WO2020101345A1 - Photosensitive resin composition, photosensitive material, display device, and method for low-temperature curing of photosensitive resin composition - Google Patents

Abstract

The present specification provides: a photosensitive resin composition comprising a binder bearing an epoxy group, and an additive bearing a thiol group and a siloxane; a photosensitive material; a display device; and a method for low-temperature curing of a photosensitive resin composition.

Description

Low temperature curing method of photosensitive resin composition, photosensitive material, display device, and photosensitive resin composition

This specification relates to a photosensitive resin composition, a photosensitive material, a display device, and a low temperature curing method of a photosensitive resin composition.

This application claims the benefit of the filing date of Korean Patent Application No. 10-2018-0141512, filed with the Korean Intellectual Property Office on November 16, 2018, all of which is incorporated herein.

Recently, an organic light emitting diode (OLED) display has been expanded and applied, and an upper touch panel has also been expanded from a film-type add on method to an on cell method. In the case of the on-cell touch screen panel, since the OLED panel is completed and directly manufactured on the top of the panel, a low temperature curing process (less than 100 ° C) that does not affect the OLED device life is essential.

For the above reasons, in the case of an insulating material used between electrodes or on an electrode in an on-cell touch screen panel applied to an OLED, a low temperature curing property should be implemented.

In order to realize low temperature curing properties, post curing by applying subsequent UV curing process in addition to UV (UV) process conditions to create a pattern is common, but in the case of these materials, processability (2 UV processes) and chemical resistance are insufficient Is the most.

[Prior literature] Korean published patent No. 10-2012-0022616

The present specification provides a photosensitive resin composition, a photosensitive material, and a display device.

Provided is a low temperature curing method using the photosensitive resin composition of the present invention.

An exemplary embodiment of the present specification, the binder resin; And an additive, wherein the binder resin includes a polymer containing an epoxy group, and the additive includes a thiol-based compound containing two or more thiol groups and a siloxane-based polymer (A) comprising siloxane units, or a thiol group is substituted. It provides a photosensitive resin composition comprising a siloxane-based polymer (B) containing a siloxane unit.

An exemplary embodiment of the present specification, a polyfunctional (meth) acrylate to the photosensitive resin composition; And it provides a photosensitive resin composition further comprising a photoinitiator.

One embodiment of the present specification provides a photosensitive material prepared using the photosensitive resin composition or a cured product.

One embodiment of the present specification provides a display device including the photosensitive material.

An exemplary embodiment of the present specification is (a) coating the photosensitive resin composition by coating it on a substrate;

(b) drying and pre-baking the coated substrate;

(c) exposing on the coated side of the substrate, then developing to form a pattern; And

(d) provides a low temperature curing method of a photosensitive resin composition comprising post-baking the substrate at 50 ° C or higher and 150 ° C or lower.

The photosensitive resin composition according to one embodiment of the present specification has excellent solubility in a solvent, and excellent heat resistance and chemical resistance.

In addition, according to an exemplary embodiment of the present specification, the photosensitive resin composition has excellent pattern characteristics when forming an organic film and is cured even at a low temperature of 100 ° C. or less to have excellent chemical resistance properties.

Hereinafter, the present specification will be described in more detail.

This specification is a binder resin; And an additive, wherein the binder resin includes a polymer containing an epoxy group, and the additive includes a thiol-based compound containing two or more thiol groups and a siloxane-based polymer (A) comprising siloxane units, or a thiol group is substituted. It provides a photosensitive resin composition comprising a siloxane-based polymer (B) containing a siloxane unit.

The photosensitive resin composition according to the present specification includes a thiol-based compound and a siloxane-based polymer as an additive or a siloxane-based polymer substituted with a thiol group (-SH). The thiol-based compound or thiol group is capable of both ultraviolet (UV) curing and thermal curing, and has excellent chemical resistance properties and forms an ultra-fine pattern. In addition, the siloxane-based polymer allows the photosensitive composition to be cured even at a low temperature and a low exposure amount of 100 ° C. or less.

In addition, the photosensitive resin composition of the present invention contains a polymer containing an epoxy group as a binder resin. The epoxy group contained in the polymer (binder) enables thermal curing. The binder resin according to an example includes an acid group (for example, a carboxy group), and an acid group in the binder structure has excellent characteristics of a pattern (development).

In the present specification, when a part “includes” a certain component, it means that the component may further include other components, not to exclude other components, unless otherwise stated.

Examples of the substituents are described below, but are not limited thereto.

In the present specification, the term “substitution” means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where the substituent is replaceable. When two or more are substituted, two or more substituents may be the same or different from each other.

The term "substituted or unsubstituted" as used herein refers to deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group (-OH); Thiol group (-SH); Alkyl groups; Alkenyl group; Aryl group; Heteroaryl group; And N, O, or one or more substituents selected from the group containing a heterocyclic group including one or more of S atoms, or two or more of the above-exemplified substituents is substituted with a linked group or means that it does not have any substituents. .

In one embodiment of the present specification, "substituted or unsubstituted" means deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Thiol group; An alkyl group having 1 to 10 carbon atoms; An alkenyl group having 2 to 10 carbon atoms; An aryl group having 6 to 30 carbon atoms; A heteroaryl group having 2 to 30 carbon atoms; And 2 to 30 carbon atoms, or one or more substituents selected from the group containing a heterocyclic group, or two or more of the above substituents are substituted with linked substituents or have no substituents.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be straight chain or branched chain, and carbon number is not particularly limited, but is preferably 1 to 60. According to an exemplary embodiment, the alkyl group has 1 to 30 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. Specific examples of the alkyl group are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-ox Tilgi, and the like, but are not limited to these.

In the present specification, the cycloalkyl group is not particularly limited, and has 3 to 30 carbon atoms; 3 to 20 carbon atoms; 3 to 10 carbon atoms; Or preferably having 3 to 6 carbon atoms, specifically cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, the alkenyl group may be a straight chain, branched chain or cyclic chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 25. As a specific example, an alkenyl group substituted with an aryl group such as a stylbenyl group or a styrenyl group is preferred, but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 30. According to one embodiment, the carbon number of the aryl group is 6 to 20, and may be 6 to 10. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., as a monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, indenyl group, phenanthrenyl group, pyrenyl group, perylene group, triphenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

In the present specification, the heteroaryl group includes one or more non-carbon atoms, that is, heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, and S. The number of carbon atoms is not particularly limited, preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heteroaryl group include a thiophene group; Furanyl group; Pyrrol group; Imidazolyl group; Thiazolyl group; Oxazolyl group; Oxadiazolyl group; Pyridyl group; Bipyridyl group; Pyrimidyl group; Triazinyl group; Triazolyl group; Acridil group; Pyridazinyl group; Pyrazinyl group; Quinolinyl group; Quinazolinyl group; Quinoxalinyl group; Phthalazinyl group; Pyridopyrimidyl group; Pyridopyrazinyl group; Pyrazino pyrazinyl group; Isoquinolinyl group; Indole group; Carbazolyl group; Benzoxazolyl group; Benzimidazole group; Benzothiazolyl group; Benzocarbazolyl group; Benzothiophene group; Dibenzothiophene group; Benzofuranyl group; Phenanthrolinyl group; Isooxazolyl group; Thiadiazolyl group; Phenothiazinyl group; And a dibenzofuranyl group, but is not limited thereto.

