KR20150005524A - Partial hydrolysis condensation product, ink-repellent agent, negative-type photosensitive resin composition, cured film, partition wall, and optical element - Google Patents

Abstract

A partial hydrolysis condensation product of a hydrolyzable silane compound, a repellent ink capable of selectively imparting good ink repellency to the upper surface of a partition wall, and an excellent ink repellency on the upper surface of the partition even in exposure at a low exposure dose, A negative-working photosensitive resin composition in which the ink does not remain well in the dot, a cured film and barrier ribs which can maintain good ink-property even after UV / O ₃ irradiation treatment, and an optical element Lt; / RTI > A first hydrolyzable silane compound having a fluoroalkylene group and / or a fluoroalkyl group and a hydrolyzable group and having no mercapto group, a first hydrolyzable silane compound having a mercapto group and a hydrolyzable group and having no fluoroalkylene group and fluoroalkyl group A partial hydrolysis condensation product of a mixture comprising a second hydrolysable silane compound.

Description

PARTIAL HYDROLYSIS CONDENSATION PRODUCT, INK-REPELLENT AGENT, NEGATIVE-TYPE PHOTOSENSITIVE RESIN COMPOSITION, CURED FILM, PARTITION WALL, AND OPTICAL ELEMENT }

The present invention relates to a partially hydrolyzed condensation product, and a repelling ink composition, a negative photosensitive resin composition, a cured film, a partition wall and an optical element using the same.

In an organic EL (Electro-Luminescence) element, there is a method of pattern printing an organic layer such as a light emitting layer by an ink jet (IJ) method. In this method, a partition wall is formed along the contour of the dot, ink containing the material of the layer to be formed is injected into the partition, and the desired pattern film is formed by drying and / or heating the ink.

In the above method, in order to prevent the color mixture of the ink between adjacent dots and to uniformly apply the ink in the dots, the upper surface of the barrier should have ink-repellency and the side of the barrier should have inkphilic property. That is, the upper surface of the partition needs to have ink repellency selectively.

The partition is patterned by photolithography using, for example, a photosensitive resin composition.

For example, when the photosensitive resin composition contains a repellent ink having a small surface free energy, the repellent property of the repellent agent to the air component side (On the upper surface side of the coating film), it is possible to selectively impart ink repellency to the upper surface of the obtained barrier rib. In this method, the top surface transfer property of the repelling agent is important. It is also important that the ink does not remain in the dot after development.

In the organic EL element, the organic layer such as the light emitting layer is easily deteriorated by the residue of the photosensitive resin composition remaining in the dots after development. Therefore, in order to remove development residues in the dots, UV (ultraviolet) / O ₃ (ozone) irradiation treatment is generally performed on the whole surface of the substrate before ink injection. It is important that the ink repellency of the upper surface of the partition wall is maintained well even after the UV / O ₃ irradiation treatment.

Patent Document 1 discloses that the surface free energy is sufficiently small and the partition wall to be formed has good ink repellency on the upper surface and also has fluorine-hydrolyzable property such that even when subjected to UV / O ₃ irradiation treatment, A negative-type photosensitive resin composition comprising a hydrolysis-condensation product of a silane compound.

International Publication No. 2010/013816

In forming barrier ribs by the photolithography method, reduction of exposure time is demanded from the viewpoint of reduction of manufacturing time and manufacturing cost. From the viewpoint of shortening the exposure time, it is preferable that the photosensitive resin composition for forming the barrier rib is capable of being exposed at a lower exposure dose.

An object of the present invention is to provide a partially hydrolyzed condensate of a hydrolyzable silane compound excellent in ink repellency and a repellent agent comprising the condensate and capable of selectively imparting good ink repellency to the upper surface of a partition wall .

The present invention also provides a negative-working photosensitive resin composition capable of selectively imparting good ink repellency to the upper surface of a partition even when exposure is performed at a low exposure dose, A cured film and a partition wall formed from a negative-type photosensitive resin composition and capable of satisfactorily maintaining the ink-repellency even after UV / O ₃ irradiation treatment, and a cured film and a partition wall having the cured film and the partition wall, The present invention also provides an optical element comprising:

The present invention provides a partial hydrolysis and condensation product, a repelling ink, a negative photosensitive resin composition, a cured film, a partition wall and an optical element having the constitutions of [1] to [15]

[1] A process for producing a fluorine-containing silane compound, which comprises reacting a first hydrolyzable silane compound having a fluoroalkylene group and / or a fluoroalkyl group and a hydrolyzable group,

A partial hydrolysis condensation product of a mixture comprising a mercapto group and a second hydrolyzable silane compound having a hydrolyzable group and not having a fluoroalkylene group and a fluoroalkyl group.

[2] The partially hydrolyzed condensate according to [1], wherein the content of the second hydrolyzable silane compound in the mixture is 0.125 to 18 moles per 1 mole of the first hydrolyzable silane compound.

[3] The partially hydrolyzed condensate according to [1] or [2], wherein the first hydrolyzable silane compound is a compound represented by the following formula (c-1)

(AR ^F1 ) _a -Si (R ^H1 ) _b X ¹ _(4-ab) (c-1)

(In the formula (c-1), each symbol is as follows.

R ^F1 represents a divalent organic group having 1 to 16 carbon atoms which may contain an etheric oxygen atom and contains at least one fluoroalkylene group.

R ^H1 represents a hydrocarbon group having 1 to 6 carbon atoms.

a is 1 or 2, b is 0 or 1, and a + b is 1 or 2.

A is a fluorine atom or a group represented by the following formula (I).

-Si (R ^H2 ) _b X ² _(3-b) (I)

And R ^H2 represents a hydrocarbon group having 1 to 6 carbon atoms.

b is 0 or 1;

X ¹ and X ² represent a hydrolyzable group.

When a plurality of X < ¹ > s exist, they may be different from or the same as each other.

When a plurality of X < ² > exist, they may be different from or the same as each other.

When a plurality of AR ^F1 exist, they may be different from each other or may be the same.)

[4] The partially hydrolyzed condensate according to [3], wherein the first hydrolyzable silane compound is a compound represented by the following formula (c-1a).

_{^{DR F2 -Q 1 -SiX 1 3 ···}} (c-1a)

(Wherein each symbol in the formula (c-1a) is as follows.

And R ^F2 is a perfluoroalkylene group which may contain an etheric oxygen atom having 2 to 15 carbon atoms.

D is a fluorine atom or a group represented by the following formula (Ia).

-Q ² -SiX ² ₃ (Ia)

X ¹ and X ² represent a hydrolyzable group.

The three X < ^{1 > s} may be mutually different or the same.

The three X < ^{2 > s} may be mutually different or the same.

Q ¹ and Q ^{2 each} represent a divalent organic group containing no fluorine atom having 1 to 10 carbon atoms.

[5] The partially hydrolyzed condensate according to any one of [1] to [4], wherein the second hydrolyzable silane compound is a compound represented by the following formula (c-2)

(HS-Q ³ ) _p -Si (R ^H3 ) _q X ³ _(4-pq) (c-2)

(In the formula (c-2), symbols are as follows.

Q ³ represents a divalent organic group having 1 to 10 carbon atoms and not containing a fluorine atom.

R ^H3 represents a hydrocarbon group having 1 to 6 carbon atoms.

X ³ represents a hydrolyzable group.

p is 1 or 2, q is 0 or 1, and p + q is 1 or 2.

When a plurality of HS-Q ³ exist, they may be the same or different.

X < ³ > are present, they may be the same or different from each other.)

[6] The partially hydrolyzed condensate according to any one of [1] to [5], wherein the mixture further comprises a third hydrolyzable silane compound represented by the following formula (c-3)

SiX ⁴ ₄ (c-3)

(In the formula (c-3), X ⁴ represents a hydrolyzable group, and four X ⁴ may be the same or different from each other.)

[7] The partial hydrolysis-condensation product according to any one of [1] to [6], wherein the mixture further comprises a fourth hydrolyzable silane compound represented by the following formula (c-4)

(YQ ⁴ ) _g -Si (R ^H4 ) _h X ⁵ _(4-gh) (c-4)

(The symbols in the formula (c-4) are as follows.

Y represents a group having an ethylenic double bond.

Q ⁴ represents a divalent organic group containing no fluorine atom having 1 to 6 carbon atoms.

R ^H4 represents a hydrocarbon group having 1 to 6 carbon atoms.

X < ⁵ > represents a hydrolyzable group.

g is 1 or 2, h is 0 or 1, and g + h is 1 or 2.

When a plurality of YQ ⁴ exist, they may be the same or different.

When a plurality of X < ⁵ > s exist, they may be the same or different.)

[8] The partial hydrolysis-condensation product according to any one of [1] to [7], wherein the mixture further comprises a fifth hydrolyzable silane compound represented by the following formula (c-5)

^{_{(R H5) j -SiX 6 (}} 4-j) ··· (c-5)

(In the formula (c-5), each symbol is as follows.

R ^H5 represents a hydrocarbon group having 1 to 6 carbon atoms.

X ⁶ represents a hydrolyzable group.

j is 2 or 3;

When a plurality of R ^H5 exist, they may be the same or different.

When a plurality of X < ⁶ > s exist, they may be the same or different.)

[9] The partial hydrolysis-condensation product according to any one of [1] to [8], wherein the fluorine atom content is 10 to 55 mass%.

[10] The partial hydrolysis and condensation product according to any one of [1] to [9], wherein the number average molecular weight is 500 or more and less than 10,000.

[11] A foot ink composition comprising the partially hydrolyzed condensate according to any one of [1] to [10].

[12] A negative-type photosensitive resin composition comprising the ink-repellent agent, the alkali-soluble resin having photo-curability, or the alkali-soluble monomer (A), the photopolymerization initiator (B) and the solvent (D)

[13] The negative-working photosensitive resin composition according to the above-mentioned [12], further comprising a crosslinking agent (E), wherein the crosslinking agent (E) is a compound having two or more ethylenic double bonds in one molecule and no acidic group .

[14] A cured film obtained by applying the negative-type photosensitive resin composition according to [12] or [13] to a substrate surface and exposing the substrate.

[15] A barrier rib comprising the cured film according to the above [14].

[16] An optical element comprising a plurality of dots and the partition described in [15] above.

[17] The optical element according to the above [16], wherein the partition is a partition for partitioning the plurality of dots, or a partition for pattern printing by a conductive pattern or a semiconductor pattern by an inkjet method.

