KR101495533B1 - Photosensitive resin composition for spacer, spacer manufactured by the composition and display device including the spacer - Google Patents

Abstract

(상기 화학식 1에서 R1은 위치에 따라 각각 독립적으로 수소원자(단 원자수는 화학적 구조상 가능한 범위내에서 0~2개 범위로 선택되며, 수소 원자수 0의 R1은 이웃하는 수소 원자수 0의 R1과 함께 이중결합을 구성하는 것을 의미함), 알킬기(탄소수 1~12), 알릴기, 페닐기, 벤질기, 할로겐 원자 또는 탄소수 1~8의 알콕시기이며, R2는 수소원자(원자수 0 또는 1), 히드록시기, 알킬기(탄소수 1~12), 또는 탄소수 1~8의 알콕시기이다.)
(A-12): (A-11) 및 (A-13)과 공중합이 가능한 불포화 결합을 갖는 화합물,
(A-13): 불포화결합과 카르복실기를 갖는 카르복실산,
(A-14): 1 분자 중에 불포화 결합과 에폭시기를 갖는 화합물.
상기한 본 발명에 따른 스페이서 형성용 감광성 수지 조성물은 스페이서 형성에 적용시 기존 스페이서와 유사한 탄성 회복률을 가지면서도 외부 압력에 변형이 적은 딱딱한 특성을 갖는다. 그에 따라서 상기한 스페이서 형성용 감광성 수지 조성물은 표시 장치용 스페이서 및 표시 장치의 제조에 유용하게 사용될 수 있다. The photosensitive resin composition for forming a spacer according to the present invention comprises a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C) and a solvent (D) (A-14) is further reacted with a copolymer obtained by copolymerizing a compound containing an unsaturated group (A-13).
(A-11): a compound represented by the following general formula (1)
≪ Formula 1 >

(In the formula (1), R1 is independently a hydrogen atom (provided that the number of atoms is selected within a range of 0 to 2 within the range of chemical structure, R1 of the number of hydrogen atoms is 0 A phenyl group, a benzyl group, a halogen atom or an alkoxy group having 1 to 8 carbon atoms, and R2 is a hydrogen atom (the number of the atoms 0 or 1 ), A hydroxy group, an alkyl group (having 1 to 12 carbon atoms), or an alkoxy group having 1 to 8 carbon atoms.
(A-12): a compound having an unsaturated bond capable of copolymerization with (A-11) and (A-13)
(A-13): a carboxylic acid having an unsaturated bond and a carboxyl group,
(A-14): a compound having an unsaturated bond and an epoxy group in one molecule.
The photosensitive resin composition for forming a spacer according to the present invention has rigidity when applied to the formation of a spacer, which has a resilience similar to that of existing spacers and has little external stress. Accordingly, the above-described photosensitive resin composition for forming a spacer can be usefully used for manufacturing a spacer for a display device and a display device.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition for forming a spacer, a spacer for a display device manufactured using the same, and a display device including the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a photosensitive resin composition for forming a spacer, a spacer for a display device manufactured using the spacer, and a display device including the same.

In general display devices, silica beads or plastic beads having a certain diameter have been used to maintain constant spacing of the upper and lower substrates. However, when such beads are randomly dispersed on the substrate and located inside the pixel, there is a problem that the aperture ratio is lowered and light leakage phenomenon occurs. In order to solve these problems, a spacer formed by photolithography has been used in a display device. Currently, a spacer used in most display devices is formed by photolithography.

A method of forming a spacer by photolithography is a method in which a photosensitive resin composition is coated on a substrate, ultraviolet rays are irradiated through the mask, and a spacer is formed at a desired position on the substrate in accordance with a pattern formed on the mask.

2. Description of the Related Art In recent years, as the demand for touch panels has increased due to the popularization of smart phones and tablet PCs, the elastic recovery rate, which is a fundamental characteristic of spacers that maintain the interval between the color filter substrate and the array substrate constituting the display device, A hard characteristic is required so that there is no pixel deformation. However, although the conventional photosensitive resin composition for forming a spacer has a sufficient elastic recovery rate, hard properties without pixel deformation due to external pressure can not be achieved satisfactorily.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a photosensitive resin composition for forming a spacer having a hardness which is similar to that of existing spacers but has little elasticity at a high external pressure.

Another object of the present invention is to provide a spacer for a display device having a high elastic recovery rate and a rigid property with little strain at an external pressure.

Another object of the present invention is to provide a high-quality display device having the spacer.

(A), a photopolymerizable compound (B), a photopolymerization initiator (C) and a solvent (D), wherein the binder resin

Wherein the binder resin comprises a first resin containing an unsaturated group and a second resin containing an unsaturated group, wherein the first resin containing an unsaturated group is obtained by copolymerizing a compound containing the following (A-11) to (A-13) (A-14) is further reacted with the resulting copolymer, and the second resin containing an unsaturated group is a copolymer obtained by copolymerizing a compound containing an epoxy group and an aliphatic polycyclic compound having an unsaturated bond Sensitive resin composition.

<화학식 3>

<화학식 4>

<화학식 5>

<화학식 6>

<화학식 7>

<화학식 8>

<화학식 9>

(A-11): at least one compound selected from compounds represented by the following formulas (2) to (9)
(2)

(3)

&Lt; Formula 4 >

&Lt; Formula 5 >

(6)

&Lt; Formula 7 >

(8)

&Lt; Formula 9 >

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(A-12): a compound having an unsaturated bond capable of copolymerization with (A-11) and (A-13)

(A-13): a carboxylic acid having an unsaturated bond and a carboxyl group,

(A-14): a compound having an unsaturated bond and an epoxy group in one molecule.

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The unsaturated group-containing first resin preferably has a molar ratio of the constituent units derived from (A-11) to (A-13) to the total molar number of the constituent units constituting the copolymer,

(A-11) is from 2 to 30 mol%,

(A-12) is from 2 to 95% by mol,

(A-13) is from 2 to 70 mol%

It is preferable that the above (A-14) is reacted in an amount of 5 to 80 mol% with respect to the structural unit derived from the (A-13) of the copolymer.

The unsaturated group-containing second resin may be a copolymer of a compound containing (A-21) and (A-22).

(A-21): a compound having an unsaturated bond and a carboxyl group,

(A-22): An aliphatic polycyclic compound having an unsaturated bond with an epoxy group selected from the group consisting of the following formulas (10a) and (10b).

