JP2013242507A - Curable resin composition for photospacer, columnar spacer and liquid crystal display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition for a photospacer capable of obtaining a columnar spacer based on a provision of the columnar spacer which is excellent in adhesion to a glass substrate or elastic recovery.SOLUTION: There is provided a curable resin composition for a photospacer which is used for manufacturing a columnar spacer of a liquid crystal cell and comprises: a photosensitive polymer obtained by reacting an acid group of an acid-group-containing polymer synthesized from a monomer component containing a monomer in which an acid group can be introduced and a monomer having two or more aromatic rings as an essential component with a compound having a radical polymerizable unsaturated double bond and a functional group reactable with an acid group; a polyfunctional monomer; and a photopolymerization initiator.

Description

  The present invention relates to a curable resin composition for a photospacer for obtaining a columnar spacer used in a liquid crystal cell, a columnar spacer obtained by curing using the same, and a liquid crystal display obtained using the columnar spacer. It is.

  The liquid crystal cell has a structure in which liquid crystal molecules are sandwiched and enclosed between two glass plates, but a spacer is used to make the gap distance between the two glass plates constant. Conventionally, spherical fine particles with a uniform particle size were dispersed as a spacer in the gap between the glass plates, but the spherical fine particles are easy to roll because they are spherical, and even when sprayed uniformly, they are swept away during liquid crystal injection. When the LCD panel is erected, it may become unevenly distributed or sink down to cause color loss.

  Therefore, recently, columnar spacers have been adopted particularly for large liquid crystal panels (for example, Patent Document 1). The columnar spacer is a resin column which is erected on a glass substrate (more precisely, on an alignment film on the glass substrate) by photolithography. The merit of the columnar spacer is that it is in close contact with the glass substrate (exactly on the alignment film on the glass substrate), so that it is not pushed away and unevenly distributed.

  Such columnar spacers are required to have elastic recovery in addition to the adhesion to the glass substrate as described above. In other words, when the liquid crystal is injected into the cell and the liquid crystal molecules are aligned, a compressive force is applied to the cell. At this time, the columnar spacer has a flexibility that can follow the compressive force and a compressive force when relaxing. Elastic recovery force is required. Since the spacer is used to keep the distance between the two glass substrates constant, there is a problem that if the elastic recovery force is insufficient, the spacer cannot be sufficiently recovered after compression and the desired distance between the substrates cannot be maintained.

JP 2003-15136 A

  Therefore, in the present invention, in consideration of the above-mentioned problems of the prior art, on the premise of providing a columnar spacer excellent in adhesion to a glass substrate and elastic recovery, it is possible to obtain such a columnar spacer. Providing a curable resin composition was raised as an issue.

  The present invention that has solved the above-mentioned problems is a curable resin composition for a photospacer used for the production of a columnar spacer of a liquid crystal cell, comprising a monomer capable of introducing an acid group and two aromatic rings. By reacting a compound having a radical polymerizable unsaturated double bond and a functional group capable of reacting with an acid group with an acid group of an acid group-containing polymer synthesized from a monomer component containing the above-described monomer as an essential monomer. It has the photosensitive polymer obtained, a polyfunctional monomer, and a photoinitiator. It is preferable that the monomer containing 2 or more aromatic rings is 5 to 70% by mass in 100% by mass of the monomer component.

The monomer component preferably further includes a monomer capable of introducing a ring structure into the main chain. In this case, an embodiment in which the monomer capable of introducing a ring structure into the main chain is N-substituted maleimides is preferable. An embodiment in which the curable resin composition for a photospacer further includes an ultraviolet absorber having a maximum absorption wavelength at a wavelength of 280 to 380 nm is also suitable. Moreover, it is preferable that the acid value of the said photosensitive polymer is 20-180 mgKOH / g.

  The present invention includes a columnar spacer obtained by curing the curable resin composition for a photospacer, and a liquid crystal display using the columnar spacer.

  The columnar spacer obtained from the curable resin composition for photospacers of the present invention has excellent substrate adhesion and elastic recovery.

  The curable resin composition for a photospacer of the present invention (hereinafter sometimes simply referred to as a curable resin composition) is used for the production of a columnar spacer of a liquid crystal cell. A compound having a functional group capable of reacting with a radically polymerizable unsaturated double bond and an acid group on an acid group of an acid group-containing polymer synthesized from a monomer component containing a monomer containing two or more rings as an essential monomer It has the photosensitive polymer obtained by making it react, a polyfunctional monomer, and a photoinitiator. Hereinafter, each component will be described.