The partially hydrolyzed and condensed product of the hydrolyzable silane compound of the present invention is excellent in ink repellency and a repellent agent comprising the condensate can selectively impart good ink repellency to the upper surface of the partition wall.

In addition, the negative-working photosensitive resin composition of the present invention contains the condensate as a repelling ink agent, and even when exposure is performed at a low exposure dose, it is possible to selectively impart good ink repellency to the upper surface of the partition, It has a property that the ink for ink-repellent does not remain well.

The cured film and the partition formed from the negative-working photosensitive resin composition of the present invention maintain favorable ink repellency even after the UV / O ₃ irradiation treatment, and the optical element having the cured film and the partition wall has the dot It is possible to uniformly apply the ink to the dots.

1A is a process diagram schematically showing a method of manufacturing a barrier rib made of a cured film according to the present invention.
Fig. 1B is a process diagram schematically showing a method of manufacturing a barrier rib made of a cured film according to the present invention.
1C is a process diagram schematically showing a method of manufacturing a barrier rib made of a cured film according to the present invention.
FIG. 1D is a process diagram schematically showing a method of manufacturing a barrier rib made of a cured film according to the present invention.
FIG. 1E is a process diagram schematically showing a method for manufacturing a barrier rib made of a cured film according to the present invention.
2A is a process diagram schematically showing a method for producing a patterned film using a barrier rib made of a cured film according to the present invention.
FIG. 2B is a process diagram schematically showing a method of manufacturing a patterned film using a barrier rib made of a cured film according to the present invention. FIG.

In the present specification, the term "(meth) acryloyl group" is a general term for "methacryloyl group" and "acryloyl group". (Meth) acrylate, (meth) acrylamide, and (meth) acrylic resin.

In the present specification, the group represented by the formula (x) may be simply referred to as a group (x).

In the present specification, a compound represented by the formula (y) may be simply referred to as a compound (y).

Here, the expressions (x) and (y) represent arbitrary expressions.

In the present specification, the term "side chain" refers to a group other than a hydrogen atom or a halogen atom, which is bonded to the carbon atom constituting the main chain in the polymer in which the repeating unit constitutes the main chain.

Refers to a component forming a cured film to be described later among the components contained in the photosensitive resin composition, and the photosensitive resin composition is heated at 140 占 폚 for 24 hours to obtain a residue from which the solvent has been removed . In addition, the total solid content can also be calculated from the amount of injection.

In the present specification, the film coated with the photosensitive resin composition is referred to as a " coated film ", the film obtained by drying it is referred to as a " dried film "

In the present specification, the " upper surface " of the partition wall is used as a term indicating only the trademark surface except for the side surface of the partition wall. Therefore, the " upper surface " of the partition does not include the side surface of the partition.

In this specification, the term " ink " includes liquids having optical and / or electrical functions injected into dots.

The term " ink " in this specification includes the whole ink used for pattern printing by the ink jet (IJ) method.

In recent years, various components can be pattern printed by the IJ method in an optical element such as an organic EL element, a color filter of a liquid crystal element, and an organic TFT (Thin Film Transistor) array.

The term " ink " in this specification includes an ink of a raw material used for such a use.

The term " ink repellency " in the present specification means both of water repellency and oil repellency due to the property of repelling the ink. The ink repellency can be evaluated, for example, by the contact angle when the ink is dripped.

The term " dot " in this specification refers to a minimum light-modulating area in an optical element. In an optical element such as an organic EL element, a color filter of a liquid crystal element, and an organic TFT array, one dot = one pixel in the case of monochrome display and three dots (R (Green), B (blue), etc.) = 1 pixel.

The " exposure amount " in this specification is an exposure amount per unit area (mJ / cm 2). Since the light used for exposure has an illuminance distribution and there is also a time variation of illuminance, it is difficult to strictly obtain the exposure amount. In the present specification, the exposure amount is obtained from the product of exposure power (exposure output) and exposure time.

Exposure can be performed by dividing the same point into a plurality of circuits. At this time, a plurality of exposure conditions may or may not be the same. Quot; exposure amount " is the sum of exposure amounts of exposure for a plurality of times.

Hereinafter, embodiments of the present invention will be described. In the present specification, unless otherwise specified,% represents mass%.

[Partial hydrolysis condensation product]

The partial hydrolyzed condensate of the present invention is a partially hydrolyzed condensate which contains a first hydrolyzable silane compound having a fluoroalkylene group and / or a fluoroalkyl group and a hydrolyzable group and having no mercapto group, a first hydrolyzable silane compound having a mercapto group and a hydrolyzable group, And a second hydrolyzable silane compound having no fluoroalkyl group (hereinafter, also referred to as a hydrolyzable silane compound mixture).

The partial hydrolyzed condensate of the present invention is usually a composition having a molecular weight distribution.

In addition, the hydrolyzable silane compound mixture of the present invention contains a first hydrolyzable silane compound and a second hydrolyzable silane compound as essential components, and optionally includes a third to fifth hydrolyzable silane compounds described later. In addition, hydrolyzable silane compounds other than the first to fifth hydrolyzable silane compounds may be included.

The partial hydrolyzed condensate of the present invention is preferably used as a foot ink composition. If that contained as the foot print on the negative-type photosensitive resin compositions, even when subjected to exposure at a low exposure amount, it is possible to give the optionally good ink repellency on the upper surface of the partition wall, and, even after the UV / O ₃ irradiation treatment, Has good ink-retaining property, and has a property that the ink does not remain well in the dot.

The partial hydrolyzed condensate of the present invention is preferably used as a depigmenting agent but can be used for other purposes.

The partial hydrolyzed condensate of the present invention is preferably used for a negative photosensitive resin composition, but can also be used for a positive photosensitive resin composition.

The photosensitive resin composition comprising the partially hydrolyzed condensate of the present invention as a depigmenting agent is preferably used as a composition for forming a barrier rib in the pattern formation by the IJ method of various components of the optical element.

The content of the fluorine atom in the partial hydrolysis and condensation product of the present invention (hereinafter also referred to as a fluorine atom content) is, ink repellency, and within the UV / O ₃ properties and the hydrolyzable silane compound that mixture commercially available in the Province , It is preferably 10 to 55 mass%, more preferably 12 to 40 mass%, and particularly preferably 15 to 30 mass%.

(First hydrolyzable silane compound)

The first hydrolyzable silane compound is a compound having a fluoroalkylene group and / or a fluoroalkyl group and a hydrolyzable group and having no mercapto group.

Examples of the hydrolyzable group include groups in which at least one hydrogen of an alkoxy group, a halogen atom, an acyl group, an isocyanate group, an amino group, and an amino group is substituted with an alkyl group. An alkoxy group having 1 to 4 carbon atoms and a halogen atom (for example, an alkoxy group having 1 to 4 carbon atoms) are preferable because the hydroxyl group (silanol group) is formed by a hydrolysis reaction and the reaction for condensation reaction between molecules to form a Si- More preferably a methoxy group, an ethoxy group and a chlorine atom, and a methoxy group and an ethoxy group are particularly preferable.

The first hydrolyzable silane compound may be used alone or in combination of two or more.

By using the first hydrolyzable silane compound containing a fluoroalkylene group and / or a fluoroalkyl group, ink repellency can be imparted to the partial hydrolysis condensation product of the present invention. In addition, good ink repellency is maintained even after UV / O ₃ irradiation treatment.

By using the first hydrolyzable silane compound, the negative type photosensitive resin composition containing the partial hydrolyzed condensate of the present invention as a releasing agent can selectively impart good ink repellency to the upper surface of the cured partition wall . In addition, good ink repellency is maintained even after UV / O ₃ irradiation treatment.

Further, in order to further manifest the effect of the first hydrolyzable silane compound, it is more preferable that the first hydrolyzable silane compound has a fluoroalkyl group, a perfluoroalkylene group or a perfluoroalkyl group, and a perfluoroalkyl group Is particularly preferable. The first hydrolyzable silane compound preferably has a perfluoroalkyl group containing an etheric oxygen atom.

That is, the most preferable compound as the first hydrolyzable silane compound is a compound having a perfluoroalkyl group and / or a perfluoroalkyl group containing an ether oxygen atom.

As the first hydrolyzable silane compound, a compound represented by the following formula (c-1) is preferable.

(AR ^F1 ) _a -Si (R ^H1 ) _b X ¹ _(4-ab) (c-1)

In the formula (c-1), each symbol is as follows.

R ^F1 represents a divalent organic group having 1 to 16 carbon atoms which may contain an etheric oxygen atom and contains at least one fluoroalkylene group.

R ^H1 represents a hydrocarbon group having 1 to 6 carbon atoms.

a is 1 or 2, b is 0 or 1, and a + b is 1 or 2.

A is a fluorine atom or a group represented by the following formula (I).

-Si (R ^H2 ) _b X ² _(3-b) (I)

And R ^H2 represents a hydrocarbon group having 1 to 6 carbon atoms.

b is 0 or 1;

X ¹ and X ² are hydrolyzable groups.

When a plurality of X < ¹ > s exist, they may be different from or the same as each other.

When a plurality of X < ² > exist, they may be different from or the same as each other.

When a plurality of AR ^F1 exist, they may be different from each other or the same.

The compound (c-1) is a fluorinated hydrolyzable silane compound having one or two hydrolyzable silyl groups having two or three functionalities.

R ^H1 and R ^H2 are hydrocarbon groups of 1 to 6 carbon atoms, more preferably hydrocarbon groups of 1 to 3 carbon atoms, and most preferably a methyl group.

In the formula (c-1), it is more preferable that a is 1 and b is 0 or 1.

X < ^{1 >} and X < ² > are hydrolyzable groups bonded to silicon atoms, and preferred embodiments thereof are the same as described above.

As the first hydrolyzable silane compound, a compound represented by the following formula (c-1a) is particularly preferable.

_{^{DR F2 -Q 1 -SiX 1 3 ···}} (c-1a)

In the formula (c-1a), each symbol is as follows.

And R ^F2 is a perfluoroalkylene group which may contain an etheric oxygen atom having 2 to 15 carbon atoms.

D is a fluorine atom or a group represented by the following formula (Ia).

-Q ² -SiX ² ₃ (Ia)

X ¹ and X ² are hydrolyzable groups.

The three X < ^{1 > s} may be mutually different or the same.

The three X < ^{2 > s} may be mutually different or the same.

Q ¹ and Q ^{2 each} represent a divalent organic group containing no fluorine atom having 1 to 10 carbon atoms.

