetic Chemical Industry Co., Ltd.

[0102] B-3: GOHSENX Z-200, manufactured by The Nippon Synthetic Chemical Industry Co., Ltd.

[0103] For the curable compositions obtained in Examples 1 to 14 and Comparative Examples 1 to 6, solution compatibility, coatability, photolithographic properties and a VHR were evaluated in accordance with the below-described procedures. The results thereof are also shown in [Table 1] to [Table 3].

(Solution Compatibility)

[0104] The state of each aqueous solution of the curable compositions obtained in Examples 1 to 14 and Comparative Examples 1 to 6 was visually checked in a transparent sample bottle. The evaluation criteria were as follows.

[0105] : transparent and uniform

[0106] : slightly turbid

[0107] : turbid, separated, or observation of precipitates

[0108] An aqueous solution with an evaluation of or has excellent storage stability and can thus be preferably used as a curable composition, and an aqueous solution with an evaluation of is particularly preferred. An aqueous solution with an evaluation of has poor storage stability and is thus not preferred as a curable composition.

(Coatability)

[0109] The curable compositions obtained in Examples 1 to 14 and Comparative Examples 1 to 6 were each coated on a glass substrate using a spin coater, and the resultants were each prebaked on a 90 C. hot plate for 5 minutes. The state of each film formed in this process was checked. It is noted here that the spin-coating conditions were adjusted such that the thickness of each film was measured to be 5.0 to 5.5 m by a stylus method. The evaluation criteria were as follows.

[0110] : transparent and uniform

[0111] : slightly turbid

[0112] : turbid or observation of precipitates

[0113] A curable composition with an evaluation of or can be preferably used in an optical material, and a curable composition with an evaluation of is particularly preferred. A curable composition with an evaluation of is not preferred as a curable composition to be used in an optical material.

(Photolithographic Properties)

a) Exposure

[0114] On a pre-baked substrate, each coating film was irradiated with a light containing a wavelength of 365 nm through a photomask (line/space=100 m/100 m) at 1,000 mJ/cm.sup.2 using a high-pressure mercury lamp.

b) Development and Drying

[0115] Each film exposed in a) was immersed in 23 C. ion exchanged water for 1 minute, and water adhering thereto was subsequently removed using an air gun, followed by 10-minute drying of the substrate in a 120 C. oven. After the development and drying, the resulting pattern was observed under a laser microscope to evaluate the photolithographic properties. The evaluation criteria were as follows.

[0116] : The pattern had a resolution within 1005 m.

[0117] : The pattern had a resolution within 10010 m.

[0118] : The pattern had a resolution of 10010 m or larger, or the pattern disappeared.

[0119] A curable composition with an evaluation of or can be preferably used as a curable composition for which photolithographic properties are required, and a curable composition with an evaluation of is particularly preferred. A curable composition with an evaluation of is not preferred as a curable composition for which photolithographic properties are required.

(VHR)

[0120] Liquid-crystal compositions composed of the liquid-crystal compounds No. 1 to No. 11 shown below were each brought into contact with the respective coating films obtained in the above-described coatability test and, after leaving the resultants at 60 C. for 24 hours, the liquid-crystal compositions were each removed, whereby a resin elution test was performed. For the thus removed liquid-crystal compositions, the VHR (voltage holding ratio) was compared before and after the resin elution test to determine the VHR reduction rate, which was evaluated based on the below-described criteria. For the evaluation, the liquid-crystal compositions were each injected into a TN cell for liquid-crystal evaluation (cell thickness: 5 m, electrode area: 8 mm8 mm, alignment film: JALS2096), and the VHR was measured using VHR-1A (manufactured by TOYO Corporation) (Measurement conditions: pulse voltage width=60 s, frame period=1.0 s, amplitude=5 V, and measuring temperature=25 C.).

[0121] : The VHR reduction rate was higher than 99%.

[0122] : The VHR reduction rate was 97 to 99%.

[0123] : The VHR reduction rate was lower than 97%.

[0124] A liquid-crystal composition with an evaluation of or exhibits low resin elution to liquid crystal and can thus be preferably used as a curable composition having excellent resin elution properties, and a liquid-crystal composition with an evaluation of is particularly preferred. A liquid-crystal composition with an evaluation of is not preferred because of high resin elution to liquid crystal.