[Acid group-containing polymer]
The photosensitive polymer which is the main component of the curable resin composition of the present invention needs to have an acid group in the side chain. This is to ensure alkali developability. Further, as will be described later, the acid group also serves as a reaction point for introducing a radical polymerizable unsaturated double bond into the side chain of the polymer.

  In the present invention, an acid group-containing polymer having no radically polymerizable unsaturated double bond is synthesized first, and then a radically polymerizable unsaturated double bond is introduced. The acid group-containing polymer can be synthesized using a monomer capable of introducing an acid group into the side chain. In addition, since the photosensitive polymer also contains an acid group, it is an “acid group-containing polymer”. However, in the following explanation, a polymer before introduction of a radical polymerizable unsaturated double bond is referred to as an acid group-containing polymer. These polymers are called photosensitive polymers.

[Monomer capable of introducing an acid group]
Monomers that can introduce an acid group into the side chain include monomers that originally have an acid group and monomers that can give an acid group after polymerization. In addition, when using the monomer which can provide an acid group after superposition | polymerization, the process (post-processing) for providing an acid group as mentioned later after superposition | polymerization is required.

  Examples of the monomer having an acid group include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, monomers having a carboxyl group such as itaconic acid, and carboxyls such as maleic anhydride and itaconic anhydride. Although the monomer etc. which have an acid anhydride group are mentioned, Especially, (meth) acrylic acid is preferable among these. Moreover, as a monomer which can provide an acid group after superposition | polymerization, the monomer which has hydroxyl groups, such as 2-hydroxyethyl (meth) acrylate, the monomer which has epoxy groups, such as glycidyl (meth) acrylate, 2-isocyanatoethyl ( And monomers having an isocyanate group such as (meth) acrylate. Only one type of monomer capable of introducing these acid groups may be used, or two or more types may be used.

The monomer capable of introducing an acid group is preferably 15% by mass or more, more preferably 20% by mass or more, and preferably 90% by mass or less, in 100% by mass of the monomer component for constituting the acid group-containing polymer. The mass% or less is more preferable. If the monomer capable of introducing an acid group is small, sufficient alkali developability may not be exhibited, and a sufficient amount of radically polymerizable unsaturated double bonds cannot be introduced into the photosensitive polymer. On the other hand, if there are too many monomers capable of introducing an acid group, there will be less monomers capable of introducing a ring structure into the main chain, which will be described later, as suitable monomers, which may result in insufficient spacer heat resistance and substrate adhesion. is there.

  The post-treatment for imparting an acid group varies depending on the type of monomer that can impart an acid group to be used. For example, when a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate is used, , Succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride and other acid anhydrides may be added. When a monomer having an epoxy group such as glycidyl (meth) acrylate is used, for example, , N-methylaminobenzoic acid, N-methylaminophenol, or the like, or after adding an acid group such as (meth) acrylic acid. For example, an acid anhydride such as succinic acid anhydride, tetrahydrophthalic acid anhydride, maleic acid anhydride or the like may be added to the hydroxyl group. Ku, in the case of using a monomer having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate may be, for example, so as to be added with a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid.

[Monomer containing two or more aromatic rings]
In the photosensitive polymer of the present invention, it is necessary to introduce two or more aromatic rings in the side chain. This is because it has been found that the elastic recovery force is improved by introducing two or more aromatic rings. The reason for this is not clear, but it is because the aromatic ring has a stack structure and the interaction is manifested, so it is not the hardness due to increasing the crosslinking density, but because the hardness due to the interaction is given. Guessed. The two or more aromatic rings may be a condensed ring such as a naphthalene ring or an anthracene ring.

  The applicant of the present application has already filed an application for a curable resin composition using a radically polymerizable monomer having a mesogenic group such as a biphenyl group at a side chain terminal (Japanese Patent Laid-Open No. 2008-239782). However, in this patent document, only the thermal conductivity of the cured product obtained from the resin composition is examined, and there is no examination (particularly, the elastic recovery rate) as a curable resin composition for a photospacer capable of alkali development. Not done.