When D in the formula (c-1a) is a fluorine atom, R ^F2 represents a perfluoroalkylene group having 4 to 8 carbon atoms and a perfluoroalkylene group containing an etheric oxygen atom having 4 to 10 carbon atoms An alkylene group is preferable, a perfluoroalkylene group having 4 to 8 carbon atoms is more preferable, and a perfluoroalkylene group having 6 carbon atoms is particularly preferable.

When D in the formula (c-1a) is the group (Ia), R ^F2 contains a perfluoroalkylene group having 3 to 15 carbon atoms and an etheric oxygen atom having 3 to 15 carbon atoms , And perfluoroalkylene groups having 4 to 6 carbon atoms are particularly preferable.

When R ^F2 is the group exemplified above, the partial hydrolyzed condensate of the present invention has good ink repellency and UV / O ₃ properties, and compound (c-1a) has excellent solubility in solvents.

The structure of R ^F2 is not particularly limited. ^Examples of the structure of R ^{F2 include} a linear structure, a branched structure, a cyclic structure, and a structure having a partially cyclic structure, and a linear structure is preferable.

Specific examples of R ^{F2 include} the following groups.

Formula (c-1a) of Q ¹ and formula (Ia) is in Q ² is, R ^F2 and the hydrolyzable silyl group (-SiX ¹ ₃₎ or a divalent organic group that connects (-SiX ² _3), respectively, the carbon And is a divalent organic group containing no fluorine atom having 1 to 10 atoms.

Q ¹ and Q ² are each a combination of - (CH ₂ ) _i 1 - (i 1 is an integer of 1 to 5, when Si is bonded to the right hand and R ^F2 is bonded to the left hand, _{), -CH 2 O (CH 2} ) i2 - (i2 is an integer of _{1 ~ 4), -SO 2 NR} 1 - (CH 2) i3 - (R 1 is a hydrogen atom, a methyl group, or ethyl group, i3 is 1 It is an integer of 1-4, R ¹ and (CH ₂₎ the sum of the number of carbon atoms _i3 is an integer of less than 4), - (C = O ) -NR 1 - (CH 2) i4 - (R 1 is as above identical and, i4 is preferably a group represented by an integer from ¹ ~ 4, R 1 and (CH ₂₎ the sum of the number of carbon atoms in the _i4 is an integer of less than 4). As Q ¹ and Q ² , - (CH ₂ ) _{i 1} -, in which i ¹ is an integer of 2 to 4, is more preferable, and - (CH ₂ ) ₂ - is particularly preferable.

When R ^F2 is a perfluoroalkylene group containing no etheric oxygen atom, Q ¹ and Q ² are preferably groups represented by - (CH ₂ ) _i1 -. i1 is more preferably an integer of 2 to 4, and i1 is particularly preferably 2.

When R ^F2 is a perfluoroalkyl group containing an etheric oxygen atom, roneun Q ¹ and _{^{Q 2, - (CH 2)}} i1 -, -CH 2 O (CH 2) i2 -, -SO 2 NR 1 - ( CH _{2) i3} -, and ^{- (C = O) -NR 1} - (CH 2) i4 - groups are preferred as shown. In this case also, - (CH ₂ ) _{i 1} - is more preferable, i 1 is more preferably an integer of 2 to 4, and i 1 is particularly preferably 2.

When D is a fluorine atom, specific examples of the compound (c-1a) include the following compounds.

When D is the group (Ia), specific examples of the compound (c-1a) include the following compounds.

In the present invention, among the compounds (c-1a), F (CF ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃ And the _{F (CF 2) 3 OCF (} CF 3) CF 2 O (CF 2) 2 CH 2 CH 2 Si (OCH 3) 3 is particularly preferred.

The content of the first hydrolyzable silane compound in the hydrolyzable silane compound mixture is preferably 10 to 55% by mass, more preferably 12 to 40% by mass, in the partial hydrolyzed condensate obtained from the mixture, , And particularly preferably from 15 to 30 mass%. If the ratio of the content of the first hydrolyzable silane compound is not less than the lower limit of the above range, good ink repellency can be imparted to the upper surface of the cured film, and if the ratio is less than the upper limit value, compatibility with other components becomes good .

(Second hydrolyzable silane compound)

The second hydrolyzable silane compound is a compound having a mercapto group and a hydrolyzable group and not having a fluoroalkylene group and a fluoroalkyl group.

As the hydrolyzable group, the same group as the hydrolyzable group of the first hydrolyzable silane compound can be used.

The second hydrolyzable silane compound may be used alone or in combination of two or more.

By using the second hydrolyzable silane compound containing a mercapto group, the negative type photosensitive resin composition containing the partially hydrolyzed condensate of the present invention as a releasing agent can be exposed at a low exposure dose . It is considered that the mercapto group in the second hydrolyzable silane compound has chain transferability and easily attaches to an ethylenic double bond or the like having an alkali-soluble resin or an alkali-soluble monomer (A) to be described later, thereby promoting photo-curing.

In addition, the second hydrolyzable silane compound having a mercapto group has a pKa of about 10, and is easy to be deprotonated, that is, dissociated in an alkali solution. Here, pKa = -log ₁₀ Ka, where Ka represents the acid dissociation constant. Therefore, it is considered that the mercapto group enhances the alkali solubility of the negative type photosensitive resin composition containing the partial hydrolyzed condensate of the present invention as the ink repellent agent upon development.

As the second hydrolyzable silane compound, a compound represented by the following formula (c-2) is preferable.

(HS-Q ³ ) _p -Si (R ^H3 ) _q X ³ _(4-pq) (c-2)

In the formula (c-2), each symbol is as follows.

Q ³ represents a divalent organic group having 1 to 10 carbon atoms and not containing a fluorine atom.

R ^H3 represents a hydrocarbon group having 1 to 6 carbon atoms.

X ³ represents a hydrolyzable group.

p is 1 or 2, q is 0 or 1, and p + q is 1 or 2.

When a plurality of HS-Q ³ exist, they may be the same or different.

When a plurality of X < ³ > exist, they may be the same or different from each other.

As X ³ , the same groups as X ¹ and X ² are used.

As Q ³ , an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 5 carbon atoms is more preferable, and an alkylene group having 1 to 3 carbon atoms is particularly preferable.

As R ^H3 , the same group as R ^H1 is used.

Concrete examples of the compound (c-2) there may be mentioned _{HS- (CH 2) 3 -Si (} OCH 3) 3, HS- (CH 2) 3 -Si (CH 3) (OCH 3) 2 .

The content of the second hydrolyzable silane compound in the hydrolyzable silane compound mixture is preferably 0.125 to 18 moles, more preferably 0.125 to 8 moles, per 1 mole of the first hydrolyzable silane compound.

(Third hydrolyzable silane compound)

The third hydrolyzable silane compound is a compound represented by the following formula (c-3).

SiX ⁴ ₄ (c-3)

In the formula (c-3), X ⁴ represents a hydrolyzable group, and four X ⁴ may be the same or different from each other.

As X < ⁴ >, the same groups as X < ^{1 >} and X < ² >

Specific examples of the compound (c-3) include the following compounds. As the compound (c-3), a partial hydrolysis-condensation product obtained by partially hydrolyzing and condensing a plurality of the compound (c-3), if necessary, may be used.

_{Si (OCH 3) 4, Si} (OCH 2 CH 3) 4,

Si (OCH _{3) 4} partially hydrolyzed condensate (e.g., Cole coat the product of methyl silicate 51 (trade name)) of,

Partial hydrolyzed condensates of Si (OCH ₂ CH ₃ ) ₄ (for example, ethyl silicate 40 and ethyl silicate 48 (all trade names) manufactured by Colcoat Co.).

As the compound (c-3), one type may be used alone, or two or more types may be used in combination.

In the cured film obtained by curing the negative photosensitive resin composition containing the partial hydrolyzed condensate of the present invention as the ink-repelling agent by incorporating the compound (c-3) in the hydrolyzable silane compound mixture, It is possible to increase the film-forming property after the drying. That is, from the point that the number of hydrolyzable groups in the compound (c-3) is large, it is considered that the partially hydrolyzed condensates are satisfactorily condensed after shifting to the upper surface, and a thin film can be formed on the entire upper surface.

In addition, by including the compound (c-3) in the hydrolyzable silane compound mixture, the homogeneity of the hydrolyzable silane compound mixture can be increased. It is believed that the presence of the compound (c-3) makes the first hydrolyzable silane compound and the second hydrolyzable silane compound easy to be bonded to each other and to be easily mixed. If the homogeneity of the hydrolyzable silane compound mixture is good, it is considered that the partial hydrolyzed condensate which can exhibit the effect of the hydrolyzable silane compound contained in the hydrolyzable silane compound mixture in a balanced manner is obtained.

Further, by including the compound (c-3) in the hydrolyzable silane compound mixture, the partial hydrolyzed condensate of the present invention is easily dissolved in the hydrocarbon-based solvent.

The content of the compound (c-3) in the hydrolyzable silane compound mixture is preferably 0.01 to 5 moles, more preferably 0.05 to 3 moles, per mole of the total amount of the first hydrolyzable silane compound and the second hydrolyzable silane compound Particularly preferred. When the content ratio is lower than the lower limit of the above range, the film-forming property is good, and if it is not more than the upper limit value, the effects of the first hydrolyzable silane compound and the second hydrolyzable silane compound can be sufficiently exhibited.

(Fourth hydrolyzable silane compound)

The fourth hydrolyzable silane compound is a hydrolyzable silane compound represented by the following formula (c-4).

(YQ ⁴ ) _g -Si (R ^H4 ) _h X ⁵ _(4-gh) (c-4)

The symbols in the formula (c-4) are as follows.

Y represents a group having an ethylenic double bond.

Q ⁴ represents a divalent organic group containing no fluorine atom having 1 to 6 carbon atoms.

R ^H4 represents a hydrocarbon group having 1 to 6 carbon atoms.

X < ⁵ > represents a hydrolyzable group.

g is 1 or 2, h is 0 or 1, and g + h is 1 or 2.

When a plurality of YQ ⁴ exist, they may be the same or different.

When a plurality of X < ⁵ > exist, they may be the same or different from each other.

As R ^H4 , the same group as R ^H1 is used.

As X < ⁵ >, the same groups as X < ^{1 >} and X < ² >

Y is preferably a (meth) acryloyloxy group and a vinylphenyl group, and particularly preferably a (meth) acryloyloxy group.