<Formula 10a>

&Lt; Formula 10b >

(Wherein R in each of formulas (10a) and (10b) is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which is substituted or unsubstituted with a hydroxyl group, and each X independently represents a single bond or a hetero atom- Lt; / RTI &gt;

The unsaturated group-containing second resin preferably has a molar ratio with respect to the total number of moles of the constituent units constituting the copolymer, the ratio of the constituent units derived from (A-21) and (A-22)

(A21); 5 to 75 mol%

(A22); And preferably 25 to 95 mol%.

The binder resin (A) preferably comprises 10 to 95% by mass of the first resin containing an unsaturated group and 5 to 90% by mass of the second resin containing an unsaturated group in a mass fraction based on the solid content.

The content of the binder resin (A) is preferably 5 to 90% by mass relative to the total solid content in the photosensitive resin composition for forming a spacer.

In order to achieve the above object, the present invention also provides a spacer for a display device, which is formed by forming the photosensitive resin composition in a predetermined pattern, followed by exposure and development.

In order to achieve the above object, the present invention also provides a display device comprising the spacer.

The photosensitive resin composition for forming a spacer according to the present invention has rigidity when applied to the formation of a spacer, which has a resilience similar to that of existing spacers and has little external stress. Accordingly, the above-described photosensitive resin composition for forming a spacer can be usefully used for manufacturing a spacer for a display device and a display device.

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

The photosensitive resin composition for forming a spacer according to the present invention (hereinafter, simply referred to as a photosensitive resin composition) comprises a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C) and a solvent (D). The photosensitive resin composition may further comprise an additive (E).

The binder resin (A)

The binder resin (A) generally has alkali solubility with reactivity due to the action of light or heat.

According to the present invention, the binder resin includes an unsaturated group-containing first resin obtained by further reacting (A-14) a copolymer obtained by copolymerizing a compound containing the following (A-11) to .

<화학식 3>

<화학식 4>

<화학식 5>

<화학식 6>

<화학식 7>

<화학식 8>

<화학식 9>

(A-11): at least one compound selected from compounds represented by the following formulas (2) to (9)
(2)

(3)

&Lt; Formula 4 >

&Lt; Formula 5 >

(6)

&Lt; Formula 7 >

(8)

&Lt; Formula 9 >

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(A-12): a compound having an unsaturated bond capable of copolymerization with (A-11) and (A-13)

(A-13): a carboxylic acid having an unsaturated bond and a carboxyl group,

(A-14): a compound having an unsaturated bond and an epoxy group in one molecule.

The binder resin (A) can be polymerized together with addition of monomers other than the above-mentioned compounds. That is, the binder resin (A) may further include monomers other than the above-mentioned (A-11) to (A-13) and may be copolymerized.

The binder resin (A) according to the present invention contains an unsaturated group-containing compound containing a constituent unit which can be obtained by polymerization of at least one compound selected from the compounds represented by the above formulas (2) to (9) Resin.

Preferably, the binder resin (A) comprises at least one compound (A-11) selected from the compounds represented by the above formulas (2) to (9), a compound having an unsaturated bond (A-12) and a compound having an unsaturated bond and a carboxyl group Containing resin obtained by further reacting a compound (A-14) having an unsaturated bond and an epoxy group in one molecule in a copolymer obtained by copolymerizing a compound containing an unsaturated group-containing compound (A-13).

Although the structure of the binder resin (A) has been specified through the production method, it is only for clarification of the structure of the binder resin (A), and only the case where the binder resin (A) The present invention is not limited thereto, and the binder resin having the structure specified in the present invention may be prepared by other methods and used as a component of the composition.

At least one compound (A-11) selected from the compounds represented by the above formulas (2) to (9) reacts with an unsaturated compound containing an epoxy group in a carboxyl group of a compound having a rosin skeleton to form a (meth) acryloyl group which is an unsaturated group . The compounds having the rosin skeleton include abietic acid, neoabietic acid, palustric acid, levopimaric acid, pimaric acid, dihydroabietic acid, dehydroabietic acid, and tetrahydroabietic acid, Usually as a mixture. Examples of the unsaturated compound containing an epoxy group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate.

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As commercial products of the above (A-11), 2-hydroxypropyldihydroabietic acid acrylate [Bismet 101], [Bismet 102], [Bismet 115] or Arakawa Chemical's [K100A ], And [UNIRESIN K900B].

Also, (meth) acrylates described in this specification means acrylate and / or methacrylate.

The compound (A-12) having an unsaturated bond capable of copolymerizing with the above (A-11) and (A-13) is not limited as long as it is a compound having an unsaturated double bond capable of polymerization. Specifically, the (A-12) may be a copolymer of (meth) acrylic acid, such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl Acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentantienyl (Meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl Unsaturated carboxylic acid ester compounds containing an alicyclic substituent, mono-saturated carboxylic acid ester compounds of glycols such as oligoethylene glycol monoalkyl (meth) acrylate, benzyl (meth) acrylate, phenoxy (meth) Aromatic vinyl compounds such as styrene,? -Methylstyrene, and vinyltoluene; carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; unsaturated carboxylic acid ester compounds such as (meth) acrylic acid Maleimide compounds such as N-cyclohexylmaleimide and N-phenylmaleimide, and the like can be given. These may be used alone or in combination of two or more.

As the compound (A-13) having an unsaturated bond and a carboxyl group, any carboxylic acid compound having an unsaturated double bond capable of polymerization can be used without limitation.

The compound (A1) having an unsaturated bond and a carboxyl group may be, for example, an unsaturated monocarboxylic acid, a dicarboxylic acid having two or more carboxyl groups in the molecule such as an unsaturated dicarboxylic acid or an unsaturated tricarboxylic acid, have.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid.

Examples of the unsaturated polycarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and the like.

The polyvalent carboxylic acid may be an acid anhydride, and examples of the unsaturated polycarboxylic acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like.

The unsaturated polycarboxylic acid may also be a mono (2-methacryloyloxyalkyl) ester thereof, for example, mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxy Ethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like.

The unsaturated polycarboxylic acid may be mono (meth) acrylate of the dicarboxylic polymer of both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like. have.

The unsaturated polycarboxylic acid may be an unsaturated acrylate containing a hydroxyl group and a carboxyl group in the same molecule, and for example,? - (hydroxymethyl) acrylic acid and the like

Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used because of high copolymerization reactivity.

The above exemplified (A-13) may be used alone or in combination of two or more.

The compound (A-14) having an unsaturated bond and an epoxy group in one molecule imparts light / heat curability to the binder resin.

Specifically, the (A-14) is at least one compound selected from the group consisting of glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 2,3-epoxycyclopentyl Hexyl methyl (meth) acrylate, methyl glycidyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate), methyl glycidyl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yl (meth) acrylate. These may be used alone or in combination of two or more.

