KR20220149673A - Positive photosensitive resin composition - Google Patents

Abstract

The present invention contains an alkali-soluble resin (A), a photosensitizer (B), a crosslinking agent having an N atom (C1), a crosslinking agent having an SH group (C2) and an ink repellent agent having an F atom (D), in a mass ratio of C2 /C1 relates to the positive photosensitive resin composition in the range of 0.3<C2/C1<1.0.

Description

Positive photosensitive resin composition

The present invention relates to a positive photosensitive resin composition.

A positive photosensitive resin composition is used for manufacture of the partition used for the pixel part of a color filter or organic electroluminescent element, and microlens (for example, patent document 1).

Japanese Patent Laid-Open No. 2010-185991

In recent years, the required performance of a product is increasing, and the performance is not enough in the conventional positive photosensitive resin composition.

Under such circumstances, a positive photosensitive resin composition having high patterning properties and excellent liquid repellency is required.

The present invention includes the following aspects.

1. Alkali-soluble resin (A),

photosensitizer (B);

a crosslinking agent having an N atom (C1);

a crosslinking agent having an SH group (C2), and

containing an ink repellent agent (D) having an F atom,

The positive photosensitive resin composition in which C2/C1 is in the range of 0.3<C2/C1<1.0 by mass ratio.

2. The proportion of the crosslinking agent (C2) is in the range of 4% by mass to 19% by mass relative to the total of (A)+(B)+(C1)+(C2)+(D) in mass ratio,

The positive photosensitive resin composition according to 1 above.

3. The positive photosensitive resin composition according to 1 or 2, wherein the photosensitive agent (B) contains a quinonediazide compound.

4. The positive photosensitive resin composition in any one of said 1-3 whose said crosslinking agent (C1) is a melamine resin.

5. The positive photosensitive resin composition as described in any one of said 1-4 in which the said crosslinking agent (C2) has 2-4 said SH groups in a molecule|numerator.

6. The positive photosensitive resin composition in any one of said 1-5 whose mass average molecular weights (Mw) of the said alkali-soluble resin (A) are 500-20000.

7. Furthermore, it has a solvent (E), The positive photosensitive resin composition in any one of said 1-6 in which the ratio of the compound whose boiling point in the said solvent is 170 degreeC or more is 10-70 mass %.

8. Hardened|cured material which hardened|cured the positive photosensitive resin composition in any one of said 1-7.

9. An optical element comprising the cured product according to 8 above as a barrier rib.

ADVANTAGE OF THE INVENTION According to this invention, patterning property is high and the positive photosensitive resin composition excellent in liquid repellency can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram of a sample cross-section image, and is a figure which shows the measuring method of a taper angle.
Fig. 2 is a schematic diagram of a cross-sectional image of a sample, and is a diagram showing a method for measuring a scum.

Hereinafter, the positive photosensitive resin composition of this invention is demonstrated.

[Positive photosensitive resin composition]

The positive photosensitive resin composition of this invention consists of a combination of an essential component and an arbitrary component. The essential component is essentially contained in the positive photosensitive resin composition and provides a major function of performance. Optional ingredients are used as needed.

In this specification, when there is no special description, % means mass %. However, in this specification, the ratio by mass (percentage, parts, etc.) is the same as the ratio by weight (percentage, parts, etc.). Numerical ranges are inclusive of rounded ranges. In addition, when a numerical range is represented by "X to Y", "X or more and Y or less" is meant.

[Essential Ingredients]

As essential components, an alkali-soluble resin (A), a photosensitizer (B), a crosslinking agent having an N atom (C1), a crosslinking agent having an SH group (C2), and an ink repellent agent having an F atom (D) are mentioned.

<Alkali-soluble resin (A)>

Alkali-soluble resin (A) is resin which melt|dissolves with respect to the alkali used in the image development process, and is resin used as a main component of the partition used in a pixel part etc.

As alkali-soluble resin (A) used by this invention, well-known resin used for a positive photosensitive resin composition can be used.