Specific examples of Q ⁴ include an alkylene group having 2 to 6 carbon atoms and a phenylene group. Among them, - (CH ₂ ) ₃ - is preferable.

g is 1, and h is 0 or 1.

Specific examples of the compound (c-4) include the following compounds.

The compound (c-4) may be used singly or in combination of two or more.

(C-4) containing a group Y having an ethylenic double bond in the hydrolyzable silane compound mixture to cure the negative type photosensitive resin composition containing the partially hydrolyzed condensate of the present invention as a ink-repelling agent In the production of barrier ribs, it is possible to promote the condensation reaction mainly by exposure of the ink-repelling agents and improve the fixability of the ink-repellent agent on the upper surface of the barrier ribs.

As described above, the second hydrolyzable silane compound has a mercapto group and, due to its chain mobility, the partial hydrolyzed condensate of the present invention is contained in the negative type photosensitive resin composition as a releasing agent, Thereby enabling exposure at an exposure amount. However, if the amount of the mercapto group is excessively large, it is likely to react with the ethylenic double bonds of the other components contained in the negative photosensitive resin composition and bond easily, thereby lowering the top surface transfer property of the ink repellent agent.

The compound (c-4) has a group Y having an ethylenic double bond, which reacts with a part of the mercapto group contained in the second hydrolyzable silane compound, and the mercapto group and the mercapto group of the second hydrolyzable silane compound The reaction of the ethylenic double bond of the other components contained in the negative-working photosensitive resin composition can be controlled. The reaction of the ethylenic double bonds of the mercapto group contained in the second hydrolyzable silane compound and the other components contained in the negative photosensitive resin composition is controlled so that the exposure of the negative type photosensitive resin composition at a lower exposure dose And it is considered that the top surface transfer property of the ink repellent agent is also improved. Further, it is considered that the storage stability of the negative-type photosensitive resin composition becomes better.

Since the compound (c-4) has the group Y having an ethylenic double bond, when the negative type photosensitive resin composition containing the partial hydrolysis-condensation product of the present invention as the ink-repelling agent is exposed, And can be copolymerized with each other or with other components having an ethylenic double bond contained in the negative-type photosensitive resin composition. It is considered that, due to this action effect, the ink for ink tends to remain on the upper surface of the cured film after exposure.

The content of the compound (c-4) in the hydrolyzable silane compound mixture is preferably 0.1 to 5 moles, more preferably 0.5 to 4 moles, per 1 mole of the total of the first hydrolyzable silane compound and the second hydrolyzable silane compound Particularly preferred. When the content ratio is not lower than the lower limit of the above range, the top surface of the ink repellent agent is favorable and the storage stability of the negative-working photosensitive resin composition is good. If it is not more than the upper limit, the effects of the first hydrolyzable silane compound and the second hydrolyzable silane compound can be sufficiently exhibited.

(Fifth hydrolyzable silane compound)

The fifth hydrolysable silane compound is a compound represented by the following formula (c-5).

^{_{(R H5) j -SiX 6 (}} 4-j) ··· (c-5)

In the formula (c-5), each symbol is as follows.

R ^H5 represents a hydrocarbon group having 1 to 6 carbon atoms.

X ⁶ represents a hydrolyzable group.

j is 2 or 3;

When a plurality of R ^H5 exist, they may be the same or different.

When a plurality of X < ⁶ > exist, they may be the same or different.

As R ^H5 , the same group as R ^H1 is used.

As X ⁶ , the same groups as X ¹ and X ² are used.

Specific examples of the compound (c-5) include the following compounds.

As the compound (c-5), one type may be used alone, or two or more types may be used in combination.

When the partial hydrolyzed condensate of the present invention contains a large amount of the component derived from the compound (c-3), in the partition wall formed by curing the negative photosensitive resin composition containing the condensate as a releasing agent, Mounting may be formed at the end of the upper surface. This is a minute level observed by a scanning electron microscope (SEM) or the like. The inventor of the present invention has confirmed that in this mounting, the content of F and / or Si is larger than other portions.

The present inventors have found that the occurrence of mounting can be suppressed by replacing part of the compound (c-3) with the compound (c-5) having a small number of hydrolyzers I found out.

The silanol groups produced by the compound (c-3) having a large number of hydrolyzers react with each other to increase the film-forming composition of the ink-repellent agent. However, since the reactivity is high, it is considered that the above-mentioned mounting occurs. That is, it is considered that the substitution of a part of the compound (c-3) with the compound (c-5) having a small number of hydrolyzers suppresses the reaction between the silanol groups and suppresses the occurrence of the mounting.

The content of the compound (c-5) in the hydrolyzable silane compound mixture is preferably from 0.05 to 5 moles, more preferably from 0.3 to 3 moles, per mole of the total of the first hydrolyzable silane compound and the second hydrolyzable silane compound Particularly preferred.

(Other hydrolyzable silane compounds)

In addition to the hydrolyzable silane compound, a hydrolyzable silane compound capable of co-condensation may also be included. For example, trimethoxyphenylsilane, 3-glycidoxypropyltrimethoxysilane, and the like.

(Combination of preferred hydrolyzable silane compounds)

The partial hydrolyzed condensate of the present invention is preferably a partially hydrolyzed condensate of a mixture containing a compound (c-1a) and a compound (c-2) (C-1), the compound (c-2), the compound (c-3) and the compound (c-4) are preferably used as the partial hydrolyzed condensate of the compound (C-2), the compound (c-3), the compound (c-4) and the compound (c-5) Is particularly preferable.

The partially hydrolyzed condensate of the present invention contains the compound (c-1a) and the compound (c-2), and optionally contains the compound (c-3), the compound (c- And the group D in the compound (c-1a) is a fluorine atom, the average composition formula is shown in the following formula (II).

In the formula (II), n1 to n5 represent the molar fraction of each constituent unit with respect to the total molar amount of the constituent units.

n1> 0, n2> 0, n3> 0, n4> 0, n5> 0, n1 + n2 + n3 + n4 + n5 = The other symbols are as described above. Provided that D is a fluorine atom.

In addition, since the hydrolyzable group or the silanol group remains in the product (partially hydrolyzed condensate) in practice, it is difficult to express this product in the formula. The average composition formula represented by the formula (II) is a formula in the case where the hydrolyzable group or the silanol group in the partial hydrolyzed condensate of the present invention is assumed to be a siloxane bond.

It is presumed that the units derived from the compound (c-1a) and the compounds (c-2) to (c-5) in the formula (II) are randomly arranged.

N1: n2: n3: n4: n5 in the average composition formula represented by the formula (II) is a ratio of the number average molecular weight of the compound (c-1a) in the hydrolyzable silane compound mixture, It corresponds to the injection composition.

The molar ratio of each component is designed from the balance of effects of each component.

n1 is preferably 0.05 to 0.4.

n2 is preferably 0.05 to 0.9, more preferably 0.05 to 0.4.

n3 is preferably 0 to 0.8, more preferably 0.05 to 0.6.

n4 is preferably from 0 to 0.8, and particularly preferably from 0.2 to 0.5.

n5 is preferably 0 to 0.5, and particularly preferably 0.05 to 0.3.

The preferable molar ratio of the respective components is the same when D in the compound (c-1a) is the group (Ia).

The number average molecular weight (Mn) of the partially hydrolyzed condensate of the present invention is preferably 500 or more, more preferably 1,000,000 or less, particularly preferably 10,000 or less. When the number average molecular weight (Mn) is not less than the lower limit value, evaporation does not occur when the cured film is formed using the negative photosensitive resin composition. If it is less than the upper limit, the solubility of the partial hydrolyzed condensate of the present invention to the solvent becomes better.

The number average molecular weight (Mn) of the partially hydrolyzed condensate of the present invention can be adjusted according to the production conditions.

(Production of partial hydrolyzed condensate)

The partial hydrolysis condensation product of the present invention can be produced by subjecting the above-described hydrolyzable silane compound mixture to hydrolysis and condensation reaction by a known method described in JP 2002-53805 A and the like.

In this reaction, it is preferable to use an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or the like which is commonly used, or an organic acid such as acetic acid, oxalic acid or maleic acid.

A known solvent may be used for the reaction. Among the solvents, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, 2-propanol, diethylene glycol monoethyl ether acetate and the like are preferably used.

[Foot ink]

The repelling ink composition of the present invention comprises the partial hydrolysis condensation product of the present invention.

The repelling ink of the present invention can be used as an additive for a negative or positive photosensitive resin composition and is particularly preferable for a negative photosensitive resin composition.

[Negative photosensitive resin composition]

The negative-working photosensitive resin composition of the present invention comprises an alkali-soluble resin having photo-curability or an alkali-soluble monomer (A), a photopolymerization initiator (B), a repelling ink (C) comprising the partial hydrolysis- And a solvent (D). If necessary, a crosslinking agent (E) and a coloring agent (F) may be contained.

Hereinafter, each component will be described.

(Alkali-soluble resin or alkali-soluble monomer (A))

The negative-working photosensitive resin composition of the present invention contains an alkali-soluble resin having photo-curability or an alkali-soluble monomer (A).

Hereinafter, the symbol (AP) is given to the alkali-soluble resin, and the symbol (AM) is given to the alkali-soluble monomer, respectively.

As the alkali-soluble resin (AP), a photosensitive resin having an acidic group and an ethylenic double bond in one molecule is preferable. Since the alkali-soluble resin (AP) has an ethylenic double bond in the molecule, the exposed part of the negative-type photosensitive resin composition is cured by the radical generated from the photopolymerization initiator (B). The exposed portion thus cured is not removed by the alkali developing solution. In addition, since the alkali-soluble resin (AP) has an acidic group in the molecule, the non-exposed portion of the uncured negative photosensitive resin composition can be selectively removed with an alkaline developer. As a result, a cured film of a desired pattern, that is, a partition wall can be formed.

Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, a sulfo group, and a phosphoric acid group, and these may be used singly or in combination of two or more kinds.

Examples of the ethylenic double bonds include double bonds having addition polymerizability such as (meth) acryloyl groups, allyl groups, vinyl groups, vinyloxy groups and vinyloxyalkyl groups.

These may be used alone or in combination of two or more. In addition, some or all of the hydrogen atoms of the ethylenic double bond may be substituted with an alkyl group such as a methyl group.

As the alkali-soluble resin (AP), a resin (A-1) having a side chain having an acidic group and a side chain having an ethylenic double bond and a resin (A-2) having an acidic group and an ethylene double bond introduced into the epoxy resin, And the like. These may be used alone or in combination of two or more.