##STR00023## ##STR00024##

TABLE-US-00001 TABLE 1 Ex- Ex- Ex- Ex- Ex- Ex- Ex- ample ample ample ample ample ample ample 1 2 3 4 5 6 7 PV-1 30 30 40 30 70 PV-2 30 PV-3 20 10 PV-4 PV-1 50 30 PV-2 60 PV-3 60 80 A-1 2 10 A-2 10 3 10 A-3 10 10 5 10 10 10 5 A-4 10 A-5 10 10 10 A-6 10 10 5 A-1 A-2 A-3 C-1 2 2 C-2 2 C-3 2 2 3 2 C-4 C-5 C-6 2 C-7 C-8 C-9 Solution compatibility Coatability Photolithographic properties VHR A-1: NK ESTER A-600 (water-soluble polyfunctional acrylate), manufactured by Shin Nakamura Chemical Co., Ltd., A-2: ND ESTER A-GLY-20E (water-soluble polyfunctional acrylate), manufactured by Shin Nakamura Chemical Co., Ltd., A-3: NK ECONOMER A-PG5054E (water-soluble polyfunctional acrylate), manufactured by Shin Nakamura Chemical Co., Ltd., A-4: NK ESTER A-BPE-30 (water-soluble polyfunctional acrylate), manufactured by Shin Nakamura Chemical Co., Ltd., A-5: FFM-2 (water-soluble polyfunctional acrylamide), manufactured by FUJIFILM Corporation, A-6: NK ESTER ATM-35E (water-soluble polyfunctional acrylate), manufactured by Shin Nakamura Chemical Co., Ltd., A-1: NK ESTER A-400 (non-water-soluble polyfunctional acrylate), manufactured by Shin Nakamura Chemical Co., Ltd., A-2: NK ESTER A-BPE-4 (non-water-soluble polyfunctional acrylate), manufactured by Shin Nakamura Chemical Co., Ltd., A-3: hydroxyethylacrylamide (HEAA)(water-soluble monofunctional acrylamide), manufactured by KJ Chemicals Corporation, PV-1: an aqueous solution prepared by allowing N-methylolacrylamide to act on GOHSENOL GL-05 and adjusting the solid content to be 10% by mass, PV-2: an aqueous solution prepared by allowing N-methylolacrylamide to act on G-Polymer OKS-1083 and adjusting the solid content to be 10% by mass, PV-3: an aqueous solution prepared by allowing formylstyrylpyridinium to act on G-Polymer OKS-1083 and adjusting the solid content to be 10% by mass, PV-4: an aqueous solution prepared by allowing formylstyrylpyridinium to act on GOHSENOL GL-05 and adjusting the solid content to be 10% by mass, C-1: [00025]C-2: [00026]C-3: [00027]C-4: [00028]C-5: IRGACURE 907, manufactured by BASF Japan Ltd., C-6: IRGACURE 2959, manufactured by BASF Japan Ltd., C-7: [00029]C-8: [00030]C-9: [00031]

TABLE-US-00002 TABLE 2 Example Example Example Example Example Example 8 Example 9 10 11 12 13 14 PV-1 80 40 40 40 40 40 PV-2 30 40 40 40 40 PV-3 PV-4 10 PV-1 PV-2 PV-3 80 A-1 A-2 10 20 A-3 5 5 10 A-4 A-5 15 10 10 10 A-6 5 5 A-1 A-2 A-3 5 10 10 10 C-1 C-2 C-3 2 5 5 5 C-4 C-5 C-6 C-7 5 C-8 5 C-9 5 Solution compatibility Coatability Photolithographic properties VHR

TABLE-US-00003 TABLE 3 Comparative Comparative Comparative Comparative Comparative Comparative Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 PV-1 30 40 PV-2 40 PV-3 PV-4 PV-1 60 30 50 60 PV-2 20 30 30 PV-3 30 A-1 10 10 A-2 10 A-3 10 A-4 10 A-5 10 A-6 10 A-1 10 20 10 10 A-2 10 10 10 10 A-3 20 C-1 C-2 2 C-3 2 5 C-4 2 2 C-5 2 C-6 C-7 C-8 C-9 Solution x x compatibility Coatability x x x x Photolithographic x x x x properties VHR x x x

[0125] From [Table 1] to [Table 3], it is seen that the curable composition of the present invention has excellent coatability, resin elution properties and the like. Therefore, the curable composition of the present invention can be suitably used as an adhesive.