Imprint material having low mold release property

Abstract

There is provided an imprint material that allows a resin film to be readily released from a mold at the time of mold release after curing, that is, an imprint material that forms a film having a low mold release property as well as high transparency, high scratch resistance, and a high fingerprint wiping-off property; and a film which is formed from the material and to which a pattern is transferred. An imprint material including: a (A) component: a compound having a propylene oxide unit and two polymerizable groups or a compound having a propylene oxide unit, an ethylene oxide unit, and two polymerizable groups; a (B) component: a silicone compound; and a (C) component: a photopolymerization initiator.

Claims

1. An imprint material comprising: a (A) component; a (B) component; a (C) component; and optionally, a (D) component, wherein the (A) component is a compound having a propylene oxide unit, an ethylene oxide unit, and two polymerizable groups, the (B) component is a silicone compound and is present in an amount of 0.2 phr to 4 phr to the mass of the (A) component and the (D) component when present, the (C) component is a photopolymerization initiator, and the (D) component is a compound having three or more polvmerizable groups.

2. The imprint material according to claim 1, further comprising the compound having three or more polymerizable groups as the (D) component.

3. The imprint material according to claim 1, further comprising a compound having an ethylene oxide unit and two polymerizable groups, as an (E) component.

4. The imprint material according to claim 1, further comprising a surfactant as an (F) component.

5. The imprint material according to claim 1, further comprising a solvent as a (G) component.

6. The imprint material according to claim 1, wherein the compound of the (A) component is a compound having two groups of at least one selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a vinyl group, and an allyl group, as the polymerizable groups.

7. The imprint material according to claim 2, wherein the compound of the (D) component is a compound having three or more groups of at least one selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a vinyl group, and an allyl group, as the polymerizable groups.

8. The imprint material according to claim 1, wherein in a test in which the imprint material is applied onto a film, the coating film on the film is bonded to the surface of a mold having unevenness, subsequently the coating film is photo-cured, and thereafter the cured film on the film is peeled at 90 from the surface of the mold having unevenness, a measured mold release force is more than 0 g/cm and 0.5 g/cm or less, the measured mold release force being a value obtained by converting a load when the cured film on the film is peeled from the surface of the mold having unevenness into a value per 1 cm of the width of the film.

9. A film which is formed from the imprint material as claimed in claim 1 and to which a pattern is transferred.

10. An optical member comprising: the film as claimed in claim 9 to which the pattern is transferred and which is provided on a substrate.

11. A solid state imaging device comprising: the film as claimed in claim 9 to which the pattern is transferred and which is provided on a substrate.

12. An LED device comprising: the film as claimed in claim 9 to which the pattern is transferred and which is provided on a substrate.

13. A semiconductor device comprising: the film as claimed in claim 9 to which the pattern is transferred.

14. A solar cell comprising: the film as claimed in claim 9 to which the pattern is transferred and which is provided on a substrate.

15. A display comprising: the film as claimed in claim 9 to which the pattern is transferred and which is provided on a substrate.

16. An electronic device comprising: the film as claimed in claim 9 to which the pattern is transferred and which is provided on a substrate.

Description

EXAMPLES

(1) Hereinafter, the present invention is further described in detail with reference to Examples and Comparative Examples. The present invention, however, is not limited to these Examples.

Preparation of Imprint Material

Example 1

(2) 5 g of NK Ester APG-700 (hereinafter abbreviated as APG-700 in this specification) (manufactured by Shin-Nakamura Chemical Co., Ltd.), and 0.05 g of BYK 333 (manufactured by BYK Japan KK) (1 phr to the mass of APG-700) were prepared and these were mixed. To the mixture, 0.125 g of Lucirin (registered trademark) TPO (manufactured by BASF Japan Ltd.) (hereinafter abbreviated as Lucirin TPO in this specification) (2.5 phr to the mass of APG-700) was added to prepare an imprint material PNI-a1.

