KR101373984B1 - Photosensitive resin composition for photo spacer - Google Patents

Abstract

A photosensitive resin composition containing a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C) and a solvent (D), wherein the photopolymerizable compound (B) contains a compound represented by formula (I) , Content of the photopolymerizable compound (B) represented by Formula (I) is 5-60 mass% in mass fraction with respect to the total amount of binder resin (A), a photopolymerizable compound (B), and a photoinitiator (C). Photosensitive resin composition for phosphorus photo spacers.

[In formula (I), R <_1> -R <_6> respectively independently represents a hydrogen atom or any group of following formula (I-1)-(I-3), and is at least 4 of R <_1> -R <_6> . Groups are any of groups (I-1) to (I-3), and at least one group of R ₁ to R ₆ is (I-2) or (I-3).]

Photosensitive Resin, Force spacer

Description

Photosensitive resin composition for photo spacers {PHOTOSENSITIVE RESIN COMPOSITION FOR PHOTO SPACER}

The present invention relates to a photosensitive resin composition for photo spacers.

Spacers are formed between the color filters constituting the display device such as a liquid crystal display device and a touch panel and the array substrate so as to maintain a gap between the two substrates. As a spacer, the photo-spacer method which forms a spacer using the photosensitive resin composition is proposed instead of the method of spreading | distributing a conventional spherical particle.

As the photosensitive resin composition used for this photo spacer method, the photosensitive resin composition for photo spacers which contains methacrylic acid / allyl methacrylate copolymer as binder resin, and dipentaerythritol hexaacrylate as a photopolymerizable compound is It is proposed (refer to Unexamined-Japanese-Patent No. 2003-302639).

However, when a photo spacer is formed using the photosensitive resin composition for photo spacers disclosed by Unexamined-Japanese-Patent No. 2003-302639, there exists a problem that the amount of plastic deformations is not enough.

MEANS TO SOLVE THE PROBLEM The present inventors examined in order to discover the photosensitive resin composition which can form the photo spacer with few problems as mentioned above, and the photosensitive resin composition containing some kind of photopolymerizable compound produces the photo spacer with a large plastic deformation amount. It was found to give.

DISCLOSURE OF INVENTION

An object of the present invention is to provide a photosensitive resin composition capable of forming a photo spacer having a large plastic deformation amount.

That is, this invention provides the following [1]-[6].

[One]. A photosensitive resin composition containing a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C) and a solvent (D), wherein the photopolymerizable compound (B) contains a compound represented by formula (I) The content of the photopolymerizable compound (B) represented by the formula (I) is 5 to 60 mass%, based on the mass fraction, with respect to the total amount of the binder resin (A), the photopolymerizable compound (B) and the photopolymerization initiator (C). Photosensitive resin composition for photo spacers.

[In formula (I), R <_1> -R <_6> respectively independently represents a hydrogen atom or any group of following formula (I-1)-(I-3), and is at least 4 of R <_1> -R <_6> . Groups are any of groups (I-1) to (I-3), and at least one group of R ₁ to R ₆ is (I-2) or (I-3).]

[2]. Content of the photopolymerizable compound (B) represented by Formula (I) is 20-40 mass% in mass fraction with respect to the total amount of binder resin (A), a photopolymerizable compound (B), and a photoinitiator (C). 1] The composition of the base material.

[3]. The composition as described in [1] or [2] whose binder resin (A) is resin obtained by copolymerizing at least 2 types of any of compound (A2)-(A5).

(A2); Compound having an unsaturated bond copolymerizable with (A4)

(A3); Carboxylic Acids Having Unsaturated Bonds

(A4); Compound having unsaturated bond and epoxy group in 1 molecule

(A5); Acid anhydride

However, (A2)-(A5) are not mutually the same, respectively.

[4]. Any of [1] to [3], in which the photopolymerization initiator (C) contains at least one compound selected from the group consisting of a triazine compound, an acetophenone compound, a biimidazole compound, an oxime compound, and an acylphosphine oxide compound The composition described in one.

[5]. The photo spacer formed using the composition in any one of [1]-[4].

[6]. [5] A liquid crystal display device containing the photo spacer of the base material.

Carrying out the invention  Form for

Hereinafter, the present invention will be described in detail.

In the photosensitive resin composition of this invention, binder resin (A), a photopolymerizable compound (B), a photoinitiator (C), and other additives (E) are melt | dissolved or disperse | distributed to the solvent (D) as needed, The photopolymerizable compound (B) is a compound represented by the formula (I), and the content of the compound represented by the formula (I) is based on the total amount of the binder resin (A), the photopolymerizable compound (B) and the photopolymerization initiator (C). It is a photosensitive resin composition for photo spacers which is 5-60 mass% with respect to mass fraction.

It is preferable that binder resin (A) is resin which has alkali solubility, or resin which has alkali solubility and has reactivity by the action of light or heat.

As such a binder resin (A), at least 2 types ((A2), (A3), (A4), and (A5) each of any of the following compounds (A2)-(A5) are considered 1 type, for example, For example, resin obtained by copolymerizing two different compounds which belong to (A2) shall be 1 type), etc. are mentioned.

(A2); Compound having an unsaturated bond copolymerizable with (A4)

(A3); Carboxylic Acids Having Unsaturated Bonds

(A4); Compound having unsaturated bond and epoxy group in 1 molecule

(A5); Acid anhydride

However, (A2)-(A5) are not mutually the same, respectively.