When the binder resin (A) according to the present invention is a copolymer obtained by copolymerizing the compounds (A-11) to (A-13) as described above (in the case of copolymerization further comprising monomers other than A-11 to A-13 (A-11) to (A-13) in the copolymer when the first resin containing an unsaturated group obtained by further reacting (A-14) The ratio is preferably within the following range in mole fraction with respect to the total number of moles of the constituent units constituting the copolymer.

(A-11): 2 to 30% by mol,

(A-12): 2 to 95 mol%,

(A-13): 2 to 70 mol%.

The above (A-14) is preferably reacted in the copolymer in an amount of 5 to 80 mol% based on the number of moles of the structural unit derived from (A-13).

In particular, it is more preferable that the ratio of the above structural units is in the following range.

(A-11): 5 to 30% by mol,

(A-12): 5 to 80 mol%,

(A-13): 5 to 65 mol%.

It is particularly preferable that the above (A-14) is reacted in the copolymer in an amount of 10 to 80 mol% based on the number of moles of the constituent unit derived from (A-13).

When the composition ratio of (A-11) to (A-13) falls within the above range, a preferable copolymer can be obtained because the balance of developability, solubility and heat resistance is good. , Sufficient photocurability and thermosetting property can be obtained, which is preferable because both the sensitivity and the pencil hardness are compatible and the reliability is excellent.

When the binder resin (A) according to the present invention contains the unsaturated group-containing first resin obtained by further reacting the copolymer (A-14) with the copolymer obtained by copolymerizing the (A-11) An example of the manufacturing method is as follows.

A solvent (D) in an amount of 0.5 to 20 times by mass based on the total amount of (A-11) to (A-13) was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen- The atmosphere is replaced by nitrogen in the air. Thereafter, the temperature of the solvent (D) was raised to 40 to 140 ° C, and then a predetermined amount of (A-11) to (A-13) and a predetermined amount of (A-11) To 20 times the amount of the solvent (D) and 0.1 to 10 mol% of the polymerization initiator such as azobisisobutyronitrile or benzoyl peroxide in the total molar amount of (A-11) to (A-13) Or stirring under heating) is added dropwise to the flask over a period of 0.1 to 8 hours, followed by stirring at 40 to 140 ° C for 1 to 10 hours.

When a solvent is used in the above step, a solvent used in a conventional radical polymerization reaction may be used as a solvent. Specific examples thereof include tetrahydrofuran, dioxane, ethylene glycol dimethylethyl, diethylene glycol Propanol, n-butanol, isopropanol, n-butanol, isopropanol, n-butanol, isobutanol, isobutanol, Ethylene glycol monomethyl ether, propylene glycol monomethyl ether, toluene, xylene, ethylbenzene, chloroform, dimethylsulfoxide and the like. These solvents may be used alone or in combination of two or more.

The polymerization initiator to be used in the above step may be added with a commonly used polymerization initiator, and is not particularly limited. Specific examples thereof include diisopropylbenzene hydroperoxide, di-t-butyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amylperoxy-2-ethylhexanoate, Organic peroxides such as peroxy-2-ethylhexanoate; Azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylbareronitolyl), dimethyl 2,2'-azobis (2-methylpropionate), etc. Nitrogen compounds; And the like. These may be used alone or in combination of two or more.

In order to control the molecular weight and the molecular weight distribution, for example, mercapto-series chain transfer agents such as n-dodecyl mercapto, mercaptoacetic acid and methyl mercaptoacetate,? -Methylstyrene dimer and the like may be used as a chain transfer agent. The amount of the? -methylstyrene dimer or mercapto compound to be used is 0.005 to 5% by mass based on the total amount of (C1) to (C3) to (C4).

In addition, the above-mentioned polymerization conditions may be appropriately adjusted depending on the production equipment or the amount of heat generated by polymerization, and the method of addition and the reaction temperature.

By doing the above, a copolymer obtained by copolymerizing the above (A-11) to (A-13) can be produced.

Subsequently, the atmosphere in the flask was replaced with air with nitrogen, and the content of the component (A-14) in the copolymer was 5 to 80 mol% based on the constitutional unit derived from the component (A-13) For example, tricydimethylaminomethylphenol in an amount of 0.01 to 5% by mass based on the total amount of (A-11) to (A-14) (A-14) can be reacted by reacting the above-mentioned copolymer with the above-mentioned copolymer (A-14) in an amount of 0.001 to 5% based on the total amount of the copolymer and A-14 in a flask at 60 to 130 ° C for 1 to 10 hours. In addition, the fixing method and the reaction temperature may be appropriately adjusted in consideration of the production facility or the amount of heat generated by polymerization, as in the above-mentioned copolymerization conditions.

When the copolymer (A-14) is further reacted with the copolymer obtained by copolymerizing (A-11) to (A-13) as described above, the unsaturated group-containing first resin can be produced.

The unsaturated group-containing first resin obtained as described above preferably has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the unsaturated group-containing first resin is in the range of 3,000 to 100,000, it exhibits hard properties without pixel deformation.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the unsaturated group-containing first resin is preferably 1.5 to 6.0, more preferably 1.8 to 4.0. When the molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) is 1.5 to 6.0, development is preferable.

The unsaturated group-containing first resin may be used alone as the binder resin (A), and if necessary, it may be mixed with other resins.

Preferably, the binder resin (A) according to the present invention may further comprise a second resin containing an unsaturated group which is a copolymer obtained by a copolymerization reaction of a compound containing the following (A-21) and (A-22).

(A-21): a compound having an unsaturated bond and a carboxyl group,

(A-22): An aliphatic polycyclic compound having an unsaturated bond with an epoxy group selected from the group consisting of the following formulas (10a) and (10b).

<Formula 10a>

&Lt; Formula 10b >

(Wherein R in each of formulas (10a) and (10b) is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which is substituted or unsubstituted with a hydroxyl group, and each X independently represents a single bond or a hetero atom- Lt; / RTI &gt;

The compound (A-21) having an unsaturated bond and a carboxyl group can be selected from those described in the above-mentioned unsaturated group-containing first resin (A-13), and a detailed description thereof will be omitted.

In the general formulas (10a) and (10b), R is specifically a hydrogen atom; An alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group; Hydroxy-n-propyl group, 3-hydroxy-n-propyl group, 1-hydroxy-1-hydroxypropyl group, N-butyl group, 3-hydroxy-n-butyl group, 4-hydroxy-n-butyl group, 2-hydroxy- -Butyl group and the like. Among them, R is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group.