Specific examples include Japanese Patent Publication No. 6177495, Japanese Patent Publication No. 5447384, Japanese Patent Publication No. 4770985, Japanese Patent Publication No. 4600477, Japanese Patent Publication No. 5444749, and International Publication No. 2019/156000 Although alkali-soluble resin is disclosed, alkali-soluble resin (A) is not limited to these.

Although the following are illustrated as a specific example of preferable alkali-soluble resin (A), alkali-soluble resin (A) is not limited to these.

As alkali-soluble resin (A), the copolymer of N-substituted maleimide with high Tg, benzyl methacrylate, and acrylic acid is preferable.

Since it is excellent in residue removability, it is preferable that the mass average molecular weight of alkali-soluble resin (A) exists in the range of 500-20000, It is more preferable that it exists in the range of 3000-10000, What exists in the range of 3000-8000 Especially preferred.

In the present specification, the mass average molecular weight (Mw) means a mass average molecular weight measured by gel permeation chromatography (GPC) using tetrahydrofuran as a mobile phase and converted on the basis of standard polystyrene.

The usage-amount of alkali-soluble resin (A) is mass ratio, and it is preferable to exist in 50 to 70% of range with respect to the sum total of (A)+(B)+(C1)+(C2)+(D). When the usage-amount exists in this range, the effect of this invention can be exhibited effectively.

<Photosensitizer (B)>

A photosensitive agent (B) is a compound which reacts with light at the time of exposure, and changes the solubility with respect to the alkaline solution of a positive photosensitive resin composition.

As a photosensitive agent (B) used by this invention, the well-known photosensitive agent used for a positive photosensitive resin composition is mentioned.

As the photosensitizer (B), a compound having a quinonediazide group (hereinafter also referred to as a quinonediazide compound) is preferable because of its excellent photosensitivity, and 4,4'-[1-[4-] from the viewpoint of control of developing solubility and heat resistance. Particularly preferred are ester compounds of [1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol and 6-diazo-5,6-dihydro-5-oxonaphthalene-1-sulfonic acid. .

The amount of the photosensitive agent (B) used is preferably in the range of 10 to 35%, and preferably in the range of 15 to 30%, relative to the total of (A)+(B)+(C1)+(C2)+(D) in terms of mass ratio. is more preferably, particularly preferably in the range of 16 to 22%, and most preferably in the range of 18 to 20%. When the usage-amount exists in this range, the effect of this invention can be exhibited effectively.

<crosslinking agent>

In the present invention, as the crosslinking agent, two types of crosslinking agents are used: a crosslinking agent having an N atom (C1) and a crosslinking agent having an SH group (C2). C2/C1 in mass ratio is more than 0.3, 0.35 or more are preferable, and 0.4 or more are more preferable. C2/C1 is less than 1.0, more preferably less than 0.9, still more preferably less than 0.8. C2/C1 is in the range of 0.3 < C2/C1 < 1.0, preferably in the range of 0.35 < C2/C1 < 0.9, more preferably in the range of 0.4 < C2/C1 < 0.8. When C2/C1 exists in this range, the effect of this invention can be exhibited preferably.

A crosslinking agent is a compound which contributes to sclerosis|hardenability of a positive photosensitive resin composition, and has two or more photo or thermosetting functional groups. As the photo- or thermosetting functional group, an alkoxymethyl group or a thiol group is preferable.

The number of the photo- or thermosetting functional groups which a crosslinking agent has is 2 or more in 1 molecule, and 3 or more are preferable. Sclerosis|hardenability of a coating film improves, so that there are many numbers of a photo- or thermosetting functional group.

The mass average molecular weight of the crosslinking agent is preferably 200 or more and less than 1000, and more preferably 300 or more and less than 800, from the viewpoint of permeation of the developer and diffusion into the solution.

The crosslinking agent may contain a crosslinking agent other than the crosslinking agent (C1) having an N atom and the crosslinking agent having an SH group (C2) as long as the effect of the present invention is exhibited.

<Crosslinking agent having N atom (C1)>

By using the crosslinking agent (C1) which has an N atom, the shape change by heating is suppressed and the patterning property of the positive photosensitive resin composition of this invention improves significantly.