As a compound (A2) which has an unsaturated bond copolymerizable with (A4), specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-hydroxyethyl (meth) acryl Unsubstituted or substituted unsaturated carboxylic acid alkyl esters, such as a rate and aminoethyl (meth) acrylate;

Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, pentyl (meth) acrylate, cyclophene Tenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylic Rate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornenyl (meth) acrylate, pineneyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl ( Unsaturated carboxylic acid ester compounds containing alicyclic groups such as meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate and dicyclopentenyloxyethyl (meth) acrylate;

Mono-saturated carboxylic acid ester compounds of glycols such as oligoethylene glycol monoalkyl (meth) acrylates;

Unsaturated carboxylic ester compounds containing aromatic rings such as benzyl (meth) acrylate and phenoxy (meth) acrylate;

Aromatic vinyl compounds such as styrene, α-methylstyrene, α-phenylstyrene and vinyltoluene;

Carboxylic acid vinyl esters, such as vinyl acetate and a vinyl propionate;

Vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile;

N-substituted maleimide compounds, such as N-cyclohexyl maleimide, N-phenyl maleimide, and N-benzyl maleimide, etc. are mentioned. These may be individual, respectively and may be used in combination of 2 or more type.

Here, (meth) acrylate in this specification means at least 1 sort (s) chosen from the group which consists of an acrylate and a methacrylate. In addition, (meth) acrylic acid means at least 1 sort (s) chosen from the group which consists of acrylic acid and methacrylic acid.

Specifically as carboxylic acid (A3) which has an unsaturated bond, acrylic acid and methacrylic acid are mentioned. Acrylic acid and methacrylic acid may be individual, respectively, and may be used in combination of both. Moreover, in addition to these acrylic acid and methacrylic acid, you may use the carboxylic acid which has another unsaturated group. Specific examples of the carboxylic acid having another unsaturated group include crotonic acid, itaconic acid, maleic acid, fumaric acid, and the like. Moreover, you may use together the carboxylic acid which contains a hydroxyl group and a carboxyl group in the same molecule, such as (alpha)-(hydroxymethyl) acrylic acid, and has an unsaturated group.

As a compound (A4) which has an unsaturated bond and an epoxy group in 1 molecule, (meth) acrylic-acid glycidyl, (meth) acrylic-acid- (beta) -methylglycidyl, (meth) acrylic-acid- (beta) -ethylglycidyl, (meth) Acrylate-β-propylglycidyl, α-ethylacrylic acid-β-methylglycidyl, (meth) acrylic acid-3-methyl-3,4-epoxybutyl, (meth) acrylic acid-3-ethyl-3,4- Epoxy butyl, (meth) acrylic acid 4-methyl-4,5-epoxypentyl, (meth) acrylic acid-5-methyl-5,6-epoxyhexyl, glycidyl vinyl ether, and the like. Glycidyl methacrylate can be mentioned.

Acid anhydride (A5) is a compound having one acid anhydride group in a molecule, specifically, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endomethylene tetra Hydrophthalic anhydride, methyl tetrahydrophthalic anhydride, trimellitic anhydride, etc. are mentioned, Preferably, tetrahydrophthalic anhydride is mentioned.

As binder resin (A) in this invention, although each said compound can be obtained by copolymerizing arbitrarily, Preferably it is a copolymer of (A2) and (A3), and the copolymer of (A2) and (A3) In the site | part of the carboxyl group derived from (A3), the copolymer which (A4) was made to react, and (A2) and (A4) were further copolymerized, the copolymer 1 is obtained, and the obtained copolymer 1 and (A3) are copolymerized Reaction is carried out at the site | part of the epoxy group derived from (A4) of 1, and copolymer 2 is obtained, and also obtained copolymer 2 and (A5) of at least one part produced | generated by reaction of (A4) and (A3) of copolymer 1 (A2)-(A5) copolymer etc. which are obtained by making it react with the site | part of a hydroxyl group, etc. are mentioned.

The copolymer of (A2) and (A3) can be manufactured under the conditions normally performed industrially. For example, 0.5-20 times the amount of solvent is introduce | transduced into the flask provided with the stirrer, the thermometer, the reflux cooling tube, the dropping funnel, and the nitrogen introduction tube by mass basis with respect to the total amount of (A2) and (A3), The atmosphere in the flask is replaced by nitrogen from air. Then, after heating a solvent at 40-140 degreeC, azobis is added to the solvent of 0-20 times amount by mass basis with respect to the total amount of (A2) and (A3), (A2), and (A3) of predetermined amount. 0.1-10 mol% of the polymerization initiators, such as isobutyronitrile and benzoyl peroxide, added with respect to the total mole number of (A2) and (A3) (0.1-mol stirring under room temperature or heating) from the dropping funnel. It is dripped at said flask over 8 hours, and also it stirs for 1 to 10 hours in 40-140 degreeC temperature range. In addition, in said process, one part or whole quantity of a polymerization initiator may be thrown in the flask side, and one part or whole quantity of (A2) and (A3) may be thrown in the flask side. Moreover, in order to control molecular weight and molecular weight distribution, (alpha) -methylstyrene dimer and a mercapto compound may be used as a chain transfer agent. The usage-amount of (alpha) -methylstyrene dimer and a mercapto compound is 0.005 to 5% normally on a mass basis with respect to the total amount of (A2) and (A3). In addition, in consideration of the amount of heat generated by the production equipment, polymerization, and the like, the charging method and the reaction temperature may be appropriately adjusted.

It is preferable that the ratio of the structural component guide | induced from each compound exists in the following ranges in mole fraction with respect to the total mole number of the structural component which comprises said copolymer.

Structural unit derived from (A2); 5 to 95 mol%

Structural unit derived from (A3); 5 to 95 mol%

Moreover, since developability is favorable in the ratio of the said structural component being the following ranges, it is more preferable.

Structural unit derived from (A2); 10 to 90 mol%

Structural unit derived from (A3); 10 to 90 mol%

In addition, in the copolymer obtained by making said copolymer of said (A2) and (A3) and (A4) react at the site | part of the carboxyl group derived from (A3) of the said copolymer, the addition amount of (A4) is It is 5-60 mol% normally with respect to the carboxyl group derived from (A3) of the said copolymer, Preferably it is 10-50 mol%.

If the composition ratio of (A4) is in the said range, since it is excellent in developability, sufficient photocurability and thermosetting are obtained, and it is excellent in reliability, it is preferable.