Monomers containing two or more aromatic rings include biphenyl (meth) acrylate, o-biphenyloxyethyl (meth) acrylate (ethoxylated o-phenylphenol (meth) acrylate), o-biphenyloxyethoxyethyl (meth) acrylate. , M-biphenyloxyethyl acrylate, p-biphenyloxyethyl (meth) acrylate, o-biphenyloxy-2-hydroxypropyl (meth) acrylate, p-biphenyloxy-2-hydroxypropyl (meth) acrylate, m-biphenyloxy 2-hydroxypropyl (meth) acrylate, N- (meth) acryloyloxyethyl-o-biphenyl = carbamate, N- (meth) acryloyloxyethyl-p-biphenyl = carbamate (the following formula (A) is N-acryloyloxyethyl-p-biphenyl = carbamate), N- (meth) acryloyloxyethyl-m-biphenyl = carbamate, biphenyl group-containing monomers such as o-phenylphenol glycidyl ether acrylate, naphthalene ring-containing monomers such as vinylnaphthalene And terphenyl group-containing monomers such as terphenyl (meth) acrylate and o-terphenyloxyethyl (meth) acrylate. Among these, a biphenyl group-containing monomer is preferable.

  The monomer containing two or more aromatic rings is preferably 5% by mass or more, more preferably 8% by mass or more, and preferably 70% by mass or less, in 100% by mass of the monomer component for constituting the acid group-containing polymer. The mass% or less is more preferable. If there are few monomers containing two or more aromatic rings, the effect of improving the elastic recovery rate may be insufficient. On the other hand, if there are too many monomers containing two or more aromatic rings, the monomer capable of introducing an acid group and the monomer capable of introducing a ring structure into the main chain, which will be described later as a suitable monomer, are reduced. May be inferior, and the heat resistance and substrate adhesion of the spacer may be insufficient.

[Monomer capable of introducing a ring structure into the main chain]
In the present invention, as an essential constituent monomer of the acid group-containing polymer and the photosensitive polymer, as described above, a monomer capable of introducing an acid group and a monomer containing two or more aromatic rings are used. In addition to these, It is also preferable to use a monomer capable of introducing a ring structure into the main chain. By introducing a ring structure into the main chain, the heat resistance of the columnar spacer is increased and the adhesion to the substrate is improved.

  Monomers that can introduce a ring structure into the main chain include monomers that originally have a ring structure and monomers that can form a ring structure by an intramolecular cyclization step.

  As the monomer having a ring structure, maleimide and N-substituted maleimides are preferable from the viewpoint of heat resistance and adhesion to a substrate. Specifically, phenylmaleimide, benzylmaleimide, naphthylmaleimide, No- (or m-, or p-) hydroxyphenylmaleimide, No- (or m-, or p-) chlorophenylmaleimide, No Aromatic substituted maleimides such as-(or m-, or p-) methylphenylmaleimide, N-o- (or m-, or p-) methoxyphenylmaleimide; methylmaleimide, ethylmaleimide, propylmaleimide, isopropylmaleimide, And alkyl-substituted maleimides such as cyclohexylmaleimide. Among these, cyclohexylmaleimide, phenylmaleimide, and benzylmaleimide are preferable, cyclohexylmaleimide and benzylmaleimide are more preferable, and benzylmaleimide is most preferable. These monomers having a ring structure may be used alone or in combination of two or more. It is preferable that the usage-amount of the monomer which has a ring structure is 2-50 mass% in 100 mass% of monomer components for comprising an acid group containing polymer. More preferably, it is 5-40 mass%, More preferably, it is 5-30 mass%.

  The monomer capable of forming a ring structure is preferably a compound that polymerizes while forming a 5-membered or 6-membered ring in the main chain. As such a compound, for example, 1,6-dienes are suitable. 1,6-dienes can be represented by the following general formula (1).

In the above formula (1), when X is —CH ₂ —CH ₂ —CH ₂ — and Y and Z are the same or different and are alkyl groups, 2,6-alkyl-substituted-1,6-heptadiene X is —CH ₂ —CH ₂ —CH ₂ —, Y and Z are the same or different, and —C (═O) —O
When it is -R (R represents an alkyl group or an aryl group which may have a substituent), it represents a 2-position-substituted bisacrylate compound, and X represents -C (= O) -O-. When C (═O) — and Y and Z are the same or different and are H or CH ₃ , they represent (meth) acrylic anhydride, X is —CH ₂ —O—CH ₂ —, When Y and Z are the same or different and are —C (═O) —O—R (R represents an alkyl group or an aryl group which may have a substituent), α-hydroxymethylacrylic acid Ester ether dimers (for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate represented by the following formula (2); also referred to as (α-hydroxymethyl) methyl acrylate dimer) At this time, either Y or Z If it represents H, 2-allyloxy methyl acrylate (the following formula (3)) a. It is preferable that the usage-amount of the monomer which can form the said ring structure is 2-50 mass% in 100 mass% of monomer components for comprising an acid group containing polymer. More preferably, it is 5-40 mass%, More preferably, it is 5-30 mass%.