The resin (A-1) can be synthesized by, for example, the following method (i) or (ii).

(i) copolymerizing a monomer having a reactive group other than the acidic group, for example, a reactive group such as a hydroxyl group or an epoxy group, and a monomer having an acidic group in the side chain, in the side chain to form a side chain having a reactive group and a side chain having an acidic group Is obtained. Subsequently, the copolymer is reacted with a compound having a functional group capable of binding to the reactive group and an ethylenic double bond. Alternatively, after a monomer having an acidic group such as a carboxyl group is copolymerized with a side chain, a compound having a functional group capable of bonding to the acidic group and an ethylenic double bond is reacted in an amount that remains after the reaction.

(ii) reacting a monomer having a reactive group other than the same acid group as the above (i) in the side chain with a compound having a functional group capable of binding to the reactive group and a protected ethylenic double bond. Then, the monomer and the monomer having an acidic group are copolymerized with the side chain, and then the protection of the ethylenic double bond is removed. Alternatively, the monomer having an acidic group in the side chain is copolymerized with a monomer having a protected ethylenic double bond in the side chain, and then the protection of the ethylenic double bond is removed.

Further, (i) and (ii) are preferably carried out in a solvent.

Among the above methods, the method of (i) is preferably used. Hereinafter, the method of (i) will be described in detail.

Examples of the monomer having a hydroxyl group as the reactive group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, 3-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (Meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl Ether, N-hydroxymethyl (meth) acrylamide, N, N-bis (hydroxymethyl) (meth) acrylamide and the like.

In the case of using a monomer having a hydroxyl group as a reactive group, examples of the monomer having an acidic group to be copolymerized include 2- (meth) acryloyloxyethyl phosphate as a monomer having a phosphate group in addition to the monomer having a carboxyl group described later. The copolymerization of the monomer having a hydroxyl group as a reactive group and the monomer having an acidic group can be carried out by a conventionally known method.

Examples of the compound having a functional group capable of binding to the hydroxyl group and having an ethylenic double bond to be reacted with the obtained copolymer include an acid anhydride having an ethylenic double bond, a compound having an isocyanate group and an ethylenic double bond, Compounds having a double bond, and the like.

Examples of the acid anhydride having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, Tetrahydrophthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-ylsuccinic anhydride and the like.

Examples of the compound having an isocyanate group and an ethylenic double bond include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate.

Examples of the compound having an acyl chloride group and an ethylenic double bond include (meth) acryloyl chloride and the like.

Examples of the monomer having an epoxy group as the reactive group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate.

As the monomer having an acid group to be copolymerized with a monomer having an epoxy group as a reactive group, the same monomer as that described above for the monomer having a hydroxyl group as a reactive group can be used. In the copolymerization of a monomer having an epoxy group as a reactive group and a monomer having an acid group Can also be carried out by a conventionally known method.

Examples of the compound having a functional group capable of binding to the epoxy group and an ethylenic double bond to be reacted with the obtained copolymer include a compound having a carboxyl group and an ethylenic double bond. Specific examples of such a compound include acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid and salts thereof, and monoesters in the case of dibasic acid. In addition, a carboxyl group may be introduced into the resin (A-1) by reacting an acid anhydride in which the dehydration condensation portion of the hydroxyl group and the carboxylic acid generated in this step forms a part of the cyclic structure.

Examples of the monomer having a carboxyl group as the reactive group include acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid and salts thereof, and monoesters in the case of dibasic acid. These monomers are also used as the above-mentioned monomers having an acidic group.

When a monomer having a carboxyl group is used as the reactive group, the monomer is polymerized as described above. Examples of the compound having a functional group capable of binding to a carboxyl group and an ethylenic double bond to be reacted with the resulting polymer include a compound having an epoxy group and an ethylenic double bond. Examples of such a compound include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate. In this case, the amount of the compound having a functional group capable of binding to a carboxyl group and the compound having an ethylenic double bond to be reacted with a polymer having a carboxyl group is such that the carboxyl group remains in the side chain as an acid group in the polymer after the reaction.

The resin (A-2) can be synthesized by reacting an epoxy resin with a compound having a carboxyl group and an ethylenic double bond, which will be described later, and then reacting the polycarboxylic acid or its anhydride.

Specifically, by reacting an epoxy resin with a compound having a carboxyl group and an ethylenic double bond, an ethylenic double bond is introduced into the epoxy resin. Next, a carboxyl group can be introduced by reacting a polyvalent carboxylic acid or its anhydride with an epoxy resin into which an ethylenic double bond has been introduced.

The epoxy resin is not particularly limited, and examples thereof include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, trisphenol methane epoxy resin, epoxy resin having naphthalene skeleton An epoxy resin having a biphenyl skeleton represented by the formula (A-2a), a fluorenyl substituted bisphenol A type epoxy resin represented by the following formula (A-2b), an epoxy resin having a biphenyl skeleton represented by the following formula Resins and the like.

[Chemical Formula 1]

(In the formula (A-2a), v is an integer of 1 to 50, preferably an integer of 2 to 10. The hydrogen atoms of the benzene ring are each independently an alkyl group having 1 to 12 carbon atoms, a halogen atom, Or a phenyl group in which some hydrogen atoms may be substituted with a substituent).

(2)

(In the formula (A-2b), R ³¹ , R ³² , R ³³ and R ³⁴ are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms, w is 0 or 1 to 10 It is an integer.)

(3)

(In the formula (A-2c), the hydrogen atom of the benzene ring may be independently substituted with an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group in which some hydrogen atoms may be substituted with a substituent and z is an integer of 0 or 1 to 10.)

When an epoxy resin represented by the formulas (A-2a) to (A-2c) is reacted with a compound having a carboxyl group and an ethylenic double bond and then reacted with a polycarboxylic acid anhydride, a polycarboxylic acid anhydride It is preferable to use a mixture of a dicarboxylic acid anhydride and a tetracarboxylic acid dianhydride.

The compound having a carboxyl group and an ethylenic double bond is preferably a monoester in the case of acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid and salts thereof and dibasic acid, (Meth) acrylic acid is particularly preferable.

As the alkali-soluble resin (AP), peeling of the cured film at the time of development is suppressed, a high-resolution pattern can be obtained, linearity of the line pattern is good, and a smooth cured film surface is easily obtained. A-2) is preferably used.

Examples of the resin (A-2) include a resin in which an acidic group and an ethylene double bond are introduced into a bisphenol A type epoxy resin, a resin in which an acidic group and an ethylene double bond are introduced into a bisphenol F type epoxy resin, A resin into which an acidic group and an ethylenic double bond are introduced into a cresol novolak type epoxy resin, a resin into which an acidic group and an ethylenic double bond are introduced into a trisphenol methane type epoxy resin, A resin in which an acidic group and an ethylenic double bond are introduced into an epoxy resin represented by the formula (2a) to (A-2c) is particularly preferable.

As the alkali-soluble monomer (AM), for example, a monomer (A-3) having a side chain having an acidic group and a side chain having an ethylenic double bond is preferably used. The acidic group and the ethylenic double bond are the same as the alkali-soluble resin (AM).

Examples of the monomer (A-3) include 2,2,2-triacryloyloxymethylethylphthalic acid and the like.

The alkali-soluble resin or the alkali-soluble monomer (A) contained in the negative-type photosensitive resin composition may be used alone or in combination of two or more.

The content of the alkali-soluble resin or the alkali-soluble monomer (A) in the total solid content in the negative-working photosensitive resin composition is preferably 5 to 80 mass%, particularly preferably 10 to 60 mass%. When the content ratio is within the above range, the negative type photosensitive resin composition has good light curability and developability.

(Photopolymerization initiator (B))

The photopolymerization initiator (B) in the present invention is not particularly limited as long as it is a compound having a function as a photopolymerization initiator, and a compound which generates a radical by light is preferable.

Examples of the photopolymerization initiator (B) include? -Diketones such as methylphenylglyoxylate and 9,10-phenanthrenequinone; An acyloin such as benzoin; Acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; Thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4- Thioxanthones such as thantone, 2,4-diisopropylthioxanthone and thioxanthone-4-sulfonic acid; Benzophenones such as benzophenone, 4,4'-bis (dimethylamino) benzophenone, and 4,4'-bis (diethylamino) benzophenone; Acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, p- Methyl-4- (methylthio) phenyl] -2-morpholino-1-propanone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Acetophenones; Quinones such as anthraquinone, 2-ethyl anthraquinone, camphorquinone, and 1,4-naphthoquinone; Aminobenzoic acids such as ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate and 2-ethylhexyl 4-dimethylaminobenzoate ; Halogen compounds such as phenacyl chloride and trihalomethylphenylsulfone; Acylphosphine oxides; Peroxide such as di-t-butyl peroxide; Oxime esters such as 1,2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime), and acetyl oxime; triethanolamine, methyldiethanolamine, triisopropanolamine, Aliphatic amines such as amine, N-methyldiethanolamine and diethylaminoethyl methacrylate; 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 1,4-butanol bis (3-mercaptobutyrate), tris (2-mercaptopropanoyloxyethyl ) Isocyanurate, pentaerythritol tetrakis (3-mercaptobutyrate), and the like.

Among the photopolymerization initiators (B), benzophenones, aminobenzoates, aliphatic amines and thiol compounds are preferred because they exhibit a sensitizing effect when used together with other radical initiators.

Examples of the photopolymerization initiator (B) include 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl- Phenyl-butan-1-one, 1,2-octanedione, 1- [4- (phenylthio) -, 2- (O- benzoyloxime), ethanone 1- [ Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), and 2,4-diethylthioxanthone are preferred. Also preferred are combinations of these and benzophenones, for example 4,4'-bis (diethylamino) benzophenone.

As the photopolymerization initiator (B), one type may be used alone, or two or more types may be used in combination.

The content of the photopolymerization initiator (B) in the total solid content in the negative-working photosensitive resin composition is preferably from 0.1 to 50 mass%, more preferably from 0.5 to 30 mass%, and particularly preferably from 5 to 15 mass% . When the content ratio is within the above range, the negative type photosensitive resin composition has good light curability and developability.

(Repellent agent (C))

The content of the ink composition (C) in the negative photosensitive resin composition of the present invention is preferably 0.01 to 10% by mass, more preferably 0.1 to 6% by mass, and particularly preferably 0.5 to 5% by mass . When the content is within the above range, the storage stability of the negative-working photosensitive resin composition becomes good, and the ink repellency of the upper surface of the partition made of the negative-type photosensitive resin composition and the UV / O ₃ property thereof are improved.