Moreover, copolymerization of said (A2) and (A4) is carried out and copolymer 1 is obtained, The obtained copolymer 1 and (A3) are made to react at the site | part of the epoxy group derived from (A4) of copolymer 1, and copolymer 2 is obtained. Moreover, the (A2)-(A5) copolymer obtained by making the obtained copolymer 2 and (A5) react with the site | part of the hydroxyl group produced by reaction of (A4) and (A3) of copolymer 1 is used preferably. .

Said (A2)-(A5) copolymer can be manufactured as follows.

First, in order to obtain copolymer 1, (A2) and (A4) are copolymerized. In this copolymerization, it is performed under normal conditions. For example, 0.5-20 times the amount of solvent is introduce | transduced into the flask equipped with the stirrer, the thermometer, the reflux cooling tube, the dropping funnel, and the nitrogen introduction tube by mass basis with respect to the total amount of (A2) and (A4). The atmosphere in the flask is replaced with nitrogen by air. Then, after heating a solvent at 40-140 degreeC, it is the solvent of 0-20 times amount by mass basis with respect to the total amount of (A2) and (A4), such as azobisisobutyronitrile and benzoyl peroxide. To the total molar number of (A2) and (A4), a solution (0.1% molten solution) to which the polymerization initiator was added was added dropwise to the flask over 0.1 to 8 hours from a dropping funnel. Furthermore, it stirs at 40-140 degreeC for 1 to 10 hours.

In addition, in said process, one part or whole quantity of a polymerization initiator may be thrown in the flask side, and one part or whole quantity of (A2) and (A4) may be put in a flask side. Moreover, in order to control molecular weight and molecular weight distribution, you may use (alpha) -methylstyrene dimer and a mercapto compound as a chain transfer agent. The usage-amount of (alpha) -methylstyrene dimer and a mercapto compound is 0.005 to 5% normally on a mass basis with respect to the total amount of (A2)-(A3). In addition, in consideration of the amount of heat generated by the production equipment, polymerization, and the like, the charging method and the reaction temperature may be appropriately adjusted.

As a ratio of the structural component guide | induced from each compound, it is preferable to exist in the following ranges in mole fraction with respect to the total mole number of the structural component which comprises said copolymer 1.

Structural unit derived from (A2); 2 to 97 mol%

Structural units derived from (A4); 3 to 98 mol%

Moreover, since the balance of flexibility and heat resistance is favorable and a preferable liver polymer is obtained, if the ratio of said structural component is the following ranges, it is more preferable.

Structural unit derived from (A2); 15 to 85 mol%

Structural units derived from (A4); 15 to 85 mol%

Next, (A3) is added to said copolymer 1, and photocurability and thermosetting are given to binder resin (A).

Reaction of copolymer 1 and (A3) can be performed, for example on the conditions of Unexamined-Japanese-Patent No. 2001-89533. Specifically, the atmosphere in the flask is replaced with nitrogen from air, and the reaction of 5 to 100 mol% of (A3), carboxyl group and epoxy group in molar fraction with respect to the structural unit derived from (A4) of Copolymer 1 above. As a catalyst, for example, trisdimethylaminomethylphenol is 0.01-5% by mass with respect to the total amount of (A2)-(A4), and a hydroquinone is used as a polymerization inhibitor, for example (A2)

Regarding the total amount of (A4), 0.001 to 5% is placed in the flask on a mass basis and reacted with Copolymer 1 and (A3) by reacting at 60 to 130 ° C for 1 to 10 hours to obtain Copolymer 2 Can be obtained. In addition, in consideration of the amount of heat generated by the production equipment, polymerization, and the like, the charging method and the reaction temperature may be appropriately adjusted.

The addition amount of (A3) is 5-100 mol% normally with respect to the epoxy group (derived from (A4) component) in resin obtained by copolymerizing (A2) and (A4), Preferably it is 10-95 mol%. .

If the composition ratio of (A4) is in the said range, since sufficient photocurability and thermosetting are obtained and it is excellent in reliability, it is preferable.

Finally, the copolymer 2 and (A5) are reacted to impart alkali solubility to the binder resin (A).

Reaction of copolymer 2 and (A5) can be performed, for example on the conditions of Unexamined-Japanese-Patent No. 2001-89533. Specifically, with respect to the structural unit derived from (A3) of the copolymer 2, 5 to 100 mol% of (A5) and a reaction catalyst, for example, triethylamine (A2) The said copolymer 2 and (A5) can be made to react by putting 0.01-5% in a flask and reacting for 1 to 10 hours in the temperature range of 60-130 degreeC with respect to the total amount of (A4) on a mass basis. . In addition, in consideration of the amount of heat generated by the production equipment, polymerization, and the like, the charging method and the reaction temperature may be appropriately adjusted.

The addition amount of (A5) is 5-100 mol% normally with respect to the mole number (derived from A3 component) of the alcoholic hydroxyl group of copolymer 2, Preferably it is 10-95 mol%.

More specifically, binder resin (A) is a copolymer (U1-2-3) consisting of structural units (U1), (U2) and (U3) and structural units (U1), (U2) and (U4) It is preferable that it is at least 1 sort (s) of copolymer chosen from the group which consists of a copolymer (U1-2-4) which consists of.

Here, the structural unit U1 displays at least 1 type of structural unit selected from the group which consists of structural unit U1-1 and structural unit U1-2.

Each R ¹ independently represents a hydrogen atom, a methyl group, or a hydroxymethyl group.

R <^2> represents the phenyl group, -COOH, or -C (= O) OR <^5> group which may be substituted by the R <^5> group.

R ³ represents an oxygen atom, a sulfur atom, a -NH-, or a -N (R ⁵ )-group.

R ⁴ represents the following divalent group.

Here, R <^5> is methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, phenyl group, benzyl group, naphthyl group, adamantyl group, isobornyl group, dicyclopentanyl group, dicyclopentane Any of a silyl group, a dicyclopentanyloxyethyl group, a dicyclopentenyloxyethyl group, or a hydroxyl group is shown.

