WO2012132755A1

WO2012132755A1 - Negative photosensitive resin composition and coating film

Info

Publication number: WO2012132755A1
Application number: PCT/JP2012/055280
Authority: WO
Inventors: 高橋　秀幸; 健二石関; 川島　正行; 古川　豊
Original assignee: 旭硝子株式会社
Priority date: 2011-03-31
Filing date: 2012-03-01
Publication date: 2012-10-04
Also published as: TW201243500A; JP2014122926A

Abstract

Provided is a photosensitive composition that has excellent ink-repellency and can produce a barrier capable of maintaining ink-repellency when irradiated with ultraviolet light or ozone, the negative photosensitive resin composition having excellent storage stability. Also provided is a homogenous coating film obtained using the negative photosensitive resin composition. The photosensitive resin composition contains an ink repellent agent (A) comprising a fluorosiloxane compound, an alkali-soluble resin (B) having an acid group and an ethylene double bond in a single molecule, and a photopolymerization initiator (C), the negative photosensitive resin composition being characterized in that the photosensitive composition has an acid value of 6-30 mg KOH/g.

Description

Negative photosensitive resin composition and coating film

The present invention relates to a negative photosensitive resin composition and a coating film.

The resist composition includes partition walls between pixels of a color filter, partition walls between pixels of an organic EL (Electro-Luminescence) display element, partition walls partitioning each TFT of an organic TFT (Thin Film Transistor) array, ITO of a liquid crystal display element It attracts attention as a material for forming permanent films such as electrode partition walls and circuit wiring substrate partition walls.
In the production of circuit wiring boards, an ink jet method has been proposed in which a metal dispersion is sprayed and applied when forming circuit wiring. A circuit wiring pattern is formed from a resist composition by photolithography, and a cured film of the resist composition is used as a partition wall.

In the ink jet method, it is necessary to prevent ink color mixing between adjacent pixels and the material ejected by the ink jet to a portion other than a predetermined region from clumping, and a resist composition containing an ink repellent agent is proposed. (Patent Document 1).

International Publication No. 2010/013816

According to the knowledge of the present inventors, the resist composition of Patent Document 1 tends to have insufficient storage stability when stored at room temperature (20 to 25 ° C.) for 2 weeks, for example, and stored at room temperature for 2 weeks. When a patterned substrate was formed using the resist composition prepared, foreign matter was sometimes observed on the coating film.
An object of the present invention is a negative photosensitive resin composition capable of producing a partition having good ink repellency and capable of maintaining ink repellency even when irradiated with ultraviolet rays / ozone, and having a storage stability. An object is to provide a good negative photosensitive resin composition and a homogeneous coating film of the negative photosensitive resin composition obtained by using the composition.

The present invention is a negative photosensitive resin composition and a coating film having the following configurations [1] to [10].
[1] An ink repellent agent (A) comprising a fluorine-containing siloxane compound;
An alkali-soluble resin (B) having an acidic group and an ethylenic double bond in one molecule;
A negative photosensitive resin composition containing a photopolymerization initiator (C),
A negative photosensitive resin composition, wherein the negative photosensitive resin composition has an acid value of 6 to 30 mgKOH / g.
[2] The negative photosensitive resin composition according to [1], wherein the proportion of the alkali-soluble resin (B) in the total solid content of the negative photosensitive resin composition is 12 to 40% by mass.
[3] The fluorine-containing siloxane compound comprises a hydrolysis condensation product of a mixture containing the following hydrolyzable silane compound (a-1) and hydrolyzable silane compound (a-2): [1] or [2 ] Negative photosensitive resin composition.
Hydrolyzable silane compound (a-1): an organic group having a perfluoroalkyl group which may contain one etheric oxygen atom having 3 to 10 carbon atoms in the silicon atom, and three hydrolyzable groups A hydrolyzable silane compound bonded with
Hydrolyzable silane compound (a-2): Hydrolyzable silane in which p hydrocarbon groups (p is 0, 1 or 2) and (4-p) hydrolyzable groups are bonded to a silicon atom Compound.
[4] The negative photosensitive resin composition according to any one of [1] to [3], wherein the fluorine atom content in the fluorine-containing siloxane compound is 10 to 55% by mass.
[5] Further comprising a crosslinking agent (D), wherein the crosslinking agent (D) is a compound having two or more ethylenic double bonds in one molecule and having no acidic group. [4] The negative photosensitive resin composition.
[6] The proportion of the total amount of the alkali-soluble resin (B) and the crosslinking agent (D) in the total solid content in the negative photosensitive resin composition is 50 to 95% by mass, and the crosslinking agent (D) The negative photosensitive resin composition according to [5], wherein the ratio of the content of the alkali-soluble resin (B) to the content of is from 15 to 85% by mass.
[7] The negative photosensitive resin composition according to any one of [1] to [6], further comprising a solvent (E).
[8] The negative photosensitive resin composition according to any one of [1] to [7], wherein the acid value of the alkali-soluble resin (B) is 10 to 200 mg KOH / g.
[9] The negative photosensitive resin composition according to any one of [1] to [8], wherein the ratio of the ink repellent agent (A) in the total solid content of the negative photosensitive resin composition is 0.01 to 10% by mass. Resin composition.
[10] A coating film in which the negative photosensitive resin composition of any one of [1] to [9] is formed on a substrate.

According to the present invention, there is provided a negative photosensitive resin composition capable of producing a partition wall having good ink repellency and capable of maintaining ink repellency even when irradiated with ultraviolet rays / ozone, and having a storage stability. It is possible to provide a good negative photosensitive resin composition and a homogeneous coating film of the negative photosensitive resin composition using the same.

It is sectional drawing which shows typically the manufacture example of the partition for optical elements using the negative photosensitive resin composition of this invention.

The acid value in this specification refers to the number of milligrams of potassium hydroxide required to neutralize resin acid or the like in 1 g of a sample, and is a value that can be measured according to the measurement method of JIS K 0070. . The unit is mgKOH / g.
The total solid content in the present specification refers to a partition-forming component among the components contained in the negative photosensitive resin composition, and other than volatile components that volatilize by heating in the partition-forming process such as solvent (E). All components are shown. Moreover, the value calculated from the case where it assumes that all the hydrolysable groups of the raw material hydrolysable silane compound become a siloxane bond and comprises the hydrolysis-condensation product is said.
The composition acid value in this specification is the acid value in the total solid content. The unit is mgKOH / g.
The fluorine atom content in the present specification is calculated from a chemical formula assuming that all of the hydrolyzable groups of the raw material hydrolyzable silane compound are composed of siloxane bonds to form the hydrolytic condensation product. Value.
In this specification, “(meth) acryloyl...” Is a general term for “methacryloyl...” And “acryloyl. The same applies to (meth) acrylate, (meth) acrylamide, and (meth) acrylic resin.
The hydrocarbon group in this specification refers to an organic group composed of only carbon and hydrogen.
In the present specification, a film coated with the negative photosensitive resin composition is referred to as a “coating film”, a dried state is referred to as a “film”, and a film obtained by curing the film is referred to as a “cured film”. .
The ink in the present specification is a general term for, for example, liquids having optically and electrically functions after being dried and cured, and is not limited to conventionally used coloring materials. Similarly, “pixels” formed by injecting the ink are also used to represent sections having optical and electrical functions, which are partitioned by the partition walls.
In this specification, the ink repellency refers to a property having moderately both water repellency and oil repellency in order to repel the ink, and can be evaluated by, for example, a method described later.
Embodiments of the present invention will be described below. In addition, unless otherwise indicated in this specification,% represents the mass%.

[Ink repellent (A)]
The ink repellent agent (A) is made of a fluorine-containing siloxane compound. The fluorine-containing siloxane compound is preferably a fluorine-containing siloxane compound having a silanol group and a fluorine atom content ratio (hereinafter also referred to as fluorine atom content) of 10 to 55% by mass. The number of silanol groups is preferably 0.2 to 3.5 as an average number per silicon atom.

The fluorine atom content in the fluorine-containing siloxane compound is more preferably 12 to 40% by mass, and particularly preferably 15 to 30% by mass. Within the above range, the partition obtained from the negative photosensitive resin composition has good ink repellency and can maintain good ink repellency even when irradiated with ultraviolet rays / ozone.

The number of silanol groups in the fluorinated siloxane compound is preferably 0.2 to 3.5, more preferably 0.2 to 2.0, and more preferably 0.5 to 1.5 as the average number per silicon atom. Is particularly preferred. When it is at least the lower limit of the above range, the solubility of the ink repellent agent (A) in the solvent and the compatibility with the other components in the negative photosensitive resin composition are improved, so that workability is improved. . When the amount is not more than the upper limit of the above range, the ink repellency of the partition obtained from the negative photosensitive resin composition becomes good.
The number of silanol groups in the fluorinated siloxane compound is calculated from the peak area ratio derived from various structures having or not having silanol groups as measured by ²⁹ Si-NMR.

Examples of the fluorinated siloxane compound include a fluorinated siloxane compound obtained by hydrolytic condensation of at least one hydrolyzable silane compound including a hydrolyzable silane compound containing at least fluorine. The hydrolytic condensation product of a hydrolyzable silane compound is usually a composition that itself has a molecular weight distribution. The fluorine-containing siloxane compound as the ink repellent agent (A) in the negative photosensitive resin composition of the present invention is composed of such a hydrolytic condensation product of a fluorine-containing hydrolyzable silane compound and is dissolved in a liquid or solvent at room temperature. Fluorine-containing curable silicones, which are normally solids and are usually called silicone resins, are preferred.

The fluorine-containing curable silicone is preferably a hydrolytic condensation product of a mixture containing a hydrolyzable silane compound (a-1) and a hydrolyzable silane compound (a-2) described below as essential components.

The hydrolyzable silane compound (a-1) includes an organic group having a perfluoroalkyl group which may contain one etheric oxygen atom having 3 to 10 carbon atoms in the silicon atom, and three hydrolyzable compounds. It is a trifunctional hydrolyzable silane compound to which groups are bonded. The number of functional groups is the total number of hydrolyzable groups bonded to one silicon atom, and optionally the number of hydroxyl groups bonded to one silicon atom (silanol group) and the number of bonds that can become silanol groups. Say. As the hydrolyzable silane compound (a-1), one type may be used alone, or two or more types may be used in combination.
By using the hydrolyzable silane compound (a-1), the cured film obtained by curing the negative photosensitive resin composition can exhibit water repellency and oil repellency (that is, ink repellency).

In the hydrolyzable silane compound (a-2), p (p is 0, 1 or 2) hydrocarbon groups and (4-p) hydrolyzable groups are bonded to a silicon atom (4- p) A functional hydrolyzable silane compound. The hydrolyzable silane compound (a-2) is preferably a tetrafunctional compound in which p is 0, or a trifunctional compound in which p is 1. As the hydrolyzable silane compound (a-2), one type may be used alone, or two or more types may be used in combination. When using 2 or more types together, a bifunctional compound can also be used together with a tetrafunctional compound and / or a trifunctional compound.

When the hydrolyzable silane compound (a-1) and the hydrolyzable silane compound (a-2) are represented using chemical formulas, the hydrolyzable silane compound (a-1) is represented by the following formula (a1): Compound (hereinafter also referred to as compound (a1)), and hydrolyzable silane compound (a-2) is a compound represented by the following formula (a2) (hereinafter also referred to as compound (a2)).

Symbols in the formulas (a1) and (a2) are as follows.
R ^F represents an organic group having a perfluoroalkyl group which may contain an etheric oxygen atom having 3 to 10 carbon atoms,
R ^H is a hydrocarbon group,
X represents a hydrolyzable group, respectively.
p represents a number which becomes 0, 1 or 2.

In the formula (a1), three Xs may be the same as or different from each other. For p = 2 in the formula (a2), the two R ^H may be the being the same or different, two X may be the being the same or different. Similarly, when p = 0, the four Xs may be the same or different from each other, and when p = 1, the three Xs may be the same or different from each other.