(Solvent (D))

The negative photosensitive resin composition of the present invention contains the solvent (D), whereby the viscosity is reduced and the application of the negative type photosensitive resin composition to the substrate surface becomes easy. As a result, a coating film of a negative-type photosensitive resin composition having a uniform film thickness can be formed.

As the solvent (D), a known solvent is used. Among them, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, 2-propanol, and diethylene glycol monoethyl ether acetate are preferably used.

The content of the solvent (D) in the negative-type photosensitive resin composition is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, and particularly preferably 65 to 90% by mass.

(Crosslinking agent (E))

As the crosslinking agent (E) in the present invention, a compound having two or more ethylenic double bonds in one molecule and having no acidic group is preferable. By including the cross-linking agent (E) in the negative-working photosensitive resin composition, the curing property of the negative-working photosensitive resin composition at the time of exposure is improved, and the partition wall can be formed even at a low exposure dose.

Examples of the crosslinking agent (E) include diethyleneglycol di (meth) acrylate, tetraethyleneglycol di (meth) acrylate, tripropyleneglycol di (meth) acrylate, neopentylglycol di (meth) (Meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethoxy isocyanuric acid triacrylate, epsilon -caprolactone modified tris- (2-acryloxyethyl) isocyanurate , Bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenyl} methane, N, N'-m-xylylene-bis (allylbicyclo [2.2. 1] hept-5-ene-2,3-dicarboxyimide), urethane acrylate And the like.

In terms of photoreactivity, it is preferable to have a large number of ethylenic double bonds. (Meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, Isocyanuric acid triacrylate, urethane acrylate, and the like.

The crosslinking agent (E) may be used alone or in combination of two or more.

The content of the crosslinking agent (E) in the total solid content in the negative-working photosensitive resin composition is preferably 10 to 60 mass%, particularly preferably 20 to 55 mass%.

(Colorant (F))

Examples of the coloring agent (F) in the present invention include carbon black, aniline black, anthraquinone-based black pigment, and perylene-based black pigment. Specific examples include C.I. Pigment Black 1, 6, 7, 12, 20, 31 and the like. A mixture of an organic pigment and / or an inorganic pigment such as a red pigment, a blue pigment and a green pigment may also be used.

When the colorant (F) is contained, the content of the colorant (F) in the total solid content in the negative-working photosensitive resin composition of the present invention is preferably 15 to 65 mass%, particularly preferably 20 to 50 mass% . Within the above range, the resulting negative-working photosensitive resin composition has good sensitivity, and the formed barrier rib is excellent in light shielding property.

(Other components)

The negative-working photosensitive resin composition of the present invention may further contain at least one component selected from the group consisting of an antioxidant, a thermal crosslinking agent, a polymer dispersant, a dispersion aid, a silane coupling agent, a fine particle, a phosphate compound, a hardening accelerator, a thickener, a plasticizer, An antioxidant, an antioxidant, an antioxidant, an antioxidant, an antioxidant, an antioxidant, an antioxidant,

(Antioxidant (G))

Examples of the antioxidant (G) include hindered phenols such as 2,6-di-tert-butyl-p-cresol, hydroquinone, catechol, resorcinol, 2-methylhydroquinone, 4-methoxyphenol, Naphthylamine, p-benzoquinone, couperone, N-nitrosophenyl-β-naphthylamine, and the like. The content of the antioxidant (G) in the total solid content in the negative-working photosensitive resin composition of the present invention is preferably in the range of 0.01 to 0.1% by mass.

According to the present invention, the upper surface of the partition wall is obtained even by carrying out exposure at a low exposure amount than conventional, after exposure and development, it is possible to give a selectively good ink repellency, and also, even after the UV / O ₃ irradiation treatment, It is possible to provide a negative-working photosensitive resin composition which has good ink-retaining property and which has a property that the ink does not remain well in the dot.

[septum]

The barrier rib of the present invention is a cured film having a pattern formed by applying the negative-working photosensitive resin composition of the present invention to the substrate surface, and exposing and developing the negative photosensitive resin composition.

Hereinafter, one example of the manufacturing method of the barrier rib will be described with reference to Figs. 1A to 1E, but the manufacturing method of the barrier rib is not limited to the following.

1A, a negative-type photosensitive resin composition is applied to the entire surface of a substrate 10 to form a coating film 21. Then, as shown in Fig. At this time, the repellent agent (C) is completely dissolved in the coating film 21 and is uniformly dispersed. In the drawings, the repellent agent (C) is schematically shown, and actually does not exist in such a particle shape.

Next, as shown in Fig. 1 (B), the coating film 21 is dried to form a dried film 22. Examples of the drying method include heat drying, vacuum drying, and drying under reduced pressure.

Depending on the type of the solvent (D), the heating temperature is preferably 50 to 120 ° C, more preferably 80 to 120 ° C in the case of heat drying.

In this drying process, the repelling agent (C) migrates to the upper surface of the dried film and its vicinity.

Next, as shown in Fig. 1C, the dry film 22 is exposed to light L through a photomask 30 having an opening 31 of a predetermined pattern. The film after the dry film 22 is exposed is referred to as an exposure film 23. In the exposure film 23, reference numeral 23A denotes an exposure portion, and reference numeral 23B denotes an unexposed portion. In this process, the exposed portion 23A is photo-cured.

As the light L to be irradiated, visible light; UV-rays ; Deep ultraviolet light; Excimer laser lights such as KrF excimer laser light, ArF excimer laser light, F ₂ excimer laser light, Kr ₂ excimer laser light, KrAr excimer laser light and Ar ₂ excimer laser light; X-rays; Electron beam and the like.

The light L to be irradiated is preferably a light having a wavelength of 100 to 600 nm and more preferably a light of 300 to 500 nm and an i-line (365 nm), h-line (405 nm) ) Is particularly preferable.

Examples of the exposure method include whole-surface batch exposure and scan exposure. Exposure may be performed by dividing the same point into a plurality of circuits. At this time, a plurality of exposure conditions may or may not be the same.

The exposure dose is preferably 5 to 1,000 mJ / cm 2, more preferably 5 to 500 mJ / cm 2, still more preferably 5 to 300 mJ / cm 2, and more preferably 5 to 200 mJ / / Cm < 2 > is particularly preferable, and 5 to 50 mJ / cm < 2 > The exposure amount is appropriately customized according to the wavelength of the light to be irradiated, the composition of the negative-type photosensitive resin composition, the thickness of the coating film, and the like.

The exposure time per unit area is not particularly limited and is designed from the exposure power of the exposure apparatus to be used and the necessary exposure amount. Further, in the case of the scan exposure, the exposure time is obtained from the scanning speed of light.

The exposure time per unit area is usually 0.01 to 60 seconds, preferably 1 to 60 seconds, particularly preferably 0.1 to 5 seconds.

The fact that the exposure can be performed at a low exposure dose is connected to the shortening of the exposure time (exposure step), so that the manufacturing cost can be reduced.

For example, if an exposure amount of 100 mJ / cm < 2 > has been conventionally required at an exposure amount of 50 mJ / cm < 2 >, the exposure time per one substrate can be halved by a simple calculation.

Particularly, in the scan exposure, time is required for the entire surface treatment of the entire substrate rather than the whole surface batch exposure, so that even if the exposure time per unit area is a second order, the effect of shortening the exposure time is large.

Next, as shown in Fig. 1D, development using an alkaline developer is performed to form a cured film 24 having a desired pattern. In the cured film 24, the exposed portion 23A in the exposure becomes the convex portion 24A, and the unexposed portion 23B becomes the pattern opening portion 24B.

The thickness of the cured film 24 is preferably 0.1 to 10 mu m, more preferably 0.5 to 5 mu m.

Further, in this step, the ink repellent agent C of the non-visible portion 23B is dissolved well in the alkaline developer, and does not remain in the pattern opening portion 24B.

The cured film 24 having a pattern may be further heated as shown in Fig. 1E. The heating temperature is preferably 130 to 250 ° C, more preferably 200 to 240 ° C. By heating, the ink repellent agent (C) binds strongly to the cured film and forms a thin layer nearer to the surface.

In order to remove development residue of the negative photosensitive resin composition remaining in the pattern opening portion 24B in applications such as barrier ribs for pattern printing of an organic layer such as a light emitting layer of the organic EL device by the IJ method after the heating, The substrate 10 is subjected to UV / O ₃ irradiation treatment.

According to the present invention, in its production, it is possible to carry out exposure at a low exposure amount than conventional, the upper surface is optionally have good ink repellency, and also, UV / O ₃ even after the irradiation treatment, the ink-repellent Can be satisfactorily maintained, and the barrier ribs having such characteristics that no ink residue remains in the dots can be provided.

The barrier rib of the present invention can be used as a partition defining the ink injection region when pattern printing is performed by the IJ method.

Since the upper surface of the partition wall of the present invention selectively has excellent ink repellency, ink can be uniformly applied within the region surrounded by the partition when pattern printing is performed by the IJ method. In addition, it is possible to suppress ink from being injected into an undesired region exceeding the barrier ribs, and to print the ink well in a desired pattern.

2A, after the cured film 24 is formed (Fig. 1E), the ink 51 is dropped from the inkjet head 40, and the ink 51 ). Subsequently, the solvent is removed by drying and / or heating or the like to obtain a desired pattern film 52 as shown in FIG. 2B.

[Optical element]

The optical element of the present invention includes a plurality of dots and the above-described barrier rib of the present invention.

Examples of the optical element include an organic EL element, a color filter of a liquid crystal element, and an organic TFT array element.

The organic TFT array element is a structure in which a plurality of dots are arranged in a matrix when viewed in a plane, TFTs are formed as pixel elements and switching elements for driving the pixel electrodes in each dot, and organic semiconductors Layer is used.

The organic TFT array element is provided as an organic EL element, a liquid crystal element, or the like as a TFT array substrate.

The organic EL device can be manufactured, for example, as follows.

A light-transmitting electrode such as tin-doped indium oxide (ITO) is formed on a transparent substrate such as glass by a sputtering method or the like. This transparent electrode is patterned as required.

Next, the negative type photosensitive resin composition of the present invention is used to form a lattice-shaped partition wall in a plan view along the outline of each dot by a photolithography method including coating, exposure and development.

Next, if necessary, the ink encapsulated in the dots surrounded by the barrier ribs is subjected to the ink-losing process by known methods.

