PHOTOSENSITIVE COMPOSITION, CURED PRODUCT, AND METHOD FOR PRODUCING CURED PRODUCT

Abstract

A photosensitive composition capable of forming a cured product with high transparency, a cured product of the photosensitive composition, and a method for producing the cured product using the photosensitive composition. In a photosensitive composition including a base component having photopolymerizability and a photopolymerization initiator, a silicone resin is used as the base component, and a phosphine oxide compound and an oxime ester compound as a photopolymerization initiator are used in combination at a specific ratio.

Claims

1. A photosensitive composition comprising a base component (A) and a photopolymerization initiator (B), wherein the base component (A) consists of a resin (A1), or a combination of the resin (A1) and a photopolymerizable monomer (A2), the resin (A1) comprises a silicone resin, when the base component does not comprise the photopolymerizable monomer (A2), the resin (A1) comprises a photopolymerizable resin (A1-1) having an ethylenically unsaturated double bond, the photopolymerization initiator (B) comprises a phosphine oxide compound (B1) and an oxime ester compound (B2) in combination.

2. The photosensitive composition according to claim 1, wherein the oxime ester compound (B2) does not comprise a compound having a peak in a wavelength range of 320 nm or longer and 400 nm or shorter in the absorption spectrum and showing a gram absorption coefficient of 10 or more at one or more wavelengths in the wavelength range of 400 nm or longer.

3. The photosensitive composition according to claim 1, wherein the oxime ester compound (B2) is a compound represented by following formula (1): ##STR00096## wherein, in the formula (1), R.sup.b1 is a hydrogen atom, a nitro group, or a monovalent organic group, R.sup.b2 and R.sup.b3 each represent an optionally substituted chain alkyl group, an optionally substituted cyclic organic group, or a hydrogen atom, R.sup.b2 and R.sup.b3 may be bonded to one another to form a ring, R.sup.b4 is a monovalent organic group, R.sup.b5 is a hydrogen atom, an optionally substituted alkyl group having 1 or more and 11 or less carbon atoms, or an optionally substituted aryl group, n1 is an integer of 0 or more and 4 or less, and n2 is 0 or 1.

4. The photosensitive composition according to claim 1, wherein a ratio of a mass W2 of the oxime ester compound (B2) is 30% by mass or more relative to sum of a mass W1 of the phosphine oxide compound (B1) and the mass W2 of the oxime ester compound (B2).

5. The photosensitive composition according to claim 1, wherein the base component (A) comprises the resin (A1) and the photopolymerizable monomer (A2).

6. The photosensitive composition according claim 1, wherein the base component (A) comprises the resin (A1), and the resin (A) comprises the silicone resin having an ethylenically unsaturated double bond.

7. A cured product of the photosensitive composition according to claim 1.

8. A method for producing a cured product comprising: shaping the photosensitive composition according to claim 1 according to the shape of the cured material to be formed; and exposing the shaped photosensitive composition.

Description

EXAMPLES

[0314] Hereinafter, the present invention is described in more detail by way of Examples, but the present invention is not limited to these Examples.

Examples 1 to 5 and Comparative Example 1

[0315] In Examples 1 to 5 and Comparative Example 1, (meth)acrylic-modified silicone resin (a silsesquioxane resin 1: a silsesquioxane resin derived from monomer composition consisting of 2-(3-triethoxysilylpropyl)carbamoyl)cyclohexane carboxylic acid (40% by mol), 3-(trimethoxysilyl)propyl methacrylate (40% by mol), and phenyltrimethoxysilane (20% by mol)) was used as the resin (A1).

[0316] In Examples 1 to 5 and Comparative Example 1, dipentaerythritol hexaacrylate was used as the photopolymerizable monomer (A2).