In Formulas (10a) and (10b), X is specifically a single bond; Alkylene groups such as a methylene group, an ethylene group and a propylene group; Containing alkylene groups such as a methylene group, an oxyethylene group, an oxyethylene group, an oxyethylene group, an oxypropylene group, a thiomethylene group, a thioethylene group, a thiopropylene group, an aminomethylene group, an aminoethylene group and an aminopropylene group. Among them, X is preferably a single bond, a methylene group, an ethylene group, an oxymethylene group or an oxyethylene group, more preferably a single bond or an oxyethylene group.

Examples of the compound represented by the formula (10a) include compounds represented by the following formulas (11) to (25).

&Lt; Formula 11 >

&Lt; Formula 12 >

&Lt; Formula 13 >

&Lt; Formula 14 >

&Lt; Formula 15 >

&Lt; Formula 16 >

&Lt; Formula 17 >

&Lt; Formula 18 >

(19)

(20)

&Lt; Formula 21 >

(22)

&Lt; Formula 23 >

&Lt; EMI ID =

&Lt; Formula 25 >

Examples of the compound represented by the formula (10b) include compounds represented by the following formulas (26) to (40).

(26)

&Lt; Formula 27 >

(28)

(29)

(30)

(31)

(32)

&Lt; Formula 33 >

(34)

&Lt; Formula 35 >

&Lt; EMI ID =

(37)

&Lt; Formula 38 >

&Lt; EMI ID =

&Lt; EMI ID =

The compounds represented by the formula (10a) and the compounds represented by the formula (10b) may be used alone or in combination of two or more.

(A-21) and (A-22) other than the above (A-21) and (A-22) Compounds having polymerizable unsaturated bonds can be copolymerized together.

Specific examples of the compound having an unsaturated bond polymerizable with the above (A-21) and (A-22) include 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2- Aminoethyl methacrylate, 2-aminopropyl methacrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl methacrylate, Unsaturated carboxylic acid aminoalkyl esters such as acrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate,? -Vinyl butyrate and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile,? -Chloroacrylonitrile, and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide,? -Chloroacrylamide, N-2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide; Maleimide, benzyl maleimide, N-phenyl maleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; And a monoacryloyl group or monomethacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, And the like.

When the unsaturated group-containing second resin is copolymerized with a copolymer other than the copolymer (A-21 and A-22) obtained by copolymerizing (A-21) and (A-22) as described above, ), The proportion of the constitutional unit derived from each of (A-21) and (A-22) in the copolymer is in a molar fraction with respect to the total number of moles of the constituent units constituting the copolymer, .

(A-21); 5 to 75 mol%

(A-22); 25 to 95 mol%.

Particularly, it is more preferable that the ratio of the constituent units is in the following range.

(A21); 10 to 70 mol%

(A22); 30 to 90 mol%

When the ratio of the above-mentioned structural units is within the above range, it becomes possible to produce a photosensitive resin composition having good developing solvent resistance, heat resistance and mechanical strength.

The unsaturated group-containing second resin is similar to the above-described method for producing a copolymer of an unsaturated group-containing first resin, so that it can be easily produced by referring to it.

The unsaturated group-containing second resin preferably has an acid value in the range of 20 to 200 (KOH mg / g). When the acid value is in the above range, it becomes possible to produce a spacer having excellent elastic recovery.

The weight average molecular weight of the unsaturated group-containing second resin in terms of polystyrene is 3,000 to 100,000, preferably 5,000 to 50,000. When the weight average molecular weight of the unsaturated group-containing second resin is within the above range, it is preferable to prevent the reduction of the film at the time of development and to improve the missability of the pattern portion.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the unsaturated group-containing second resin is preferably 1.5 to 6.0, more preferably 1.8 to 4.0. When the molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) is within the above range, the developability is preferable.

When the first unsaturated group-containing resin and the second unsaturated group-containing resin are used in combination as the binder resin (A), the binder resin (A) contains the unsaturated group-containing first resin in a mass fraction of from 10 to 95 By mass and 5 to 90% by mass of a second resin containing an unsaturated group.

When the content of the unsaturated group-containing first resin and the unsaturated group-containing second resin is within the above-mentioned range, it becomes possible to produce a spacer having a hardness characteristic with little change in external pressure while having a good elastic recovery rate.

The content of the binder resin (A) is usually in the range of 5 to 90 mass%, preferably 10 to 70 mass%, based on the total solid content in the photosensitive resin composition. When the content of the binder resin (A) is 5 to 90% by mass on the basis of the above-mentioned criteria, the solubility in a developing solution is sufficient and the developability is excellent, and the spacer having a hardness characteristic Manufacturing becomes possible.

In the present invention, the solid content means the sum of the components from which the solvent has been removed.

Photopolymerization  The compound (B)

The photopolymerizable compound (B) is a compound capable of polymerizing under the action of light and a photopolymerization initiator described later, and examples thereof include monofunctional monomers, bifunctional monomers, and other polyfunctional monomers.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Money and so on.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol Hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

Among the photopolymerizable compounds (B) exemplified above, multifunctional monomers having two or more functional groups are preferably used. Particularly preferred is a polyfunctional monomer having five or more functionalities. The above-mentioned photopolymerizable compounds (B) may be used alone or in combination of two or more.

The photopolymerizable compound (B) is used in an amount of 1 to 90 parts by mass, preferably 10 to 80 parts by mass based on the total 100 parts by mass of the binder resin (A) and the photopolymerizable compound (B) . When the photopolymerizable compound (B) is in the above range, it is preferable because the strength and smoothness of the spacer pattern can be improved.

Light curing Initiator (C)

The photopolymerization initiator (C) can be applied without limitation to those commonly used in the art.

For example, the photopolymerization initiator (C) may use at least one compound selected from the group consisting of a triazine-based compound, an acetophenone-based compound, a nonimidazole-based compound and an oxime compound. The photosensitive resin composition containing the photopolymerization initiator (C) described above has high sensitivity, and the strength and surface smoothness of the spacer pattern formed using the composition are improved.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) (Trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) Bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- (2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane -1-one oligomers and the like.

Examples of the acetophenone-based compound include compounds represented by the following formula (41).

&Lt; EMI ID =

In Formula 41, R 1 to R 4 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group which may be substituted with an alkyl group having 1 to 12 carbon atoms, a benzyl group which may be substituted with an alkyl group having 1 to 12 carbon atoms, Or a naphthyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms.

Specific examples of the compound represented by the formula (41) include 2-methyl-2-amino (4-morpholinophenyl) ethan- 2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl-2 2-amino (4-morpholinophenyl) propan-1-one, 2-methyl- 2-methyl-2-methylamino (4-morpholinophenyl) propan-1-one 2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino .

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, the phenyl group at the 4,4', 5,5 ' An imidazole compound substituted by an alkoxy group, and the like. Of these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- 5,5'-tetraphenylbiimidazole is preferably used.