Next, the materials of the hole injection layer, the hole transporting layer, the light emitting layer, the hole blocking layer and the electron injection layer are coated and dried in the dots by the IJ method, respectively, and these layers are sequentially laminated. The type and the number of organic layers formed in the dots are appropriately designed.

Finally, reflective electrodes such as aluminum are formed by vapor deposition or the like.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Further, Examples 1 to 9 and Examples 11 to 19 are Examples, and Examples 10 and 20 are Comparative Examples.

Each measurement was carried out in the following manner.

[Number average molecular weight (Mn) and mass average molecular weight (Mw)] [

Gel permeation chromatography (GPC) of a plurality of kinds of monodispersed polystyrene polymers having different degrees of polymerization, which are commercially available as standard samples for molecular weight measurement, was carried out using a commercially available GPC measuring apparatus (manufactured by Tosoh Corporation, HLC-8320GPC) Respectively. A calibration curve was prepared based on the relationship between the molecular weight of polystyrene and the retention time (retention time).

Each sample was diluted with tetrahydrofuran to 1.0% by mass, passed through a filter of 0.5 탆, and then GPC was measured using the above apparatus. Using the calibration curve, the GPC spectrum was subjected to computer analysis to determine the number average molecular weight (Mn) and mass average molecular weight (Mw) of the sample.

[PGMEA contact angle]

According to JIS R3257 " Test Method for Wettability of Substrate Glass Surface " by static method, PGMEA droplets were placed at three points of the measurement surface on the substrate and measured for each PGMEA droplet. The droplet was adjusted to 2 쨉 l / drop, and the measurement was carried out at 20 째 C. The contact angle was obtained from the average of three measurements (n = 3). In addition, PGMEA is an abbreviation for propylene glycol monomethyl ether acetate.

The abbreviations of the compounds used in each example are as follows.

(A hydrolyzable silane compound as a raw material of the ink-repellent agent (C)),

Compound (1a-c) Compound (c-11) corresponding _{to: CF 3 (CF 2) 5} CH 2 CH 2 Si (OCH 3) 3 ( manufactured by Asahi Glass Co., Ltd.).

Compound (c-21) corresponding to compound (c- ₂ ): SH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ (KBM-803: trade name; manufactured by Shin-Etsu Chemical Co., Ltd.)

Compound (c-31) corresponding to compound (c-3): Si (OC ₂ H ₅ ) ₄ (manufactured by Colcoat Co.).

Compound (c-32) corresponding to compound (c-3): Partial hydrolysis condensation product of Si (OC ₂ H ₅ ) ₄ (trade name: ethyl silicate 48 manufactured by Colcoat Co.).

Compound (c-33) corresponding to compound (c-3): partial hydrolysis condensation product of Si (OCH ₃ ) ₄ (trade name: methyl silicate 51, manufactured by Colcoat Co.).

Compound (c-41) corresponding to compound (c-4): CH ₂ CHCOO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.).

Compound (c-51) corresponding to compound (c-5): (CH ₃ ) ₃ SiOCH ₃ (manufactured by Tokyo Chemical Industry Co., Ltd.).

Compound (c-61) corresponding to compound (c-6): trimethoxyphenylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.).

Compound (c-62) corresponding to compound (c-6): 3-glycidoxypropyl (manufactured by Tokyo Chemical Industry Co., Ltd.).

(Alkali soluble resin (AP))

A-11: A resin obtained by reacting a cresol novolak type epoxy resin with acrylic acid and then 1,2,3,6-tetrahydrophthalic anhydride to obtain a resin having an acryloyl group and a carboxyl group introduced thereinto and purified with hexane; a resin having a solid content of 70% , An acid value of 60 mgKOH / g.

A-21: A resin having a carboxyl group and an ethylenic double bond introduced into a bisphenol A type epoxy resin (trade name: KAYARAD ZAR-2002H, manufactured by Nippon Kayaku Co., Ltd., solid content: 70% by mass, acid value: 60 mgKOH / g)

A-31: A resin (solid content: 70% by mass, PGMEA: 30% by mass, MW = 4000, acid value: 70%) having an ethylenic double bond and an acidic group introduced into an epoxy resin having a biphenyl skeleton represented by the formula MgKOH / g).

A-41: A resin (solid content: 70% by mass, PGMEA: 30% by mass, MW = 3000, acid value: 50 mgKOH / g) having an ethylenic double bond and an acidic group introduced into the epoxy resin represented by the formula (A- ).

(Photopolymerization initiator (B))

IR907: trade name; IRGACURE 907, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one manufactured by BASF.

IR369: trade name: IRGACURE369, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one manufactured by BASF.

EAB: 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.).

OXE01: 1.2-octanedione, 1- [4- (phenylthio) phenyl] -, 2- (0-benzoyloxime) manufactured by BASF, trade name: OXE01).

OXE02: Ethanone 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbamoyl-3-yl] -1- (O- acetyloxime) (trade name: OXE02, manufactured by Ciba Specialty Chemicals) .

(Solvent (D))

PGMEA: Propylene glycol monomethyl ether acetate,

PGME: propylene glycol monomethyl ether,

EDM: diethylene glycol ethyl methyl ether,

IPA: 2-propanol,

EDGAC: diethylene glycol monoethyl ether acetate.

(Crosslinking agent (E))

A9530: trade name; NK Ester A-9530, a product of Shin Nakamura Chemical Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate.

V802: trade name; V # 802 A mixture of pentaerythritol acrylate, dipentaerythritol acrylate, tripentaerythritol acrylate, and tetrapentaerythritol acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.

(Antioxidant (G))

BHT: 2,6-di-tert-butyl-p-cresol,

MHQ: 2-methylhydroquinone,

MEHQ: 4-methoxyphenol.

[Example 1: Preparation of ink for liquid of repellent (C1)] [

32.3 g of the compound (c-11) and 67.7 g of the compound (c-21) were placed in a 1,000 cm 3 three-necked flask equipped with a stirrer to obtain a hydrolyzable silane compound mixture. Subsequently, 569.4 g of PGME was added to the mixture to prepare a raw material solution.

To the obtained raw material solution, 44.7 g of a 0.1 mass% hydrochloric acid aqueous solution was added dropwise. After completion of the dropwise addition, the mixture was stirred at 40 DEG C for 5 hours to obtain a PGME solution (repellent agent (C1) concentration: 10% by mass) of the repelling agent C1. This solution is hereinafter referred to as (C1) solution.

After completion of the reaction, the reaction solution was measured by using gas chromatography to confirm that each compound as a raw material was below the detection limit.

Table 1 shows the composition (mol%) of the injection amount of the ink repellent agent.

[Examples 2 to 10: Preparation of liquid for ink-repellent agents (C2) to (C9) and (H1)] [

(Solutions) of the repellent agents (C2) to (C9) and (H1) were prepared in the same manner as in Example 1, except that the composition (mol% Concentration of ink: 10% by mass). Each solution is hereinafter referred to as (C 2) to (C 9) and (H 1) solutions.

In Example 10, a solution of a repellent agent (H1) was prepared without using the compound (c-2). Since this repelling ink agent is not a repelling ink agent (C) of the present invention, the sign of the repelling agent is changed. (H) was used as the entire ink composition for comparison, and (H1) was used as the ink repellent agent of Example 10.

(evaluation)

The following evaluations were carried out on the ink-repellent agents obtained in Examples 1 to 10.

≪ Number average molecular weight (Mn) and mass average molecular weight (Mw) >

The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured for each of the ink-repelling agents obtained in Examples 1 to 10 by the above-mentioned method.

<Content of fluorine atoms>

For each of the ink-repellent agents obtained in Examples 1 to 10, the content of fluorine atoms was determined from the injection composition.

The evaluation results of the ink repellent agent obtained in Examples 1 to 10 are shown in Table 1.

[Example 11: Preparation of negative-working photosensitive resin composition and preparation of cured film]

(Production of negative-type photosensitive resin composition)

0.23 g of the liquid C1 obtained in Example 1 (containing 0.023 g as solids of the ink repellent (C1) and the remainder being PGME as a solvent), 16.1 g of A-11 (solid content: 11.3 g, ), 1.1 g of IR907, 1.1 g of EAB, 11.3 g of A9530, 65.2 g of PGMEA, 2.5 g of IPA and 2.5 g of water were placed in a 200 cm 3 stirring vessel and stirred for 5 hours to obtain a negative photosensitive resin composition .

With regard to the repellent agent (C1), the solids content is calculated to be 0.026 g in terms of injection, but the hydrolyzable group is eliminated to produce methanol or ethanol, so that it is actually 0.026 g or less. Since it is difficult to determine how much of the hydrolyzable group has disappeared, assuming that almost all of the hydrolyzable group has disappeared, the solid content was set at 0.023 g.

(Preparation of barrier rib)

A glass substrate with a length of 10 cm was ultrasonically cleaned with ethanol for 30 seconds, followed by UV / O ₃ treatment for 5 minutes. For the UV / O ₃ treatment, PL2001N-58 (Sen Engineering) was used as a UV / O ₃ generator. The optical power (optical output) in terms of 254 nm was 10 mW / cm 2. In addition, the present apparatus was also used for all UV / O ₃ treatment.

The negative photosensitive resin composition was coated on the cleaned glass substrate surface using a spinner and then dried on a hot plate at 100 캜 for 2 minutes to form a dried film having a thickness of 2.4 탆. The obtained dried film was irradiated with UV light of an ultrahigh pressure mercury lamp having an exposure power (exposure power) of 25 mW / cm 2 in terms of 365 nm as a whole through a photomask having an opening pattern (2.5 cm x 5 cm) . At the time of exposure, light of 330 nm or less was cut. The distance between the dried film and the photomask was set to 50 탆.

In each example, exposure was performed under the exposure conditions shown in the following 2.

<Exposure condition 1> The exposure time was 2 seconds and the exposure amount was 50 mJ / cm 2.

&Lt; Exposure condition 2 &gt; The exposure time was 4 seconds and the exposure amount was 100 mJ / cm &lt; 2 &gt;.

Subsequently, the glass substrate after the exposure treatment was immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide for 40 seconds to develop, and the unexposed portion was washed while flowing with water, followed by drying. Subsequently, the substrate was heated on a hot plate at 230 DEG C for 60 minutes to obtain a cured film (partition wall) having a pattern corresponding to the opening pattern of the photomask.