In the present specification, the hydrocarbon ring may be an aromatic, aliphatic or aromatic and aliphatic condensed ring, and may be selected from examples of the cycloalkyl group or aryl group except for the non-monovalent.

In the present specification, the aliphatic hydrocarbon ring may be selected from examples of the cycloalkyl group described above, except that it is not the monovalent.

In the present specification, the alkylene group means that the alkyl group has two bonding positions, that is, a divalent group. These may be applied to the description of the above-mentioned alkyl group, except that each is a divalent group.

In the present specification, the alkenylene group means that the alkenyl group has two binding sites, that is, a divalent group. These can be applied to the description of the alkenyl group described above, except that each is a divalent group.

In the present specification, the arylene group means that the aryl group has two bonding positions, that is, a divalent group. These may be applied to the description of the aryl group described above, except that each is a divalent group.

In the present specification, the heteroarylene group means that the heteroaryl group has two bonding positions, that is, a divalent group. These may be applied to the description of the heteroaryl group described above, except that each is a divalent group.

In the present specification, the heterocycle contains one or more non-carbon atoms and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, and S. The heterocycle may be monocyclic or polycyclic, and may be aromatic, aliphatic or aromatic and aliphatic condensed ring, and may be selected from examples of the heteroaryl group except that it is not monovalent.

In the present specification, (meth) acrylate may include acrylate and methacrylate, and may be acrylate or methacrylate. The (meth) acrylate may be monovalent or divalent.

In one embodiment of the present specification, the binder resin includes a polymer containing an epoxy group. Epoxy groups have thermosetting properties.

According to the exemplary embodiment of the present specification, the binder resin may have a weight average molecular weight of 5,000 g / mol or more and 150,000 g / mol or less. When the weight average molecular weight of the binder resin is within the above range, the viscosity of the solution is easy to control and there is an effect that phase separation does not occur with other components.

In addition, according to an exemplary embodiment of the present specification, as the binder resin containing the epoxy group as a functional group, those generally used in the art may be used.

In one embodiment of the present specification, the binder resin is a copolymer containing one or more epoxy group-containing monomers.

The epoxy group-containing monomer is glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 4,5-epoxyhexyl (meth) acrylate, 6,7-epoxypeptyl (meth) acrylate 1 However, it is not limited thereto.

According to an exemplary embodiment of the present specification, the binder resin may be a copolymer polymerized from a composition for a binder resin containing an epoxy-based monomer and a (meth) acrylate-based monomer.

Examples of the epoxy monomers include oxetenyl methacrylate, allyl glycidyl ether, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and glycidyl 5-norbornene-2 One or more compounds selected from the group consisting of -methyl-2-carboxylate (endo, exo mixture), 1,2-epoxy-5-hexene and 1,2-epoxy-9-decene can be used, but only It is not limited.

The (meth) acrylate-based monomers include methacrylic acid, (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, Isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, ethylhexyl (meth) acrylate, 2-phenoxyethyl (meth) acrylic Group consisting of acrylate, tetrahydrofurryl (meth) acrylate, hydroxyethyl (meth) acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate and butyl α-hydroxymethyl acrylate It may be selected from, but is not limited to.

In one embodiment of the present specification, the binder resin includes a first unit represented by the following Chemical Formula 3-1; A second unit represented by the following Chemical Formula 3-2; A third unit represented by the following Chemical Formula 3-3; And a fourth unit represented by the following Chemical Formula 3-4.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

In Chemical Formulas 3-1 to 3-4,

Ar is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

L101 and L102 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted alkylene group; Or a substituted or unsubstituted arylene group,

R101 and R102 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

T is a substituted or unsubstituted aliphatic hydrocarbon ring,

a is 0 <a <1 as a mole fraction,

b is 0 <b <1 as a mole fraction,

c is 0 <c <1 as a mole fraction,

d is 0 <d <1 as a mole fraction,

a + b + c + d ≤ 1,

r101 is an integer from 1 to 3, and when r101 is 2 or more, R101 is the same or different from each other,

r102 is an integer of 1 or more, and when r102 is 2 or more, R102 is the same or different from each other

Is a position connected to another functional group.

The molar fraction of a, b, c and d refers to a value obtained by dividing the number of each unit repetition by the sum of the unit repetitions. That is, a is a value obtained by dividing the number of unit repeats of Formula 3-1 by the total number of units of the copolymer, b is a value obtained by dividing the number of unit repeats of Formula 3-2 by the total number of units of the copolymer, and c is Formula 3-3. The number of unit repeats of is divided by the total number of units of the copolymer, and d is the number of unit repeats of the formula 3-4 divided by the total number of units of the copolymer. Molar fraction does not mean the order of repetition or number of repetitions.

In one embodiment of the present specification, Ar is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.

In one embodiment of the present specification, Ar is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 20 carbon atoms.

In one embodiment of the present specification, Ar is a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted naphthyl group; Or a substituted or unsubstituted fluorenyl group.

In one embodiment of the present specification, Ar is a phenyl group.

In one embodiment of the present specification, L101 and L102 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted alkylene group; Or a substituted or unsubstituted arylene group.

In one embodiment of the present specification, L101 and L102 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; Or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In one embodiment of the present specification, L101 and L102 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted alkylene group having 1 to 5 carbon atoms; Or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms.

In one embodiment of the present specification, L101 and L102 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted methylene group; A substituted or unsubstituted ethylene group; A substituted or unsubstituted propylene group; A substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylene group; Or a substituted or unsubstituted naphthylene group.

In one embodiment of the present specification, L101 and L102 are the same as or different from each other, and each independently a direct bond; Methylene group; Or an ethylene group.

In one embodiment of the present specification, L101 and L102 are methylene groups.

In one embodiment of the present specification, R101 and R102 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, R101 and R102 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; A substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.

In one embodiment of the present specification, R101 and R102 are hydrogen.

In one embodiment of the present specification, T is a substituted or unsubstituted aliphatic hydrocarbon ring.