Examples of the oxime compound include 0-ethoxycarbonyl- alpha -oximimino-1-phenylpropan-1-one, and the following chemical formulas (42), (43) and (44).

(42)

&Lt; Formula 43 >

&Lt; Formula 44 >

Further, as long as the effect of the present invention is not impaired, other photopolymerization initiators generally used in this field may be further used in combination. Examples of other photopolymerization initiators include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and anthracene-based compounds. These may be used alone or in combination of two or more.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- .

Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, .

Other examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclyoxylic acid Methyl, titanocene compounds and the like can be mentioned as other photopolymerization initiators.

Further, a photopolymerization initiator having a group capable of chain transfer with the photopolymerization initiator (C) may be used. Examples of such a photopolymerization initiator include those described in Japanese Patent Application Laid-Open No. 2002-544205.

Examples of the photopolymerization initiator having a group capable of causing chain transfer include the compounds represented by the following formulas (45) to (50).

<Formula 45>

&Lt; EMI ID =

&Lt; EMI ID =

(48)

(49)

(50)

The photopolymerization initiator (C) may be used in combination with the photopolymerization initiator (C-1). When the photopolymerization initiator (C) is used in combination with the photopolymerization initiator (C-1), the photosensitive resin composition containing the photopolymerization initiator (C-1) is more preferable because the sensitivity can be improved and the productivity can be improved when forming the spacer.

As the photopolymerization initiation auxiliary (C-1), an amine compound or a carboxylic acid compound is preferably used.

Specific examples of the amine compound in the photopolymerization initiation assistant (C-1) include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine; aliphatic amine compounds such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, N, N-dimethyl para-toluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone) , 4,4'-bis (diethylamino) benzophenone, and the like. Of these, an aromatic amine compound is preferably used as the amine compound.

Specific examples of the carboxylic acid compound in the photopolymerization initiation auxiliary (C-1) include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenyl Aromatic heteroacetic acids such as thioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

The photopolymerization initiator (C) is used in an amount of 0.1 to 40 parts by mass, preferably 1 to 30 parts by mass based on 100 parts by mass of the total of the binder resin (A) and the photopolymerizable compound (B) 1) is used in an amount of 0.1 to 50 parts by mass, preferably 1 to 40 parts by mass, based on the above-mentioned standards.

When the amount of the photopolymerization initiator (C) is in the above range, the photosensitive resin composition is highly sensitized and the strength and smoothness of the spacer formed using the composition are favorable. When the amount of the photopolymerization initiator (C-1) used is within the above range, the sensitivity of the photosensitive resin composition is higher and the productivity of the spacer pattern formed using the composition is improved.

Solvent (D)

The above-mentioned solvent (D) can be used without limitation as long as it is commonly used in the art.

Specific examples of the solvent (D) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate and ethylene glycol monoethyl ether acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propyl methyl ether and propylene glycol ethyl propyl ether; Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; Butyldiol monoalkyl ethers such as methoxybutyl alcohol, ethoxybutyl alcohol, propoxybutyl alcohol and butoxybutyl alcohol; Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate and butoxybutyl acetate; Butanediol monoalkyl ether propionates such as methoxy butyl propionate, ethoxy butyl propionate, propoxy butyl propionate and butoxy butyl propionate; Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and dipropylene glycol methyl ethyl ether; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Examples of the solvent include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxypropionate, methylhydroxyacetate, , Hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, Methyl methoxyacetate, methyl methoxyacetate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetate, ethoxyacetate, ethoxyacetate, propoxy Methyl acetate, ethyl propoxyacetate, propoxypropylacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, butyl Methoxypropionate, ethyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, , Propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, Ethoxypropionate, propyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, Propoxy propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxypropionic acid ethyl, 3-propoxypropionate, Esters such as ropil, 3-butoxy-propionic acid butyl; Cyclic ethers such as tetrahydrofuran and pyran; and cyclic esters such as? -butyrolactone. The solvents (D) exemplified herein may be used alone or in combination of two or more.

The solvent (D) is preferably at least one selected from the group consisting of alkylene glycol alkyl ether acetates, ketones, butanediol alkyl ether acetates, butanediol monoalkyl ethers, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate Ethers such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate, 3- Methyl methoxypropionate and the like can be used.

The content of the above-mentioned solvent (D) is 60 to 90% by mass, preferably 70 to 85% by mass, based on the mass of the photosensitive resin composition containing it. When the content of the solvent (D) is within the above range, the coating property is good when applied by a coating apparatus such as a spin coater, a slit & spin coater, a slit coater (sometimes referred to as a die coater or a curtain flow coater) .

The photosensitive resin composition according to the present invention may further contain additives (E) such as fillers, other polymer compounds, curing agents, leveling agents, adhesion promoters, antioxidants, ultraviolet absorbers, .

Specific examples of the filler include glass, silica and alumina.

Specific examples of the other polymer compound include curable resins such as epoxy resin and maleimide resin; And thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

The above-mentioned curing agent is used for enhancing deep curing and mechanical strength, and specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin, Aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides, isoprene (co) polymers other than the brominated derivatives, epoxy resins and their brominated derivatives of these epoxy resins, glycidyl ester resins, glycidyl amine resins, ) Polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidylisocyanurate.

Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

The curing agent may be used together with a curing agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. Examples of the curing aid compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, acid generators, and the like.

The carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Examples of the epoxy resin curing agents include epoxy resins such as those available under the trade names (ADEKA HARDONE EH-700) (ADEKA INDUSTRY CO., LTD.), Trade names (RICACIDO HH) Manufactured by Shin-Etsu Chemical Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.

As the leveling agent, commercially available surfactants can be used, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants. Two or more species may be used in combination.

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, (Manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-top (manufactured by TOKEM PRODUCTS CO., LTD.), Megapak (manufactured by Dainippon Ink Chemical Industry Co., (Manufactured by Asahi Glass Co., Ltd.), SORPARS (manufactured by Zeneca), EFKA (manufactured by EFKA CHEMICALS Co., Ltd.), FERRAD (manufactured by Sumitomo 3M Ltd.) , And PB821 (manufactured by Ajinomoto Co., Ltd.).

As the adhesion promoter, silane compounds are preferable, and specific examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) Aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like.

Specific examples of the antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- -3,5-di-tert-butylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3- Bis [2- {3- [3- tert -butyl] benzo [d, f] [1,3,2] dioxaphospepine, 3,9- -Butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylenebis 6-tert-butyl-4-methylphenol), 4,4'-butylidenebis (6-tert- Methylphenol), 2,2'-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate , Distearyl 3,3'-thiodipropionate, pentaerythrityl tetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert (3H, 3H, 5H) -triene, 3,3 ', 3 ", 5,5' 5 '' - hexa-tert-butyl-a, a ', a' '- (mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- Di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol and the like.