The weight average molecular weight of polystyrene conversion of binder resin (A) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-30,000. If the weight average molecular weight of binder resin (A) exists in the said range, applicability | paintability is favorable, and film | membrane decrease hardly arises at the time of image development, and also there exists a tendency for the omission of the unexposed part at the time of image development to be favorable. It is preferable because of that.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of binder resin (A) becomes like this. Preferably it is 1.5-6.0, More preferably, it is 1.8-4.0. When molecular weight distribution exists in the said range, since developability is excellent, it is preferable.

Binder resin (A) used for the photosensitive resin composition for photo spacers of this invention

The content of is in a mass fraction with respect to the solid content of the photosensitive resin composition for photo spacers, Preferably it is 5-90 mass%, More preferably, it is 10-70 mass%. When the content of the binder resin (A) is in the above range, the solubility in the developer is sufficient, the development residue is less likely to occur on the substrate of the unexposed portion, and the film reduction of the pixel portion of the exposed portion occurs during development. It is difficult to do this, and it is preferable because the missing property of the unexposed part tends to be good.

The photopolymerizable compound (B) used for the photosensitive resin composition for photo spacers of this invention contains the compound represented by Formula (I), or is a compound represented by Formula (I).

In formula (I), R <_1> -R <_6> respectively independently represents a hydrogen atom or any group of following formula (I-1)-(I-3), and at least 4 of R <_1> -R <_6> The group is any one of (I-1) to (I-3), and at least one group of R ₁ to R ₆ is (I-2) or (I-3).

As a compound represented by Formula (I), the polyfunctional acrylate compound which modified | denatured dipentaerythritol with caprolactone is mentioned. Specifically, commercially available products such as Nippon Gunpowder Co., Ltd. KAYARAD DPCA-60 (trade name), KAYARAD DPCA-120 (brand name), and the like can be given.

As long as the composition of this invention is a range which does not impair the effect of this invention, polymeric compounds other than binder resin (A) of this invention and a photopolymerizable compound (B) may contain, and as a compound, it is monofunctional In addition to a monomer, a bifunctional monomer and a trifunctional or more than trifunctional monomer (except the compound represented by Formula (I)) can be used together.

As a specific example of a monofunctional monomer, nonylphenyl carbitol acrylate, 2-hydroxy-3- phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl py A ralidone etc. are mentioned.

As a specific example of a bifunctional monomer, 1, 6- hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethyleneglycol di (meth) acrylate And bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

As a specific example of a trifunctional or more than trifunctional monomer, a trimethylol propane tri (meth) acrylate, a pentaerythritol tri (meth) acrylate, a pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate and a reaction product of an acid anhydride, dipentaerythritol penta (meth) acrylate and a reaction product of an acid anhydride, and the like.

Of these, trifunctional or higher polyfunctional monomers are preferably used.

Content of a photopolymerizable compound (B) needs to be 5-60 mass parts with respect to a total of 100 mass parts of binder resin (A), photopolymerizable compound (B), and photoinitiator (C) in the photosensitive resin composition for photo spacers. Preferably it is 10-50 mass parts, More preferably, it is 20-40 mass parts. When content of a photopolymerizable compound (B) exists in the said range, since the plastic deformation amount of a photo spacer is large and surface smoothness tends to become favorable, it is preferable.

As a photoinitiator (C) contained in the photosensitive resin composition for photo spacers of this invention, an acetophenone type compound, a biimidazole type compound, an oxime type compound, a triazine type compound is mentioned, for example. Furthermore, by using together said photoinitiator (C) and a photoinitiator start adjuvant (C-1), since the photosensitive resin composition becomes more highly sensitive and productivity at the time of forming a pattern using this is preferable, it is preferable. However, when the absorption wavelength of the photopolymerization initiation assistant (C-1) is on the longer wavelength side than the absorption wavelength of the photopolymerization initiator (C), the transmittance of the formed film is lowered. Do.

As said acetophenone type compound, diethoxy acetophenone, 2-hydroxy-2-methyl-1- phenyl propane- 1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane- Specifically as 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, and acetophenone system, 2- (2-methylbenzyl) -2- Dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4- Methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone , 2- (2-propylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholi Nophenyl) -butanone, 2- (2,3-dimethylbenzyl) -2-dimethylamino-1- (4-mo Polynophenyl) -butanone, 2- (2,4-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-chlorobenzyl) -2-dimethyl Amino-1- (4-morpholinophenyl) -butanone, 2- (2-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3- Chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone , 2- (3-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-bromobenzyl) -2-dimethylamino-1- (4- Morpholinophenyl) -butanone, 2- (2-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-methoxybenzyl) -2- Dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2 -Methyl-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-bromobenzyl) -2-dimethylamino-1- (4- Morpholinophenyl) -butanone, 2- (2-bromo-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-hydroxy-2- And oligomers of methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one.

As said biimidazole type compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis ( 2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see, eg, JP-A-6-75372, JP-A-6-75373, etc.) , 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5, 5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'- Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (for example, Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Laid-Open No. 62-174204 And imidazole compounds in which the phenyl group at the 4,4 ', 5,5'-position is substituted by a carboalkoxy group (see, for example, JP-A-7-10913, etc.); And preferably 2,2'-bis (2- Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole Can be mentioned.

As said oxime type compound, For example, O-ethoxycarbonyl- (alpha)-oxyimino-1-phenylpropan-1-one, the compound represented by Formula (a), and the compound represented by Formula (b) Etc. can be mentioned.

As said triazine type compound, it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloro), for example. Methyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2 , 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methyl Furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3, 5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

Moreover, as long as it does not impair the effect of this invention, the photoinitiator etc. which are normally used in this field can be used together further, For example, a benzoin type compound, a benzophenone type compound, a thioxanthone type compound, an anthracene Photoinitiators, such as a system compound, are mentioned.

More specifically, the following compounds are mentioned, These may be individual, respectively and may be used in combination of 2 or more type.