[0317] In Examples 1 to 5 and Comparative Example 1, the following compounds were used as the phosphine oxide compound (B1). [0318] (B1-1): Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide [0319] (B1-2): 2,4,6-trimethyulbenzoyl-diphenyl-phosphine oxide [0320] (B1-3): ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate

[0321] In Examples 1 to 5 and Comparative Example 1, compound OE1 and compound OE2 respectively having the following structure were used as the oxime ester compound (B2). The compound OE1 and the compound OE2 have a peak in a wavelength range of 320 nm or longer and 400 nm or shorter in the absorption spectrum and show a gram absorption coefficient of 10 or more at one or more wavelengths in the wavelength range of 400 nm or longer.

##STR00095##

[0322] In Examples 1 to 5 and Comparative Example 1, propylene glycol monomethyl ether was used as the solvent (S).

[0323] The photosensitive compositions of Examples 1 to 5 and Comparative Example 1 were obtained by uniformly mixing each of the components described above in the proportions shown in Table 3. Sensitivities of the obtained photosensitive compositions and light transmittances of the cured films formed using the obtained photosensitive compositions were measured according to the following methods. These measurement results are shown in Table 3.

<Method for Measuring Sensitivity>

[0324] Photosensitive compositions of Examples and Comparative Examples were spin-coated on a glass substrate, and dried at 100° C. for 2 minutes. Thereafter, light exposure using a 395 nm UV-LED exposure system was conducted, and coating films were obtained. The resulting films were immersed in an aqueous solution of TMAH (tetramethylammonium hydroxide) at a concentration of 2.38% by mass. After 2 minutes, the glass substrates were pulled out. Thereafter, thicknesses of films were measured after rinsing with pure water and drying. The case that exposure dose at which the film thickness after TMAH immersion is thicker than 90% thickness of the film before TMAH immersion is lower than 200 mJ/cm.sup.2 was judged to be Very Good, and the case that above exposure dose is 200 mJ/cm.sup.2 or higher and lower than 1 J/cm.sup.2 is judged to be Good. In addition, the case of no curing even with exposure dose of 1 J/cm.sup.2 was judged to be Poor.

<Method for Measuring Light Transmittance>

[0325] Photosensitive compositions of Examples 1 to 5 and Comparative Example 1 were spin-coated on a glass substrate, and dried at 100° C. for 2 minutes. Thereafter, light exposure of coating films using a 395 nm UV-LED exposure system was conducted, and cured films were obtained. The light transmittances of obtained films were measured using a MCPD transmittance meter (manufactured by Otsuka Electronics Co. Ltd.). Based on the light transmittances measured, the light transmittances of the cured product formed by using the photosensitive compositions of each of the Examples 1 to 5 and Comparative Example 1 were evaluated according to the following criteria.

Very Good: Light transmittance is 95% or higher.
Good: Light transmittance is 93% or higher and lower than 95%.
Poor: Light transmittance is lower than 93%.

TABLE-US-00003 TABLE 3 Ex. Comp. Ex. 1 2 3 4 5 1 Base component (A) Resin (A1) 66 66 66 66 66 66 (Type/Parts by mass) Photopolymerizable 30 30 30 30 30 30 monomer (A2) (Parts by mass) Photopolymerization Phosphine oxide B1-1/2 B1-1/1 B1-1/3 B1-2/2 B1-3/2 B1-1/4 initiator (B) compound (B1) (Type/Parts by mass) Oxime ester OE1/2 OE1/3 OE1/1 OE1/2 OE1/2 — compound (B2) OE2/2 (Type/Parts by mass) Solvent (S) 200  200  200  200  200  200  Sensitivity Very Good Very Good Very Good Very Good Very Good Good Light transmittance of the cured product Very Good Very Good Very Good Very Good Very Good Poor

[0326] According to Examples 1 to 5, it is found that the photosensitive composition including the base component (A) including the silicone resin and the photopolymerization initiator (B), and including the phosphine oxide compound (B1) and the oxime ester compound (B2) in combination gives the cured product with high transparency.

[0327] According to Comparative Example 1, it is found that the cured product with high transparency can not be formed, when the photosensitive composition including the base component (A) and the photopolymerization initiator (B), but not including a combination of the phosphine oxide compound (B1) and the oxime ester compound (B2) as the photopolymerization initiator (B) is used.