Example 2

(3) An imprint material PNI-a2 was prepared in the same manner as Example 1 except that APG-700 in Example 1 was replaced by FANCRYL (registered trademark) FA-023M (hereinafter abbreviated as FA-023M in this specification) (manufactured by Hitachi Chemical Industry Co. Ltd).

Example 3

(4) An imprint material PNI-a3 was prepared in the same manner as Example 1 except that APG-700 in Example 1 was replaced by NK Economer A-1000PER (hereinafter abbreviated as A-1000PER in this specification) (manufactured by Shin-Nakamura Chemical Co., Ltd.).

Example 4

(5) 0.5 g of KAYARAD (registered trademark) DPEA-12 (hereinafter abbreviated as DPEA-12 in this specification) (manufactured by Nippon Kayaku Co., Ltd.), 2 g of UA-306H (hereinafter abbreviated as 306H in this specification) (manufactured by Kyoeisha Chemical Co., Ltd.), 2.5 g of APG-700, and 0.05 g of BYK-333 (1 phr to the total mass of DPEA-12, 306H, and APG-700) were prepared and these were mixed. To the mixture, 0.125 g of Lucirin TPO (2.5 phr to the total mass of DPEA-12, 306H, and APG-700) was added to prepare an imprint material PNI-a4.

Example 5

(6) An imprint material PNI-a5 was prepared in the same manner as Example 4 except that the amount of BYK-333 in Example 4 was changed to 0.1 g (2 phr to the total mass of DPEA-12, 306H, and APG-700).

Example 6

(7) An imprint material PNI-a6 was prepared in the same manner as Example 4 except that APG-700 in Example 4 was replaced by A-1000PER and the amount of BYK-333 in Example 4 was changed to 0.025 g (0.5 phr to the total mass of DPEA-12, 306H, and A-1000PER).

Example 7

(8) An imprint material PNI-a7 was prepared in the same manner as Example 6 except that the amount of BYK-333 in Example 6 was changed to 0.05 g (1 phr to the total mass of DPEA-12, 306H, and A-1000PER).

Example 8

(9) An imprint material PNI-a8 was prepared in the same manner as Example 6 except that the amount of BYK-333 in Example 6 was changed to 0.1 g (2 phr to the total mass of DPEA-12, 306H, and A-1000PER).

Example 9

(10) 2.25 g of 306H and 2.75 g of A-1000PER were prepared and these were mixed. To the mixture, 0.05 g of BYK-333 (1 phr to the total mass of 306H and A-1000PER) and 0.125 g of Lucirin TPO (2.5 phr to the mass of 306H and A-1000PER) were added to prepare an imprint material PNI-a9.

Example 10

(11) 1.25 g of DPEA-12, 1.25 g of KAYARAD (registered trademark) PET-30 (hereinafter abbreviated as PET30 in this specification) (manufactured by Nippon Kayaku Co., Ltd.) and 2.5 g of A-1000PER were prepared and these were mixed. To the mixture, 0.1 g of BYK-333 (2 phr to the total mass of DPEA-12, PET30, and A-1000PER) and 0.125 g of Lucirin TPO (2.5 phr to the mass of DPEA-12, PET30, and A-1000PER) were added to prepare an imprint material PNI-a10.

Example 11

(12) 2 g of PET30 and 3 g of A-1000PER were prepared and these were mixed. To the mixture, 0.1 g of BYK-333 (2 phr to the total mass of PET30 and A-1000PER) and 0.125 g of Lucirin TPO (2.5 phr to the mass of PET30 and A-1000PER) were added to prepare an imprint material PNI-a11.

Example 12

(13) 1.5 g of NK Ester A-200 (hereinafter abbreviated as A-200 in this specification) (manufactured by Shin-Nakamura Chemical Co., Ltd.), and 3 g of A-1000PER, and 0.5 g of DPEA-12 were prepared and these were mixed. To the mixture, 0.05 g of BYK-333 (1 phr to the total mass of A-200, A-1000PER, and DPEA-12) and 0.125 g of Lucirin TPO (2.5 phr to the mass of A-200, A-1000PER, and DPEA-12) were added to prepare an imprint material PNI-a12.