In one embodiment of the present specification, T is a substituted or unsubstituted aliphatic hydrocarbon ring having 3 to 10 carbon atoms.

In one embodiment of the present specification, T is a cyclohexane ring.

In one embodiment of the present specification, a is a molar fraction, more than 0 and less than 1, preferably 0.1 to 0.6; Or 0.3 to 0.4. Appropriate film strength properties are realized when a is within the above range. Particularly, if it is 0.3 or more, the film strength is excellent, and if it is 0.4 or less, the pattern properties are excellent.

In one embodiment of the present specification, b is a molar fraction, more than 0 and less than 1, preferably 0.01 to 0.5; Or 0.1 to 0.2. When b is within the above range, it is possible to implement desired fine pattern characteristics. Particularly, when it is 0.1 or more, the developing characteristics are excellent, and when it is 0.2 or less, there is no fear of pattern dropping due to over-development because no over-development occurs.

In one embodiment of the present specification, c is a molar fraction, more than 0 and less than 1, and preferably 0.1 to 0.6: or 0.2 to 0.4. When c is within the above range, desired thermosetting properties are realized. In particular, when it is 0.2 or more, it has excellent thermosetting properties, and when it is 0.4 or less, it is advantageous for realizing a fine pattern.

In one embodiment of the present specification, d is a molar fraction, more than 0 and less than 1, preferably 0.01 to 0.5; Or 0.1 to 0.3. When d is within the above range, thermosetting properties (especially chemical resistance properties) are realized. Particularly, when it is 0.1 or more, it has excellent chemical resistance, and when it is 0.3 or less, it is advantageous for realizing fine properties by thermal curing.

In an exemplary embodiment of the present specification, a + b + c + d is 1.

In one embodiment of the present specification, r101 is 3.

In one embodiment of the present specification, r102 is an integer from 1 to 9.

In one embodiment of the present specification, r102 is 9.

According to one embodiment of the present specification, the content of the binder resin may be 50 parts by weight or more and 99.9 parts by weight or less with respect to 100 parts by weight of the total solid content of the photosensitive resin composition. It is preferably 60 parts by weight or more and 80 parts by weight or less. When the content of the binder resin is 50 parts by weight or more, a polymer component is suitable, and thus a thin film is easily formed. When the content of the binder resin is 99.9 parts by weight or less, an additive such as a surfactant can be added to expect an effect.

The total weight of the solid content means the sum of the total weight of the components excluding the solvent in the resin composition. The basis of the solid content and the weight percent based on the solid content of each component can be measured by general analytical means used in the art, such as liquid chromatography or gas chromatography.

According to an exemplary embodiment of the present specification, the acid value of the binder resin is 20 to 150 KOH mg / g.

In one embodiment of the present specification, the additive includes a thiol-based compound containing two or more thiol groups, and a siloxane-based polymer (A) containing siloxane units, or a siloxane-based polymer containing thiol-substituted siloxane units ( B).

In one embodiment of the present specification, the thiol-based compound contains 2 or more and 10 or less thiol groups.

In one embodiment of the present specification, the thiol-based compound contains 2 or more and 5 or less of thiol groups.

In one embodiment of the present specification, the thiol-based compound is 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercapto Butyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mergaptopropionate), pentaerythritol tetrakis ( 3-mercaptobutylate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) or tetraethylene glycol bis (3-mercaptopropionate) Nate), and two or more of them may be mixed, but is not limited thereto.

In one embodiment of the present specification, the siloxane-based polymer (A) containing the siloxane unit is a copolymer in which two or more silane monomers are polymerized.

In one embodiment of the present specification, the siloxane-based polymer (B) including the siloxane unit substituted with the thiol group is a copolymer in which two or more silane monomers are polymerized.

In one embodiment of the present specification, the siloxane-based polymer (A) containing the siloxane unit is a copolymer in which three or more silane monomers are polymerized.

In one embodiment of the present specification, the siloxane-based polymer (B) including the siloxane unit substituted with the thiol group is a copolymer of three or more silane monomers polymerized.

In one embodiment of the present specification, the siloxane-based polymer (A) containing the siloxane unit is in the form of a mesh.

In one embodiment of the present specification, the siloxane-based polymer (B) comprising the siloxane unit substituted with the thiol group is in the form of a mesh.

In one embodiment of the present specification, the siloxane-based polymer (A) containing the siloxane unit includes a first unit represented by the following Chemical Formula 1-1; A second unit represented by the following Chemical Formula 1-2; And a third unit represented by the following Chemical Formula 1-3.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Chemical Formulas 1-1 to 1-3,

R1 is an unsaturated functional group including a (meth) acrylate group or a vinyl group,

R2 is an epoxy-based functional group including an epoxy group,

x1 is 0 <x1 <1 as a mole fraction,

y1 is 0 <y1 <1 as a mole fraction,

z1 is 0 <z1 <1 as a mole fraction,

x1 + y1 + z1 ≤ 1,

Is a position connected to another functional group.

The mole fractions of x1, y1 and z1 refer to a value obtained by dividing the number of each unit repetition by the sum of unit repetitions. That is, x1 is a value obtained by dividing the number of unit repeats of Formula 1-1 by the total number of units of the copolymer, y1 is a value obtained by dividing the number of unit repeats of Formula 1-2 by the total number of units of the copolymer, and z1 is Formula 1-3 It is a value obtained by dividing the number of unit repeats by the total number of units of the copolymer. Molar fraction does not mean the order of repetition or number of repetitions.

In one embodiment of the present specification, the siloxane-based polymer (B) containing the thiol group-substituted siloxane unit is a first unit represented by the following Chemical Formula 2-1; A second unit represented by the following Chemical Formula 2-2; And a third unit represented by the following Chemical Formula 2-3.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In Chemical Formulas 2-1 to 2-3,

R3 is an unsaturated functional group containing a (meth) acrylate group or a vinyl group or an epoxy-based functional group including an epoxy group,

R4 is a thiol-mechanical functional group containing a thiol group at the terminal,

x2 is 0 <x2 <1 as a mole fraction,

y2 is 0 <y2 <1 as a mole fraction,

z2 is 0 <z2 <1 as a mole fraction,

x2 + y2 + z2 ≤ 1,

Is a position connected to another functional group.

The molar fraction of x2, y2 and z2 refers to a value obtained by dividing the number of each unit repetition by the total sum of unit repetitions. That is, x2 is a value obtained by dividing the number of unit repeats of Formula 2-1 by the total number of units of the copolymer, y2 is a value obtained by dividing the number of unit repeats of Formula 2-2 by the total number of units of the copolymer, and z2 is Formula 2-3 It is a value obtained by dividing the number of unit repeats by the total number of units of the copolymer. Molar fraction does not mean the order of repetition or number of repetitions.