Specific examples of the crosslinking agent (C1) having an N atom are shown below, but the crosslinking agent (C1) having an N atom is not limited to these.

Examples of the crosslinking agent (C1) having an N atom include a urea resin, a melamine resin, and an amide resin, and a melamine resin is particularly preferable from the viewpoint of heat resistance. Although it shows below as a specific example of a melamine resin, a melamine resin is not limited to these.

Mitsui Cytec Co., Ltd. Methoxymethyl type melamine compound (trade name: Cymel (registered trademark) 300, copper 301, copper 303, copper 350), butoxymethyl type melamine compound (trade name: Mycoat (registered trademark) 506, 508), Sanwa Chemical Co., Ltd. Methoxymethyl type melamine compound (trade name: Nickarak (registered trademark) MW-30, Dong MW-22, Dong MW-11, Dong MW-100LM, Dong MS-001, Dong MX- 002, copper MX-730, copper MX-750, copper MX-035), butoxymethyl type melamine compound (trade name: Nikalac (registered trademark) MX-45, copper MX-410, copper MX-302), Cymel (registered trademark) 303 (manufactured by Mitsui Cytech Co., Ltd.).

The amount of the crosslinking agent (C1) used is preferably 8% or more, more preferably 10% or more, based on the total of (A)+(B)+(C1)+(C2)+(D), in mass ratio, 11 % or more is more preferable. Moreover, as for this usage-amount, 25 % or less is preferable, 20 % or less is more preferable, and 18 % or less is still more preferable. The usage-amount is preferably in the range of 8 to 25%, more preferably in the range of 10 to 20%, particularly preferably in the range of 11 to 18%. When the usage-amount of a crosslinking agent (C1) exists in this range, the effect of this invention can be exhibited effectively.

<Crosslinking agent having SH group (C2)>

By using the crosslinking agent (C2) which has an SH group, there exists interaction like an ink repellent agent and a hydrogen bond, the developing solution tolerance in image development improves, and the liquid repellency of the positive photosensitive resin composition of this invention improves significantly.

Specific examples of the crosslinking agent (C2) having an SH group are shown below, but the crosslinking agent (C2) having an SH group is not limited to these. Examples of the crosslinking agent (C2) having an SH group include 1,4-bis(3-mercaptopropyloxy)butane, 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritoltetrakis(3). -mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropylate), 1,3,5-tris (3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4, 6(1H,3H,5H)-trione, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexanedithiol, 1,12-dodecanedithiol, 1,2-bis- 2-mercaptoethylthioethane, 1,2-bis-3-mercaptopropylthioethane, 1,3-bis-2-mercaptoethylthiopropane, 1,4-bis-2-mercaptoethylthiobutane, 1,6-bis-2-mercaptoethylthiohexane, bis-2-(2-mercaptoethylthio)ethyl sulfide, 1,4-cyclohexanedithiol, bis-2-mercaptoethoxymethane, 1 ,2-bis-2-mercaptoethoxyethane, bis-2-(2-mercaptoethoxy)ethyl ether, 1,4-benzenedithiol, 1,3-benzenedithiol, 1,2-benzenedithi Ol, 4-t-butyl-1,2-benzenedithiol, 1,2-bis(mercaptomethylene)benzene, 1,3-bis(mercaptomethylene)benzene, 1,4-bis(mercaptomethylene) Benzene, 1,2-bis(mercaptoethylene)benzene, 1,3-bis(mercaptoethylene)benzene, 1,4-bis(mercaptoethylene)benzene, 1,2-bis(2-mercaptoethylenethio ) Benzene, 1,3-bis (2-mercaptoethylene thio) benzene, 1,4-bis (2-mercapto ethylene thio) benzene, 1,2-bis (2-mercapto ethylene thiomethylene) benzene, 1 ,3-bis(2-mercaptoethylenethiomethylene)benzene, 1,4-bis(2-mercaptoethylenethiomethylene)benzene, 1,2-bis(mercaptoethyleneoxy)benzene, 1,3-bis( Mercaptoethyleneoxy)benzene, 1,4-bis(mercaptoethyleneoxy)benzene, 4,4'-dithiophenol, 4,4'-biphenyldithiol, 1,3,5-trimercaptobenzene, trimercaptoethyl isocyanurate, pentaerythritol tetrathioglycolate, pentaerythritol trithioglycolate, and the like.