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.

Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.

Specific examples of the chain transfer agent include dodecyl mercaptan, 2,4-diphenyl-4-methyl-1-pentene and the like.

The photosensitive resin composition of the present invention can be produced by, for example, a method of adding and mixing a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C) and other additives, . &Lt; / RTI &gt; However, the present invention is not limited to such a method.

According to the present invention, there is provided a display device spacer formed by exposing and developing the above-mentioned photosensitive resin composition in a predetermined pattern, and a display device having the same.

The spacer for a display device can be produced, for example, by coating a photosensitive resin composition on a substrate as follows, and photo-curing and developing it to form a pattern.

First, a photosensitive resin composition is coated on a substrate (usually glass) or a layer composed of a solid content of a previously formed photosensitive resin composition, followed by heating and drying to remove volatile components such as a solvent to obtain a smooth coated film.

The coating method can be carried out by, for example, a spin coating method, a flexible coating method, a roll coating method, a slit and spin coating method, a slit coating method or the like.

After application, heating and drying (prebaking), or drying under reduced pressure to evaporate the volatile components such as solvent. Here, the heating temperature is usually 70 to 200 占 폚, preferably 80 to 130 占 폚. The thickness of the coated film after heat drying is usually about 1 to 8 mu m.

Ultraviolet rays are applied to the thus obtained coating film through a mask for forming a desired pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so as to uniformly irradiate a parallel light beam onto the entire exposed portion and accurately align the mask and the substrate. When ultraviolet light is irradiated, the site irradiated with ultraviolet light is cured.

The ultraviolet rays may be g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), or the like. The dose of ultraviolet rays can be appropriately selected according to need, and the present invention is not limited thereto.

When the coating film after curing is brought into contact with a developing solution to dissolve and develop the non-visible portion, a spacer having a desired pattern shape can be obtained.

The developing method may be any of a liquid addition method, a dipping method, and a spraying method. Further, the substrate may be inclined at an arbitrary angle during development.

The developer is usually an aqueous solution containing an alkaline compound and a surfactant.

The alkaline compound may be either an inorganic or an organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate , Sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, and ammonia. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine, and the like. These inorganic and organic alkaline compounds may be used alone or in combination of two or more. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass.

The surfactant in the alkali developer may be at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts.

Each of these surfactants may be used alone or in combination of two or more.

The concentration of the surfactant in the developer is usually 0.01 to 10% by mass, preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass.

After development, it is washed with water, and post baking at 150 to 230 캜 for 10 to 60 minutes may be carried out if necessary.

Using the photosensitive resin composition of the present invention, a pattern can be formed on a substrate or a color filter substrate through each of the steps described above. This pattern is useful as a photo spacer used in a display device.

Therefore, the spacer having the pattern thus obtained can be effectively used in a display device such as a liquid crystal display device. In particular, when applied to a touch panel, the spacer has a resilience recovery similar to that of conventional spacers and has a rigid property with little external stress.

Hereinafter, the present invention will be described in more detail with reference to examples, but it is needless to say that the present invention is not limited to the examples. In the following Examples and Comparative Examples, "%" and "part" representing the content are on a mass basis unless otherwise specified.

Synthesis Example 1 Synthesis of unsaturated group-containing first resin A

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube. The atmosphere in the flask was changed to nitrogen in air. After raising the temperature to 100 캜, 47.2 g of vinyltoluene 44.5 g (0.1 mole) of 2-hydroxypropyldihydroabietic acid acrylate [Bimaseet 101, Arakawa Chemical Industries, Ltd.] and 136 g of propylene glycol monomethyl ether acetate, , 3.6 g of azobisisobutyronitrile was added dropwise to the flask over 2 hours from the dropping funnel, and stirring was further continued at 100 캜 for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 30 g of glycidyl methacrylate (0.20 mol (40 mol% based on the methacrylic acid used in the present reaction)), 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone The reaction was continued at 110 캜 for 6 hours to obtain a first resin A containing an unsaturated group having a solid acid value of 99 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 28,000 and the molecular weight distribution (Mw / Mn) was 2.2.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the dispersion resin were measured by using HLC-8120GPC (manufactured by TOSOH CORPORATION), and the columns were TSK-GELG4000HXL and TSK-GELG2000HXL connected in series , The column temperature was 40 占 폚, the mobile phase solvent was tetrahydrofuran, the flow rate was 1.0 ml / min, the injection amount was 50 占, and the detector RI was used. The concentration of the test sample was 0.6 mass% (solvent = tetrahydrofuran) TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500 and A-500 (manufactured by TOSOH CORPORATION) were used.

The ratio of the weight average molecular weight to the number average molecular weight obtained above was defined as a molecular weight distribution (Mw / Mn).

Synthesis Example 2 Synthesis of unsaturated group-containing first resin B

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube. The atmosphere in the flask was changed to nitrogen in air, and after raising the temperature to 100 캜, 35.4 g of vinyltoluene (0.20 mole) of propylene glycol monomethyl ether acetate and 36.0 g (0.50 mole) of acrylic acid, 2-hydroxypropyldihydroabietic acid acrylate [Bimaseet 101, Arakawa Chemical Industry Co., Ltd.] A solution prepared by adding 3.6 g of azobisisobutyronitrile to the mixture was added dropwise to the flask over 2 hours from the dropping funnel, and stirring was further continued at 100 캜 for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 22.5 g [0.15 mol (50 mol% based on the acrylic acid used in the present reaction) of glycidyl methacrylate], 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone And the reaction was continued at 110 캜 for 6 hours to obtain a first resin B containing an unsaturated group having a solid acid value of 123.7 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 20,000 and the molecular weight distribution (Mw / Mn) was 2.3.

Synthesis Example 3 Synthesis of unsaturated group-containing second resin C

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube, and the atmosphere in the flask was changed to nitrogen in air. After heating to 70 DEG C, (0.25 mol), 240.0 g (0.75 mol) of a mixture of 4-epoxytricyclo [5.2.1.02.6] decyl acrylate in a molar ratio of 50:50 of the compounds represented by the formulas 11 and 26] and propylene glycol And 136 g of monomethyl ether acetate, 3.6 g of azobisisobutyronitrile was added dropwise to the flask over 2 hours from the dropping funnel, and stirring was further continued at 70 캜 for 4 hours. A first resin D containing an unsaturated group having a solid acid value of 110 mgKOH / g was obtained. The weight average molecular weight measured by GPC in terms of polystyrene was 13,000 and the molecular weight distribution (Mw / Mn) was 2.5.