In one embodiment of the present specification, x1 is a molar fraction, more than 0 and less than 1, preferably 0.1 to 0.5; Or 0.2 to 0.3. When x1 is within the above range, film formation is possible by photocuring (UV). Particularly, when it is 0.2 or more, film formation is smooth, and when it is 0.3 or less, it is advantageous for forming a fine pattern.

In one embodiment of the present specification, y1 is a molar fraction, more than 0 and less than 1, preferably 0.1 to 0.9; Or 0.4 to 0.6. When y1 is within the above range, film formation is possible by thermal curing. In particular, when it is 0.4 or more, it has excellent chemical resistance, and when it is 0.6 or less, it is advantageous for forming fine patterns.

In one embodiment of the present specification, z1 is a molar fraction, more than 0 and less than 1, preferably 0.1 to 0.7; Or 0.3 to 0.5. When z1 is within the above range, it has excellent pattern forming properties and heat curing is possible. Particularly, when it is 0.3 or more, a clear phenomenon is possible because pattern residue does not occur during development, and when it is 0.5 or more, there is no fear of pattern dropping due to over-development because it does not occur.

In one embodiment of the present specification, x1 + y1 + z1 is 1.

In one embodiment of the present specification, x2 is a molar fraction, more than 0 and less than 1, preferably 0.1 to 0.7; Or 0.3 to 0.5. When x2 is within the above range, photocuring and heat curing are possible. Particularly, when it is 0.3 or more, pattern formation is excellent, and when it is 0.5 or less, a pattern phenomenon does not occur and a clear phenomenon is possible.

In one embodiment of the present specification, y2 is a molar fraction, more than 0 and less than 1, preferably 0.1 to 0.7; Or 0.3 to 0.5. When y2 is within the above range, photocuring and thermal curing are possible. In particular, when it is 0.3 or more, the chemical resistance is excellent, and when it is 0.5 or less, it is advantageous for forming a fine pattern.

In one embodiment of the present specification, z2 is a molar fraction, more than 0 and less than 1, preferably 0.1 to 0.7; Or 0.3 to 0.5. When z2 is within the above range, it has excellent pattern forming characteristics and heat curing is possible. Particularly, when it is 0.3 or more, a clear phenomenon is possible because pattern residue does not occur during development, and when it is 0.5 or more, there is no fear of pattern dropping due to over-development because it does not occur.

In one embodiment of the present specification, x2 + y2 + z2 is 1.

In an exemplary embodiment of the present specification, unsaturated functional groups including the acrylate group, methacrylate group, or vinyl group may be used.

In an exemplary embodiment of the present specification, epoxy-based functional groups including the epoxy group may be those commonly used in the art.

Examples of the unsaturated functional group and the epoxy functional group include (meth) acrylate group, styryl group, vinyl ketone group, butadiene group, vinyl ether group, oxiranyl group, aziridinyl group, or oxetane group. Among these, a (meth) acrylate group, a styryl group, an oxiranyl group or an oxetane group is more preferable, and a (meth) acrylate group or an oxiranyl group is more preferable.

In one embodiment of the present specification, R4 is represented by the following formula (a).

[Formula a]

In the above formula a,

L2 is a substituted or unsubstituted alkylene group; A substituted or unsubstituted alkenylene group; A substituted or unsubstituted (meth) acrylate group; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

n2 is an integer from 1 to 10,

Is a position connected to another functional group.

In one embodiment of the present specification, L2 is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; A substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms; A substituted or unsubstituted (meth) acrylate group having 4 to 20 carbon atoms; A substituted or unsubstituted arylene group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms.

In one embodiment of the present specification, L2 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; A substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms; A substituted or unsubstituted (meth) acrylate group having 4 to 10 carbon atoms; A substituted or unsubstituted arylene group having 6 to 20 carbon atoms; Or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms.

In one embodiment of the present specification, L2 is an alkylene group having 1 to 10 carbon atoms.

In one embodiment of the present specification, the weight average molecular weight of the siloxane-based polymer (A) containing the siloxane unit is 0 to 500,000 g / mol. Preferably from 1,000 g / mol to 100,000 g / mol; Alternatively 2,000 to 5,000 g / mol. When the weight average molecular weight of the siloxane-based polymer (A) is less than 1,000 g / mol, the heat resistance and chemical resistance deteriorate, and when it exceeds 100,000 g / mol, the solubility in the developer is lowered, so that it does not develop and the viscosity of the solution increases too much Therefore, it is difficult to apply uniformly, which is not preferable.

In one embodiment of the present specification, the weight average molecular weight of the siloxane-based polymer (B) including the siloxane unit substituted with the thiol group is 0 to 500,000 g / mol. Preferably from 1,000 g / mol to 100,000 g / mol; Or 2,000 g / mol to 5,000 g / mol. When the weight average molecular weight of the siloxane-based polymer (B) is less than 1,000 g / mol, the heat resistance and chemical resistance deteriorate, and when it exceeds 100,000 g / mol, the solubility in the developer is lowered, so that it does not develop and the viscosity of the solution increases excessively Therefore, it is difficult to apply uniformly, which is not preferable.

The weight average molecular weight is a value obtained by averaging the molecular weights of the molecular weights of the component molecular species of the polymer compound having a molecular weight distribution as one of the average molecular weights in which the molecular weight is not uniform and the molecular weight of a certain polymer material is used as a standard.

The weight average molecular weight can be measured through Gel Permeation Chromatography (GPC) analysis.

According to an exemplary embodiment of the present specification, the content of the thiol-based compound containing two or more thiol groups and the siloxane-based polymer (A) containing siloxane units exceeds 0 parts by weight based on 100 parts by weight of the total solid content of the photosensitive resin composition 50 It may be less than parts by weight. Preferably 0.1 part by weight or more and 25 parts by weight or less; Or 1 part by weight or more and 10 parts by weight or less. When the thiol-based compound containing two or more thiol groups and the siloxane-based polymer (A) containing siloxane units are not included in the composition, there is no effect on improving the chemical resistance, and when it exceeds the above range, the alkali developer It may not be easy to control the development time and form patterns according to the overdevelopment.

According to an exemplary embodiment of the present specification, the content of the siloxane-based polymer (B) containing the thiol group substituted siloxane unit may be greater than 0 parts by weight and 50 parts by weight or less with respect to 100 parts by weight of the total solid content of the photosensitive resin composition. Preferably 0.1 part by weight or more and 25 parts by weight or less; Or 1 part by weight or more and 10 parts by weight or less. When the siloxane-based polymer (B) containing the thiol group substituted siloxane unit is not included in the composition, there is no effect on improving chemical resistance, and when it exceeds the above range, the development time is controlled and overdeveloped by an alkali developer. Pattern formation according to may not be easy.