[Amide group-containing monomer]
It is also a preferable embodiment to introduce an amide bond into the photosensitive polymer of the present invention. By introducing an amide bond, the elastic recovery force can be further improved. The reason is not clear, but if an amide bond is present, interaction such as hydrogen bonding between polymer molecular chains becomes strong, so that even after a strong compressive force is applied, excellent resilience is achieved. Presumed to be expressed. In addition, the photosensitive polymer of the present invention has hydrophilicity to the extent that alkali development is possible, but since the hydrophilicity is further increased by the presence of an amide bond, the vicinity of the surface of the cured product is also dissolved during development, It has also been found that it is easier to make a cured product having a smaller diameter than the pattern.

  Therefore, the monomer component for obtaining the acid group-containing polymer preferably contains an amide group-containing monomer. The amide group-containing monomer is represented by the following general formula (4).

(In Formula (4), R ¹ and R ² each independently represents a hydrogen atom other than a (meth) acryloyl group, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. Includes a phenyl group, a hydroxyl group, an alkoxy group, etc. R ¹ and R ² may form a ring structure composed of a nonmetallic atom together with the nitrogen atom bonded to these, for example, as shown below. Ring structure.)

  Examples of the amide group-containing monomer include (meth) acryloylmorpholine (morpholino (meth) acrylate), (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N -Isobutyl (meth) acrylamide, Nt-butyl (meth) acrylamide, Nt-octyl (meth) acrylamide, diacetone (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) Acrylamide, N-cyclohexyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, N-triphenylmethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide And the like, may be used alone or two or more thereof.

  The amide group-containing monomer is preferably 2% by mass or more, more preferably 5% by mass or more, preferably 70% by mass or less, and more preferably 40% by mass or less, in 100% by mass of the monomer component for constituting the acid group-containing polymer. preferable. If there are few amide group-containing monomers, sufficient elastic recovery may not be exhibited, but if there are too many amide group-containing monomers, the adhesion to the substrate will decrease and the hydrophilicity will become too strong, so it will be good It is difficult to form a spacer with a simple shape.

  The monomer component used for obtaining the acid group-containing polymer can introduce a ring structure into the main chain, which is an essential monomer such as the monomer capable of introducing an acid group and a monomer containing two or more aromatic rings, as described above. In addition to the monomer and the amide group-containing monomer, other copolymerizable monomers can be included as necessary in order to satisfy the required properties as a spacer. Examples of such copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate. Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, ( (Meth) acrylic acid esters such as tricyclodecyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate; styrene, vinyltoluene, α -Aromatic vinyl compounds such as methylstyrene; Butadie such as butadiene and isoprene Or substituted butadiene compounds, ethylene, propylene, vinyl chloride, ethylene or substituted ethylene compound such as acrylonitrile, vinyl esters such as vinyl acetate; and the like.

  Among these, (meth) acrylic acid esters are preferable. These other copolymerizable monomers may be used alone or in combination of two or more.

When these other copolymerizable monomers are used, the content ratio in the monomer component for constituting the acid group-containing polymer is not particularly limited, but is preferably 5% by mass or more in 100% by mass of the monomer component. % By mass or more is more preferable, 75% by mass or less is preferable,
65 mass% or less is more preferable.