As said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As said benzophenone type compound, benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzo phenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'- Tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-, for example Chloro-4-propoxy oxanthone etc. are mentioned.

As said anthracene type compound, 9,10- dimethoxy anthracene, 2-ethyl-9,10- dimethoxy anthracene, 9,10- diethoxy anthracene, 2-ethyl-9, 10- diethoxy Anthracene and the like.

In addition, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylglyoxyl Photoinitiators, such as methyl acid and a titanocene compound, can be used together.

Moreover, what was described in Unexamined-Japanese-Patent No. 2002-544205 can be used together as a photoinitiator which has group which can cause chain transfer.

As a photoinitiator which has group which can cause said chain transfer, the compound represented by following formula (2)-(7) is mentioned, for example.

The photoinitiator which has group which can cause said chain transfer can be used as a structural component (A2) of copolymer 1. And binder resin (A) obtained using (A2) can be used together with the binder resin of this invention.

Moreover, you can use combining a photoinitiator adjuvant (C-1) with a photoinitiator. As a photoinitiator, it is preferable that an amine compound and the following carboxylic acid compound are preferable, and, as for an amine compound, an aromatic amine compound is more preferable. However, when the absorption wavelength of the photopolymerization initiation assistant (C-1) is on the longer wavelength side than the absorption wavelength of the photopolymerization initiator (C), the transmittance of the formed film is lowered. Do.

Specific examples of the photopolymerization initiation assistant include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid isoamyl. 2-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively; michler's ketone), 4, Aromatic amine compounds, such as 4'-bis (diethylamino)-benzophenone, etc. are mentioned.

As said carboxylic acid compound, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chloro, for example And aromatic heteroacetic acids such as phenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

Content of a photoinitiator (C) becomes like this. Preferably it is 0.1-40 mass parts, More preferably, it is 1-30 mass parts with respect to 100 mass parts of total of binder resin (A) and a photopolymerizable compound (B).

In addition, when using a photoinitiator adjuvant (C-1), the content is 0.1-50 mass parts on the said reference | standard, More preferably, it is 0.1-40 mass parts.

When content of a photoinitiator (C) exists in said range, the photosensitive resin composition for photo spacers will become high sensitivity, and smoothness in the surface of the photo spacer formed using said photosensitive resin composition for photo spacer formation is favorable. It is preferable because it tends to be lost. In addition to the above, when the amount of the photopolymerization initiation assistant (C-1) is in the above range, the sensitivity of the photosensitive resin composition for photo spacer formation obtained is further increased, and the patterned substrate is formed using the photosensitive resin composition for photo spacers. It is preferable because the productivity tends to be improved.

As a solvent (D) contained in the photosensitive resin composition for photo spacers of this invention, various organic solvents used in the field of the photosensitive resin composition are mentioned.

Specific examples thereof 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 dipropyl ether, and diethylene glycol dibutyl ether;

Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;

Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy butyl acetate and methoxy pentyl acetate;

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;

Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate;

Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned.

Of the solvents described above, in view of coatability and dryness, preferably an organic solvent having a boiling point of 100 to 200 ° C is used in the solvent, and more preferably alkylene glycol alkyl ether acetates, ketones and 3-ethoxypropionic acid. Esters such as ethyl and methyl 3-methoxypropionate are used, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxypropionate ethyl, 3-methoxypropionic acid Methyl is used.

These solvents (D) may be individual, respectively, and may mix and use two or more types.

Content of the solvent (D) in the photosensitive resin composition for photo spacers of this invention is mass fraction with respect to the photosensitive resin composition for photo spacer formation, Preferably it is 60-95 mass%, More preferably, it is 70-90 mass % to be. When content of the solvent (D) exists in the said range, when apply | coating with coating apparatuses, such as a spin coater, a slit & spin coater, a slit coater (it may also be called a die coater and a curtain flow coater), and inkjet, applicability | paintability It is preferable because it tends to be good.

To the photosensitive resin composition for photo spacers of this invention, other compounds ((E) component), such as a filler, another high molecular compound, surfactant, an adhesion promoter, antioxidant, a ultraviolet absorber, a flocculant, a chain transfer agent, are used together as needed. You may.

As a filler, glass, silica, alumina, etc. are illustrated, for example.

As another polymer compound, it is epoxy resin (as a commercial item, Mitsui Chemicals Techmoa VG3101L (brand name), Sumitomo Chemical Co., Ltd. Sumiepoxy series (brand name), Japan Epoxy Resin Co., Ltd. epicoat series (brand name) Hardening resins, such as maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethyleneglycol monoalkylether, polyfluoroalkylacrylate, polyester, polyurethane, etc. are mentioned. .

As surfactant, commercially available surfactant can be used, For example, surfactant, such as a silicone type, a fluorine type, ester type, cationic type, anionic type, nonionic type, amphoteric, etc., etc. are mentioned, Each may be individual. You may use in combination of 2 or more type. Examples of the above-mentioned surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes and polyethylene In addition to imines, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoe Chemical Co., Ltd.), F-Top (manufactured by Tochem Products Co., Ltd.), Megapack (Dainippon Ink Chemical Co., Ltd.) ), Florade (manufactured by Sumitomos Reem Co., Ltd.), Asahigard, Supron (above, manufactured by Asahigaras Co., Ltd.), Soapspar (manufactured by Geneca Co., Ltd.), EFKA (manufactured by EFKA CHEMICALS Co., Ltd.) And PB821 (manufactured by Ajinomoto Co., Ltd.).

Specific examples of adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N. -(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercapto Propyl trimethoxysilane, etc. are mentioned.

Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-tert-butylphenol), 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, alkoxybenzophenone and the like.

Moreover, sodium polyacrylate etc. are mentioned specifically as a flocculant.

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

The photosensitive resin composition for photo spacers of this invention can be easily adjusted by methods, such as mixing each component of said (A)-(D), (E) component in arbitrary order as needed.