In one embodiment of the present specification, the photosensitive resin composition is a polyfunctional (meth) acrylate; And a photoinitiator.

In one embodiment of the present specification, the photosensitive resin composition is a polyfunctional (meth) acrylate; Photoinitiators; And a solvent.

The polyfunctional (meth) acrylate is a monomer that serves to form a photoresist phase by light, and includes a polyfunctional urethane acrylate. The number of functional waters is not limited, and is preferably 2 or more and 20 or less. Specifically, propylene glycol methacrylate, dipentaerythritol hexaacrylate, dipentaerythritol acrylate, neopentyl glycol diacrylate, 6-hexanediol diacrylate, 1,6-hexanediol acrylate tetra Ethylene glycol methacrylate, bisphenoxy ethyl alcohol diacrylate, trishydroxyethyl isocyanurate trimethacrylate, trimethylpropane trimethacrylate, diphenylpentaerythritol hexaacrylate, pentaerythritol It may be one or a mixture of two or more selected from the group consisting of trimethacrylate, pentaerythritol tetramethacrylate and dipentaerythritol hexamethacrylate.

The photoinitiator is not particularly limited as long as it is an initiator that generates radicals by light to trigger crosslinking, but is selected from the group consisting of, for example, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, and oxime-based compounds. It may be one or more.

According to one embodiment of the present specification, the photoinitiator is an initiator capable of generating and reacting radicals by ultraviolet (UV) light.

The acetophenone-based compounds are 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, benzoinmethyl ether, benzoinethyl ether, benzoinisobutyl ether, benzoin Butyl ether, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- (4-methylthio) phenyl-2-morpholino-1-propan-1-one, 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) -butan-1-one, 2- (4-bromo-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one or 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, and the like, but is not limited thereto.

The biimidazole-based compound is 2,2-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, 2,2'-bis (o-chlorophenyl) -4 , 4 ', 5,5'-tetrakis (3,4,5-trimethoxyphenyl) -1,2'-biimidazole, 2,2'-bis (2,3-dichlorophenyl) -4, 4 ', 5,5'-tetraphenyl biimidazole, 2,2'-bis (o-chlorophenyl) -4,4,5,5'-tetraphenyl-1,2'-biimidazole, etc. , But is not limited to this.

The triazine-based compound is 3- {4- [2,4-bis (trichloromethyl) -s-triazine-6-yl] phenylthio} propionic acid, 1,1,1,3,3,3- Hexafluoroisopropyl-3- {4- [2,4-bis (trichloromethyl) -s-triazine-6-yl] phenylthio} propionate, ethyl-2- {4- [2,4 -Bis (trichloromethyl) -s-triazine-6-yl] phenylthio} acetate, 2-epoxyethyl-2- {4- [2,4-bis (trichloromethyl) -s-triazine-6 -Yl] phenylthio} acetate, cyclohexyl-2- {4- [2,4-bis (trichloromethyl) -s-triazine-6-yl] phenylthio} acetate, benzyl-2- {4- [ 2,4-bis (trichloromethyl) -s-triazine-6-yl] phenylthio} acetate, 3- {chloro-4- [2,4-bis (trichloromethyl) -s-triazine-6 -Yl] phenylthio} propionic acid, 3- {4- [2,4-bis (trichloromethyl) -s-triazine-6-yl] phenylthio} propionamide, 2,4-bis (trichloro Methyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3, -butadienyl-s -Triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, and the like.

The oxime-based compound is 1,2-octadione, -1- (4-phenylthio) phenyl, -2- (o-benzoyloxime) (Shibagai, Shijii124), ethanone, -1- (9 -Ethyl) -6- (2-methylbenzoyl-3-yl)-, 1- (O-acetyloxime) (CG 242), N-1919 (Adeka), and the like.

The solvent is acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether , Propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, 1 , 1,2-trichloroethane, 1,1,2-trichloroethene, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol, propanol, butanol, t-butanol, 2 -Ethoxy propanol, 2-methoxy propanol, 3-methoxy butanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate (PGMEA), propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3 -Ethoxy propionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether may be one or more selected from the group consisting of, but is not limited to .

According to one embodiment of the present specification, based on the total weight of solids in the resin composition, the content of the binder resin is 50% to 90% by weight, and the content of the additive is 1% to 20% by weight, The content of the photoinitiator is 0.1% to 10% by weight, and the content of the polyfunctional (meth) acrylate is 0.1% to 40% by weight.

According to one embodiment of the present specification, the resin composition further comprises one or two additives selected from the group consisting of a photocrosslinker, a curing accelerator, an adhesion aid, a surfactant, a thermal polymerization inhibitor, an antioxidant, and an ultraviolet absorber. Includes.

According to an exemplary embodiment of the present specification, the content of the additive is 0.1% to 20% by weight based on the total weight of solids in the resin composition.

The photocrosslinking agent is benzophenone, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylaminobenzophenone, methyl-o-benzoyl Benzophenone compounds such as benzoate, 3,3-dimethyl-4-methoxybenzophenone, 3,3,4,4-tetra (t-butylperoxycarbonyl) benzophenone; Florenone-based compounds, such as 9-Florenone, 2-Croro-9-Prorenone, and 2-methyl-9-Florenone; Thioxanthone series such as thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 1-chloro-4-propyloxy thioxanthone, isopropyl thioxanthone, and diisopropyl thioxanthone compound; Xanthone compounds such as xanthone and 2-methylxanthone; Anthraquinone compounds such as anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, t-butyl anthraquinone, and 2,6-dichloro-9,10-anthraquinone; 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, 1,5-bis (9-acridinylpentane), 1,3-bis (9-acridinyl) propane, etc. Acridine compounds; Dicarbonyl compounds such as benzyl, 1,7,7-trimethyl-bicyclo [2,2,1] heptane-2,3-dione, and 9,10-phenanthrenequinone; Phosphine oxide compounds such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide; Benzoate compounds such as methyl-4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate, and 2-n-butoxyethyl-4- (dimethylamino) benzoate; 2,5-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-diethylaminobenzal) cyclohexanone, 2,6-bis (4-diethylaminobenzal) -4- Amino synergists such as methyl-cyclopentanone; 3,3-carbonylvinyl-7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl-7- (diethylamino) coumarin, 3 -Benzoyl-7-methoxy-coumarin, 10,10-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H-C1] -benzo Coumarin-based compounds such as pyrano [6,7,8-ij] -quinolinazine-11-one; Chalcone compounds such as 4-diethylamino chalcone and 4-azide benzal acetophenone; 2-benzoylmethylene, 3-methyl-b-naphthothiazoline; one or more selected from the group consisting of;

The curing accelerator is used to increase curing and mechanical strength, specifically 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3 , 4-thiadiazole, 2-mercapto-4,6-dimethylaminopyridine, pentaerythritol-tetrakis (3-mercaptopropionate), pentaerythritol-tris (3-mercaptopropionate), penta Erythritol-tetrakis (2-mercaptoacetate), pentaerythritol-tris (2-mercaptoacetate), trimethylolpropane-tris (2-mercaptoacetate), and trimethylolpropane-tris (3-mercaptopropio) Nate) can be used one or more selected from the group consisting of.