The group R ^F and the group R ^H in the ink repellent agent (A) used in the present invention are groups that exhibit water repellency, and oil repellency is mainly expressed by the group R ^F. The reason why the cured product of the ink repellent agent (A) exhibits sufficient oil repellency is considered to be because there is a group R ^F bonded to a silicon atom to which the group ^RH that impairs oil repellency is not bonded. In order for the cured product of the ink repellent agent (A) to exhibit sufficient oil repellency, the relative ratio of the group R ^F to the total of the groups R ^F and R ^{H in} the ink repellent agent (A). Is preferably high. For p = 0, is improved relative proportion becomes high oil repellency of groups R ^F in the ink repellent (A), also has the advantage of excellent film forming properties. When p = 1 or 2, the presence of the group ^RH to some extent makes the ink repellent agent (A) easily dissolved in a hydrocarbon solvent, and the negative photosensitive resin composition is applied to the surface of the substrate. There is an advantage that a relatively inexpensive solvent can be selected when forming the film.

The fluorine-containing curable silicone used in the present invention is a hydrolytic condensation product of a mixture containing a hydrolyzable silane compound (a-1) and a hydrolyzable silane compound not classified into the hydrolyzable silane compound (a-2). It may be.
Examples of hydrolyzable silane compounds other than the hydrolyzable silane compound (a-1) and the hydrolyzable silane compound (a-2) include hydrolyzable silane compounds (a-3), hexamethyldisiloxane and the like described later. A hydrolyzable silane compound having a functional group-containing organic group called a silane coupling agent, an organodisiloxane (a-4) described later, a cyclic organopolysiloxane such as octamethylcyclotetrasiloxane, and the like. (Excluding the hydrolyzable silane compounds (a-1) and (a-2)), hydrolyzable silane compounds (a-5) described later, and the like.
Among these, it is preferable to contain a hydrolyzable silane compound (a-3) and / or a hydrolyzable silane compound (a-5). In particular, the hydrolyzable silane compound (a-5) or the hydrolyzable silane compound (a-3) and the hydrolyzable silane compound (a-5) are preferably included.

The hydrolyzable silane compound (a-3) is a monofunctional hydrolyzable silane compound in which three organic groups and one hydrolyzable group are bonded to a silicon atom. A hydrolyzable silane compound represented by the following formula (a3) (hereinafter also referred to as compound (a3)) is preferred.

The organodisiloxane (a-4) is preferably an organodisiloxane represented by the following formula (a4) (hereinafter also referred to as compound (a4)). These are silane compounds capable of producing monofunctional siloxane units.

The symbols X and ^{R H} in the formula (a3) and (a4) is a similar to the X and ^{R H} in the formula (a1) and (a2). In formulas (a3) and (a4), W independently represents an organic group having one or more polymerizable functional groups selected from the group consisting of R ^F , R ^H or acryloyl group and methacryloyl group as a partial structure. To express. In formula (a4), W may be the same as or different from each other. In the formula (a3), two R ^H (three R ^H when W is R ^H ) may be the same or different from each other. In the formula (a4), four R ^H ( When W is R ^H , 5 or 6 R ^H ) may be the same as or different from each other.

When using the hydrolyzable silane compound (a3) or the organodisiloxane (a4), W of the compound the use of compounds such that R ^F, the relative proportions of radicals R ^F of the ink repellent (A) It is preferable because it can enhance and exhibit excellent oil repellency. It is preferable to use a compound in which W is ^RH because the solubility of the ink repellent agent (A) in a hydrocarbon solvent is improved. When a compound in which W is an organic group having one or more polymerizable functional groups selected from an acryloyl group and a methacryloyl group as a partial structure is used, the curability of the ink repellent agent (A) is improved, and hydrocarbons are used. This is preferable because the solubility in a system solvent is improved.

The hydrolyzable silane compound (a-5) includes an organic group having at least one polymerizable functional group selected from the group consisting of q (q is 1 or 2) acryloyl group and methacryloyl group on a silicon atom. , A hydrolyzable silane compound in which r (where r is 0 or 1 and q + r is 1 or 2) hydrocarbon groups and (4-qr) hydrolyzable groups are combined. is there. When the hydrolyzable silane compound (a-5) is used, the resulting ink repellent agent (A) tends to stay on the upper surface of the partition wall after exposure, and has the effect of making the upper surface of the partition wall ink repellent and making the side wall surface of the partition wall ink-philic. is there.
On the other hand, if a hydrolyzable silane compound having such a polymerizable functional group is not used as a raw material cocondensation component of the hydrolysis condensation product that preferably constitutes the ink repellent agent (A), the ink repellent agent is exposed after exposure. Since (A) easily moves to the side wall of the partition, there is an effect of making the upper surface of the partition and the side of the partition both have ink repellency. What is necessary is just to use these suitably according to a use.

As the hydrolyzable silane compound (a-5), a hydrolyzable silane compound represented by the following formula (a5) (hereinafter also referred to as compound (a5)) is preferable.

The symbols X and ^{R H} in the formula (a5) is a similar to the X and ^{R H} in the formula (a1) and (a2). In formula (a5), Q represents an organic group having a polymerizable functional group selected from the group consisting of an acryloyl group and a methacryloyl group. q is 1 or 2, r is 0 or 1 and q + r is 1 or 2. In the formula (a5), when q = 2, two Qs may be the same or different from each other. When q + r = 1, the three Xs are the same or different from each other. In the case of q + r = 2, the two Xs may be the same or different.

The hydrolyzable silane compound (a-5) is preferably a bifunctional monomer having q = 1 and r = 1, or a trifunctional monomer having q = 1 and r = 0. When the hydrolyzable silane compound (a-5) is used, one kind can be used alone, or two or more kinds can be used in combination.

Hereinafter, the compound (a1) to the compound (a5) will be described more specifically with examples. As the compounds (a1) to (a5), oligomers that are compounds obtained by hydrolytic condensation of a plurality of monomers classified into the respective compounds may be used as necessary.
X in the compounds (a1) to (a5) is a hydrolyzable group, for example, an organic group obtained by removing a hydrogen atom of a hydroxyl group from a monoalcohol, a halogen atom, an acyl group, an isocyanate group, or an amino group from an amine compound. There are organic groups excluding hydrogen atoms. X is preferably an alkoxy group having 4 or less carbon atoms or a halogen atom, particularly preferably CH ₃ O—, C ₂ H ₅ O—, or Cl—. These groups (X) become hydroxyl groups (silanol groups) by hydrolysis reaction, and further react between molecules to form Si—O—Si bonds.

As R ^F optionally contained in the compound (a3) and the compound (a4), the group represented by R ^F1 —Y— is preferable. R ^F1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 3 to 10 carbon atoms, and Y represents a divalent linking group containing no fluorine atom.

R ^F1 is preferably a perfluoroalkyl group having 4 to 8 carbon atoms or a perfluoroalkyl group containing an etheric oxygen atom having 4 to 9 carbon atoms, and particularly preferably a perfluoroalkyl group having 6 carbon atoms. When R ^F1 is in the above range, the partition obtained from the negative photosensitive resin composition has good ink repellency and can maintain good ink repellency even when irradiated with ultraviolet rays / ozone. Further, the ink repellent agent (A) is preferable because of its excellent solubility in a general-purpose solvent.
^Examples of the structure of R ^F1 include a linear structure, a branched structure, a ring structure, or a structure having a partial ring, but a linear structure is preferable.

Specific examples of R ^F1 include the following groups.
F (CF ₂ ) ₄ —, F (CF ₂ ) ₆ —, F (CF ₂ ) ₈ —.
CF ₃ CF ₂ OCF ₂ CF ₂ OCF _2- , CF ₃ CF ₂ OCF ₂ CF ₂ OCF ₂ CF _2- , CF ₃ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF _2- , CF ₃ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ —.
CF ₃ CF ₂ CF ₂ OCF _2- , CF ₃ CF ₂ CF ₂ OCF ₂ CF _2- , CF ₃ CF ₂ CF ₂ OCF (CF ₃ )-, CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF _2- , CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF _2- , CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ )-, CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CF ₂ —.

Y is not particularly limited as long as it is a divalent linking group, but — (CH ₂ ) _g —, —CH ₂ O (CH ₂ ) _g —, —SO ₂ NR ² — (CH ₂ ) _g —, or — A group represented by (C═O) —NR ² — (CH ₂ ) _g — is preferred. Here, g represents an integer of 1 to 5, and R ² represents a hydrogen atom, a methyl group, or an ethyl group. Y is particularly preferably — (CH ₂ ) _g — where g is 2 or 3. The direction of the group Y means that Si is bonded to the right side and R ^F1 is bonded to the left side.
When R ^F1 is a perfluoroalkyl group having 4 to 8 carbon atoms, Y is preferably a group represented by — (CH ₂ ) _g —. g is preferably an integer of 2 to 4, and — (CH ₂ ) ₂ — in which g is 2 is particularly preferable.

When R ^F1 is a perfluoroalkyl group containing an etheric oxygen atom having 4 to 9 carbon atoms, Y represents — (CH ₂ ) _h —, —CH ₂ O (CH ₂ ) _h —, —SO ₂ NR A group represented by ² — (CH ₂ ) _h — or — (C═O) —NR ² — (CH ₂ ) _h — is preferred. Here, h represents an integer of 1 to 5, and R ² represents a hydrogen atom, a methyl group, or an ethyl group. Y is particularly preferably — (CH ₂ ) ₂ — in which h is 2. The direction of bonding of the group Y means that Si is bonded to the right side and R ^F1 is bonded to the left side.

R ^H of the compound (a2), compound (a3), compound (a4) and compound (a5) is preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group, more preferably a methyl group or an ethyl group. A methyl group is particularly preferred.
As Q of the compound (a5), a group represented by Q ¹ -Z- is preferable. However, Q ¹ represents a (meth) acryloyloxy group. Z represents — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ —, or — (CH ₂ ) ₆ —, and — (CH ₂ ) ₃ — is preferred. Moreover, the same group is preferable also as a polymerizable functional group selected from the group consisting of an acryloyl group and a methacryloyl group that the compound (a3) and the compound (a4) optionally have.

As specific examples of the compound (a1), the following examples are preferable.
F (CF ₂ ) ₄ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
F (CF ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
F (CF ₂ ) ₈ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
_{_{_{_{CF 3 CF 2 CF 2 OCF (}}}} CF 3) CF 2 OCF 2 CF 2 CH 2 CH 2 Si (OCH 3) 3.

As specific examples of the compound (a2), the following examples are preferable.
Si (OCH ₃ ) ₄ , Si (OCH ₂ CH ₃ ) ₄ , CH ₃ Si (OCH ₃ ) ₃ ,
CH ₃ Si (OCH ₂ CH ₃ ) ₃ , CH ₃ CH ₂ Si (OCH ₃ ) ₃ ,
CH ₃ CH ₂ Si (OCH ₂ CH ₃ ) ₃ , (CH ₃ ) ₂ Si (OCH ₃ ) ₂ ,
(CH ₃ ) ₂ Si (OCH ₂ CH ₃ ) ₂ ,
A compound obtained by hydrolytic condensation of Si (OCH ₃ ) ₄ (for example, methyl silicate 51 (trade name) manufactured by Colcoat Co.),
Compounds obtained by hydrolytic condensation of Si (OCH ₂ CH ₃ ) ₄ (for example, ethyl silicate 40 and ethyl silicate 48 (both trade names) manufactured by Colcoat).

As specific examples of the compound (a3), the following examples are preferable.
_{_{_{_{F (CF 2) 6 CH 2}}}} CH 2 (CH 3) 2 Si (OCH 3), (CH 3) 3 Si (OCH 3), [CH 2 = C (CH 3) COO (CH 2) 3] (CH ₃ ) ₂ Si (OCH ₃ ).
As specific examples of the compound (a4), the following examples are preferable.
(CH ₃ ) ₃ SiOSi (CH ₃ ) ₃ .