Example 13

(14) 1.5 g of A-200, 2.5 g of A-1000PER, and 1 g of DPEA-12 were prepared and these were mixed. To the mixture, 0.05 g of BYK-333 (1 phr to the total mass of A-200, A-1000PER, and DPEA-12) and 0.125 g of Lucirin TPO (2.5 phr to the mass of A-200, A-1000PER, and DPEA-12) were added to prepare an imprint material PNI-a13.

Example 14

(15) 1.5 g of A-200, 2 g of A-1000PER, and 1.5 g of DPEA-12 were prepared and these were mixed. To the mixture, 0.05 g of BYK-333 (1 phr to the total mass of A-200, A-1000PER, and DPEA-12) and 0.125 g of Lucirin TPO (2.5 phr to the mass of A-200, A-1000PER, and DPEA-12) were added to prepare an imprint material PNI-a14.

Example 15

(16) 1.5 g of A-200, 1.5 g of A-1000PER, and 2 g of DPEA-12 were prepared and these were mixed. To the mixture, 0.05 g of BYK-333 (1 phr to the total mass of A-200, A-1000PER, and DPEA-12) and 0.125 g of Lucirin TPO (2.5 phr to the mass of A-200, A-1000PER, and DPEA-12) were added to prepare an imprint material PNI-a15.

Example 16

(17) 1.5 g of A-200, 1 g of A-1000PER, and 2.5 g of DPEA-12 were prepared and these were mixed. To the mixture, 0.05 g of BYK-333 (1 phr to the total mass of A-200, A-1000PER, and DPEA-12) and 0.125 g of Lucirin TPO (2.5 phr to the mass of A-200, A-1000PER, and DPEA-12) were added to prepare an imprint material PNI-a16.

Example 17

(18) 1.5 g of A-200, 0.5 g of A-1000PER, and 3 g of DPEA-12 were prepared and these were mixed. To the mixture, 0.05 g of BYK-333 (1 phr to the total mass of A-200, A-1000PER, and DPEA-12) and 0.125 g of Lucirin TPO (2.5 phr to the mass of A-200, A-1000PER, and DPEA-12) were added to prepare an imprint material PNI-a17.

Example 18

(19) 1 g of A-200, 1.5 g of A-1000PER, and 2.5 g of DPEA-12 were prepared and these were mixed. To the mixture, 0.05 g of BYK-333 (1 phr to the total mass of A-200, A-1000PER, and DPEA-12) and 0.125 g of Lucirin TPO (2.5 phr to the mass of A-200, A-1000PER, and DPEA-12) were added to prepare an imprint material PNI-a18.

Example 19

(20) 1 g of A-200, 1 g of A-1000PER, and 3 g of DPEA-12 were prepared and these were mixed. To the mixture, 0.05 g of BYK-333 (1 phr to the total mass of A-200, A-1000PER, and DPEA-12) and 0.125 g of Lucirin TPO (2.5 phr to the mass of A-200, A-1000PER, and DPEA-12) were added to prepare an imprint material PNI-a19.

Comparative Example 1

(21) 5 g of 306H, 0.05 g of BYK-333 (1 phr to the mass of 306H), and 0.125 g of Lucirin TPO (2.5 phr to the mass of 306H) were prepared and these were mixed to prepare an imprint material PNI-b1.

Comparative Example 2

(22) An imprint material PNI-b2 was prepared in the same manner as Comparative Example 1 except that the amount of BYK-333 in Comparative Example 1 was changed to 0.1 g (2 phr to the mass of 306H).

Comparative Example 3

(23) An imprint material PNI-b3 was prepared in the same manner as Comparative Example 1 except that 306H in Comparative Example 1 was replaced by PET30.

Comparative Example 4

(24) An imprint material PNI-b4 was prepared in the same manner as Comparative Example 2 except that 306H in Comparative Example 2 was replaced by PET30.