The photosensitive resin composition for photo spacers can be apply | coated on a base material as follows, for example, can photocure and develop, and can form a pattern. First, this composition is apply | coated on the board | substrate (usually glass or film) or the layer which consists of solid content of the other photosensitive resin composition formed previously, and forms the photosensitive resin composition layer. Application | coating is performed using well-known apparatuses, such as a spin coater, a slit coater, a curtain flow coater, and a bar coater.

The coated and formed photosensitive resin composition layer is obtained as a smooth coating film by removing volatile components, such as a solvent, by prebaking. The thickness of the coating film at this time is about 1-6 micrometers normally. The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use apparatuses, such as a mask aligner and a stepper, so that the parallel light beam may be irradiated uniformly to the whole exposure part, and the exact alignment of a mask and a board | substrate may be performed. Furthermore, the target pattern shape is obtained by then contacting alkali aqueous solution with the coating film which hardened | cured, dissolving and developing a non-exposed part. As the developing method, any method such as a liquid stacking method, a dipping method, a spray method, or the like may be adopted. In addition, during development, the substrate may be tilted at an appropriate angle. After image development, water washing may be performed, and also post-baking may be performed by maintaining for 10 to 60 minutes in the temperature range of 150-230 degreeC as needed.

The developing solution used for image development after patterning exposure is the aqueous solution containing an alkaline compound and surfactant normally.

The alkaline compound may be either an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compounds include sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate And sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like.

Moreover, as an example of an organic alkaline compound, tetramethylammonium hydroxide, 2-hydroxyethyl trimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine , Monoisopropylamine, diisopropylamine, ethanolamine and the like. These inorganic and organic alkaline compounds may be individual, respectively, and may be used in combination of 2 or more type. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

The surfactant in the alkaline developer may be any of a nonionic surfactant, anionic surfactant, or 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, and sorbitan fatty acid esters. , Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.

Specific examples of the anionic surfactants include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, and sodium dodecylbenzenesulfonate And alkyl aryl sulfonates such as sodium dodecyl naphthalene sulfonate.

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

These surfactant may be used independently, respectively and may be used in combination of 2 or more type.

The density | concentration of surfactant in alkaline developing solution is 0.01-10 mass% normally, Preferably it is 0.05-8 mass%, More preferably, it is 0.1-5 mass%.

A photo spacer can be formed on a board | substrate, a color filter board | substrate, or a liquid crystal drive board | substrate through each operation of application | coating of the photosensitive resin composition for photo spacers, drying, patterning exposure to the obtained dry coating film, and image development, and image development. have.

Moreover, this photo spacer is useful for a liquid crystal display device. In addition, among the liquid crystal display devices, a multi-domain vertical alignment (hereinafter referred to as MVA) liquid crystal display device having improved viewing angles is provided with a structure locally provided on the base of the alignment film, and protrusions are formed. The photo spacer formed using the photosensitive resin composition of this invention is useful. Moreover, when the photosensitive resin composition for photo spacers of this invention is used, when a photomask for hole formation is used at the time of patterning exposure to a dry coating film, a hole can be formed and this is useful as an interlayer insulation film. Moreover, when the photosensitive resin composition for photo spacers of this invention is used, a resin film can be formed only by exposure and heat-hardening or heat-curing, without using a photo mask at the time of exposure to a dry coating film, and this resin film is an overcoat. useful.

The photo spacer produced using the photosensitive resin composition for photo spacers of the present invention has a small in-plane film thickness difference, for example, a film thickness of 1 to 6 μm, and an in-plane film thickness difference of 0.15 μm or less, furthermore, 0.05 μm. It can be set as follows. Therefore, the photo spacer obtained in this way is excellent in smoothness, and can be manufactured in high yield by attaching this to a color liquid crystal display device of excellent quality.

The following method is illustrated as a method of manufacturing a liquid crystal display device.

Photosensitive resin composition for photo spacer formation of this invention is apply | coated to the TFT array board | substrate which passed through the formation process of an orientation film, and a rubbing process, and is dried, and it carries out the operation of patterning exposure to the dry coating film on the board | substrate obtained, and image development, and operation. Prepare the attached substrate. Then, the color filter with ITO film and the substrate with photo spacer are bonded together so that the ITO film forming surface and the photo spacer forming surface face each other, liquid crystal is injected into the space formed by the photo spacer between the color filter and the TFT array substrate, By sealing, a liquid crystal display device can be manufactured.

Since the photosensitive resin composition for photo spacers of this invention has favorable storage stability and high sensitivity, it becomes possible to form the photo spacer with a large plastic deformation amount by using this photosensitive resin composition.

Example

Hereinafter, although this invention is demonstrated in detail based on an Example, it cannot be overemphasized that this invention is not limited by these Examples.

Examples 1 and 2 and Comparative Example 1

The structure, molar ratio, and the like of the binder resin Aa used in Example 1 are shown in Formula (X) and Table 1 below. In Table 1, a-d shows molar ratio.

Description of the constituent unit

a: Structural unit derived from (A2) in the copolymer 1.

b: Structural unit derived from (A2) in the copolymer 1.

c: Structural unit derived by making (A3) react with the structural unit guide | induced from (A4) in the copolymer 1.

d: Structural unit derived by making (A5) react with the site | part derived from (A3) in the copolymer 2.

Resin Aa a 0.25 b 0.25 c 0.15 d 0.35 R _I H M _w 18,000 M _w / M _n 2.2

About the measurement of the polystyrene conversion weight average molecular weight (Mw) and number average molecular weight (Mn) of the said binder polymer, it carried out on condition of the following using GPC method.

Device ; HLC-8120GPC (manufactured by Tosso Corporation)

column ; TSK-GELG4000HXL + TSK-GELG2000HXL

(Serial connection)

Column temperature; 40 ℃

Solvent; THF

Flow rate; 1.0 mL / min

Injection volume; 50 μL

Detector; RI

Measurement sample concentration; 0.6 mass% (solvent; THF)

Calibration standard; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio of the weight average molecular weight and number average molecular weight obtained above was made into molecular weight distribution (Mw / Mn).

