CROSSLINKING AGENT COMPOUND, PHOTOSENSITIVE COMPOSITION COMPRISING THE SAME, AND PHOTOSENSITIVE MATERIAL USING THE SAME

Abstract

The present invention relates to a crosslinking agent compound in which a terminal crosslinkable functional group is capped with a silane-based protecting group, a photosensitive composition including the same, and a photosensitive material using the same.

Claims

1. A crosslinking agent compound represented by Chemical Formula 1: ##STR00025## wherein, in the Chemical Formula 1, A is a monovalent to tetravalent aromatic functional group, j is an integer of 1 to 4, L.sub.1 and L.sub.2 are each independently an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, and R.sub.1 and R.sub.2 are each independently a silicon-containing monovalent functional group.

2. The crosslinking agent compound according to claim 1, wherein in the Chemical Formula 1, A is a divalent aromatic functional group represented by Chemical Formula 2, and j is 2: ##STR00026## wherein, in the Chemical Formula 2, L.sub.3 is a single bond, O, CO, S, SO.sub.2, C(CH.sub.3).sub.2, C(CF.sub.3).sub.2, COO, (CH.sub.2).sub.z, O(CH.sub.2).sub.zO, O(CH.sub.2).sub.z, OCH.sub.2C(CH.sub.3).sub.2CH.sub.2O, COO(CH.sub.2).sub.zOCO, or OCO(CH.sub.2).sub.zCOO, each z is independently an integer of 1 to 10, k is an integer of 1 to 3, and n and m are each independently an integer of 0 to 3.

3. The crosslinking agent compound according to claim 1, wherein in the Chemical Formula 1, L.sub.1 and L.sub.2 are each independently an alkylene group having 1 to 5 carbon atoms.

4. The crosslinking agent compound according to claim 1, wherein the crosslinking agent compound represented by the Chemical Formula 1 includes a compound represented by Chemical Formula 1-1: ##STR00027## wherein, in the Chemical Formula 1-1, A is a divalent aromatic functional group, L.sub.4 to L.sub.7 are each independently an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, and R.sub.3, R.sub.3, R.sub.4, and R.sub.4 are each independently silicon-containing monovalent functional groups.

5. The crosslinking agent compound according to claim 1, wherein in the Chemical Formula 1, the silicon-containing monovalent functional group is a functional group represented by Chemical Formula 3: ##STR00028## wherein, in the Chemical Formula 3, R.sub.5 to R.sub.7 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms.

6. (canceled)

7. A photosensitive composition comprising the crosslinking agent compound of claim 1.

8. A photosensitive composition comprising: a crosslinking agent compound represented by Chemical Formula 1; and a polymer containing one or more carboxyl groups: ##STR00029## wherein, in the Chemical Formula 1, A is a monovalent to tetravalent aromatic functional group, j is an integer of 1 to 4, L.sub.1 and L.sub.2 are each independently an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, and R.sub.1 and R.sub.2 are each independently a silicon-containing monovalent functional group.

9. The photosensitive composition according to claim 8, further comprising a compound represented by Chemical Formula 4: ##STR00030## wherein, in the Chemical Formula 4, A is a monovalent to tetravalent functional group, a is an integer of 1 to 4, b is an integer of 0 to 3, a sum of a and b is 1 to 4, L.sub.8 to L.sub.11 are each independently an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, at least one of R.sub.21 and R.sub.22 is hydrogen and the other is a silicon-containing monovalent functional group, and R.sub.23 and R.sub.24 are each independently a silicon-containing monovalent functional group.

10. The photosensitive composition according to claim 9, wherein a content of the compound represented by the Chemical Formula 4 is 0.001 parts by weight to 10 parts by weight based on 100 parts by weight of the crosslinking agent compound represented by the Chemical Formula 1.

11. The photosensitive composition according to claim 10, further comprising a compound represented by Chemical Formula 5: ##STR00031## wherein, in the Chemical Formula 5, R.sub.5 to R.sub.7 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms.