Specific examples of preferred acid group-containing polymers in the present invention include the following embodiments.
A polymer obtained by copolymerizing benzyl maleimide / (meth) acrylic acid / ethoxylated o-phenylphenol acrylate (trade name “A-LEN-10” manufactured by Shin-Nakamura Chemical Co., Ltd.). Benzyl maleimide / (meth) acrylic acid / ethoxy O-phenylphenol acrylate / dicyclopentanyl (meth) acrylate copolymerized polymer benzylmaleimide / (meth) acrylic acid / ethoxylated o-phenylphenol acrylate / (meth) acryloylmorpholine copolymerized polymer ( Polymer obtained by copolymerization of [alpha] -hydroxymethyl) methyl acrylate dimer / (meth) acrylic acid / ethoxylated o-phenylphenol acrylate / [[alpha] -hydroxymethyl) methyl acrylate dimer / (meth) acrylic acid / ethoxylated o- Phenylph Copolymers of enol acrylate / dicyclopentanyl (meth) acrylate copolymerized (α-hydroxymethyl) methyl acrylate dimer / (meth) acrylic acid / ethoxylated o-phenylphenol acrylate / (meth) acryloylmorpholine Polymer ・ Methyl 2-allyloxymethyl acrylate / (meth) acrylic acid / ethoxylated o-phenylphenol acrylate copolymerized ・ Methyl 2-allyloxymethyl acrylate / (meth) acrylic acid / ethoxylated o- Polymer obtained by copolymerization of phenylphenol acrylate / dicyclopentanyl (meth) acrylate, methyl 2-allyloxymethyl acrylate / (meth) acrylic acid / ethoxylated o-phenylphenol acrylate / (meth) acryloyl Polymers obtained by copolymerizing morpholine

[Method of introducing radically polymerizable unsaturated double bond into acid group-containing polymer]
The photosensitive polymer of the present invention needs to have a radical polymerizable unsaturated double bond in the side chain in addition to the acid group. If a photosensitive polymer having a double bond is used as the polymer component of the curable resin composition, the photosensitive polymers can be radically polymerized, or the photosensitive polymer and the polyfunctional monomer can be radically polymerized. A three-dimensionally crosslinked cured coating film can be obtained. In order to obtain a photosensitive polymer by introducing a double bond into an acid group-containing polymer, for example, a functional group-containing monomer (hereinafter sometimes referred to as “monomer for introducing a double bond”) is used as a monomer component. In addition, after obtaining an acid group-containing polymer by polymerization, a monomer having a functional group capable of reacting with the functional group and a double bond may be added to the functional group in the acid group-containing polymer.

  Examples of the monomer for introducing a double bond include monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; monomers having a carboxylic acid anhydride group such as maleic anhydride and itaconic anhydride; ) Monomers having an epoxy group such as glycidyl acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether; 2-isocyanatoethyl (meth) acrylate, etc. And a monomer having a vinyl ether group such as 2-vinyloxyethoxyethyl (meth) acrylate. Only one type of monomer for introducing these double bonds may be used, or two or more types may be used.

The treatment for imparting a double bond to the acid group-containing polymer differs depending on the type of monomer for introducing the double bond. For example, when obtaining an acid group-containing polymer, the treatment for introducing the double bond is performed. When a monomer having a carboxyl group such as (meth) acrylic acid or itaconic acid is used as the monomer, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, Or p-) a compound having an epoxy group and a double bond such as vinylbenzyl glycidyl ether, or a compound having an isocyanate group and a double bond such as 2-isocyanatoethyl (meth) acrylate, A compound having a vinyl ether group and a double bond, such as 2-vinyloxyethoxyethyl (meth) acrylate, is attached. It is sufficient to. When a monomer having a carboxylic anhydride group such as maleic anhydride or itaconic anhydride is used as a monomer for introducing a double bond, a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a double bond As a monomer for introducing a double bond, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p- When a monomer having an epoxy group such as vinylbenzyl glycidyl ether is used, a compound having an acid group such as (meth) acrylic acid and a polymerizable double bond may be added.

  Among these, the method of adding glycidyl (meth) acrylate to the acid groups in the acid group-containing polymer (including the case where they are imparted by post-treatment) has the advantage of being simple and less colored. Since acid groups are consumed by this double bond introduction reaction, the amount of monomer that can introduce acid groups in the monomer component in consideration of the amount of acid groups consumed (double bond introduction amount) is used. Need to be determined. This is because if there are too few acid groups in the photosensitive polymer, alkali developability may not be exhibited. Therefore, the acid value of the finally obtained photosensitive polymer is preferably about 20 to 180 mgKOH / g, more preferably 30 to 150 mgKOH / g, and further preferably 30 to 130 mgKOH / g.