Comparative Example 5

(25) 0.5 of DPEA-12, 2 g of 306H, and 2.5 g of APG-700 were prepared and these were mixed. To the mixture, 0.125 g of Lucirin TPO (2.5 phr to the total mass of DPEA-12, 306H, and APG-700) was added to prepare an imprint material PNI-b5.

Comparative Example 6

(26) An imprint material PNI-b6 was prepared in the same manner as Comparative Example 5 except that APG700 in Comparative Example 5 was replaced by A-1000PER.

(27) [Mold Release Treatment of Mold]

(28) A moth-eye pattern mold made from nickel and having a pitch of 250 nm and a height of 250 nm (manufactured by InnoX Co., Ltd.) and a silicon wafer were immersed in the solution made by diluting OPTOOL (registered trademark) DSX (manufactured by DAIKIN INDUSTRIES, LTD.) with Novec (registered trademark) HFE-7100 (hydrofluoro ether, manufactured by Sumitomo 3M Ltd.) (hereinafter abbreviated as Novec HFE-7100 in this specification) to 0.1% by mass, and were treated using a constant temperature and constant humidity device at a temperature of 90 and a humidity of 90 RH % for 1 hour. Thereafter, the treated mold and silicon wafer were rinsed with Novec HFE-7100 and then dried with air.

(29) [Photo-Imprint and Mold Release Force Test]

(30) Each imprint material obtained in Examples 1 to 19 and Comparative Examples 1 to 6 was applied onto a triacetyl cellulose film (FUJITAC (registered trademark) manufactured by FUJIFILM Corporation was used) (hereinafter abbreviated as TAC film in this specification) having a thickness of 80 m using a bar coater (Full Automatic Film Applicator KT-AB3120, manufactured by COTEC CORPORATION). The coating film on the TAC film was bonded to the mold-release treated moth-eye pattern mold by pressure with a roller. Subsequently, photo-curing of the coating film was carried out through a light exposure at 350 mJ/cm.sup.2 from the TAC film side using an electrodeless uniform radiation device (QRE-4016A, manufactured by ORC MANUFACTURING CO., LTD.). With reference to JIS Z0237, the 90 peeling test was carried out to measure a load when the cured film formed on the TAC film bonded to the surface of the mold having unevenness is completely peeled from the surface of the mold having unevenness. A load per film width of 1 cm was calculated and the obtained value was determined to be the mold release force (g/cm). The results are shown in Table 1.

(31) [Scratch Test Using Steel Wool]

(32) A scratch test using steel wool was carried out for the cured film obtained after the mold release force test. A test device manufactured by DAIEI KAGAKU SEIKI MFG. CO., LTD was used and #0000 steel wool was used. The load per unit area was set to 20.4 g/cm.sup.2 and the steel wool was reciprocated 10 times. The number of scratches after scratching operation was evaluated as indicated below. The results are shown in Table 1.

(33) 0 to 5: A

(34) 6 to 10: B

(35) 11 to 20: C

(36) 21 to 30: D

(37) 31 to 40: E

(38) [Measurement of Transmittance]

(39) Each imprint material obtained in Examples 1 to 19 and Comparative Examples 1 to 6 was applied onto a quartz substrate by spin coating. The coated film was bonded to the mold-release treated silicon wafer and the bonded sample was placed in the nano-imprint device (NM-0801HB, manufactured by MEISYO KIKO Co., Ltd). Bubbles in the coated film were removed by pressurizing to 100 N over 10 seconds and the pressure was removed over 10 seconds. A light exposure at 350 mJ/cm.sup.2 was then carried out using the electrodeless uniform radiation device. Subsequently, the silicon wafer was peeled off and a transmittance was measured for the coated film having a thickness of 5 m prepared on the quartz substrate. The average transmittance in the visible light region was measured using SHIMADSU UV-3600 (manufactured by SHIMADZU CORPORATION). The obtained results are shown in Table 1.