A silane coupling agent is used as the adhesive agent used in the present specification, specifically, methacryloyloxy propyltrimethoxy silane, methacryloyloxy propyldimethoxy silane, methacryloyloxy propyltriethoxy silane, It is possible to select and use one or more of methacryloyl silane coupling agents such as methacryloyloxy propyldimethoxysilane, and octyltrimethoxy silane, dodecyl trimethoxy silane, and octadecyl as the alkyl trimethoxy silane. Trimethoxysilane etc. can be used selecting 1 or more types.

The surfactant is a silicone-based surfactant or a fluorine-based surfactant. Specifically, the silicone-based surfactant is BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307 , BYK-310, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341v344, BYK-345v346, BYK-348, BYK -354, BYK-355, BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, BYK-390, etc. can be used. DIC is a fluorine-based surfactant (DaiNippon Ink & Chemicals) F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F-445, F-446 , F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F-484, F -486, F-487, F-172D, MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130, TF-1116SF , TF-1131, TF1132, TF1027SF, TF-1441, TF-1442, etc. may be used, but is not limited thereto.

The antioxidant may be at least one selected from the group consisting of hindered phenol antioxidants, amine antioxidants, thio antioxidants, and phosphine antioxidants, but is not limited thereto.

Specific examples of the antioxidant include phosphoric acid-based thermal stabilizers such as phosphoric acid, trimethylphosphate or triethylphosphate; 2,6-di-t-butyl-p-cresol, octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, tetrabis [methylene-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxy Benzyl) benzene, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-g, t-butylphenol 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol) or bis [3 , 3-bis- (4'-hydroxy-3'-tert-butylphenyl) butanoic acid] glycol ester (Bis [3,3-bis- (4'-hydroxy-3'-tert-butylphenyl) butanoicacid] glycol esters, such as hindered phenol-based primary antioxidants; Amines such as phenyl-α-naphthylamine, phenyl-β-naphthylamine, N, N'-diphenyl-p-phenylenediamine or N, N'-di-β-naphthyl-p-phenylenediamine Secondary antioxidants; Thio such as dilauryl disulfide, dilaurylthiopropionate, distearylthiopropionate, mercaptobenzothiazole or tetramethylthiuramdisulfide tetrabis [methylene-3- (laurylthio) propionate] methane Secondary antioxidants; Or triphenyl phosphite, tris (nonylphenyl) phosphite, triisodecylphosphite, bis (2,4-dibutylphenyl) pentaerythritol diphosphite (Bis (2,4-ditbutylphenyl) Pentaerythritol Diphosphite or (1, 1'-biphenyl) -4,4'-diylbisphosphonoic acid tetrakis [2,4-bis (1,1-dimethylethyl) phenyl] ester ((1,1'-Biphenyl) -4,4 ' And phosphite-based secondary antioxidants such as -Diylbisphosphonous acid tetrakis [2,4-bis (1,1-dimethylethyl) phenyl] ester).

As the ultraviolet absorber, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chloro-benzotriazole, alkoxy benzophenone, etc. may be used, but is not limited thereto, and in the art Anything commonly used can be used.

Examples of the thermal polymerization inhibitor include p-anisole, hydroquinone, pyrocatechol, t-butyl catechol, N-nitrosophenylhydroxyamine ammonium salt, and N-nitrosophenylhydroxy Amine aluminum salt, p-methoxyphenol, di-t-butyl-p-cresol, pyrogarol, benzoquinone, 4,4-thiobis (3-methyl-6-t-butylphenol), 2,2- Methylene bis (4-methyl-6-t-butylphenol), 2-mercaptoimidazole, and phenothiazine (phenothiazine) may include one or more selected from the group consisting of, but are not limited to these, and the sugar technology These may include those commonly known in the art.

According to an exemplary embodiment of the present specification, to provide a photosensitive material prepared using the photosensitive resin composition or a cured product thereof.

More specifically, the photosensitive resin composition of the present specification is applied on a substrate in an appropriate manner to form a thin film or patterned photosensitive material.

Although the coating method is not particularly limited, a spray method, a roll coating method, a spin coating method, or the like can be used, and the spin coating method is generally widely used. In addition, after forming the coating film, in some cases, the residual solvent may be partially removed under reduced pressure.

As a light source for curing the photosensitive resin composition according to the present specification, there are, for example, mercury vapor arcs that emit light having a wavelength of 250 nm to 450 nm, carbon arcs, Xe arcs, metal halides, etc., but are not limited thereto. Does not.

The photosensitive resin composition according to the present specification is a thin film transistor liquid crystal display (TFT LCD) or organic light emitting diode, a photosensitive material for forming a black matrix, a photosensitive material for forming an overcoat layer, a column spacer photosensitive material, a photocurable paint, and a photocurable ink , Photo-curable adhesives, printing plates, photosensitive materials for printed wiring boards, photosensitive materials for plasma display panels (PDP), and the like, and the use is not particularly limited.

The photosensitive material according to the exemplary embodiment of the present specification is used as an insulating film, a protective film, or a planarization film.

The photosensitive material according to an exemplary embodiment of the present specification is manufactured by a low temperature curing method of a photosensitive resin composition described later.

The photosensitive material according to the exemplary embodiment of the present specification has excellent chemical resistance. Specifically, when exposed to chemical reagents, the rate of change in thickness is small.

In the present specification, the chemical resistance evaluation is performed by measuring the rate of change in thickness before and after treatment when a photosensitive material is treated at 50 ° C for 200 seconds with one reagent.

The photosensitive material according to the exemplary embodiment of the present specification has a thickness change rate of 5% or less with respect to the chemical reagent.

The photosensitive material according to an exemplary embodiment of the present specification has a thickness change rate with respect to 5% KOH, 2.38% tetramethylammonium hydroxide (TMAH), 5% oxalic acid (Oxalic acid), or Stripper (LGC's LGS-900 grade). 5% or less.

It provides a display device comprising a photosensitive material according to the present specification.