Table 2 shows the compounding compositions of Examples and Comparative Examples. The numerical value of Table 2 shows the mass part.

Example
One Example
2 Comparative Example
One bookbinder
Resin (A) Resin Aa 70 70 70 Photopolymerization
compound
(B) of ε-caprolactone modified dipentaerythritol
Polyacrylate
(KAYARAD DPCA-60; manufactured by Nippon Gunpowder Co., Ltd.)
In Formula (I), R1-R6 is (I-2). 30 30 0 Dipentaerythritol hexaacrylate
(KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
In Formula (I), R1-R6 is (I-1). 0 0 30 Photopolymerization
Initiator
(C) 2-benzyl-2-dimethylamino-1- (4-morpholino
Phenyl) -butanone
Irgacure 369; Ciba Specialty
Chemicals company) 6 6 6 Photoinitiation
Supplements
(C-1) 4,4'-di (N, N-diethylamino) -benzophenone
(EAB-F; Hodogaya Chemical Industry Co., Ltd. product) One One One solvent
(D) Propylene glycol monomethyl ether acetate 38 38 38 Ethyl 3-ethoxypropionate 24 24 24 Other
compound Epoxy resin
(Techmo VG3101L; manufactured by Mitsui Chemicals, Inc.) 5 0 5

A 2 inch square glass substrate (# 1737; manufactured by Corning) was washed sequentially with a neutral detergent, water, and alcohol, and then dried. On this glass substrate, the photosensitive resin composition (Table 2) is exposed by the exposure amount (365 nm) of 100 mJ / cm <^2> , spin-coated so that the film thickness after image development, water washing, and postbaking may be set to 4.7 micrometers, and it is the clean oven next. Prebaking was carried out at 100 ° C for 3 minutes. After cooling, the space | interval of the board | substrate to which this photosensitive resin composition was apply | coated, and the quartz glass photo mask (the square of one side of 10 micrometers and the space part have a pattern of 100 micrometers) were made into 150 micrometers, and the ultrahigh pressure mercury lamp (USH-250D) It was irradiated with the exposure amount (365 nm) of 100 mJ / cm <^2> in air | atmosphere using Ushio Electric Co., Ltd. product. Subsequently, the coating film was immersed in a developing solution stirred at 23 ° C. (300 rpm with a magnetic stirrer) at 23 ° C. for 80 seconds in an aqueous developer containing 0.12 mass% of nonionic surfactant and 0.05 mass% of potassium hydroxide, followed by washing with water. And post-baking was performed at 220 degreeC for 30 minutes, and the cured resin pattern was obtained.

Table 3 shows the results of measurement and the like in the following items of the obtained cured resin pattern.

c Example 1 Example 2 Comparative Example 1 Surface smoothness ○ ○ ○ Line width (탆) 27.3 27.6 27.0 shape Net taper Net taper Net taper Total displacement (㎛) 0.64 0.65 0.48 Storage stability 102 102 102 Coefficient of linear expansion (10 ^-6 / ℃) 527 520 244 Thermal analysis 98.5 97.5 99.0

(Explanation in Table 3)

Surface smoothness; The standard of surface smoothness observes a surface by visual observation, and if it is glossy, (circle) and white (opacity), it displays x.

Line width; The dimension of two sides in the bottom part of a pattern was measured using SEM (model number S-4100; the Hitachi, Ltd. make), and the average value of the two sides obtained was calculated | required.

shape ; The cross section with respect to the cross section perpendicular | vertical to the board | substrate etc. of a pattern was observed using the same SEM as the above. When the ridgeline of the pattern was smaller than 90 degrees with respect to the substrate, the taper was described as a forward taper.

Total displacement; The total displacement amount (micrometer) was measured on condition of the following using the dynamic ultramicro hardness tester (DUH-W201S; the Shimadzu Corporation make). In general, when the plastic deformation amount is large, it can be said that the total displacement amount is also large.

Test mode; Load-Unload Test

Test force; 5gf (SI unit equivalent; 0.049N)

Load speed; 0.45 gf / sec (SI unit equivalent value; 0.0044 N / sec)

Holding time; 5 seconds

Indenter; Conical indenter (diameter 50 mmφ)

Storage stability; The viscosity change rate before and after 3 months storage at 23 degreeC was calculated | required by the following formula.

% Viscosity change = [(viscosity after storage) / (viscosity before storage)] × 100

Linear expansion coefficient; On the 4-inch silicon wafer, the photosensitive resin composition was formed into a film so that it might become 0.3 micrometer after post-baking. At this time, except having not used a photomask and omitting the image development process, operation similar to the case where film | membrane was formed in the 2-inch square glass substrate was performed.

The film thickness change in 30 degreeC from 200 degreeC was measured for the obtained coating film using the X-ray X-ray analyzer (X'PertMRD; Philips make). X-ray output; 45 kV / 40 mA, X-ray; CuKα1 line, atmosphere; It was carried out with nitrogen.

Moreover, the unit of linear expansion coefficient is 10 <^-6> / ^degreeC .

Thermal analysis; In the operation of forming a cured resin pattern, the same operation was performed except that the entire surface was exposed without using a photomask, thereby obtaining a cured coating film having a thickness of 3 μm. The cured coating film was removed with a razor, and the heating loss at 240 ° C. × 1 hour (weight when the sample temperature reached 240 ° C. was set to 100, and the mass after keeping at 240 ° C. × 1 hour, is expressed as a percentage). Measured.

Device ; Differential thermal thermogravimetry simultaneous measuring device (TG / DTA220; manufactured by Seiko Instruments Co., Ltd.)