Moreover, as a crosslinking agent (C2) which has an SH group, the compound which has the following structure is mentioned, for example.

HS-(CH ₂ CH ₂ S) _n -H [n represents an integer of 1 to 4.]

HS-(CH ₂ CH ₂ S) _m -CH ₂ -C ₆ H ₆ -CH ₂ -(S-CH ₂ CH ₂ ) _m -SH [wherein m represents an integer of 0 to 3]

HS-C ₆ H ₆ -SC ₆ H ₆ -SH

Among these compounds, the crosslinking agent (C2) is preferably a compound having 2 to 4 SH groups in the molecule, and particularly preferably a compound having 3 SH groups.

The amount of the crosslinking agent (C2) used is preferably 4% or more, more preferably 5% or more, based on the total of (A)+(B)+(C1)+(C2)+(D) in mass ratio, 6 % or more is more preferable. Moreover, 19 % or less of this usage-amount is preferable, 15 % or less is more preferable, and 12 % or less is still more preferable. The amount used is preferably in the range of 4 to 19%, more preferably in the range of 5 to 15%, particularly preferably in the range of 6 to 12%. When the usage-amount of a crosslinking agent (C2) exists in this range, the effect of this invention can be exhibited effectively.

<Ink repellent agent having F atom (D)>

Ink repellent agent (D) provides the function which repels ink to the partition produced with the positive photosensitive resin composition of this invention. Therefore, the ink repellent agent (D) of this invention has an F atom, and has moderate hydrophobicity and hydrophilicity.

As the ink repellent agent (D) which has an F atom, as long as it has an F atom, it can select from the ink repellent agent normally used for a positive photosensitive resin composition.

Preferred specific examples include acrylic copolymers and resins having a silicone skeleton. When the ink repellent agent (D) contains these, it is excellent in liquid repellency and the image development residue reduction effect.

Moreover, the ink repellent agent described below is mentioned as a more preferable specific example.

Japanese Patent Publication No. 4609587, Japanese Patent Publication No. 4905563, Japanese Patent Publication No. 5152332, Japanese Patent Publication No. 5173543, Japanese Patent Publication No. 5466375, Japanese Patent Publication No. 5338258, International Publication No. 2013/024764, The ink repellent agent which has F atom as described in International Publication No. 2013/133392, Japanese Patent Publication No. 5516484, International Publication No. 2016/088757, and International Publication No. 2019/156000.

Especially, it is preferable that an ink repellent agent (D) has a component which can be bridge|crosslinked by light or a heat|fever. As said component, the component etc. which contain a specific functional group are specifically mentioned, for example. As such a functional group, a (meth)acryloyl group, an epoxy group, a glycidyl group, and a thiol group are mentioned.

Moreover, in order for an ink repellent agent (D) to improve stability in the composition of an ink repellent agent, it is preferable to have a compatibility improvement component. Specific examples of the compatibility improving component include a component containing a specific functional group. As such a functional group, an alkyl group, a phenyl group, a phenylamino group, a hydroxyphenyl group, etc. are mentioned.

It is preferable that the usage-amount of ink repellent agent (D) exists in 0.1 to 2.0% of range with respect to the sum total of (A)+(B)+(C1)+(C2)+(D) by mass ratio, and 0.5- It is particularly preferable to be in the range of 1.0%. When the usage-amount exists in this range, the effect of this invention can be exhibited effectively.

[Optional Ingredients]

<Solvent (E)>

The positive photosensitive resin composition of the present invention may contain a solvent (E).

By containing a solvent (E), it is excellent in the coatability of a positive photosensitive resin composition, the adhesiveness to a board|substrate, and stability.

As a solvent (E), the well-known solvent used for a positive photosensitive resin composition can be used. Specific examples thereof include alcohols, ethers, aromatics, and hydrocarbons, but the solvent (E) is not limited thereto.