Synthesis Example 4 Synthesis of unsaturated group-containing resin D

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube, and the atmosphere in the flask was changed to nitrogen in air. After raising the temperature to 100 캜, benzyl methacrylate 88.1 A solution of 3.6 g of azobisisobutyronitrile added to a mixture of g (0.50 mol), methacrylic acid (43.0 g, 0.50 mol) and propylene glycol monomethyl ether acetate (136 g) was added dropwise to the flask Followed by further stirring at 100 DEG C for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 30 g (0.20 mol) of glycidyl methacrylate (50 mol% with respect to the carboxyl group of the methacrylic acid used in the present reaction)], 0.9 g of trisdimethylaminomethylphenol, And the reaction was continued at 110 DEG C for 6 hours to obtain a resin C having a solid acid value of 94 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 30,000 and the molecular weight distribution (Mw / Mn) was 2.1.

&Lt; Examples 1 to 7 and Comparative Examples 1 to 4 >

Each component shown in Table 1 below was mixed to prepare a photosensitive resin composition for forming a spacer. Here, the content of each component represents the mass part.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 (A) Binder resin A-A 55.00 30.00 15.00 5.25 30.00 2.50 A-B 55.00 30.00 2.50 A-C 25.00 25.00 40.00 49.75 55.00 52.50 A-D 25.00 55.00 52.50 (B) a photopolymerizable compound 45.00 45.00 45.00 45.00 45.00 45.00 45.00 45.00 45.00 45.00 45.00 (C) a photopolymerization initiator C-A 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.0 C-B 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.0 (C-1) a photopolymerization initiator C-1 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.0 (D) Solvent D-1 53.00 53.00 53.00 53.00 53.00 53.00 53.00 53.00 53.00 53.00 53.00 D-2 42.00 42.00 42.00 42.00 42.00 42.00 42.00 42.00 42.00 42.00 42.0 D-3 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.0 D-4 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.0 (F) Additive 0.80 0.80 0.80 0.80 0.80 0.80 0.80 0.80 0.80 0.80 0.80

The components used in Table 1 are as follows.

(A) Binder resin A-A: The first resin A containing unsaturated group prepared in Synthesis Example 1

(A) Binder resin A-B: The first resin B containing an unsaturated group prepared in Synthesis Example 2

(A) Binder Resin A-C: The unsaturated group-containing second resin C prepared in Synthesis Example 3

(A) Binder resin A-D: The unsaturated group-containing resin D

(B) Photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Yakuza Co., Ltd.)

(C) Photopolymerization initiator C-A: 2-Benzyl-2-dimethylamino-1 (4-morpholinophenyl) butanone (Irgacure 369;

(C) Photopolymerization initiator C-B: 2-Methyl-2-morpholino (4-thiomethylphenyl) propan-1-one (Irgacure-907, manufactured by Ciba Specialty Chemicals)

C-1: 4,4'-di (N, N'-dimethylamino) -benzophenone (EAB-F, manufactured by Hodogaya Chemical Co., Ltd.)

(D) Solvent D-1: Propylene glycol monomethyl ether acetate

(D) Solvent D-2: 3-ethoxyethyl propionate

(D) Solvent D-3: 3-Methoxy-1-butanol

(D) Solvent D-4: 3-methoxybutyl acetate

(F) Additive (antioxidant): 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine- , 3H, 5H) -thione (Irganox 3141 (manufactured by Ciba Specialty Chemicals)

<Experimental Example>

A glass substrate (Eagle 2000; Corning) having an aspect ratio of 2 inches was sequentially washed with a neutral detergent, water and alcohol, and then dried. The photosensitive resin compositions prepared in the above Examples and Comparative Examples were each spin-coated on the glass substrate, and then prebaked in a clean oven at 90 占 폚 for 3 minutes. The prebaked substrate was cooled to room temperature and light was irradiated at an exposure dose of 100 mJ / cm 2 (based on 405 nm) using an exposure apparatus (TME-150RSK; Topcon Co., Ltd.) with an interval of 10 μm from the quartz glass photomask Respectively.

The irradiation of the polymerizable resin composition at this time was carried out by passing the radiation from the ultra-high pressure mercury lamp through an optical filter (LU0400, manufactured by Asahi Spectroscopy) and cutting light having a wavelength of 400 nm or less.

At this time, the photomask used was a photomask in which the following pattern was formed on the same plane.

(Pattern) having a side of 10 mu m and a square interval of 100 mu m.

After light irradiation, the coating film was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 캜 for 100 seconds and developed. After washing with water, post-baking was performed in an oven at 220 캜 for 20 minutes. The obtained film thickness was 3 占 퐉. The film thickness was measured using a film thickness measuring apparatus (DEKTAK 6M; Veeco).

The pattern thus obtained was evaluated for physical properties as described below, and the results are shown in Table 2 below.

- Transmittance -

The transmittance (%) at 400 nm of the cured film obtained above was measured using a microscopic spectrophotometric apparatus (OSP-SP200, manufactured by OLYMPUS). The transmittance is shown in Table 2 below in terms of the transmittance at a film thickness of 3.0 μm. The closer the transmittance is to 100%, the better.

- Line width, sectional shape -

The line width of the cured film obtained above was measured using a scanning electron microscope (S-4200, manufactured by Hitachi, Ltd.), and the sectional shape was evaluated as follows.

The cross sectional shape was determined as a reverse taper when the angle of the pattern with respect to the substrate was less than 90 degrees and as a reverse taper when the angle was greater than 90 degrees.

A net taper is preferable because disconnection of ITO wirings hardly occurs at the time of forming a display device.

- Mechanical properties (total displacement and recovery rate) -

The total amount of displacement (占 퐉) and the amount of elastic displacement (占 퐉) were measured under the following measurement conditions using a dynamic ultra-microhardness tester (DUH-W201; manufactured by Shimadzu Corporation) The recovery rate (%) was calculated as follows. When the total displacement was small and the recovery rate was high, it was judged to be rigid.

Recovery rate (%) = [elastic displacement amount (占 퐉)] / [total displacement amount (占 퐉)] 占 100

Measuring conditions:

Test mode; Load - unloading test

Test force; 5gf [SI conversion value; 49.0 mN]

Load speed; 0.45 gf / sec [SI unit conversion value; 4.41 mN / sec]

Retention time; 5sec

Indenter; Conical indenter indenter (diameter 50 탆)

- Solvent resistance -

The pattern obtained above was immersed in N-methylpyrrolidone at 30 占 폚 for 30 minutes, and the film thickness and transmittance (measured wavelength: 400 nm) before and after immersion were measured, and the change was determined according to the following formula. The adhesion was also measured by the following method.