As specific examples of the compound (a5), the following examples are preferable.
_{_{_{_{CH 2 = C (CH 3)}}}} COO (CH 2) 3 Si (OCH 3) 3,
_{_{_{_{CH 2 = C (CH 3)}}}} COO (CH 2) 3 Si (OCH 2 CH 3) 3,
_{_{_{CH 2 = CHCOO (CH 2)}}} 3 Si (OCH 3) 3,
_{_{_{CH 2 = CHCOO (CH 2)}}} 3 Si (OCH 2 CH 3) 3,
_{_{_{_{[CH 2 = C (CH 3}}}} ) COO (CH 2) 3] CH 3 Si (OCH 3) 2,
_{_{_{_{[CH 2 = C (CH 3}}}} ) COO (CH 2) 3] CH 3 Si (OCH 2 CH 3) 2.

The ink repellent agent (A) is a reaction product obtained by reacting each of the above compounds. This reaction is the production | generation of the silanol group by the hydrolysis reaction of a hydrolysable group, and the production | generation of the siloxane bond by the dehydration condensation reaction of silanol groups. In the ink-repellent agent (A) used in the negative photosensitive resin composition of the present invention, the silanol group generated by the hydrolysis reaction remains as a preferable embodiment in the hydrolysis-condensation product thus obtained. The number of silanol groups is preferably 0.2 to 3.5 on average per silicon atom.

When the ink repellent agent (A) is produced using the hydrolyzable silane compound (a-1) and the hydrolyzable silane compound (a-2), the hydrolyzable silane compound (a-1) and the hydrolyzing agent The co-condensation ratio with the functional silane compound (a-2) is not particularly limited as long as the fluorine atom content can be obtained, but 1 mol of the hydrolyzable silane compound (a-1) The hydrolyzable silane compound (a-2) is preferably used in an amount of 0.1 to 9 mol, particularly preferably 0.5 to 9 mol.

In addition to the hydrolyzable silane compound (a-1) and the hydrolyzable silane compound (a-2), the ink repellent agent (A) is added to the hydrolyzable silane compound (a-3) and / or the organodisiloxane ( When producing using a silane compound capable of producing a monofunctional siloxane unit such as a-4), the total amount of hydrolyzable silane compound (a-1) and hydrolyzable silane compound (a-2) The co-condensation ratio of the hydrolyzable silane compound (a-3) and / or organodisiloxane (a-4) is preferably 300 mol% or less, particularly preferably 200 mol% or less. However, when only organodisiloxane (a-4) is used, it is preferably at most 50 mol%, particularly preferably at most 5 mol%.

When the ink repellent agent (A) is produced using the hydrolyzable silane compound (a-5) in addition to the hydrolyzable silane compound (a-1) and the hydrolyzable silane compound (a-2), The cocondensation ratio of the hydrolyzable silane compound (a-5) with respect to the total amount of the hydrolyzable silane compound (a-1) and the hydrolyzable silane compound (a-2) is preferably 500 mol% or less, particularly 400 Mole% or less is preferable.

Further, in addition to the hydrolyzable silane compound (a-1) and the hydrolyzable silane compound (a-2), the ink repellent agent (A) is added to the monofunctional hydrolyzable silane compound (a-3) and hydrolyzate. In the case of producing using the degradable silane compound (a-5), the hydrolyzable silane compound (a-1) with respect to the total amount of the hydrolyzable silane compound (a-1) and the hydrolyzable silane compound (a-2) The co-condensation ratio of -3) is preferably 300 mol% or less, and the co-condensation ratio of the hydrolyzable silane compound (a-5) is preferably 500 mol% or less. Particularly preferably, the cocondensation ratio of the hydrolyzable silane compound (a-3) to the total amount of the hydrolyzable silane compound (a-1) and the hydrolyzable silane compound (a-2) is 200 mol% or less. The co-condensation ratio of the hydrolyzable silane compound (a-5) is 400 mol% or less.

The ink repellent agent (A) in the present invention may be composed of a single compound, but is usually a mixture composed of a plurality of compounds having different degrees of polymerization. That is, the ink repellent agent (A) uses hydrolyzable silane compound (a-1) and hydrolyzable silane compound (a-2) as essential components, and optionally hydrolyzable silane compound (a-3) and When produced using organodisiloxane (a-4), a compound having a structure having an average composition formula represented by the following formula (1) is obtained. However, since it is actually a product (partially hydrolyzed condensation product) in which a hydrolyzable group or silanol group remains, it is difficult to express this product by a chemical formula, and the average composition represented by formula (1) The formula is a chemical formula assuming that all of the hydrolyzable groups or silanol groups are siloxane bonds in the hydrolytic condensation product produced as described above.

In formula (1), preferred ranges of R ^F , R ^H , W, and p are the same as described above. m and n are each an integer of 1 or more, and k is 0 or an integer of 1 or more.

In the hydrolysis-condensation product having the structure of the average composition formula represented by the formula (1), the compound (a1) and the compound (a2), the compound (a3) and / or the compound (a4) optionally blended The monomer units derived from each are presumed to be randomly arranged. Note that the values of m and n are average values of the entire ink repellent agent (A), and m: n is a value for each of the hydrolyzable silane compound (a-2) and hydrolyzable silane compound (a-2). The condensation ratio is preferably within the above-mentioned range. The value of k is preferably (m + n): k as an average value of the entire ink repellent agent (A), and k is 1 or less with respect to 1 in the above-mentioned range, that is, (m + n). More preferably, it is more preferably at most .5, particularly preferably at most 0.1.

The ink repellent agent (A) uses hydrolyzable silane compound (a-1) and hydrolyzable silane compound (a-2) as essential components, and optionally hydrolyzable silane compound (a-5). When manufactured, it becomes a compound having the structure of the average composition formula represented by the following formula (2). However, since it is actually a product (partially hydrolyzed condensation product) in which a hydrolyzable group or silanol group remains, it is difficult to express this product by a chemical formula, and the average composition represented by formula (2) The formula is a chemical formula assuming that all of the hydrolyzable groups or silanol groups are siloxane bonds in the hydrolytic condensation product produced as described above.

In Formula (2), R ^F , R ^H , Q, and preferred ranges of p, q, and r are the same as described above. Each of s and t is an integer of 1 or more, and u is 0 or an integer of 1 or more.

In the hydrolysis-condensation product having the structure of the average composition formula represented by the formula (2), the compound (a1) and the compound (a2), any of the hydrolysis-condensation products represented by the formula (1) It is presumed that the monomer units derived from the compound (a5) blended in the above are randomly arranged. The values of s and t are the average values of the entire ink repellent agent (A), and s: t is the value of each of the hydrolyzable silane compound (a-2) and the hydrolyzable silane compound (a-2). The condensation ratio is preferably within the above-mentioned range. Further, the value of u is preferably (s + t): u as an average value of the entire ink repellent agent (A), and u is preferably 1 or less with respect to 1 in the above-mentioned range, that is, (s + t). It is more preferable that the ratio is 0.8 or less, and it is particularly preferable that the ratio be 0.1 or less.

The ink repellent agent (A) uses a hydrolyzable silane compound (a-3) and a hydrolyzable silane using the hydrolyzable silane compound (a-1) and the hydrolyzable silane compound (a-2) as essential components. When produced using the compound (a-5), it has a structure of an average composition formula in which the monomer unit derived from the compound (a5) of the formula (2) is further co-condensed with the formula (1). . The above-mentioned range is mentioned as a cocondensation ratio of each compound.

The number average molecular weight (Mn) of the ink repellent agent (A) in the present invention is preferably 500 or more, preferably less than 1,000,000, particularly preferably less than 10,000. When the number average molecular weight (Mn) is not less than the lower limit, the liquid repellency of the partition obtained using the negative photosensitive resin composition becomes good. When the number average molecular weight (Mn) is less than the upper limit value, the solubility in a solvent is improved, so that there is an advantage that workability is improved. The number average molecular weight (Mn) of the ink repellent agent (A) can be adjusted by selecting reaction conditions and the like.

(Manufacture of ink repellent agent (A))
The ink repellent agent (A) comprising a fluorine-containing siloxane compound can be produced by subjecting the above-mentioned mixture of hydrolyzable silane compounds to hydrolysis and condensation reactions. The reaction conditions usually used for the reaction for hydrolyzing and condensing the hydrolyzable silane compound can be applied to the reaction without any particular limitation. In this reaction, it is preferable to use a commonly used inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, or an organic acid such as acetic acid, oxalic acid or maleic acid as a catalyst. The amount of the catalyst used is preferably 0.01 to 10% by mass, particularly preferably 0.1 to 1% by mass, based on the total amount of the hydrolyzable silane compound.

A solvent may be used for the reaction. Examples of the solvent include water; alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, 2-methyl-2-propanol, ethylene glycol, glycerin, and propylene glycol; Ketones such as acetone, methyl isobutyl ketone and cyclohexanone; Cellsolves such as 2-methoxyethanol and 2-ethoxyethanol; 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2 -Carbitols such as butoxyethoxy) ethanol; Esters such as methyl acetate, ethyl acetate, propylene glycol monomethyl ether acetate, 4-butyrolactone, butyl acetate, 3-methoxybutyl acetate; Glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, monoalkyl ethers of glycols such as dipropylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, dialkyl ethers glycol and dipropylene glycol dimethyl ether. Other examples include benzyl alcohol, N, N-dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone and the like. A solvent may be used individually by 1 type, or may use 2 or more types together.
The solvent is blended in the negative photosensitive resin composition of the present invention in the form of an ink repellent solution.

The content ratio of the ink repellent agent (A) in the negative photosensitive resin composition of the present invention is preferably 0.01 to 10% by mass in the total solid content in the negative photosensitive resin composition, preferably 0.1 to 6 mass% is more preferred, and 0.5-3 mass% is particularly preferred. By setting the content ratio of the ink repellent agent (A) in the above range, the storage stability of the negative photosensitive resin composition is improved, and the partition wall of the optical element obtained from the negative photosensitive resin composition is improved. Ink repellency is improved, and a partition having a smooth surface is obtained.

[Alkali-soluble resin (B)]
The alkali-soluble resin (B) is a photosensitive resin having an acidic group and an ethylenic double bond in one molecule. By having an ethylenic double bond in the molecule, the exposed portion of the negative photosensitive resin composition is polymerized and cured by the radical generated by the photopolymerization initiator (C). By having an acidic group, an unexposed portion of the uncured negative photosensitive resin composition can be selectively removed using an alkali developer, and as a result, a partition can be formed.

Although it does not specifically limit as said acidic group, A carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a phosphoric acid group etc. are mentioned, These may be used individually by 1 type and may use 2 or more types together. Good.

Although it does not specifically limit as said ethylenic double bond, The double bond which addition polymerization groups, such as a (meth) acryloyl group, an allyl group, a vinyl group, a vinyloxy group, is mentioned, These are used individually by 1 type. Or two or more of them may be used in combination. In addition, part or all of the hydrogen atoms of the addition polymerizable group may be substituted with a hydrocarbon group, preferably a methyl group.

The alkali-soluble resin (B) is not particularly limited, but is a resin (B1-1) having a side chain having an acidic group and a side chain having an ethylenic double bond, and an epoxy group having an acidic group and an ethylenic double chain. And a resin (B1-2) into which a bond is introduced. These may be used alone or in combination of two or more.

Resin (B1-1) includes a side chain having a reactive group obtained by copolymerizing a monomer having a reactive group such as a hydroxyl group, a carboxyl group, and an epoxy group and a monomer having an acidic group; It can be synthesized by dissolving a copolymer having a side chain having an acidic group, a compound having a functional group capable of bonding to the reactive group and an ethylenic double bond in a solvent and reacting them.

Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl ( (Meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N-hydroxymethyl (meth) acrylate Amide, N, N-bis (hydroxymethyl) (meth) acrylamide.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof. These monomers are also used as monomers having an acidic group.
Examples of the monomer having an epoxy group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate.
The monomer having an acidic group is not particularly limited, but in addition to the monomer having a carboxyl group, examples of the monomer having a phosphate group include 2- (meth) acryloyloxyethanephosphoric acid. It is done.