The display device includes a plasma display panel (PDP), a light emitting diode (LED), an organic light emitting diode (OLED), a liquid crystal display (LCD), a touch screen The panel may be any one of a touch screen panel (TSP), a thin film transistor liquid crystal display (LCD-TFT), and a cathode ray tube (CRT).

According to another exemplary embodiment according to the present specification, (a) applying the above-described photosensitive resin composition to a substrate to coat;

(b) drying and pre-baking the coated substrate;

(c) exposing on the coated side of the substrate, then developing to form a pattern; And

(d) provides a low temperature curing method of a photosensitive resin composition comprising post-baking the substrate at 50 ° C or higher and 150 ° C or lower.

In the present specification, the step of drying and pre-baking the coated substrate means removing the solvent contained in the coating film. The pre-baking step is preferably carried out at a lower temperature than the subsequent curing process. For example, the pre-baking temperature may be performed at a temperature of about 80 ° C to 120 ° C for 1 minute to 5 minutes.

In an exemplary embodiment of the present specification, in the step of exposing the resin film, ultraviolet rays or visible rays having a wavelength of 200 to 500 nm may be irradiated using a photomask on which a pattern to be processed is formed, and an exposure amount during irradiation is 10 to 4,000 mJ / Cm2 is preferred. The exposure time is also not particularly limited, and can be appropriately changed depending on the exposure apparatus used, the wavelength of the irradiated light or the exposure amount, and specifically, the exposure time can be changed within a range of 5 to 250 seconds.

In the present specification, after exposing on the coated surface of the substrate, developing to form a pattern means selectively developing the film after exposing the coating film using a mask to form a pattern on the substrate. .

In the step of forming the photosensitive resin film, an alkaline aqueous developer commonly known to be usable in the semiconductor or display production step can be used without any other limitation.

Hereinafter, examples will be described in detail to specifically describe the present specification. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not interpreted to be limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art.

<Product composition>

Example 1

Based on 100 parts by weight of solids, 63 parts by weight of a binder having an epoxy as a functional group, 22.5 parts by weight of a polyfunctional acrylate (6-functional, 10-functional mixture, DPHA, DPHA-40H, Japanese Chemicals), adhesion aid (silane coupling agent, KBM-503, Shin-Etsu Corporation) 2 parts by weight, photoinitiator (oxime ester system, OXE-02, BASF Corporation) 3.4 parts by weight, thiol-based compound (tetrafunctional, Karenz PE-1, Showa Denko Corporation) 3 parts by weight as an additive , 6 parts by weight of a siloxane-based polymer (A) containing a siloxane unit, 0.1 parts by weight of a surfactant (BYK-307, BYK-331, BYK), PGMEA as a solvent to obtain a composition 1 having a solid content of 21%.

The binder is the following copolymer. Molar fractions are a = 0.3, b = 0.2, c = 0.4, d = 0.1. The weight average molecular weight is 10,000 g / mol. In the case of the monomers used for the polymerization of the following copolymers, styrene (styrene, Duksan Chemical Company), methacrylic acid (Methacrylic acid) (MAA, Samcheon Chemical Company). Glycidyl methacrylate (GMA, Daejung Kumsa), 3,4-Epoxy-Cyclohexyl methyl-Methacrylate (Cyclomer M100, Daicel) Monomer was applied.

The siloxane-based polymer (A) containing the siloxane unit includes a first unit represented by Formula 1-1; A second unit represented by Formula 1-2; And a third unit represented by Chemical Formula 1-3. The mole fractions are x1 = 0.3, y1 = 0.4, and z1 = 0.3. The weight average molecular weight is 3,500 g / mol. R1 contains a methacrylate group, and R2 contains an epoxy (glycidyl type) group. In the case of the monomers used in the polymerization of the following copolymers 3-methacryloxypropyl trimethoxysilane (KBM-503, Shin-Etsu Corporation), 3-glycidoxypropyl trimethoxysilane (KBM-403, Shin-Etsu Corporation), A monomer of tetraethoxysilane (KBE-04, Shin-Etsu) was applied.

In the case of the weight average molecular weight (Mw), GPC (Gel Permeation Chromatography, Viscotek, Malvern), and eluent were measured using tetrahydrofuran (Stabilized) from J.T.Baker.

Example 2

As an additive in Example 1, 3 parts by weight of a thiol-based compound (tetrafunctional, Karenz PE-1, Showa Denko), a siloxane unit substituted with a thiol group other than 6 parts by weight of a siloxane-based polymer (A) containing siloxane units Composition 2 was prepared in the same manner as in Example 1, except that 9 parts by weight of the containing siloxane polymer (B) was used.

The siloxane-based polymer (B) containing the thiol group-substituted siloxane unit includes a first unit represented by Formula 2-1; A second unit represented by Formula 2-2; And a third unit represented by Chemical Formula 2-3. The mole fractions are x2 = 0.3, y2 = 0.4, and z2 = 0.3. The weight average molecular weight is 4,000 g / mol. R3 includes an epoxy (glycidyl type) group, and R4 is a mercaptopropyl group. In the case of the monomers used in the polymerization of the following copolymers 3-glycidoxypropyl trimethoxysilane (KBM-403, Shin-Etsu Corporation), 3-mercaptopropyl trimethoxysilane (KBM-803, Shin-Etsu Corporation), tetra A monomer of ethoxysilane (KBE-04, Shin-Etsu) was applied.

Comparative Examples 1 to 3

The composition was prepared in the same manner as in Example 1, except that the additive was changed as shown in Table 1.

	Example 1	Example 2	Comparative Example 1	Comparative Example 2	Comparative Example 3
bookbinder	63	63	68	67	65
Thiol-based compound (tetrafunctional)	3	-	-	3	-
Siloxane-based polymer (A)	6	-	-	-	6
Thiol-substituted siloxane-based polymer (B)	-	9	-	-	-
Polyfunctional acrylate	22.5	22.5	26.5	24.5	23.5
Adhesive	2	2	2	2	2
Photoinitiator	3.4	3.4	3.4	3.4	3.4
Surfactants	0.1	0.1	0.1	0.1	0.1

<Coating film formation>

The compositions prepared in Examples 1 and 2 and Comparative Examples 1 to 3 were coated on a substrate (SiNx, Ti / Al / Ti), spin-coated, and dried under vacuum at 65 Pa. Pre-bake on a hot plate at 85 ° C. for 160 seconds. After exposure to 50 mJ / cm ² intensity with a light source (i, g, h complex wavelength, Projection type exposure machine), it is developed for 80 seconds at 23 ° C., 2.38% TMAH (tetramethylammonium hydroxide). Wash for 20 seconds with distilled water and post-bake for 85 seconds at 85 ° C. in a convection oven. A coating film having a hole pattern is formed.