Film thickness change (%) = [Film thickness after immersion (占 퐉) / Film thickness before immersion (占 퐉)] × 100

Transmittance change (%) = [Transmittance (%) after immersion / Transmittance (%) before immersion] × 100

The film thickness change and the transmittance change are preferably 90 to 103%, respectively.

- Adhesion to the base material -

As for the solvent adhesion, the substrate after immersion in the solvent resistance test was subjected to a peeling test using a commercially available cellophane tape, and then the adhesive property of the substrate was evaluated with a square water remaining on the substrate without peeling.

The larger the value, the better the adhesion.

- Heat resistance -

The pattern thus obtained was allowed to stand in a clean oven at 230 占 폚 for 1 hour, and the film thickness and transmittance (measured wavelength: 400 nm) before and after heating were measured, and the change was determined according to the following formula. Also, the adhesion was measured as follows.

Film thickness change (%) = [Film thickness after heating (占 퐉) / Film thickness before heating (占 퐉)] × 100

Transmittance change (%) = [Transmittance (%) after heating / Transmittance (%) before heating] × 100

It is preferable that the film thickness change and the transmittance change are 90 to 103%, respectively.

- Heat resistance -

As for the heat-resistant adhesion, the substrate after heating in the heat resistance test was subjected to a peeling test using a commercially available cellophane tape, and then heat-resistant adhesion was evaluated by the square water remaining on the substrate without peeling.

The larger the number is, the better the adhesion is.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Transmittance (%) 99 98 99 99 99 99 98 97 96 98 97 pattern Line width (탆) 10.0 10.1 9.8 9.8 9.7 9.8 9.9 10.0 12.0 10.0 11.3 shape Sun Taper Sun Taper Sun Taper Sun Taper Sun Taper Sun Taper Sun Taper Reverse taper Sun Taper Reverse taper Sun Taper Mechanical properties Total displacement
(탆) 0.69 0.71 0.62 0.66 0.69 0.80 0.74 1.20 0.76 1.04 0.84 Recovery Rate (%) 59.7 59.8 61.3 61.7 59.9 58.9 58.6 56.7 38.3 55.8 39.6 Solvent resistance Transmittance change
(%) 99 99 98 98 97 96 98 97 86 98 89 Film thickness change
(%) 98 99 97 97 96 95 96 97 89 99 91 Adhesiveness
(n / 100) 100 100 100 100 100 100 100 98 87 99 90 Heat resistance Transmittance change
(%) 99 99 98 98 97 96 98 96 85 99 90 Film thickness change
(%) 98 99 97 97 96 95 96 95 88 98 91 Adhesiveness
(n / 100) 100 100 100 100 100 100 100 100 98 100 99

As shown in Table 2, in Examples 1 to 7 using the binder resin containing the unsaturated group-containing first resin according to the present invention, the pattern shape was better than those of Comparative Examples 1 and 2, It is possible to confirm that it is excellent not only in mechanical properties with a small total amount of displacement but also excellent solvent resistance and heat resistance.

Also in the examples, the first unsaturated group-containing resin and the second unsaturated group-containing resin were mixed, and in the case of Examples 3 to 5 in which the mixing ratio was within the preferred range of the present invention, It is possible to confirm that the pattern shape is good, the elastic recovery rate is excellent and the total amount of displacement is small as well as mechanical properties and solvent resistance and heat resistance are superior to those of Example 6 in which the unsaturated group- It can be confirmed that the pattern shape is good, the elastic recovery rate is excellent, and the total displacement amount is small, compared with Examples 1 and 2 which are used alone.

Claims (9)

delete A binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C) and a solvent (D)
Wherein the binder resin comprises a first resin containing an unsaturated group and a second resin containing an unsaturated group,
The unsaturated group-containing first resin is obtained by further reacting the copolymer (A-14) with a copolymer obtained by copolymerizing a compound containing the following (A-11) to (A-13)
Wherein the second unsaturated group-containing resin is a copolymer obtained by copolymerizing an epoxy group and a compound containing an aliphatic polycyclic compound having an unsaturated bond:
(A-11): at least one compound selected from compounds represented by the following formulas (2) to (9)
(2)

(3)

&Lt; Formula 4 >

&Lt; Formula 5 >

(6)

&Lt; Formula 7 >

(8)

&Lt; Formula 9 >

(A-12): a compound having an unsaturated bond capable of copolymerization with (A-11) and (A-13)
(A-13): a carboxylic acid having an unsaturated bond and a carboxyl group,
(A-14): a compound having an unsaturated bond and an epoxy group in one molecule.
3. The resin composition according to claim 2, wherein the unsaturated group-containing first resin has a molar ratio to the total number of moles of the constituent units constituting the copolymer (A-11) to (A-13)
(A-11) is from 2 to 30 mol%,
(A-12) is from 2 to 95% by mol,
(A-13) is from 2 to 70 mol%
The photosensitive resin composition for forming a spacer according to (A-14), wherein the copolymer is reacted in an amount of 5 to 80 mol% based on the structural unit derived from the (A-13).
The photosensitive resin composition for forming a spacer according to claim 2, wherein the unsaturated group-containing second resin is a copolymer of a compound containing (A-21) and (A-22)
(A-21): a compound having an unsaturated bond and a carboxyl group,
(A-22): An aliphatic polycyclic compound having an unsaturated bond with an epoxy group selected from the group consisting of the following formulas (10a) and (10b).
<Formula 10a>

&Lt; Formula 10b >

(Wherein R in each of formulas (10a) and (10b) is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which is substituted or unsubstituted with a hydroxyl group, and each X independently represents a single bond or a hetero atom- Lt; / RTI &gt;
5. The resin composition according to claim 4, wherein the unsaturated group-containing second resin has a molar ratio of the constituent units derived from (A-21) and (A-22) to the total number of the constituent units constituting the copolymer,
(A21); 5 to 75 mol%
(A22); Is 25 to 95 mol% based on the total weight of the photosensitive resin composition.
The binder resin composition according to claim 4, wherein the binder resin (A) comprises 10 to 95% by mass of a first resin containing an unsaturated group and 5 to 90% by mass of a second resin containing an unsaturated group in a mass fraction based on the solid content Sensitive resin composition.
The photosensitive resin composition for forming a spacer according to claim 2, wherein the content of the binder resin (A) is in the range of 5 to 90 mass% with respect to the total solid content in the photosensitive resin composition for forming a spacer.
A spacer for a display device formed by forming the photosensitive resin composition according to any one of claims 2 to 7 in a predetermined pattern, followed by exposure and development.
A display device comprising the spacer of claim 8.