  The glycidyl (meth) acrylate is preferably reacted in an amount of 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more with respect to 100 parts by mass of the acid group-containing polymer. preferable. When the amount of glycidyl (meth) acrylate is less than 5 parts by mass, the amount of double bonds in the side chain of the resulting photosensitive polymer is too small, and the exposure sensitivity is lowered, or a dense cured coating film cannot be formed. There is a risk that the characteristics will deteriorate. In addition, the hydroxyl group produced by adding glycidyl (meth) acrylate to the acid group has the effect of increasing the solubility in an alkali developer, but the solubility in the alkali developer is insufficient due to the reduction of the hydroxyl group. In addition, the plate-forming characteristics of the spacer shape may be deteriorated. The addition amount of glycidyl (meth) acrylate is preferably 170 parts by mass or less, more preferably 150 parts by mass or less, and still more preferably 140 parts by mass or less with respect to 100 parts by mass of the acid group-containing polymer. If the addition amount of glycidyl (meth) acrylate is too large, the storage stability of the resin composition may be reduced, or the solubility in an organic solvent may be reduced.

[Method of polymerizing acid group-containing polymer]
In the present invention, a chain transfer agent may be used in the polymerization of the acid group-containing polymer. As chain transfer agents, in addition to known monofunctional thiol compounds such as n-dodecyl mercaptan and β-mercaptopropionic acid, both terminal mercapto-modified polysiloxanes (manufactured by Shin-Etsu Silicone; X-22-167B; the following formula; R Is a bifunctional thiol compound such as an alkylene group), and a side-chain polyfunctional mercapto-modified polysiloxane having a side chain mercapto-modified (manufactured by Shin-Etsu Silicone; KF2001, KF2004; the following formula; R is an alkylene group). When both terminal mercapto-modified polysiloxane is used, a polymer in which two molecules of acid group-containing polymer are bonded via both terminal mercapto-modified polysiloxane is obtained. When a side chain polyfunctional mercapto-modified polysiloxane is used, a branched polymer in which an acid group-containing polymer is bonded to a side chain mercapto group is obtained. By using these mercapto-modified polysiloxanes, polysiloxane bonds are introduced into the resulting polymer. One or more of these mercapto-modified polysiloxanes may be used in combination with a known monofunctional thiol compound such as n-dodecyl mercaptan or β-mercaptopropionic acid. When a mercapto-modified polysiloxane is used, the elastic recovery rate is further improved. The reason for this is that by introducing a polysiloxane part that is sparingly soluble in a solvent into the polymer, the polysiloxane part aggregates in the resin composition, forming pseudo fine particles, and these pseudo fine particles are elastically recovered. Presumably because it contributes to the improvement of the rate.

  The chain transfer agent is preferably used in an amount of 0.1 to 20 parts by mass (more preferably 0.2 to 20 parts by mass and further preferably 0.3 to 20 parts by mass) with respect to 100 parts by mass of the monomer component. Within this range, an acid group-containing polymer having a weight average molecular weight (Mw) of about 3000 to 50000 can be obtained. When Mw exceeds 50000, the finally obtained photosensitive polymer becomes too viscous to form a coating film, and when it is less than 3000, sufficient heat resistance tends to be difficult to ensure.

  As the polymerization method, a solution polymerization method is preferable, and a polymerization temperature and a polymerization concentration (polymerization concentration = [total mass of monomer component / (total mass of monomer component + solvent mass)] × 100) are determined based on the monomer component used. Although it varies depending on the composition and ratio and the molecular weight of the target polymer, the polymerization temperature is preferably 40 to 150 ° C. and the polymerization concentration is 5 to 60% by mass, and more preferably, the polymerization temperature is 60 to 130 ° C. It is good to set it as 10-50 mass%.

  When a solvent is used in the polymerization of the monomer component, a solvent used in a normal radical polymerization reaction may be used. Specifically, for example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl Esters such as ether acetate and 3-methoxybutyl acetate; Alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; Aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; Chloroform; dimethyl sulfoxide; and the like. These solvents may be used alone or in combination of two or more.

When radically polymerizing the monomer component, a commonly used radical polymerization initiator may be added as necessary. Although it does not specifically limit as a polymerization initiator, For example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amyl Organic peroxides such as peroxy-2-ethylhexanoate and t-butylperoxy-2-ethylhexanoate; 2,2′-
Azobis (isobutyronitrile), 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl-2,2′-azobis (2-methylpropio) Azo compounds such as nate). These polymerization initiators may be used alone or in combination of two or more. The amount of the initiator used may be appropriately set according to the composition of the monomer component used, the reaction conditions, the molecular weight of the target polymer, etc., and is not particularly limited, but the weight average molecular weight is several times without gelation. It is 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of all monomer components in that 1,000 to tens of thousands of polymers can be obtained. Good.