The copolymerization of the monomer having a reactive group and the monomer having an acidic group can be performed by a conventionally known method.
Examples of the monomer having a hydroxyl group as a reactive group include an acid anhydride having an ethylenic double bond, a compound having an isocyanate group and an ethylenic double bond, and a compound having an acyl chloride group and an ethylenic double bond. Can be mentioned.
Examples of the acid anhydride having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 3,4,5,6-tetrahydrophthal And acid 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.

Examples of the monomer having a carboxyl group as a reactive group include compounds having a carboxy group and an ethylenic double bond. Specific examples of the compound include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof. The hydroxyl group generated here may be reacted with an acid anhydride in which the dehydration condensation part of carboxylic acid forms part of the cyclic structure to introduce a carboxyl group into the resin (B1-1).

Examples of the monomer having an epoxy group as a reactive group include compounds having an epoxy group and an ethylenic double bond. Examples of the compound include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate.

Resin (B1-2) can be synthesized by reacting an epoxy resin with a compound having a carboxyl group and an ethylenic double bond and then reacting with a polybasic carboxylic acid or its anhydride. .
Specifically, an ethylenic double bond is introduced into the epoxy resin by reacting an epoxy resin with a compound having a carboxyl group and an ethylenic double bond. Next, a carboxyl group can be introduce | transduced by making polybasic carboxylic acid or its anhydride react with the epoxy resin in which the ethylenic double bond was introduce | transduced.

The epoxy resin is not particularly limited, but bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenol methane type epoxy resin, epoxy resin having naphthalene skeleton, An epoxy resin having a biphenyl skeleton represented by (B1-2a), an epoxy resin represented by the following formula (B1-2b), an epoxy resin having a biphenyl skeleton represented by the following formula (B1-2c), and the like It is done.

(In the formula (B1-2a), v is 1 to 50, preferably 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 substituent. (It may be substituted with an optionally substituted phenyl group.)

(In the formula (B1-2b), 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, and w is 0 to 10 .)

(In Formula (B1-2c), each hydrogen atom of the benzene ring may be independently substituted with an alkyl group having 1 to 12 carbon atoms, a halogen atom, or an optionally substituted phenyl group. u is 0-10.)

The epoxy resins represented by the formulas (B1-2a) to (B1-2c) are reacted with a compound having a carboxyl group and an ethylenic double bond, and then reacted with a polybasic carboxylic acid anhydride. In this case, it is preferable to use a mixture of dicarboxylic anhydride and tetracarboxylic dianhydride as the polybasic carboxylic anhydride. By changing the ratio of dicarboxylic anhydride and tetracarboxylic dianhydride, the molecular weight can be controlled.

As the resin (B1-2), a commercially available product can be used. As commercial products, all are trade names, such as KAYARAD PCR-1069, K-48C, CCR-1105, CCR-1115, CCR-1159H, CCR-1235, TCR-1025, TCR-1064H, TCR-1286H, ZAR- 1535H, ZAR-2002H, ZFR-1491H, ZFR-1492H, ZCR-1571H, ZCR-1569H, ZCR-1580H, ZCR-1581H, ZCR-1588H, ZCR-1642H, ZCR-1664H (above, manufactured by Nippon Kayaku Co., Ltd.) And EX1010 (manufactured by Nagase ChemteX Corporation).

Examples of the monomer (B1-3) include 2,2,2-triacryloyloxymethylethylphthalic acid (NK ester, CBX-1, manufactured by Shin-Nakamura Chemical Co., Ltd.).

As the alkali-soluble resin (B), peeling of the coating film during development is suppressed, a high-resolution pattern can be obtained, the linearity of the line is good, and the appearance after the post-baking process is maintained. The resin (B1-2) is preferably used in that a smooth coating surface can be easily obtained.
Examples of the resin (B1-2) include a resin in which an acidic group and an ethylenic double bond are introduced into a bisphenol A type epoxy resin, a resin in which an acidic group and an ethylenic double bond are introduced into a bisphenol F type epoxy resin, phenol Resin with acidic group and ethylenic double bond introduced into novolac epoxy resin, resin with acidic group and ethylenic double bond introduced into cresol novolac epoxy resin, or acidic group into trisphenolmethane epoxy resin A resin in which an ethylenic double bond is introduced, and a resin in which an acidic group and an ethylenic double bond are introduced into the epoxy resins represented by the formulas (B1-2a) to (B1-2c) are particularly preferable.

The mass average molecular weight (Mw) of the alkali-soluble resin (B) used in the present invention is preferably 1.5 × 10 ³ to 30 × 10 ³ , particularly preferably 2 × 10 ³ to 15 × 10 ³ . The number average molecular weight (Mn) is preferably 500 to 20 × 10 ³ and particularly preferably 1.0 × 10 ³ to 10 × 10 ³ . When the mass average molecular weight (Mw) and the mass average molecular weight (Mn) are not less than the lower limit of the above range, curing at the time of exposure is sufficient, and when the mass average molecular weight (Mw) is not more than the upper limit of the above range, the developability is good.

The number of ethylenic double bonds that the alkali-soluble resin (B) has in one molecule is preferably 3 or more on average, and particularly preferably 6 or more. When the number of ethylenic double bonds is at least the lower limit of the above range, the alkali solubility between the exposed and unexposed portions is likely to be different, and a fine pattern can be formed with a smaller exposure amount.

The acid value of the alkali-soluble resin (B) is preferably 10 to 200 mgKOH / g, more preferably 30 to 150 mgKOH / g, and particularly preferably 50 to 100 mgKOH / g. When the acid value is in the above range, the negative photosensitive resin composition has good storage stability and developability.

The alkali-soluble resin (B) contained in the negative photosensitive resin composition may be one type or a mixture of two or more types.
The content of the alkali-soluble resin (B) in the total solid content in the negative photosensitive resin composition of the present invention is preferably 12 to 40% by mass, more preferably 14 to 38% by mass, and 16 to 36% by mass. Particularly preferred. When the content ratio is in the above range, the storage stability of the negative photosensitive resin composition is good.

[Photoinitiator (C)]
The photopolymerization initiator (C) is not particularly limited as long as it is a compound having a function as a photopolymerization initiator, but is preferably a compound that generates a radical by light.

Examples of the photopolymerization initiator (C) include α-diketones such as benzyl, diacetyl, methylphenylglyoxylate, and 9,10-phenanthrenequinone; acyloins such as benzoin; benzoin methyl ether, benzoin ethyl ether, benzoin Acyloin ethers such as isopropyl ether; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diisopropyl Thioxanthones such as thioxanthone and thioxanthone-4-sulfonic acid; benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, etc. Nzophenones; acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2′-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl- [4- Acetophenones such as (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; anthraquinone, 2-ethylanthraquinone, Quinones such as camphorquinone and 1,4-naphthoquinone; ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate Aminobenzoic acids such as 2-ethylhexyl perfume; Halogen compounds such as phenacyl chloride and trihalomethylphenyl sulfone; Acylphosphine oxides; Peroxides such as di-t-butyl peroxide; 1,2-octanedione, 1 -[4- (phenylthio)-, 2- (O-benzoyloxime), ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyl) Oxime esters such as triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine, N-methyldiethanolamine, and aliphatic amines such as diethylaminoethyl methacrylate; 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mel Hept benzothiazole, 1,4-butanol-bis (3-mercapto butyrate), tris (2-mercapto-propanoyl oxyethyl) isocyanurate, pentaerythritol tetrakis (3-mercapto butyrate) thiol compound such as and the like.

Of these, benzophenones, aminobenzoic acids, aliphatic amines, and thiol compounds are preferably used together with other radical initiators because they may exhibit a sensitizing effect.

As the photopolymerization initiator (C), 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Butan-1-one, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime), ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazoyl-3-yl] -1- (O-acetyloxime), 4,4'-bis (diethylamino) benzophenone, or 2,4-diethylthioxanthone is preferred. Furthermore, the combination of these and the said benzophenones is especially preferable.

A commercial item can be used for a photoinitiator (C). Commercially available products include IRGACURE907 (trade name, manufactured by BASF, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one), IRGACURE369 (trade name, manufactured by BASF, 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one) and the like.
The photopolymerization initiator (C) contained in the negative photosensitive resin composition may be one type or a mixture of two or more types.
The content of the photopolymerization initiator (C) in the total solid content in the negative photosensitive resin composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and 5 to 15% by mass. % Is particularly preferred. Within the above range, the developability of the negative photosensitive resin composition is good.

[Crosslinking agent (D)]
The negative photosensitive resin composition of the present invention may contain a crosslinking agent (D) as an optional component that promotes radical curing. As a crosslinking agent (D), the compound which has two or more ethylenic double bonds in 1 molecule, and does not have an acidic group is preferable. When a negative photosensitive resin composition contains a crosslinking agent (D), the sclerosis | hardenability of the said alkali-soluble resin (B) at the time of exposure improves, and the exposure amount at the time of forming a partition can be reduced.

The crosslinking agent (D) having two or more ethylenic double bonds in one molecule and having no acidic group is not particularly limited as long as it is a compound having this condition, but diethylene glycol di (meth) acrylate, tetra Ethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etoxy Isocyanuric acid triacrylate, ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) Phenyl} methane, N, N′-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), urethane acrylate and the like. These may be used alone or in combination of two or more.

Commercial products can be used as the crosslinking agent (D). Commercially available products include KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), NK ester A-9530 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., dipenta Erythritol pentaacrylate and dipentaerythritol hexaacrylate)), NK Este A-9300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated isocyanuric acid triacrylate), NK ester A-9300-1CL (trade name, new Nakamura Chemical Co., Ltd., ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate), BANI-M (trade name, manufactured by Maruzen Petrochemical Co., Ltd., Bis {4- (allylbicyclo [2.2.1] Hept-5-ene-2,3-dicarboxy (Mid) phenyl} methane), BANI-X (trade name, manufactured by Maruzen Petrochemical Co., Ltd., N, N′-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3- Dicarboximide)) and the like. Examples of urethane acrylate include KAYARAD UX series manufactured by Nippon Kayaku Co., Ltd., and specific product names include UX-3204, UX-6101, UX-0937, DPHA-40H, UX-5000, UX-5002D-P20. V # 802 (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd., a mixture of dipentaerythritol acrylate, tripentaerythritol acrylate, and tetrapentaerythritol acrylate).

Among them, KAYARAD DPHA and NK ester A-9530 are preferable because they improve the sensitivity of the cured film obtained from the negative photosensitive resin composition. NK esters A-9300, BANI-M and BANI-X are preferred from the viewpoint of imparting hardness to the cured film and suppressing thermal sagging. NK ester A-9300-1CL is preferable from the viewpoint of imparting flexibility to the cured film. Urethane acrylate is preferable because an appropriate development time can be realized and developability is improved.

The content ratio of the crosslinking agent (D) contained in the negative photosensitive resin composition is preferably in the following range. The total amount of the alkali-soluble resin (B) and the crosslinking agent (D) is 50 to 95% by mass in the total solid content, and the content of the alkali-soluble resin (B) with respect to the content of the crosslinking agent (D) The mass% of the amount, that is, the mass of the alkali-soluble resin (B) / the mass of the crosslinking agent (D) × 100 is preferably adjusted to be 15 to 85 mass%. The total amount of the alkali-soluble resin (B) and the crosslinking agent (D) is 60 to 92% by mass in the total solid content, and the mass of the alkali-soluble resin (B) / the mass of the crosslinking agent (D) × 100. 20 to 70% by mass, the total amount of the alkali-soluble resin (B) and the crosslinking agent (D) is 65 to 90% by mass in the total solid content, and the mass / weight of the alkali-soluble resin (B) / The mass × 100 of the crosslinking agent (D) is particularly preferably 20 to 55% by mass. When it is in the above range, the storage stability of the negative photosensitive resin composition becomes good, and when the patterned substrate obtained using the negative photosensitive resin composition is formed, the ink-jet ink in the pixel becomes wet. Good.