(40) [Fingerprint Wiping-Off Property]

(41) Each imprint material obtained in Examples 1 to 8 and Examples 12 to 19 was applied onto the TAC film having a thickness of 80 m using the bar coater (Full Automatic Film Applicator KT-AB3120, manufactured by COTEC CORPORATION). The coating film on the TAC film is bonded to the mold-release treated moth-eye pattern mold by pressure with a roller. Subsequently, photo-curing of the coated film was carried out through a light exposure at 350 mJ/cm.sup.2 from the TAC film side using the electrodeless uniform radiation device (QRE-4016A, manufactured by ORC MANUFACTURING CO., LTD.). After the film was released from the mold, the surface of the TAC film opposite to the surface on which the cured film to which the moth-eye pattern was transferred had been formed was painted in black with Supper Lacquer Spray (manufactured by Asahipen Corporation). The following finger print wiping-off test was carried out. An artificial fingerprint liquid (manufactured by TDK Corporation) was attached to the moth-eye pattern on the cured film formed on the TAC film. Subsequently, BEMCOT (registered trademark) M-1 (manufactured by Asahi Kasei Fibers Co., Ltd.) attached to the test device used in the scratch test using steel wool was reciprocated 50 times with a load of 570 g/cm.sup.2. The fingerprint wiping-off property was determined through visual observation. Wiping in this test was dry wiping. After the wiping-off test, the case where fingerprints were able to be wiped off was determined to be , whereas the case where fingerprints were not able to be wiped off, that is, the fingerprints remained was determined to be x. The results are shown in Table 2.

(42) TABLE-US-00001 TABLE 1 Mold release force Scratch resistance Transmittance (g/cm) using steel wool (%) Example 1 0.26 A 99.4 Example 2 0.27 A 99.5 Example 3 0.26 A 99.4 Example 4 0.39 B 99.5 Example 5 0.33 B 99.5 Example 6 0.35 A 99.5 Example 7 0.31 A 99.5 Example 8 0.27 A 99.5 Example 9 0.33 A 99.5 Example 10 0.29 B 99.4 Example 11 0.33 A 99.4 Example 12 0.15 A 99.5 Example 13 0.17 A 99.5 Example 14 0.18 A 99.6 Example 15 0.20 A 99.4 Example 16 0.22 A 99.5 Example 17 0.24 A 99.5 Example 18 0.18 A 99.4 Example 19 0.24 A 99.5 Comparative 0.71 D 99.5 Example 1 Comparative 0.65 D 99.4 Example 2 Comparative 0.72 E 99.4 Example 3 Comparative 0.65 E 99.4 Example 4 Comparative 1.31 D 99.5 Example 5 Comparative 0.72 D 99.5 Example 6

(43) TABLE-US-00002 TABLE 2 Fingerprint wiping-off property Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19

(44) From the results in Table 1, when the imprint materials obtained in Examples 1 to 19 were used, any of the imprint materials showed low mold release forces of 0.5 g/cm or less. The obtained cured films had high transparency in the visible light region, and had a small number of scratches formed after the scratch test using steel wool and thus the scratch resistance of the cured films was confirmed. In contrast, when the imprint materials obtained in Comparative Examples 1 to 6 were used, any of the imprint materials showed mold release forces of far greater than 0.5 g/cm. The obtained cured films had a number of scratches after the scratch test using steel wool. Form the results in Table 2, when the imprint materials obtained in Examples 1 to 8 and Examples 12 to 19 were used, it was confirmed that fingerprint was able to be wiped off from any of the cured films formed from the imprint materials.

(45) As described above, the film obtained from the imprint material of the present invention has low mold release property, has the excellent scratch resistance and fingerprint wiping-off property after the imprint, and has excellent transparency.

INDUSTRIAL APPLICABILITY

(46) The imprint material of the present invention can provide a cured film that is formed from the imprint material and that can be easily peeled from the mold. The cured film is also excellent in scratch resistance, a fingerprint wiping-off property, and transparency. Therefore, the cured film formed from the imprint material can be suitably used for products such as a solar cell, an LED device, and a display.