12. The photosensitive composition according to claim 8, wherein the polymer containing one or more carboxyl groups includes a first polyamic acid (co)polymer containing a repeating unit represented by Chemical Formula 6, and a second polyamic acid (co)polymer containing a repeating unit represented by Chemical Formula 7: ##STR00032## wherein, in the Chemical Formulaes 6 and 7, X.sub.3 and X.sub.6 are each independently a tetravalent organic group represented by Chemical Formula 8: ##STR00033## wherein, in the Chemical Formula 8, R.sub.13 to R.sub.18 are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, L is any one selected from a single bond, O, CO, COO, S, SO, SO.sub.2, CR.sub.19R.sub.20, (CH.sub.2).sub.z, O(CH.sub.2).sub.zO, COO(CH.sub.2).sub.zOCO, CONH, and phenylene, R.sub.19 and R.sub.20 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms, z is an integer of 1 to 10, and Y.sub.3 is a divalent organic group represented by Chemical Formula 9: ##STR00034## wherein, in the Chemical Formula 9, T is a tetravalent organic group represented the Chemical Formula 8, D.sub.1 and D.sub.2 are each independently any one selected from an alkylene group having 1 to 20 carbon atoms, a hetero-alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 2.0 carbon atoms, and a heteroarylene group having 2 to 20 carbon atoms, and Y.sub.6 is a divalent organic group represented by Chemical Formula 10: ##STR00035## wherein, in the Chemical Formula 10, A is a group 15 element selected from the group of nitrogen (N), phosphorus (P), arsenic (As), tin (Sn), and bismuth (Bi), R is hydrogen or an alkyl having 1 to 10 carbon atoms, a is an integer 1 to 3, and at least one of Z.sub.1 to Z.sub.4 is nitrogen and the rest are carbon.

13. A photosensitive material comprising a cured product of the photosensitive composition of claim.

14. The photosensitive material according to claim 13, wherein the cured product of the photosensitive composition includes a combination of a crosslinking agent compound represented by Chemical Formula 11 and a polymer containing one or more carboxyl groups: ##STR00036## wherein, in the Chemical Formula 11, A is a monovalent to tetravalent aromatic functional group, j is an integer of 1 to 4, and L.sub.1 and L.sub.2 are each independently an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms.

15. A photosensitive material comprising a cured product of the photosensitive composition of claim 8.

16. The photosensitive composition according to claim 12, wherein the first polyamic acid (co)polymer further includes one or more repeating units selected from the group consisting of a repeating unit represented by Chemical Formula 12 and a repeating unit represented by Chemical Formula 13: ##STR00037## wherein, in the Chemical Formulae 12 and 13, at least one of R.sub.9 and R.sub.10 is an alkyl group having 1 to 10 carbon atoms and the other is hydrogen, X.sub.1 to X.sub.2 are each independently a tetravalent organic group represented by the Chemical Formula 8, and Y.sub.1 to Y.sub.2 are each independently a divalent organic group represented by the Chemical Formula 9.

17. The photosensitive composition according to claim 12, wherein the second polyamic acid (co)polymer further includes one or more repeating units selected from the group consisting of a repeating unit represented by Chemical Formula 14 and a repeating unit represented by Chemical Formula 15: ##STR00038## wherein, in the Chemical Formulae 14 and 15, at least one of R.sub.11 and R.sub.12 is an alkyl group having 1 to 10 carbon atoms and the other is hydrogen, X.sub.4 to X.sub.5 are each independently a tetravalent organic group represented by the Chemical Formula 8, and Y.sub.4 to Y.sub.5 are each independently a divalent organic group represented by the Chemical Formula 10.

Description

EXAMPLES

Preparation of Photosensitive Composition and Photosensitive Material

EXAMPLE

Example 1

Preparation of Photosensitive Composition

[0141] 5.0 g (13.3 mmol) of diamine DA1 represented by Chemical Formula A below was completely dissolved in 71.27 g of anhydrous N-methyl pyrrolidone (NMP). Then, 2.92 g (13.03 mmol) of 1,3-dimethyl-cyclobutane-1,2,3,4-tetracarboxylic dianhydride (DMCBDA) was added to the solution under an ice bath, and then stirred at room temperature for about 16 hours to prepare polymer P-1. The molecular weight of the polymer P-1 was measured by GPC, and as a result, the number average molecular weight (Mn) was 15,500 g/mol and the weight average molecular weight (Mw) was 31,000 g/mol. In addition, the monomer structure of the polymer P-1 was determined by the equivalence ratio of the monomer used, the ratio of the intramolecular imide structure was 50.5%, and the ratio of the amic acid structure was 49.5%.

##STR00023##

[0142] 19.743 g (0.099 mol) of diamine DA2 represented by Chemical Formula B below was completely dissolved in 225.213 g of anhydrous N-methyl pyrrolidone (NMP). Then, 20.0 g (0.092 mol) of pyromellitic dianhydride (PMDA) was added to the solution under an ice bath, and then stirred at room temperature for about 16 hours to prepare polymer Q-1. The molecular weight of the polymer Q-1 was measured by GPC, and as a result, the weight average molecular weight (Mw) was 27,000 g/mol.