[Solvent (E)]
The negative photosensitive resin composition of this invention contains a solvent (E) as needed. When the solvent (E) is contained, the viscosity of the negative photosensitive resin composition is reduced, so that the negative photosensitive resin composition can be easily applied on the substrate. A uniform negative photosensitive resin composition coating film can be formed. In addition, when a negative photosensitive resin composition does not contain a solvent (E), the coating film of a negative photosensitive resin composition becomes the same as the film | membrane of a negative photosensitive resin composition.
The solvent (E) contained in the negative photosensitive resin composition of the present invention is the ink repellent agent (A), alkali-soluble resin (B), photopolymerization initiator (C) contained in the negative photosensitive resin composition. ) If necessary, the cross-linking agent (D) and further optional components described later are uniformly dissolved or dispersed to uniformly and easily apply the negative photosensitive resin composition to the substrate on which the partition walls are formed. The solvent is not particularly limited as long as it has a function of reacting and does not have reactivity with these components. For example, a solvent similar to the solvent used in the synthesis of the ink repellent agent (A) can be used.

The content of the solvent (E) contained in the negative photosensitive resin composition varies depending on the composition and use of the negative photosensitive resin composition, but is 50 to 99% by mass in the negative photosensitive resin composition. It is preferably blended, more preferably 60 to 95% by mass, and particularly preferably 65 to 90% by mass.

[Negative photosensitive resin composition and coating film]
The acid value (hereinafter also referred to as composition acid value) of the negative photosensitive resin composition of the present invention is from 6 to 30 mgKOH / g, preferably from 8 to 25 mgKOH / g, particularly preferably from 10 to 22 mgKOH / g. When the acid value of the negative photosensitive resin composition is in the above range, the storage stability of the negative photosensitive resin composition becomes good, and a coating film of the negative photosensitive resin composition is formed on the substrate. The coating film of the present invention having an excellent appearance can be obtained. The formation of the coating film can be performed, for example, in the same manner as in the coating film forming step for the optical element partition wall described below.
The reason why the storage stability is improved when the acid value of the negative photosensitive resin composition is in the above range is not clear. The ink repellent agent (A) has a silanol group and is easily self-condensed by an acid catalyst. When the composition acid value is not less than the lower limit of the above range, the developability of the coating film of the negative photosensitive resin composition becomes good, and when it is not more than the upper limit of the above range, the negative photosensitive resin composition It is considered that the storage stability is excellent.
The composition acid value is determined by the acid value and content of the alkali-soluble resin (B). Each preferred range is as described above.

The negative photosensitive resin composition of the present invention contains an ink repellent agent (A), an alkali-soluble resin (B), and a photopolymerization initiator (C). Furthermore, a crosslinking agent (D) and a solvent (E) are contained as needed. Further, the following thermal crosslinking agent (F), black colorant (G), polymer dispersant (H), dispersion aid (I), silane coupling agent (J), fine particles (K), phosphoric acid compound ( L) and other additives may be included.

(Thermal crosslinking agent (F))
The thermal crosslinking agent (F) is a compound having two or more groups capable of reacting with a carboxyl group and / or a hydroxyl group. When the alkali-soluble resin (B) has a carboxyl group and / or a hydroxyl group, the thermal crosslinking agent (F) reacts with the alkali-soluble resin (B) to increase the crosslinking density of the cured film and improve the heat resistance. Have

Preferred examples of the thermal crosslinking agent (F) include at least one selected from the group consisting of amino resins, epoxy compounds, oxazoline compounds, polyisocyanate compounds, and polycarbodiimide compounds. These compounds may be used alone or in combination of two or more.

The content of the thermal crosslinking agent (F) in the total solid content in the negative photosensitive resin composition of the present invention is preferably 1 to 50% by mass, particularly preferably 5 to 30% by mass. The developability of the negative photosensitive resin composition obtained when it is in the above range becomes good.

(Black colorant (G))
When the negative photosensitive resin composition of the present invention is used for forming a black matrix that is a grid-like black portion surrounding the three color pixels R, G, and B of a color filter of a liquid crystal display element, a black colorant ( G) is preferably included. Examples of the black colorant (G) include carbon black, aniline black, anthraquinone black pigment, and perylene black pigment. I. Pigment black 1, 6, 7, 12, 20, 31 etc. are mentioned. As the black colorant (G), organic pigments such as red pigments, blue pigments, green pigments, azomethine pigments, and mixtures of inorganic pigments can also be used. As the black colorant (G), carbon black is preferable from the viewpoint of cost and light shielding properties, and the carbon black may be surface-treated with a resin or the like. Moreover, in order to adjust a color tone, a blue pigment and a purple pigment can be used together.

Carbon black having a specific surface area of 50 to 200 m ² / g by the BET method is preferable from the viewpoint of the shape of the black matrix. When the specific surface area is 50 m ² / g or more, the black matrix shape is hardly deteriorated. When it is 200 m ² / g or less, it is not necessary to blend a large amount of dispersion aid in order to develop various physical properties without excessively adsorbing the dispersion aid on carbon black.
Moreover, as carbon black, the oil absorption amount of dibutyl phthalate is preferably 120 cc / 100 g or less from the viewpoint of sensitivity, and a smaller amount is more preferable.

Furthermore, the average primary particle diameter of the carbon black observed with a transmission electron microscope is preferably 20 to 50 nm. When the average primary particle diameter is 20 nm or more, the negative photosensitive resin composition can be dispersed at a high concentration with the negative photosensitive resin composition, and a negative photosensitive resin composition with good temporal stability can be easily obtained. When it is 50 nm or less, the shape of the black matrix is hardly deteriorated. Further, the average secondary particle diameter by observation with a transmission electron microscope is preferably 80 to 200 nm.

When the negative photosensitive resin composition of the present invention contains a black colorant (G) and is used for black matrix formation or the like, the black colorant (G) in the total solid content of the negative photosensitive resin composition is contained. The proportion is preferably 15 to 65% by mass, particularly preferably 20 to 50% by mass. The negative photosensitive resin composition obtained when it is in the above range has good sensitivity, and the formed partition has excellent light shielding properties.

(Polymer dispersant (H))
When the negative photosensitive resin composition contains a dispersible material such as the black colorant (G), it is preferable to contain a polymer dispersant (H) in order to improve the dispersibility. The polymer dispersant (H) is not particularly limited, and is urethane, polyimide, alkyd, epoxy, polyester, melamine, phenol, acrylic, polyether, vinyl chloride, vinyl chloride acetic acid. A vinyl copolymer system, a polyamide system, a polycarbonate system, and the like can be mentioned, and a urethane system or a polyester system is preferable. The polymer dispersant (H) may have a structural unit derived from ethylene oxide and / or propylene oxide.

When the polymer dispersant (H) is used for dispersing the black colorant (G), the polymer dispersant (H) having a basic group is used in consideration of the affinity for the black colorant (G). It is preferable to use it. Although it does not specifically limit as a basic group, A primary, secondary, or tertiary amino group is mentioned.
A commercially available product may be used as the polymer dispersant (H). Commercially available products include Disparon DA-7301 (trade name, manufactured by Enomoto Kasei Co., Ltd.), BYK161, BYK162, BYK163, BYK182 (all trade names, manufactured by BYK-Chemie), Solspurs 5000, Solspers 17000 (all trade names, Zeneca).
The amount of the polymer dispersant (H) used is preferably 5 to 30% by mass, particularly preferably 10 to 25% by mass, based on the black colorant (G). When the amount used is not less than the lower limit of the above range, the dispersibility of the black colorant (G) is improved, and when it is not more than the upper limit of the above range, the developability of the negative photosensitive resin composition becomes good. .

(Dispersion aid (I))
The negative photosensitive resin composition of the present invention may contain a phthalocyanine pigment derivative or a metal phthalocyanine sulfonamide compound as the dispersion aid (I). The dispersion aid (I) is considered to have a function of improving the dispersion stability by adsorbing to the dispersible material such as the black colorant (G) and the polymer dispersant (H).

(Silane coupling agent (J))
When the silane coupling agent (J) is used, the substrate adhesion of the cured film formed from the obtained negative photosensitive resin composition is improved.
Specific examples of the silane coupling agent (J) include tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-chloropropyl. Examples include trimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, heptadecafluorooctylethyltrimethoxysilane, polyoxyalkylene chain-containing triethoxysilane, and the like. These may be used alone or in combination of two or more.

The content of the silane coupling agent (J) in the total solid content in the negative photosensitive resin composition of the present invention is preferably 0.1 to 20% by mass, particularly preferably 1 to 10% by mass. When it is at least the lower limit of the above range, the substrate adhesion of the cured film formed from the negative photosensitive resin composition is improved, and when it is at most the upper limit of the above range, the ink repellency is good.

(Fine particles (K))
The negative photosensitive resin composition may contain fine particles (K) as necessary. By mix | blending microparticles | fine-particles (K), it becomes possible to prevent the heat dripping of the partition obtained from a negative photosensitive resin composition.
The fine particles (K) are not particularly limited, and inorganic fine particles such as silica, zirconia, magnesium fluoride, tin-doped indium oxide (ITO) and antimony-doped tin oxide (ATO); organic materials such as polyethylene and polymethyl methacrylate (PMMA) In view of heat resistance, inorganic fine particles are preferable, and in view of availability and dispersion stability, silica or zirconia is particularly preferable. In addition, when the negative photosensitive resin composition contains the black colorant (G) and the polymer dispersant (H), the fine particles ( K) is preferably negatively charged. Furthermore, considering the exposure sensitivity of the negative photosensitive resin composition, it is preferable that the fine particles do not absorb the light irradiated at the time of exposure, and i-line (365 nm), h-line ( 405 nm) and g-line (436 nm) are not particularly absorbed.
The particle diameter of the fine particles (K) is preferably 1 μm or less, particularly preferably 200 nm or less, because the surface smoothness of the partition wall is improved.

(Phosphate compound (L))
The negative photosensitive resin composition of the present invention may contain a phosphoric acid compound (L) as necessary. Adhesiveness with a board | substrate can be improved because a negative photosensitive resin composition contains a phosphoric acid compound (L). Examples of the phosphoric acid compound (L) include mono (meth) acryloyloxyethyl phosphate, di (meth) acryloyloxyethyl phosphate, tris (meth) acryloyloxyethyl phosphate, and the like.

(Other additives)
The negative photosensitive resin composition of the present invention may further contain a curing accelerator, a thickener, a plasticizer, an antifoaming agent, a leveling agent, a repellency inhibitor, an ultraviolet absorber, and the like as necessary. .

(Preferred combination of negative photosensitive resin composition)
In the negative photosensitive resin composition of the present invention, it is preferable to select a composition and a blending ratio in accordance with applications and required characteristics.
The preferable composition of the various compounding components in the negative photosensitive resin composition of the present invention is shown below.

<Combination 1>
Ink repellent agent (A): Hydrolyzable co-condensate of hydrolyzable silane compounds (a-1), (a-2), (a-3), hydrolyzable silane compounds (a-1), (a- 2) From the hydrolyzed cocondensate of (a-5) and the hydrolyzable cocondensate of hydrolyzable silane compounds (a-1), (a-2), (a-3) and (a-5) At least one ink repellent agent selected from 0.01 to 10% by mass in the total solid content of the negative photosensitive resin composition;
Alkali-soluble resin (B): a resin in which acidic groups and ethylenic double bonds are introduced into bisphenol A type epoxy resin, a resin in which acidic groups and ethylenic double bonds are introduced into bisphenol F type epoxy resin, phenol novolac type Resins with acidic groups and ethylenic double bonds introduced into epoxy resins, resins with acidic groups and ethylenic double bonds introduced into cresol novolac type epoxy resins, and acidic groups and ethylenic groups into trisphenolmethane type epoxy resins At least one resin selected from the group consisting of resins into which a double bond has been introduced, wherein 12 to 40% by mass in the total solid content in the negative photosensitive resin composition;

Photopolymerization initiator (C): 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane It is at least one photopolymerization initiator selected from 1-one, 1,2-octanedione and 4,4′-bis (diethylamino) benzophenone, and is added to the total solid content in the negative photosensitive resin composition by 0.1. 1-50% by mass,
Solvent (E): at least one selected from the group consisting of water, 2-propanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol ethyl methyl ether, butyl acetate, 4-butyrolactone and cyclohexanone One solvent, 50 to 99% by mass in the negative photosensitive resin composition.