Measurement atmosphere; nitrogen

Nitrogen gas flow rate; 300 mL / min

In the photosensitive resin composition for photo spacer formation of Examples 1 and 2 containing the photopolymerizable compound represented by Formula (1), it turns out that the photo-spacer with a large total displacement amount and excellent surface smoothness and a pattern shape is obtained. , The total amount of displacement is small in the photosensitive resin composition for photo spacer formation of Comparative Example 1 which does not contain the photopolymerizable compound represented by Formula (1).

Example 3, Comparative Example 2, Comparative Example 3

In Example 3, Comparative Example 2, and Comparative Example 3, the structural Ab, the composition, and the like of the resin used as the binder resin (A) are shown in Formula (Y) and Table 4. In Table 4, a-d shows molar ratio.

In the composition shown in Table 5, it carried out similarly to Example 1, and evaluated. The results are shown in Table 6.

Description of the constituent unit

a: Structural unit derived from (A2) in the copolymer 1.

b: Structural unit derived from (A2) in the copolymer 1.

c: Structural unit derived from (A2) in the copolymer 1.

d: Structural unit derived from (A3) in the copolymer 1.

e: The structural unit guide | induced by making (A4) react with the structural unit guide | induced from (A3) in the copolymer 1.

Resin Ab a 0.07 b 0.47 c 0.19 d 0.16 e 0.11 M _w 8,500 M _w / M _n 1.8

The measurement of the polystyrene reduced weight molecular weight and the number average molecular weight of the resin Ab was carried out in the same manner as in Example 1.

<Preparation of the photosensitive resin composition for photo spacer formation>

Table 5 shows the compounding compositions of Examples and Comparative Examples. The numerical value of Table 5 shows the mass part.

Example
3 Comparative Example
2 Comparative Example
3 Binder resin
(A) Resin Ab 60 33 33 Photopolymerization
compound
(B) of ε-caprolactone modified dipentaerythritol
Polyacrylate
(KAYARAD DPCA-60; manufactured by Nippon Gunpowder Co., Ltd.)
In Formula (I), R1-R6 is (I-2). 40 67 0 of ε-caprolactone modified dipentaerythritol
Polyacrylate
(KAYARAD DPCA-120; manufactured by Nippon Gunpowder Co., Ltd.)
In Formula (I), R1-R6 is (I-3). 0 0 67 Photopolymerization
Initiator
(C) 2-benzyl-2-dimethylamino-1- (4-morpholino
Phenyl) -butanone
Irgacure 369; Ciba Specialty
Chemicals company) 6 6 6 Photoinitiation
Supplements (C-1) 4,4'-di (N, N-diethylamino) -benzophenone
(EAB-F; Hodogaya Chemical Industry Co., Ltd. product) One One One solvent
(D) Propylene glycol monomethyl ether acetate 38 38 38 Ethyl 3-ethoxypropionate 24 24 24 Other
compound Epoxy resin
(Techmo VG3101L; Mitsui Chemicals, Inc.) 10 10 10

Table 6 shows the results of the evaluation.

Example 3 Surface smoothness ○ Line width (탆) 20.3 shape Net taper Total displacement (㎛) 0.98 Storage stability 101 Coefficient of linear expansion (10 ^-6 / ℃) 529 Thermal analysis 97.9

Adhesion test

After cutting the glass substrate (# 1737; the Corning company) which formed the cured resin pattern into 1 cm x 5 cm, and overlapping the glass substrate of the same size (# 1737; the Corning company) in cross shape through the cured resin pattern ( The bonded area was crimped under conditions of 1 cm ² ) and 300 Pa at 150 ° C. for 1 hour.

When the test piece was taken out and cooled to room temperature, and the bonded board | substrate was removed, in the cured resin pattern formed using the composition of Examples 1-3, the hardening formed using the composition of the comparative example 1 compared with the board | substrate to which it adhered. The substrate was not bonded in the resin pattern. Moreover, in the composition of Comparative Examples 2-3, since cured resin pattern could not be formed (there is a residual film in a non-exposed part), it could not test.

The photo spacer formed from the photosensitive resin composition for forming a photo spacer of the present invention has a large plastic deformation amount, is excellent in surface smoothness, and capable of resolving to a fine pattern of 3 to 50 μm, and thus has good omission property, Ideal for leaving the same pattern.

The photosensitive resin composition for forming a photo spacer of the present invention can be used for formation of a photo spacer in a liquid crystal display device, and also includes an insulating film (contact hole formation), an overcoat (flattening film), and a projection forming material for liquid crystal alignment control. It can also be used for formation. Moreover, it can use as an adhesive agent used for their adhesion.

Claims (6)

A photosensitive resin composition containing a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C) and a solvent (D), wherein the photopolymerizable compound (B) contains a compound represented by formula (I) The content of the photopolymerizable compound (B) represented by the formula (I) is 20 to 40 mass%, based on the mass fraction, of the total amount of the binder resin (A), the photopolymerizable compound (B), and the photopolymerization initiator (C). And photosensitive resin composition for photo spacers whose molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of binder resin (A) is 1.5-6.0.

[In formula (I), R <_1> -R <_6> respectively independently represents a hydrogen atom or any group of following formula (I-1)-(I-3), and is at least 4 of R <_1> -R <_6> . Groups are any of groups (I-1) to (I-3), and at least one group of R ₁ to R ₆ is (I-2) or (I-3).]

delete The method of claim 1, A composition in which the binder resin (A) is a resin obtained by copolymerizing at least two kinds of any of the compounds (A2) to (A5). (A2); Compound having an unsaturated bond copolymerizable with (A4) (A3); Carboxylic Acids Having Unsaturated Bonds (A4); Compound having unsaturated bond and epoxy group in 1 molecule (A5); Acid anhydride However, (A2)-(A5) are not mutually the same, respectively. The method according to claim 1 or 3, The composition in which a photoinitiator (C) contains at least 1 sort (s) of compound chosen from the group which consists of a triazine compound, an acetophenone compound, a biimidazole compound, an oxime compound, and an acylphosphine oxide compound. A photo spacer formed using the composition according to claim 1. The liquid crystal display device containing the photo spacer of Claim 5.