##STR00024##

[0143] 10 g of the polymer P-1 and 10 g of the polymer Q-1 prepared as described above were added to 12.4 g of NMP and 7.6 g of n-butoxyethanol (weight ratio of 8:2) to obtain a 5 wt % solution. Then, as a crosslinking agent, the crosslinking agent obtained in Preparation Example 1 was added to the solution at 5 wt % based on the total solution, and then stirred at 25 C. for 16 hours. The obtained solution was filtered under pressure through a filter made of poly(tetrafluorene ethylene) having a pore size of 0.1 m to produce a photosensitive composition.

Example 2

Preparation of Photosensitive Composition

[0144] A photosensitive composition was prepared in the same manner as in Example 1, except that the crosslinking agent obtained in Preparation Example 1 was added at 10 wt % based on the total solution.

Example 3

Preparation of Photosensitive Composition

[0145] A photosensitive composition was prepared in the same manner as in Example 1, except that the crosslinking agent obtained in Preparation Example 2 was added instead of the crosslinking agent obtained in Preparation Example 1.

Example 4

Preparation of Photosensitive Composition

[0146] A photosensitive composition was prepared in the same manner as in Example 2, except that the crosslinking agent obtained in Preparation Example 2 instead of the crosslinking agent obtained in Preparation Example 1 was added at 10 wt % based on the total solution.

Comparative Example 1

Preparation of Photosensitive Composition

[0147] A photosensitive composition was prepared in the same manner as in Example 1, except that N4,N4,N4,N4-tetrakis(2-hydroxyethyl)biphenyl-4,4-dicarboxamide of Comparative Preparation Example 1 was added instead of the crosslinking agent obtained in Preparation Example 1.

[0148] The composition of the photosensitive compositions of Examples and Comparative Example above are summarized in Table 1 below.

TABLE-US-00001 TABLE 1 First polymer Second polymer Mixing Crosslinking agent Added Added weight ratio of Added amount amount first and second amount Type (g) Type (g) polymers Type (wt %) Example 1 P-1 10 Q-1 10 20:80 Preparative 5 Example 1 Example 2 P-1 10 Q-1 10 20:80 Preparative 10 Example 1 Example 3 P-1 10 Q-1 10 20:80 Preparative 5 Example 2 Example 4 P-1 10 Q-1 10 20:80 Preparative 10 Example 2 Comparative P-1 10 Q-1 10 20:80 Comparative 5 Example 1 Preparative Example 1

[0149] <Experimental Example>

[0150] 1) Storage Stability

[0151] For the photosensitive compositions prepared in the examples and the comparative example, the initial viscosity and the viscosity after storage at room temperature for 30 days were measured, respectively, and the change rate of viscosity was determined by the following Equation 1.

[0152] The viscosity of the photosensitive composition was measured according to the torque using a Brookfield viscometer with an RV-7 spindle at a temperature of 25 C. and a rotational speed of 0.5 rpm.

Change rate of viscosity (%)=(Viscosity of photosensitive composition after storage for 30 days at room temperatureViscosity of original photosensitive composition)/Viscosity of original photosensitive composition*100. (1)

[0153] The smaller the change rate of viscosity calculated by Equation 1, the better the storage stability.

[0154] 2) Solubility

[0155] The crosslinking agents respectively used in the photosensitive compositions of the examples and the comparative example were added to a solvent (-butyrolactone) so as to satisfy the addition amount of crosslinking agent shown in Table 1, and then mixed for 10 seconds to prepare a mixed solution. The transparency of the mixed solution was visually confirmed and the solubility level was evaluated under the following criteria.

[0156] In the measurement results, if the mixed solution was transparent, it was evaluated as excellent, and if the mixed solution was opaque, it was evaluated as inferior. The results are shown in Table 2 below.

TABLE-US-00002 TABLE 2 Storage stability (%) Solubility Example 1 2.9 Excellent Example 2 1.5 Excellent Example 3 2.3 Excellent Example 4 1.4 Excellent Comparative Example 1 more than 8 Inferior

[0157] As shown in Table 2, as the photosensitive compositions of Examples 1 to 4 use the crosslinking agent compounds having specific structures synthesized in Preparation Examples 1 and 2, the change rate in viscosity of the photosensitive composition has been found to be 2.9% or less, which exhibits excellent storage stability, and simultaneously exhibits excellent solubility.

[0158] On the other hand, as the photosensitive composition of Comparative Example 1 uses the crosslinking agent compound of Comparative Preparation Example 1 containing no silicon-containing monovalent functional group, not only is the storage stability very inferior but also the solubility is inferior, as compared with the photosensitive compositions of the examples above.