  After the polymerization, a double bond introduction reaction is performed as described above. For the double bond introduction reaction, a known method can be adopted. In the presence of oxygen or other polymerization inhibitor and catalyst, a double bond introduction monomer (for example, glycidyl (meth) acrylate) is added to the acid in the acid group-containing polymer. What is necessary is just to make it react with group. Thereby, the photosensitive polymer which is a main component of the curable resin composition of this invention is obtained.

[Curable resin composition]
The curable resin composition of the present invention contains a polyfunctional monomer. A curable resin is composed of the photosensitive polymer and the polyfunctional monomer. Depending on the specifications of the polyfunctional monomer, during photopolymerization or post-baking, the polyfunctional monomers react with each other, or the polyfunctional monomer and the double bond in the photosensitive polymer react to form a three-dimensionally crosslinked cured coating. A film is formed. Specific examples of the polyfunctional monomer include polyfunctional aromatic vinyl monomers such as divinylbenzene, diallyl phthalate, and diallylbenzene phosphonate; (di) ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipenta Erythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol And polyfunctional (meth) acrylates such as trihexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, and tris (hydroxyethyl) isocyanurate tri (meth) acrylate. . Among them, (di) pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meta) having a large number of functional groups ) Acrylate, trimethylolpropane tri (meth) acrylate, tris (hydroxyethyl) isocyanurate tri (meth) acrylate, and the like are preferable. Further, these polyfunctional (meth) acrylates are modified with ethoxylation (eg, pentaerythritol or the like, which is a raw material of polyfunctional (meth) acrylate) to add ethylene oxide to extend the chain, and the resulting polyfunctional alcohol ( Meth) acrylated: ethoxylated pentaerythritol tetra (meth) acrylate, ethoxylated dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, ethoxylated tripentaerythritol hepta (meth) acrylate, Ethoxylated tripentaerythritol octa (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, etc.) and ε-caprolactone modified products (eg, pentae which is a raw material of polyfunctional (meth) acrylate) Ε-caprolactone is added to sitolol to extend the chain, and the resulting polyfunctional alcohol is (meth) acrylated: ε-caprolactone modified pentaerythritol tetra (meth) acrylate, ε-caprolactone modified dipentaerythritol penta ( (Meth) acrylate, ε-caprolactone-modified dipentaerythritol hexa (meth) acrylate, ε-caprolactone-modified tripentaerythritol hepta (meth) acrylate, ε-caprolactone-modified tripentaerythritol octa (meth) acrylate, ε-caprolactone-modified trimethylolpropane Tri (meth) acrylate) can also be preferably used. These polyfunctional monomers may be used alone or in combination of two or more.

  These polyfunctional monomers are preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, and 95% by mass or less when the total mass with the photosensitive polymer is 100% by mass. Is preferable, 90 mass% or less is more preferable, and 85 mass% or less is further more preferable. When the amount of the polyfunctional monomer is out of the above range, there is a possibility that a sufficient crosslinking effect cannot be obtained and the elastic recovery force cannot be obtained satisfactorily.

The curable resin composition of the present invention contains a photopolymerization initiator. Examples of the photopolymerization initiator include benzoin such as benzoin, benzoin methyl ether, and benzoin ethyl ether and alkyl ethers thereof; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; 2 -Anthraquinones such as methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone; acetophenone dimethyl Ketals such as ketal and benzyldimethyl ketal; benzophenones such as benzophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane- - one or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) - butanone-1; acylphosphine oxides and xanthones and the like.

  These photopolymerization initiators are preferably 0.1 parts by mass to 50 parts with respect to 100 parts by mass in total of the photosensitive polymer, the polyfunctional monomer, and a radical polymerizable oligomer (described later) added as necessary. Parts by mass, more preferably 0.5 to 30 parts by mass.

  In addition to the photopolymerization initiator, cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butyl peroxide, lauryl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-butylperoxy- Organic peroxides such as 2-ethylhexanoate and t-amylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 1,1′-azobis (cyclohexanecarbonitrile) Thermal polymerization initiators such as azo compounds such as 2,2′-azobis (2,4-dimethylvaleronitrile) and dimethyl 2,2′-azobis (2-methylpropionate) may be added.