<Combination 2>
Ink repellent agent (A): Hydrolyzable co-condensate of hydrolyzable silane compounds (a-1), (a-2), (a-3), hydrolyzable silane compounds (a-1), (a- 2) Hydrolyzed cocondensate of (a-5) and hydrolyzed cocondensate of hydrolyzable silane compounds (a-1), (a-2), (a-3), (a-5) At least one ink repellent agent selected from the group consisting of 0.01 to 10% by mass in the total solid content of the negative photosensitive resin composition,
Alkali-soluble resin (B): a resin in which acidic groups and ethylenic double bonds are introduced into bisphenol A type epoxy resin, a resin in which acidic groups and ethylenic double bonds are introduced into bisphenol F type epoxy resin, phenol novolac type Resins with acidic groups and ethylenic double bonds introduced into epoxy resins, resins with acidic groups and ethylenic double bonds introduced into cresol novolac type epoxy resins, and acidic groups and ethylenic groups into trisphenolmethane type epoxy resins At least one resin selected from the group consisting of resins into which a double bond has been introduced, wherein 12 to 40% by mass in the total solid content in the negative photosensitive resin composition;

Photopolymerization initiator (C): 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane At least one photopolymerization initiator selected from the group consisting of 1-one, 1,2-octanedione, and 4,4′-bis (diethylamino) benzophenone, wherein the total solid content in the negative photosensitive resin composition is 0.1 to 50% by mass,

Cross-linking agent (D): pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated isocyanuric acid triacrylate, and urethane At least one cross-linking agent selected from the group consisting of acrylates, 50 to 75% by mass in the total solid content in the negative photosensitive resin composition,

Solvent (E): at least one selected from the group consisting of water, 2-propanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol ethyl methyl ether, butyl acetate, 4-butyrolactone, and cyclohexanone One solvent, 50 to 99% by mass in the negative photosensitive resin composition.

<Combination 3>
Ink repellent agent (A): Hydrolyzable co-condensate of hydrolyzable silane compounds (a-1), (a-2), (a-3), hydrolyzable silane compounds (a-1), (a- 2) Hydrolyzed cocondensate of (a-5) and hydrolyzed cocondensate of hydrolyzable silane compounds (a-1), (a-2), (a-3), (a-5) At least one ink repellent agent selected from the group consisting of 0.01 to 10% by mass in the total solid content of the negative photosensitive resin composition,
Alkali-soluble resin (B): an epoxy resin having a biphenyl skeleton represented by general formula (B1-2a), an epoxy resin represented by general formula (B1-2b), and a general formula (B1-2c) At least one resin selected from the group consisting of epoxy resins having a biphenyl skeleton, wherein the total solid content in the negative photosensitive resin composition is 12 to 40% by mass;

Photopolymerization initiator (C): 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime), and ethanone 1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), which is at least one photoinitiator selected from 0% in the total solid content in the negative photosensitive resin composition. 1-50% by mass,

Cross-linking agent (D): pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated isocyanuric acid triacrylate, and urethane At least one cross-linking agent selected from the group consisting of acrylates, 20 to 50% by mass in the total solid content in the negative photosensitive resin composition;
Solvent (E): at least one selected from the group consisting of water, 2-propanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol ethyl methyl ether, butyl acetate, 4-butyrolactone, and cyclohexanone One solvent, 50 to 99% by mass in the negative photosensitive resin composition,
Black colorant (G): at least one black colorant selected from the group consisting of a mixture of organic pigments such as carbon black, red pigment, blue pigment, and green pigment, and an azomethine pigment, a negative photosensitive resin 15-65% by weight in the total solids in the composition.

[Method for producing negative photosensitive resin composition]
As a method for producing a negative photosensitive resin composition, an ink repellent agent (A), an alkali-soluble resin (B), a photopolymerization initiator (C), a crosslinking agent (D) as necessary, a solvent (E), Crosslinker (F), black colorant (G), polymer dispersant (H), dispersion aid (I), silane coupling agent (J), fine particles (K), phosphate compound (L) and other A method of mixing with an additive is preferred.

The negative photosensitive resin composition of the present invention is used as a material such as photolithography in the same manner as an ordinary negative photosensitive resin composition, and the obtained cured film is an ordinary negative photosensitive resin composition. It can be used as a member of an optical element in which a cured film is used. In particular, when the negative photosensitive resin composition of the present invention is used for forming a partition for an optical element having a plurality of pixels and a partition located between adjacent pixels on a substrate, such as ultraviolet / ozone cleaning treatment A partition wall having sufficient ink repellency can be obtained even after the lyophilic treatment, which is preferable.

[Method for producing partition for optical element]
The present invention is applied to the manufacture of a partition for an optical element having a plurality of pixels and a partition located between adjacent pixels on a substrate.
The negative photosensitive resin composition of the present invention is applied onto the substrate to form a coating film (coating film forming step), then the coating film is heated (prebaking step), and then the partition walls of the coating film Then, only the part to be exposed is photocured (exposure process), then the coating film other than the photocured part is removed to form a partition consisting of the photocured part of the coating film (development process), and then By heating the formed partition wall (post-baking step), a partition wall for an optical element can be manufactured.

The material of the substrate is not particularly limited. For example, various glass plates; polyester (polyethylene terephthalate, etc.), polyolefin (polyethylene, polypropylene, etc.), polycarbonate, polymethyl methacrylate, polysulfone, polyimide, poly (meth) acrylic resin Thermosetting plastic sheets such as epoxy resins, and cured sheets of thermosetting resins such as epoxy resins and unsaturated polyesters can be used. In particular, a heat resistant plastic such as a glass plate or polyimide is preferable from the viewpoint of heat resistance.

FIG. 1 is a cross-sectional view schematically showing a production example of an optical element partition using the negative photosensitive resin composition of the present invention. FIG. 1 (I) is a view showing a cross section in a state where a coating film 2 made of the negative photosensitive resin composition of the present invention is formed on a substrate 1. (II) is a figure which shows an exposure process typically. (III) is sectional drawing which shows the board | substrate 1 after the image development process, and the partition 6 formed on the board | substrate.
Hereinafter, the manufacturing method of the partition for optical elements using the negative photosensitive resin composition of this invention is demonstrated concretely using FIG.

(Coating film formation process)
As shown in a cross section in FIG. 1 (I), the negative photosensitive resin composition of the present invention is applied onto a substrate 1 to form a coating film 2 made of the negative photosensitive resin composition. In addition, before forming the coating film 2 of the negative photosensitive resin composition on the board | substrate 1, the application surface of the negative photosensitive resin composition of the board | substrate 1 is wash | cleaned by alcohol washing | cleaning, ultraviolet rays / ozone washing | cleaning, etc. preferable.

The coating method of the negative photosensitive resin composition is not particularly limited as long as a coating film having a uniform film thickness is formed. Spin coating, spraying, slit coating, roll coating, spin coating The method used for normal coating-film formation, such as a method and a bar coating method, is mentioned.
The film thickness of the coating film 2 is determined in consideration of the height of the partition wall finally obtained. The film thickness of the coating film 2 is preferably 100 to 200%, particularly preferably 100 to 130% of the height of the partition wall finally obtained. The thickness of the coating film 2 is preferably from 0.3 to 325 μm, particularly preferably from 1.3 to 65 μm.

(Pre-baking process)
The coating film 2 formed on the substrate 1 in the coating film forming step is heated to obtain the film 2. By heating, a volatile component including a solvent contained in the negative photosensitive resin composition constituting the coating film is volatilized and removed, and a film having less adhesiveness is obtained. Further, the ink repellent agent (A) moves to the vicinity of the coating film surface. Examples of the heating method include a method in which the coating film 2 is heated together with the substrate 1 at 50 to 120 ° C. for about 10 to 2,000 seconds using a heating device such as a hot plate or an oven.

In addition, although it is possible to remove volatile components such as a solvent by heating in the pre-baking step as described above, a drying step such as vacuum drying other than heating (drying) is performed in order to remove volatile components such as a solvent. You may provide separately before a prebaking process. Further, in order to efficiently dry the coating film without causing unevenness in the appearance of the coating film, it is more preferable to use heating combined with the drying by the prebaking step and vacuum drying in combination. The conditions for vacuum drying vary depending on the type of each component, the blending ratio, and the like, but can be preferably performed at 500 to 10 Pa for a wide range of about 10 to 300 seconds.

(Exposure process)
As shown in FIG. 1 (II), the film 2 is irradiated with light 5 through a mask 4 having a predetermined pattern. Only the predetermined pattern portion cut by the mask 4 is transmitted through the light 5, reaches the film on the substrate 1, and only the portion is photocured. Therefore, when the partition is formed, the predetermined pattern is provided in a shape that matches the shape of the partition.
For example, the average partition wall width after the post-baking step is preferably 100 μm or less, and particularly preferably 20 μm or less. Further, the average distance between adjacent partition walls is preferably 500 μm or less, more preferably 300 μm or less, and particularly preferably 100 μm or less. It is preferable to use a mask in which a pattern is formed so as to be in this range.

In FIG. 1 (II), the exposed portion 3 of the film irradiated with light is composed of a cured film of a negative photosensitive resin composition, while the unexposed portion is a film 2 of an uncured negative photosensitive resin composition. It is a state in which it remains.

The irradiation light 5 is visible light; ultraviolet light; far ultraviolet light; excimer laser such as KrF excimer laser, ArF excimer laser, F ₂ excimer laser, Kr ₂ excimer laser, KrAr excimer laser, Ar ₂ excimer laser; X-ray; Examples include lines. Further, the irradiation light 5 is preferably an electromagnetic wave having a wavelength of 100 to 600 nm, more preferably a light ray having a distribution in the range of 300 to 500 nm, particularly i-line (365 nm), h-line (405 nm), and g-line (436 nm). preferable.

As the irradiation device (not shown), a known ultra-high pressure mercury lamp, deep UV lamp, or the like can be used. Exposure is preferably 5 ~ 1,000mJ / cm ^2, particularly preferably 50 ~ 400mJ / cm ^2. When the exposure amount is at least the lower limit of the above range, the negative photosensitive resin composition serving as a partition is sufficiently cured, and subsequent development does not easily cause dissolution or peeling from the substrate 1. A high resolution is obtained when it is not more than the upper limit of the above range. The exposure time depends on the exposure amount, the composition of the photosensitive composition, the thickness of the coating film, etc., but is preferably 1 to 60 seconds, and particularly preferably 5 to 20 seconds.

(Development process)
Development is performed using a developer, and the unexposed portion 2 on the substrate 1 shown in FIG. 1 (II) is removed. Thereby, the structure of the partition 6 formed by the cured film of the negative photosensitive resin composition on the board | substrate 1 and the said board | substrate which a cross-sectional view is shown by FIG.1 (III) is obtained. A portion surrounded by the partition wall 6 and the substrate 1 is a portion called a dot 7 where a pixel is formed by ink injection or the like. The obtained substrate 10 becomes a substrate that can be used for manufacturing an optical element by an inkjet method through a post-bake process described later.

As the developer, an alkaline aqueous solution containing an alkali such as an inorganic alkali, an amine, an alcohol amine, or a quaternary ammonium salt can be used. Further, an organic solvent such as a surfactant or alcohol can be added to the developer in order to improve solubility and remove residues.