In the case of the exposure mask, a mask in which a hole pattern of 5 to 50 micrometer size was split was used.

<Coating film evaluation>

[Evaluation of chemical resistance]

The coating film was treated with 50% 200 seconds by dipping the 5% KOH, 2.38% tetramethylammonium hydroxide (TMAH), 5% oxalic acid, and stripper (LGC's LGS-900 grade), respectively. By measuring the thickness before and after the treatment, the rate of change in thickness was confirmed by the following formula.

When the thickness change rate was within 5%, it was evaluated as O, and when the thickness change was more than 5% or damage occurred in the coating film, it was evaluated as X. Table 2 below shows the evaluation results.

[Evaluation of pattern characteristics]

The minimum hole resolution was measured by applying a hole pattern mask. Table 2 below shows the measurement results.

Pattern characteristics were analyzed by SNU 3D profiler, Optical microscope, and SEM.

division	Example 1	Example 2	Comparative Example 1	Comparative Example 2	Comparative Example 3
5% KOH	O	O	X	X	X
2.38% TMAH	O	O	X	X	X
5% Oxalic acid	O	O	X	O	X
Stripper	O	O	X	X	X
Pattern characteristics (Hole pattern size, ㎛)	5㎛ or less	5㎛ or less	5㎛ or less	10㎛ or less	5㎛ or less

Examples 1 and 2 prepared from the composition of the present invention were excellent in chemical resistance and hole pattern characteristics. In Comparative Examples 1 and 3, which did not contain a thiol group, the hole pattern properties were excellent, but the chemical resistance to all reagents was poor. In Comparative Example 2 containing a thiol group but not a siloxane group, the chemical resistance to oxalic acid is excellent, but the chemical resistance to other reagents is poor and the hole pattern characteristics are poor.

Therefore, it can be seen that the photosensitive resin composition according to the present invention can be cured at low temperature and has excellent chemical resistance and pattern characteristics.

Claims (13)

1. Binder resin; And additives,

   The binder resin includes a polymer containing an epoxy group,

   The additive includes a thiol-based compound containing two or more thiol groups and a siloxane-based polymer (A) containing siloxane units, or a photosensitive resin comprising a siloxane-based polymer (B) containing thiol-substituted siloxane units. Composition.
2. The method according to claim 1,

   The siloxane-based polymer (A) containing the siloxane unit includes a first unit represented by the following Chemical Formula 1-1; A second unit represented by the following Chemical Formula 1-2; And a photosensitive resin composition comprising a third unit represented by the following formula 1-3:

   [Formula 1-1]

   

   [Formula 1-2]

   

   [Formula 1-3]

   

   In Chemical Formulas 1-1 to 1-3,

   R1 is an unsaturated functional group including a (meth) acrylate group or a vinyl group,

   R2 is an epoxy-based functional group including an epoxy group,

   x1 is 0 <x1 <1 as a mole fraction,

   y1 is 0 <y1 <1 as a mole fraction,

   z1 is 0 <z1 <1 as a mole fraction,

   x1 + y1 + z1 ≤ 1,

   

   Is a position connected to another functional group.
3. The method according to claim 1,

   The siloxane-based polymer (B) containing the thiol group substituted siloxane unit includes a first unit represented by the following Chemical Formula 2-1; A second unit represented by the following Chemical Formula 2-2; And a third unit represented by the following Chemical Formula 2-3:

   [Formula 2-1]

   

   [Formula 2-2]

   

   [Formula 2-3]

   

   In Chemical Formulas 2-1 to 2-3,

   R3 is an unsaturated functional group containing a (meth) acrylate group or a vinyl group or an epoxy-based functional group including an epoxy group,

   R4 is a thiol-mechanical functional group containing a thiol group at the terminal,

   x2 is 0 <x2 <1 as a mole fraction,

   y2 is 0 <y2 <1 as a mole fraction,

   z2 is 0 <z2 <1 as a mole fraction,

   x2 + y2 + z2 ≤ 1,

   

   Is a position connected to another functional group.
4. The method according to claim 1,

   The binder resin is a first unit represented by the following formula 3-1; A second unit represented by the following Chemical Formula 3-2; A third unit represented by the following Chemical Formula 3-3; And a photosensitive resin composition comprising a polymer comprising a fourth unit represented by the following formula 3-4:

   [Formula 3-1]

   

   [Formula 3-2]

   

   [Formula 3-3]

   

   [Formula 3-4]

   

   In Chemical Formulas 3-1 to 3-4,

   Ar is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

   L101 and L102 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted alkylene group; Or a substituted or unsubstituted arylene group,

   R101 and R102 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

   T is a substituted or unsubstituted aliphatic hydrocarbon ring,

   a is 0 <a <1 as a mole fraction,

   b is 0 <b <1 as a mole fraction,

   c is 0 <c <1 as a mole fraction,

   d is 0 <d <1 as a mole fraction,

   a + b + c + d ≤ 1,

   r101 is an integer from 1 to 3, and when r101 is 2 or more, R101 is the same or different from each other,

   r102 is an integer of 1 or more, and when r102 is 2 or more, R102 is the same or different from each other,

   

   Is a position connected to another functional group.
5. The method according to claim 1,

   The weight average molecular weight of the siloxane-based polymer (A) containing the siloxane unit is 0 to 500,000 g / mol,

   The weight average molecular weight of the siloxane-based polymer (B) containing the siloxane unit substituted with the thiol group is 0 to 500,000 g / mol.
6. The photosensitive resin composition of claim 2, wherein x1 is 0.2 to 0.3, y1 is 0.4 to 0.6, and z1 is 0.3 to 0.5.
7. The photosensitive resin composition according to claim 3, wherein x2 is 0.3 to 0.5, y2 is 0.3 to 0.5, and z2 is 0.3 to 0.5.
8. The photosensitive resin composition according to claim 4, wherein Ar is a phenyl group, L101 and L102 are methylene groups, R101 and R102 are hydrogen, and T is a cyclohexane ring.
9. The method according to claim 1, polyfunctional (meth) acrylate; And a photoinitiator.
10. The photosensitive resin composition according to claim 1, further comprising a solvent.
11. A photosensitive material prepared using the photosensitive resin composition according to any one of claims 1 to 10 or a cured product thereof.
12. Display device comprising a photosensitive material according to claim 11.
13. (A) coating the photosensitive resin composition according to one of claims 1 to 10 on a substrate to coat;

    (b) drying and pre-baking the coated substrate;

    (c) exposing on the coated side of the substrate, then developing to form a pattern; And

    (d) a low temperature curing method of a photosensitive resin composition comprising the step of post-baking the substrate at 50 ° C or more and 150 ° C or less.