Since the uniformity of the coating film of the positive photosensitive resin composition becomes high and it is excellent in layer separation, it is preferable that the ratio of the compound whose boiling point in a solvent (E) is 170 degreeC or more is 10-70% of range, 20- The range of 60% is more preferable, and the range of 30-50% is especially preferable. When the ratio of the compound with a boiling point of 170 degreeC or more exists in this range, it can exhibit more effectively with respect to the liquid repellency of the surface of hardened|cured material.

<Other ingredients>

The positive photosensitive resin composition of the present invention, if necessary, as long as the effects of the present invention are not impaired, a thermosetting agent, a thermosetting accelerator, a colorant, a silane coupling agent, fine particles, a thickener, a plasticizer, an antifoaming agent, a leveling agent, a repelling agent You may add well-known components added as a positive photosensitive resin composition, such as an inhibitor and a ultraviolet absorber. More specifically, you may add the component etc. of Unexamined-Japanese-Patent No. 6098635 and Paragraph 0080-0095.

[Method for preparing positive photosensitive resin composition]

The positive photosensitive resin composition comprises an alkali-soluble resin (A), a photosensitive agent (B), a crosslinking agent (C1), a crosslinking agent (C2) and an ink repellent agent (D), and optionally a solvent (E) and other components uniformly It is prepared by mixing it until it dissolves.

Although the positive photosensitive resin composition of this invention is used suitably for optical elements, such as an organic electroluminescent element, a microlens, a color filter, and an organic TFT array, a use is not limited to these. For example, the hardened|cured material which hardened|cured the positive photosensitive resin composition of this invention can be used suitably for the said use etc.

As an example, the manufacturing method of an organic electroluminescent element is shown.

A transparent electrode such as tin-doped indium oxide (ITO) is formed on a transparent substrate such as glass by a sputtering method or the like, and the transparent electrode is etched in a desired pattern if necessary. Next, a barrier rib is formed using the positive photosensitive resin composition of the present invention, and after the ink-philic treatment of the dots is performed, a solution of a hole transport material and a light emitting material is sequentially applied to the dots using an inkjet method, followed by drying. Thus, a hole transport layer and a light emitting layer are formed. Then, the pixel of an organic electroluminescent element is obtained by forming electrodes, such as aluminum, by vapor deposition or the like.

Example

Although an Example and a comparative example demonstrate this invention concretely, as long as the effect of this invention is exhibited, embodiment can be changed suitably. Examples 1 to 8 are Examples, and Examples 9 to 14 are comparative examples.

<Measurement conditions/Evaluation conditions>

[Sample for evaluation]

Using the positive photosensitive resin composition of Table 1, the cured film was produced on the ITO board|substrate, and it was set as the sample for evaluation. Two types of evaluation samples 1 and 2 were prepared as evaluation samples.

Sample 1 for evaluation was used to evaluate patternability.

The liquid repellency was evaluated using the sample 2 for evaluation.

[Sample 1 for evaluation]

An ITO substrate (ITO product with a resistance value of 10 Ω/sq or less, dimensions of 7.5 cm × 7.5 cm × 0.7 mm manufactured by Kuramoto Corporation) was ultrasonically cleaned (30 seconds) in ethanol. Then, ultraviolet/ozone cleaning (apparatus: PL7-200 by Sen Engineering Co., Ltd.) was performed for 5 minutes.

Using a spinner (IH-DX2 manufactured by Mikasa Co., Ltd.) on the surface of the glass substrate after washing, the positive photosensitive resin composition was held at a rotation speed of 610 rpm for 10 seconds, and spin-coated. Next, it dried on a hot plate at 100 degreeC for 2 minutes, and formed the film|membrane with a film thickness of 1.3 micrometers.

The surface of the obtained film|membrane was exposed on condition of the following.

<condition>

[Photomask]: It has a light-shielding part in the following pattern in the range of 20 mm x 20 mm.

Shape of light shielding part: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 30, 40, 50 μm × 1000 μm, respectively

Pattern spacing: 50 μm

[Lamp]: USH-255BY manufactured by Ushio Electric Co., Ltd., 365 nm equivalent exposure power (exposure output) is 25 mW/cm ²

[Irradiation conditions]: Light of 330 nm or less was cut, and at that time, a gap of 50 µm was left and irradiated at 25 mW/cm ² for 8 seconds.