Develop time (time for contacting with developer) is preferably 5 to 180 seconds. Examples of the developing method include a liquid piling method, a dipping method, and a shower method. After development, water on the substrate 1 and the partition wall 6 can be removed by performing high-pressure water washing or running water washing and air-drying with compressed air or compressed nitrogen.

(Post bake process)
The partition 6 on the substrate 1 is heated. Examples of the heating method include a method in which the partition wall 6 and the substrate 1 are heat-treated at 150 to 250 ° C. for 5 to 90 minutes using a heating device such as a hot plate or an oven. By the heat treatment, the partition walls 6 made of a cured film of the negative photosensitive resin composition on the substrate 1 are further cured, and the shape of the dots 7 surrounded by the partition walls 6 and the substrate 1 is further fixed. The heating temperature is particularly preferably 180 ° C. or higher. If the heating temperature is too low, curing of the partition wall 6 is insufficient, so that sufficient chemical resistance cannot be obtained, and when the ink is injected into the dots 7 in the subsequent inkjet coating process, the solvent contained in the ink As a result, the partition wall 6 may swell or ink may ooze. On the other hand, if the heating temperature is too high, thermal decomposition of the partition walls 6 may occur.

In the negative photosensitive resin composition of the present invention, the average width of the partition walls is preferably 100 μm or less, more preferably 50 μm or less, and particularly preferably 20 μm or less. Moreover, the average of the distance (dot width) between adjacent partition walls is preferably 500 μm or less, more preferably 300 μm or less, and particularly preferably 100 μm or less. Further, the average height of the partition walls is preferably 0.05 to 50 μm, particularly preferably 0.2 to 10 μm.

[Method for Manufacturing Optical Element]
After the partition wall is formed on the substrate by the above manufacturing method, the substrate surface exposed in the region surrounded by the substrate and the partition wall is subjected to an ink affinity treatment (ink affinity treatment step), and then the ink jet is applied to the region. Ink is injected by the method to form the pixel (ink injection step).

(Ink affinity process)
Examples of the lyophilic process include a cleaning process using an alkaline aqueous solution, an ultraviolet cleaning process, an ultraviolet / ozone cleaning process, an excimer cleaning process, a corona discharge process, and an oxygen plasma process.
The cleaning process using an alkaline aqueous solution is a wet process of cleaning the substrate surface using an alkaline aqueous solution (potassium hydroxide, tetramethylammonium hydroxide aqueous solution or the like).
The ultraviolet cleaning process is a dry process for cleaning the substrate surface using ultraviolet rays.
The ultraviolet / ozone cleaning process is a dry process that cleans the substrate surface using a low-pressure mercury lamp that emits light of 185 nm and 254 nm.
The excimer cleaning process is a dry process for cleaning the substrate surface using a xenon excimer lamp that emits light at 172 nm.
The corona discharge treatment is a dry treatment that uses a high-frequency high voltage to generate corona discharge in the air and cleans the substrate surface.
The oxygen plasma process is a dry process in which the substrate surface is cleaned using a highly reactive “plasma state” in which oxygen is excited by using a high frequency power source or the like as a trigger in vacuum.

As the method for the ink-philic treatment, a dry treatment method such as an ultraviolet / ozone cleaning treatment is preferable because it is simple. UV / ozone can be generated using commercially available equipment. An ink-repellent treatment can be performed by placing a substrate on which a partition wall is formed in an ultraviolet / ozone apparatus and performing the treatment in air at room temperature for about 1 to 10 minutes within a range that does not impair the oil repellency of the partition wall. it can. In addition, about processing time, what is necessary is just to adjust to the time used as the range which does not impair the oil repellency of a partition according to each ultraviolet-ray / ozone apparatus.

By this ink repellency treatment, the removal of impurities remaining on the dots after the formation of the partition walls can be sufficiently performed to sufficiently measure the dot ink fondness, such as a color display device using an optical element obtained. It is possible to prevent white spots. In addition, when the partition obtained from the negative photosensitive resin composition of the present invention is used, it is possible to make the ink affinity by the ultraviolet cleaning treatment or the like without reducing the ink repellency of the partition.

Here, the ink repellency (water / oil repellency) of the cured film formed from the negative photosensitive resin composition is water and PGMEA (propylene glycol monomethyl ether acetate: an organic solvent often used as a solvent for the ink. ) And the contact angle can be estimated. When an optical element is produced using a substrate having a partition formed using the negative photosensitive resin composition of the present invention, the partition is required to have sufficient ink repellency even after the ink-philic treatment. It is done. Therefore, the water contact angle of the partition walls is preferably 90 ° or more, and particularly preferably 95 ° or more. Similarly, the contact angle of PGMEA of the partition walls is preferably 35 degrees or more, more preferably 40 degrees or more, and particularly preferably 50 degrees or more. On the other hand, when an optical element is produced using a substrate having a partition wall formed using the negative photosensitive resin composition of the present invention, the dots are required to be ink-philic, and the water The contact angle is preferably 20 degrees or less, and particularly preferably 10 degrees or less.

(Ink injection process)
This is a step of forming pixels by injecting ink into the dots after the ink affinity treatment step by an ink jet method. This step can be performed in the same manner as a normal method using an ink jet apparatus generally used in the ink jet method. An ink jet apparatus used for forming such a pixel is not particularly limited, but a method in which charged ink is continuously ejected and controlled by a magnetic field, and ink is ejected intermittently using a piezoelectric element. An ink jet apparatus using various methods such as a method, a method of heating ink, and intermittently ejecting the ink using the foaming can be used.

Examples of optical elements produced using the negative photosensitive resin composition of the present invention include color filters, organic EL display elements, and organic TFT arrays.

[Manufacture of color filters]
The formation of the partition walls, the process of making dots ink-philic, and the ink injection by the ink jet method are as described above. In the color filter, the shape of the pixel to be formed can be any known arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type.

The ink used for forming the pixel mainly includes a coloring component, a binder resin component, and a solvent. As the coloring component, it is preferable to use pigments and dyes excellent in heat resistance, light resistance and the like. As the binder resin component, a resin that is transparent and excellent in heat resistance is preferable, and examples thereof include an acrylic resin, a melamine resin, and a urethane resin. The water-based ink contains water and a water-soluble organic solvent as necessary, a water-soluble resin or a water-dispersible resin as a binder resin component, and various auxiliary agents as necessary. The oil-based ink contains an organic solvent as a solvent, a resin soluble in an organic solvent as a binder resin component, and various auxiliary agents as necessary.
Moreover, after injecting an ink by the inkjet method, it is preferable to perform drying, heat curing, and ultraviolet curing as necessary.

After the pixel formation, a protective film layer is formed as necessary. The protective film layer is preferably formed for the purpose of increasing the surface flatness and for blocking the eluate from the ink in the partition walls and the pixel portion from reaching the liquid crystal layer. When forming the protective film layer, it is preferable to remove the ink repellency of the partition wall in advance. If the ink repellency is not removed, the overcoat coating solution is repelled, and a uniform film thickness cannot be obtained. Examples of a method for removing the ink repellency of the partition include plasma ashing and optical ashing.
Further, if necessary, it is preferable to form a photo spacer on a black matrix composed of partition walls in order to improve the quality of a liquid crystal panel manufactured using a color filter.

[Manufacture of organic EL display elements]
Before forming the partition walls, a transparent electrode such as tin-doped indium oxide (ITO) is formed on a transparent substrate such as glass by sputtering or the like, and the transparent electrode is etched into a desired pattern as necessary. Next, a barrier rib is formed using the negative photosensitive resin composition of the present invention, and after the dot is made into an ink-inking treatment, a solution of a hole transport material and a light emitting material is sequentially applied to the dot using an ink jet method and dried. Thus, a hole transport layer and a light emitting layer are formed. Then, an organic EL display element pixel is obtained by forming an electrode such as aluminum by vapor deposition or the like.

[Manufacture of organic TFT array]
An organic TFT array can be manufactured through the following steps (1) to (3).
(1) A partition wall is formed on a transparent substrate such as glass using the negative photosensitive resin composition of the present invention. After the dot is made into an ink-philic process, a gate electrode material is formed by applying a solution of a gate electrode material to the dots using an inkjet method.
(2) After forming the gate electrode, a gate insulating film is formed thereon. A barrier rib is formed on the gate insulating film using the negative photosensitive resin composition of the present invention, and after the dot is made into an ink-philic process, a solution of a source / drain electrode material is applied to the dot using an ink jet method. A drain electrode is formed.
(3) After forming the source / drain electrodes, a partition is formed using the negative photosensitive resin composition of the present invention so as to surround a region including the pair of source / drain electrodes, and the ink is made to be an ink-insensitive dot. Thereafter, an organic semiconductor solution is applied to the dots using an ink jet method to form an organic semiconductor layer between the source and drain electrodes.
In each of (1) to (3), the partition using the negative photosensitive resin composition of the present invention may be used in only one step, or the negative photosensitive resin of the present invention in two or more steps. You may utilize the partition using a conductive resin composition.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. Examples 1 to 7 are examples, and examples 8 and 9 are comparative examples.

Each measurement was performed by the following method.
[Number average molecular weight (Mn)]
GPC of several types of monodisperse polystyrene polymers with different degrees of polymerization, which are commercially available as standard samples for molecular weight measurement, are measured using a commercially available GPC measuring device (manufactured by Tosoh Corporation, device name: HLC-8320GPC). A calibration curve was prepared based on the relationship between the molecular weight of polystyrene and the retention time (retention time).
The sample was diluted to 1.0% by mass with tetrahydrofuran and passed through a 0.5 μm filter, and then GPC of the sample was measured using the GPC measurement apparatus.
The number average molecular weight (Mn) of the sample was determined by computer analysis of the GPC spectrum of the sample using the calibration curve.

[Contact angle to water]
In accordance with JIS R3257 “Testing method for wettability of substrate glass surface”, water droplets were placed on three measurement surfaces on the substrate by the sessile drop method, and each water droplet was measured. The droplet was 2 μL / droplet, and the measurement was performed at 20 ° C. The contact angle is indicated by an average value of three measured values (n = 3).

[Contact angle against PGMEA]
According to JIS R3257 “Test method for wettability of substrate glass surface”, PGMEA droplets were placed at three locations on the measurement surface on the substrate by the sessile drop method, and each PGMEA droplet was measured. The droplet was 2 μL / droplet, and the measurement was performed at 20 ° C. The contact angle is indicated by an average value of three measured values (n = 3).

[Method for evaluating storage stability]
The negative photosensitive resin composition was stored in a glass screw bottle at 23 ° C. (room temperature) for 2 weeks. After storage for 2 weeks, a negative photosensitive resin composition was applied using a spinner on a 10 cm × 10 cm glass substrate washed in the same manner as in the production of a cured film 1 described later to form a coating film. Furthermore, it was dried on a hot plate at 100 ° C. for 2 minutes to form a film having a thickness of 1 μm. The appearance of the film was visually observed and evaluated as follows.
A (Excellent): No more than 5 foreign substances on the film.
○ (Good): 6 to 20 foreign matter on the film.
X (defect): 21 or more foreign matters on the film, and radial streaks were observed from the center of the glass substrate.

[Photolitho evaluation method]
The glass substrate was observed with a laser microscope (manufactured by Keyence Corporation), and the film thickness and line width (bottom) of the 20 μm line portion were measured.

Abbreviations of the compounds used in Synthesis Examples and Examples are as follows.
(Alkali-soluble resin (B))
ZAR2002H: trade name; KAYARAD ZAR-2002H, manufactured by Nippon Kayaku Co., Ltd., a resin in which a carboxyl group and an ethylenic double bond are introduced into a bisphenol A type epoxy resin, solid content 60%, acid value 60 mgKOH / g.
CCR1235: Trade name: KAYARAD CCR-1235, manufactured by Nippon Kayaku Co., Ltd., a resin obtained by introducing a carboxyl group and an ethylenic double bond into a cresol novolac type epoxy resin, solid content 60%, acid value 60 mgKOH / g.
CCR1115: Trade name; KAYARAD CCR-1115, manufactured by Nippon Kayaku Co., Ltd., a resin obtained by introducing a carboxyl group and an ethylenic double bond into a cresol novolac type epoxy resin, acid value 100 mgKOH / g.
(Photopolymerization initiator (C))
IR907: Trade name: IRGACURE907, manufactured by BASF, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one.
IR369: Trade name: IRGACURE 369, manufactured by BASF, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one.
EAB: 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.).
(Crosslinking agent (D))
A9530: Trade name; NK ester A-9530, manufactured by Shin-Nakamura Chemical Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate.
(Solvent (E))
PGMEA: Propylene glycol monomethyl ether acetate.
PGME: Propylene glycol monomethyl ether.