[Examples 12 to 20]

A negative-working photosensitive resin composition and a barrier rib were prepared in the same manner as in Example 11 except that the composition of the negative-working photosensitive resin composition was changed to the composition shown in Table 2.

(evaluation)

The following evaluations were carried out on the barrier ribs obtained in Examples 12 to 20.

&Lt; Film thickness of cured film &

The measurement was carried out using a laser microscope (manufactured by KEYENCE CORPORATION, device name: VK-8500).

&Lt; Repellability of the upper surface of the partition &

The contact angle of PGMEA on the upper surface of the obtained cured film was measured by the above method.

&Lt; UV / O ₃ property of ink-repellent property on the upper surface of barrier rib>

The glass substrate on which the cured film was formed was subjected to the UV / O ₃ irradiation treatment for 3 minutes (the light amount was 1,800 mJ / cm 2 in terms of 254 nm) on the entire surface, and then the contact angle of PGMEA on the surface of the cured film was measured again.

In each example, evaluation of the UV / O ₃ resistance of the ink-repellent property was carried out only on a sample having an exposure amount of 50 mJ / cm 2.

<Storage Stability of Negative-Based Photosensitive Resin Composition>

The negative-working photosensitive resin composition prepared in each example was kept at room temperature for one month, and then the barrier ribs were prepared in the same manner as in Example 11 (using an exposure dose of 50 mJ / cm 2). The value obtained by subtracting the PGMEA contact angle of the upper surface of the partition obtained from the initial negative photosensitive resin composition from the PGMEA contact angle on the upper surface of the barrier was evaluated based on the following criteria.

○ (Good): -5 ° or more.

△ (A): above -10 ° and below -5 °.

× (not allowed): Less than -10 °.

&Lt; SEM observation of the end portion of the upper surface of the partition &

SEM observation of the obtained upper surface of the barrier rib was performed (5,000 times), and the presence or absence of mounting of the end portion of the upper surface of the barrier rib was observed and evaluated based on the following criteria. As the apparatus, a 3D real surface view microscope VE-9800 (manufactured by Keens) was used. Since the mounting of the end portion of the upper surface of the partition wall is not particularly troublesome as the partition wall, the evaluation in the case of the mounting of the end portion of the upper surface of the partition is?.

(Good): No mounting was observed at the end of the upper surface of the partition wall.

(A): Mounting was observed at the end of the upper surface of the partition wall.

Table 2 shows the evaluation results of the barrier ribs obtained in Examples 12 to 20.

Since the negative type photosensitive resin compositions of Examples 11 to 19 used the repelling ink (C) of the present invention, the upper surface of the partition obtained even at a low exposure dose had excellent ink repellency and the ink repellency was UV / O ₃ treatment It was maintained well afterwards.

On the other hand, the negative-working photosensitive resin composition of Example 20 had inadequate ink repellency on the upper surface of the cured film at a low exposure dose, because a repellent agent (H1) prepared without using the compound (c-2) was used.

Examples 13 to 16 using the ink-repellent agent (C) using the compound (c-4) of the present invention were used in Examples 11, 12, 17, 19, the storage stability of the negative-working photosensitive resin composition and the ink repellency of the upper surface of the partition wall were excellent.

In Example 16 using the repellent agent (C) using the compound (c-5) of the present invention, the mounting of the end portion of the upper surface of the partition could not be seen, and the partition wall having a beautiful shape could be formed.

Industrial availability

The partial hydrolysis-condensation product of the present invention is contained in a photosensitive resin composition or the like for forming a barrier rib when performing pattern printing by an ink-jet method in an organic EL device, a color filter of a liquid crystal device, and an optical device such as an organic TFT array An ink for ink-jet recording, and the like.

In the organic EL device according to the present invention, the partition wall (bank) for pattern printing the organic layer such as the light emitting layer by the IJ method or the partition wall for pattern printing the color filter in the IJ method in the liquid crystal element A black matrix (BM)), a barrier rib for pattern printing of a conductor pattern or a semiconductor pattern in the organic TFT array by the IJ method, an organic semiconductor layer constituting a channel layer of the TFT, a gate electrode, a source electrode, Gate wirings, source wirings, etc. can be used as barrier ribs for pattern printing by the IJ method.

The entire contents of the specification, claims, drawings and summary of Japanese Patent Application No. 2012-102984 filed on April 27, 2012 are hereby incorporated herein by reference and the disclosure of the specification of the present invention.

10: substrate
21: Coating film
22: Dry film
23: Exposure film
23A:
23B: Non-
24:
24A:
24B: pattern opening
30: Photomask
52: pattern film
L: Light

Claims (17)

A first hydrolyzable silane compound having a fluoroalkylene group and / or a fluoroalkyl group and a hydrolyzable group and having no mercapto group,
A partially hydrolyzed condensate of a mixture characterized by comprising a mercapto group and a second hydrolyzable silane compound having a hydrolyzable group and not having a fluoroalkylene group and a fluoroalkyl group. The method according to claim 1,
The content of the second hydrolyzable silane compound in the mixture is 0.125 to 18 moles per 1 mole of the first hydrolyzable silane compound. 3. The method according to claim 1 or 2,
Wherein the first hydrolyzable silane compound is a compound represented by the following formula (c-1).
(AR ^F1 ) _a -Si (R ^H1 ) _b X ¹ _(4-ab) (c-1)
(In the formula (c-1), each symbol is as follows.
R ^F1 represents a divalent organic group having 1 to 16 carbon atoms which may contain an etheric oxygen atom and contains at least one fluoroalkylene group.
R ^H1 represents a hydrocarbon group having 1 to 6 carbon atoms.
a is 1 or 2, b is 0 or 1, and a + b is 1 or 2.
A is a fluorine atom or a group represented by the following formula (I).
-Si (R ^H2 ) _b X ² _(3-b) (I)
And R ^H2 represents a hydrocarbon group having 1 to 6 carbon atoms.
b is 0 or 1;
X ¹ and X ² represent a hydrolyzable group.
When a plurality of X &lt; ¹ &gt; s exist, they may be different from or the same as each other.
When a plurality of X &lt; ² &gt; exist, they may be different from or the same as each other.
When a plurality of AR ^F1 exist, they may be different from each other or may be the same.) The method of claim 3,
Wherein the first hydrolyzable silane compound is a compound represented by the following formula (c-1a).
_{^{DR F2 -Q 1 -SiX 1 3 ···}} (c-1a)
(Wherein each symbol in the formula (c-1a) is as follows.
And R ^F2 is a perfluoroalkylene group which may contain an etheric oxygen atom having 2 to 15 carbon atoms.
D is a fluorine atom or a group represented by the following formula (Ia).
-Q ² -SiX ² ₃ (Ia)
X ¹ and X ² represent a hydrolyzable group.
The three X &lt; ^{1 &gt; s} may be mutually different or the same.
The three X &lt; ^{2 &gt; s} may be mutually different or the same.
Q ¹ and Q ^{2 each} represent a divalent organic group containing no fluorine atom having 1 to 10 carbon atoms. 5. The method according to any one of claims 1 to 4,
And the second hydrolyzable silane compound is a compound represented by the following formula (c-2).
(HS-Q ³ ) _p -Si (R ^H3 ) _q X ³ _(4-pq) (c-2)
(In the formula (c-2), symbols are as follows.
Q ³ represents a divalent organic group having 1 to 10 carbon atoms and not containing a fluorine atom.
R ^H3 represents a hydrocarbon group having 1 to 6 carbon atoms.
X ³ represents a hydrolyzable group.
p is 1 or 2, q is 0 or 1, and p + q is 1 or 2.
When a plurality of HS-Q ³ exist, they may be the same or different.
X &lt; ³ &gt; are present, they may be the same or different from each other.) 6. The method according to any one of claims 1 to 5,
Wherein the mixture further comprises a third hydrolyzable silane compound represented by the following formula (c-3).
SiX ⁴ ₄ (c-3)
(In the formula (c-3), X ⁴ represents a hydrolyzable group, and four X ⁴ may be the same or different from each other.) 7. The method according to any one of claims 1 to 6,
Wherein said mixture further comprises a fourth hydrolyzable silane compound represented by the following formula (c-4).
(YQ ⁴ ) _g -Si (R ^H4 ) _h X ⁵ _(4-gh) (c-4)
(The symbols in the formula (c-4) are as follows.
Y represents a group having an ethylenic double bond.
Q ⁴ represents a divalent organic group containing no fluorine atom having 1 to 6 carbon atoms.
R ^H4 represents a hydrocarbon group having 1 to 6 carbon atoms.
X &lt; ⁵ &gt; represents a hydrolyzable group.
g is 1 or 2, h is 0 or 1, and g + h is 1 or 2.
When a plurality of YQ ⁴ exist, they may be the same or different.
When a plurality of X &lt; ⁵ &gt; s exist, they may be the same or different.) 8. The method according to any one of claims 1 to 7,
Wherein the mixture further comprises a fifth hydrolyzable silane compound represented by the following formula (c-5).
_{^{(R H5) j -SiX 6 (}} 4-j) ··· (c-5)
(In the formula (c-5), each symbol is as follows.
R ^H5 represents a hydrocarbon group having 1 to 6 carbon atoms.
X ⁶ represents a hydrolyzable group.
j is 2 or 3;
When a plurality of R ^H5 exist, they may be the same or different.
When a plurality of X &lt; ⁶ &gt; s exist, they may be the same or different.) 9. The method according to any one of claims 1 to 8,
A partial hydrolysis-condensation product having a fluorine atom content of 10 to 55 mass%. 10. The method according to any one of claims 1 to 9,
A partial hydrolysis condensation product having a number average molecular weight of 500 or more and less than 10,000. A foot ink composition comprising the partial hydrolyzed condensate according to any one of claims 1 to 10. (A), a photopolymerization initiator (B), and a solvent (D) according to any one of claims 1 to 11, an alkali-soluble resin having photo-curability, or an alkali-soluble monomer. 13. The method of claim 12,
Wherein the crosslinking agent (E) further comprises a crosslinking agent (E), wherein the crosslinking agent (E) has two or more ethylenic double bonds in one molecule and does not have an acidic group. A cured film characterized by coating the substrate surface with the negative-working photosensitive resin composition according to claim 12 or 13 and exposing it. A barrier rib comprising the cured film according to claim 14. An optical element comprising a plurality of dots and the barrier rib according to claim 15. 17. The method of claim 16,
Wherein the partition is a partition for partitioning the plurality of dots or a partition for pattern printing by a conductive pattern or a semiconductor pattern of an inkjet method.

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