The ITO substrate subjected to the post-exposure treatment was immersed in an aqueous solution of tetramethylammonium hydroxide (0.4 mass%) for 40 seconds to develop. Then, water washing and drying were performed.

The board|substrate after drying was heated (220 degreeC, 60 minutes) on the hotplate, and the ITO board|substrate which has a cured film which has a specific pattern was produced (sample 1 for evaluation).

[Sample 2 for evaluation]

Sample 2 for evaluation was produced in the same manner as in Sample 1 for evaluation except for the step of exposing.

[Patternability]

About the sample 1 for evaluation, the taper angle and the quantity of a scum were evaluated as patterning property evaluation.

[Taper Angle]

The cross-sectional image of the cured film of the sample 1 for evaluation was image|photographed using XL-30ESEM of FEI as an analysis apparatus. And the taper angle was measured from the cross-sectional image about the 30 micrometers width pattern of a cured film.

<Measuring method of taper angle from cross-sectional image>

A tangent line was drawn in the portion where the thickness of the cured film became the height of 80% of the maximum value of the film thickness, and the angle between the tangent line and the substrate surface was defined as the taper angle (θ) ( FIG. 1 ).

Evaluation was performed on the following reference|standard.

Excellent: 25°≤θ.

Good: 20°≤θ<25°.

Impossible: θ < 20°.

Excellent or good was set as pass.

[Scum]

The amount of scum was measured from the cross-sectional view used in the measurement of the taper angle.

First, the edge part which a board|substrate surface and a cured film contact|connected was made into A point. Next, a tangent line was drawn in the part used as the height of 50% of the maximum value of a film thickness, and the thickness of a cured film made the point where a tangent line and a board|substrate surface cross|intersect B point. The distance between point A and point B was set to d, and the amount of scum was evaluated using d based on the following criteria (FIG. 2).

Good: It was 2 micrometers > d.

Impossible: 2 μm ≤ d.

Good was set as pass.

[Liquid repellency]

With respect to the sample 2 for evaluation, the contact angle with respect to PGMEA was measured by the (theta)/2 method. Evaluation is based on the following criteria.

Excellent: The contact angle was 45° or more.

Good: The contact angle was 40 degrees or more and less than 45 degrees.

Possible: The contact angle was more than 30° and less than 40°.

Impossible: The contact angle was less than 30°.

Excellent, good, and possible were set as pass.

[Examples and Comparative Examples]

At the ratio of Table 1, the raw material was stirred (about 30 minutes) until it became uniform, and the positive photosensitive resin composition was prepared. Using this, samples 1 and 2 for evaluation were respectively produced and evaluated. Table 1 shows the evaluation results. In addition, a blank in a table|surface indicates that the component of the said column is not contained.

<Explanation of abbreviations>

[Alkali-soluble resin (A)]

A1: copolymer of N-phenylmaleimide, benzyl methacrylate, and acrylic acid (Mw 6200, solid content 20%)

[Photosensitizer (B)]

B1: (4-｛4-[1,1-bis(4-hydroxyphenyl)ethyl]-α,α-dimethylbenzyl｝phenol and 6-diazo-5,6-dihydro-5-oxo-naphthalene -1-sulfonic acid (mono to tetra) esters)

[Crosslinking agent having N atom (C1)]

C1-1: N-hexa (or penta or tetra) methylolmelamine poly (2 to 6) alkyl (C = 1 to 4) etherhexamethoxymethylmelamine monomer (molecular weight 390) 96% or more

C1-2: N-hexa (or penta or tetra) methylolmelamine poly (2 to 6) alkyl (C = 1 to 4) etherhexamethoxymethylmelamine monomer (molecular weight 390) 70 to 80%

[Crosslinker having SH group (C2)]

C2-1: 1,3,5-tris(2-(3-sulfanylbutanoyloxy)ethyl)-1,3,5-triazinane-2,4,6-trione monomer (molecular weight 567)

C2-2: pentaerythritol tetrakis (3-mercaptobutyrate) monomer (molecular weight 545)

[Ink repellent agent (D)]

D1: What was synthesized by the following method was used.