[Synthesis Example 1: Synthesis of ink repellent agent (A1) and preparation of (A1-1) liquid]
In a 50 cm ³ three-necked flask equipped with a stirrer, 0.5 g of the above compound (a1) CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃ (Asahi Glass Co., Ltd.), the above compound (a2) ) 1.11 g of Si (OC ₂ H ₅ ) ₄ (manufactured by Colcoat Co.), CH ₂ ═CHCOO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ (manufactured by Tokyo Chemical Industry Co., Ltd.) which is the above compound (a5) And 0.28 g of (CH ₃ ) ₃ SiOCH ₃ (manufactured by Tokyo Chemical Industry Co., Ltd.), which is the above compound (a3), were added. Next, 10.26 g of PGME was added to obtain a mixture.
While stirring the mixture at room temperature, 1.27 g of a 1.0% aqueous nitric acid solution was added dropwise. After completion of dropping, the mixture was further stirred for 5 hours. A PGME solution containing the ink repellent agent (A1) at 10% by mass is referred to as (A1-1) solution. The obtained fluorine-containing content (mass% of fluorine atoms) of the composition excluding the solvent of the liquid (A1-1) is 18.8 mass%. The number average molecular weight (Mn) of the composition excluding the solvent of the solution (A1-1) was 740.

[Synthesis Example 2: Synthesis of ink repellent agent (A2) and preparation of liquid (A2-1)]
A mixture was prepared in the same manner as in Synthesis Example 1 except that 0.76 g of ethyl silicate 48 (manufactured by Colcoat Co.) and 10.26 g of PGME were used as the compound (a2).
While stirring the mixture at room temperature, 0.93 g of a 1.0% nitric acid aqueous solution was added dropwise. After completion of dropping, the mixture was further stirred for 5 hours. A PGME solution containing the ink repellent agent (A2) at 10% by mass is referred to as (A2-1) solution. The fluorine-containing content (mass% of fluorine atoms) of the composition excluding the solvent of the obtained (A2-1) liquid is 18.8 mass%. The number average molecular weight (Mn) of the composition excluding the solvent of the solution (A2-1) was 866.

[Synthesis Example 3: Synthesis of ink repellent agent (A3) and preparation of (A3-1) liquid]
In a 50 cm ³ three-necked flask equipped with a stirrer, 0.5 g of the above compound (a1) CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃ (Asahi Glass Co., Ltd.), the above compound (a2) ) 0.83 g of Si (OC ₂ H ₅ ) ₄ (manufactured by Colcoat Co.) and CH ₂ ═CHCOO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ (manufactured by Tokyo Chemical Industry Co., Ltd.) ) 0.94 g was added. Next, 9.89 g of PGME was added to obtain a mixture.
While stirring the above mixture at room temperature, 1.12 g of a 1.0% nitric acid aqueous solution was added dropwise. After completion of dropping, the mixture was further stirred for 5 hours. A PGME solution containing the ink repellent agent (A3) at 10% by mass is referred to as (A3-1) solution. The obtained fluorine-containing content (mass% of fluorine atoms) of the composition excluding the solvent of the liquid (A3-1) is 18.8 mass%. The number average molecular weight (Mn) of the composition excluding the solvent of the solution (A3-1) was 768.

[Synthesis Example 4: Synthesis of ink repellent agent (A4) and preparation of liquid (A4-1)]
In a 50 cm ³ three-necked flask equipped with a stirrer, 0.5 g of the above compound (a1) CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃ (Asahi Glass Co., Ltd.), the above compound (a2) ) 0.22 g of Si (OC ₂ H ₅ ) ₄ (manufactured by Colcoat Co.) and CH ₂ ═CHCOO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.00 g) was added. Next, 9.51 g of PGME was added to obtain a mixture.
While stirring the above mixture at room temperature, 0.73 g of a 1.0% nitric acid aqueous solution was dropped. After completion of dropping, the mixture was further stirred for 5 hours. A PGME solution containing the ink repellent agent (A4) at 10% by mass is referred to as (A4-1) solution. The resulting fluorine-containing content (mass% of fluorine atoms) of the composition excluding the solvent of the liquid (A4-1) is 22.1 mass%. The number average molecular weight (Mn) of the composition excluding the solvent of the solution (A4-1) was 678.

[Example 1]
(Preparation of negative photosensitive resin composition)
(A1-1) solution 10 g (solid content is 1.0 g), ZAR2002 45 g (solid content is 27 g, the remaining 18 g is PGMEA as a solvent), IR907 5.4 g, EAB 3.6 g, A9530 63 g and 240 g of PGME were put into a 1,000 cm ³ stirring container and stirred for 30 minutes to prepare a negative photosensitive resin composition 1. Table 1 shows the composition of the negative photosensitive resin composition 1 and the composition (mass%) of the solid content in the composition 1.
Table 1 shows both the composition in the solid content of the negative photosensitive resin composition and the composition in the composition.

(Manufacture of cured film 1)
A 5 cm square glass substrate was ultrasonically cleaned with ethanol for 30 seconds, and then subjected to ultraviolet / ozone cleaning for 5 minutes. For UV / ozone cleaning, PL7-200 (manufactured by Sen Engineering) was used as an UV / ozone generator. In addition, this apparatus was used as an ultraviolet / ozone generator for all the following ultraviolet / ozone treatments.

The negative photosensitive resin composition 1 was applied on the glass substrate after the washing using a spinner, and then dried on a hot plate at 100 ° C. for 2 minutes to form a film having a thickness of 1 μm. A 50 μm gap was opened on the surface of the obtained film from the film side through a photomask having an opening pattern (2.5 cm × 5 cm), and ultraviolet light from a high-pressure mercury lamp was irradiated at 25 mW / cm ² for 10 seconds. A cured film was obtained.

Next, the exposed glass substrate was developed by immersing in a 0.4% tetramethylammonium hydroxide aqueous solution for 40 seconds, and the unexposed film was washed away with water and dried. Next, this was heated on a hot plate at 230 ° C. for 20 minutes to obtain a glass substrate (1) in which a cured film of the negative photosensitive resin composition 1 was formed in a region excluding the hole pattern portion. .

(Manufacture of cured film 2)
A glass substrate (2) on which a cured film of a negative photosensitive resin composition was formed was obtained in the same manner as in Production of cured film 1 except that a photomask having a line / space of 20 μm was used.

(Evaluation)
The contact angle with respect to PGMEA of the cured film surface (exposed part) of the obtained glass substrate (1) and the contact angle with water of the part where the coating film was removed by development (glass substrate surface) were measured. Thereafter, the entire surface of the glass substrate (1) on which the cured film was formed was irradiated with ultraviolet rays / ozone for 2 minutes. The contact angle with respect to PGMEA on the surface of the cured film after irradiation for 2 minutes and the contact angle with water on the surface of the glass substrate were measured. The measuring method is as described above. The results are shown in Table 1.

[Examples 2 to 7, Examples 8 and 9]
A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that the formulation was changed as shown in Table 1, and a negative photosensitive resin composition film, a cured film, and a glass substrate were obtained. In Example 3, 240 g of PGMEA was used in place of 240 g of PGMEA.
The obtained negative photosensitive resin composition film, cured film, and glass substrate were evaluated in the same manner as in Example 1. The results are shown in Table 1.

As can be seen from Table 1, the negative photosensitive resin compositions of Examples 1 to 7 having a composition acid value of 6 to 30 mg KOH / g were not formed even when a coating film was formed after storage at 23 ° C. for 2 weeks. The appearance was good. Further, the cured film obtained from the negative photosensitive resin composition exhibits good ink repellency, maintains high ink repellency even after irradiation with ultraviolet rays / ozone, and the glass substrate surface has good hydrophilicity. . On the other hand, in Example 8, since the composition acid value was 36 mgKOH / g, when a film was formed using the negative photosensitive resin composition after being stored at 23 ° C. for 2 weeks, many foreign matters were observed, and glass A radial streak pattern was observed from the center of. In Example 9, the composition acid value was 5.4 mgKOH / g, so that development was not possible.

The negative photosensitive resin composition of the present invention is a negative photosensitive resin composition capable of producing a partition having good ink repellency and capable of retaining ink repellency even when irradiated with ultraviolet rays / ozone. In addition, the storage stability is good, and a homogeneous coating film can be formed by using the negative photosensitive resin composition.
The negative photosensitive resin composition of the present invention is suitably used for forming barrier ribs for color filter production, organic EL display element production, and organic TFT array production using the inkjet recording technique.
The entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2011-079394 filed on March 31, 2011 are cited here as disclosure of the specification of the present invention. Incorporated.

DESCRIPTION OF SYMBOLS 1 ... Board | substrate, 2 ... Coating film of negative photosensitive resin composition, 3 ... Coating film exposure part, 4 ... Mask, 5 ... Light, 6 ... Partition, 7 ... Dot, 10 ... Substrate for optical elements used for inkjet system

Claims

An ink repellent agent (A) comprising a fluorine-containing siloxane compound;
An alkali-soluble resin (B) having an acidic group and an ethylenic double bond in one molecule;
A negative photosensitive resin composition containing a photopolymerization initiator (C),
A negative photosensitive resin composition, wherein the negative photosensitive resin composition has an acid value of 6 to 30 mgKOH / g.
The negative photosensitive resin composition according to claim 1, wherein the proportion of the alkali-soluble resin (B) in the total solid content of the negative photosensitive resin composition is 12 to 40% by mass.
The negative according to claim 1 or 2, wherein the fluorine-containing siloxane compound comprises a hydrolysis condensation product of a mixture containing the following hydrolyzable silane compound (a-1) and hydrolyzable silane compound (a-2). Type photosensitive resin composition.
Hydrolyzable silane compound (a-1): an organic group having a perfluoroalkyl group which may contain one etheric oxygen atom having 3 to 10 carbon atoms in the silicon atom, and three hydrolyzable groups A hydrolyzable silane compound bonded with
Hydrolyzable silane compound (a-2): Hydrolyzable silane in which p hydrocarbon groups (p is 0, 1 or 2) and (4-p) hydrolyzable groups are bonded to a silicon atom Compound.
The negative photosensitive resin composition according to any one of claims 1 to 3, wherein the fluorine atom content in the fluorine-containing siloxane compound is 10 to 55 mass%.
Furthermore, the composition further comprises a crosslinking agent (D), and the crosslinking agent (D) is a compound having two or more ethylenic double bonds in one molecule and having no acidic group. The negative photosensitive resin composition of Claim 1.
The total amount of the alkali-soluble resin (B) and the crosslinking agent (D) in the total solid content in the negative photosensitive resin composition is 50 to 95% by mass, and the content of the crosslinking agent (D) The negative photosensitive resin composition according to claim 5, wherein the content ratio of the alkali-soluble resin (B) to 15 to 85 mass%.
The negative photosensitive resin composition according to any one of claims 1 to 6, further comprising a solvent (E).
The negative photosensitive resin composition according to any one of claims 1 to 7, wherein the acid value of the alkali-soluble resin (B) is 10 to 200 mgKOH / g.
The negative photosensitive resin according to any one of claims 1 to 8, wherein the proportion of the ink repellent agent (A) in the total solid content of the negative photosensitive resin composition is 0.01 to 10% by mass. Resin composition.
A coating film formed by forming the negative photosensitive resin composition according to any one of claims 1 to 9 on a substrate.