(synthesis method)

2-butanone (415.1 g), CH ₂ =C(CH ₃ )COOCH ₂ CH ₂ (CF ₂ ) ₆ F (81.0 g), methacrylic acid (18.0 g), 2-hydroxyethyl methacrylate (81.0 g), 2,2'-azobis(2,4-dimethylvaleronitrile) (5.0 g) and n-dodecylmercaptan (4.7 g) were polymerized at 50°C for 24 hours while stirring under a nitrogen atmosphere. Furthermore, it heated at 70 degreeC for 5 hours, the polymerization initiator was deactivated, and the solution of the copolymer was obtained. The copolymer had a number average molecular weight of 5540 and a mass average molecular weight of 13200.

Then, 130.0 g of a solution of the above copolymer, 1,1-(bisacryloyloxymethyl)ethyl isocyanate (33.5 g), dibutyltindilaurate (0.13 g), t-butyl-p-benzoquinone (1.5 g) was polymerized at 40°C for 24 hours while stirring.

The polymer was purified using hexane, followed by drying to obtain 65.6 g of an ink repellent agent (D1).

D2: What was synthesized by the following method was used.

(synthesis method)

F(CF ₂ ) ₆ CH ₂ CH ₂ Si(OCH ₃ ) ₃ (0.38 g), Si(OC ₂ H ₅ ) ₄ (0.63 g), CH ₂ =CHCOO(CH ₂ ) ₃ Si(OCH ₃ ) ₃ ( 0.71 g) and PGME: propylene glycol monomethyl ether (7.44 g) were mixed until uniform.

To the mixed solution, 0.85 g of 1% hydrochloric acid aqueous solution was added dropwise. After completion|finish of dripping, it reacted by stirring at 40 degreeC for 5 hours, and this reaction liquid was made into the ink repellent agent (D2).

[Solvent (E)]

EDM: Diethylene glycol ethyl methyl ether (boiling point 176 ℃)

EDEGAC: Diethylene glycol monoethyl ether acetate (boiling point 217 ℃)

PGME: propylene glycol monomethyl ether (boiling point 120 ℃)

PGMEA: propylene glycol monomethyl ether acetate (boiling point 146 ℃)

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on the Japanese Patent Application (Japanese Patent Application No. 2020-037173) for which it applied on March 4, 2020, The content is taken in here as a reference.

Claims (9)

alkali-soluble resin (A);
photosensitizer (B);
a crosslinking agent having an N atom (C1);
a crosslinking agent having an SH group (C2), and
containing an ink repellent agent (D) having an F atom,
The positive photosensitive resin composition in which C2/C1 is in the range of 0.3<C2/C1<1.0 by mass ratio. The method of claim 1,
Positive photosensitivity, wherein the proportion of the crosslinking agent (C2) is in the range of 4% by mass to 19% by mass relative to the total of (A)+(B)+(C1)+(C2)+(D) in mass ratio resin composition. 3. The method according to claim 1 or 2,
The positive photosensitive resin composition in which the said photosensitive agent (B) contains a quinonediazide compound. 4. The method according to any one of claims 1 to 3,
The positive photosensitive resin composition in which the said crosslinking agent (C1) is a melamine resin. 5. The method according to any one of claims 1 to 4,
The positive photosensitive resin composition in which the said crosslinking agent (C2) has 2-4 said SH groups in a molecule|numerator. 6. The method according to any one of claims 1 to 5,
The positive photosensitive resin composition whose mass average molecular weights (Mw) of the said alkali-soluble resin (A) are 500-20000. 7. The method according to any one of claims 1 to 6,
The positive photosensitive resin composition further contains a solvent (E), and the ratio of the compound whose boiling point in the said solvent is 170 degreeC or more is 10-70 mass %. Hardened|cured material which hardened|cured the positive photosensitive resin composition in any one of Claims 1-7. An optical element comprising the cured product according to claim 8 as a barrier rib.

Images