  In addition to the photopolymerization initiator, a photopolymerization initiation assistant can be used in combination, and the photopolymerization initiation assistant can be used in a plurality of combinations. Specific examples of the photopolymerization initiation assistant include 1,3,5-tris (3-mercaptopropionyloxyethyl) -isocyanurate, 1,3,5-tris (3-mercaptobutyloxyethyl) -isocyanurate (Showa Manufactured by Denko Co., Ltd., Karenz MT (registered trademark) NR1), trimethylolpropane tris (trifunctional thiol compounds such as 3-mercaptopropionate; pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercapto) Butyrate) (made by Showa Denko KK, Karenz MT (registered trademark) PEI) and the like; and polyfunctional thiols such as hexafunctional thiol compounds such as dipentaerythritol hexakis (3-propionate).

  Radical polymerizable oligomers such as unsaturated polyester, epoxy acrylate, urethane acrylate, and polyester acrylate may be added to the curable resin composition of the present invention, and curable resins such as epoxy resins are cured as necessary. You may add with an agent.

  The curable resin composition of this invention may contain the solvent as a diluent as needed. The solvent is not particularly limited as long as it can uniformly dissolve each component of the photosensitive polymer, the polyfunctional monomer, the radically polymerizable oligomer used as necessary, and the photopolymerization initiator, and does not react with each component. There is no. Specifically, for example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3- Esters such as methoxybutyl acetate; Alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; Aromatic hydrocarbons such as toluene, xylene and ethylbenzene; Chloroform and dimethyl sulfoxide; Etc. In addition, what is necessary is just to set content of a solvent suitably according to the optimal viscosity at the time of using a resin composition.

You may mix | blend a ultraviolet absorber with the curable resin composition of this invention. When manufacturing the spacer, the lower diameter tends to be larger than the upper diameter. This is because the light reaching the glass substrate is reflected, and the coating film on the bottom of the spacer reflects the incident light from above and the glass substrate. It was found that this was because both the reflected light from the light received and the photocuring progressed too much. And when the ultraviolet absorber contains in a composition, since excess light energy is absorbed, it can suppress that the lower diameter of a spacer becomes large.

  As the ultraviolet absorber, those having a maximum absorption wavelength (peak) at a wavelength of 280 to 380 nm are preferable. This is because it does not overlap with the peak of the photopolymerization initiator. Specifically, a compound represented by the following chemical formula is preferable because the maximum absorption wavelength does not overlap with the peak of the photopolymerization initiator and is easily available.

  Among the above compounds, Tinuvin (registered trademark) series and CHIMASSORB (registered trademark) can be obtained from BASF Japan, and SEESORB (registered trademark) from Cypro Kasei.

  The amount of the ultraviolet absorber is preferably 0.03 to 1.0% by mass in 100% by mass of the solid content of the resin composition. Within this range, it is possible to obtain a spacer having a level of elastic recovery with no problem in practical use and a small lower diameter. If the ultraviolet absorber is added too much, the upper side of the spacer is cured even if the amount of the photopolymerization initiator is increased, but the lower side may be insufficiently cured, which is not preferable. On the other hand, if the ultraviolet absorber is less than 0.03% by mass, it is not possible to absorb excess light, and the suppression of reflected light to the glass substrate becomes insufficient, and the lower diameter of the spacer may not be reduced. . The ultraviolet absorber is more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, more preferably 1.0% by mass or less, further preferably 0.75% by mass or less, and 0.6% by mass. The following are particularly preferred:

  The curable resin composition of the present invention is within the range that does not impair the effects of the present invention, and further, fillers such as aluminum hydroxide, talc, clay, barium sulfate, dyes, pigments, antifoaming agents, coupling agents, leveling It may contain known additives such as an agent, a sensitizer, a release agent, a lubricant, a plasticizer, an antioxidant, a flame retardant, a polymerization inhibitor, a thickener, and a dispersant.

  The curable resin composition of the present invention is an essential component of a photosensitive polymer, a polyfunctional monomer, a photopolymerization initiator, a radical polymerizable oligomer, a solvent, an ultraviolet absorber and other additives used as necessary. Can be prepared by mixing uniformly.

The present invention includes a columnar spacer obtained by curing the curable resin composition of the present invention. The method for forming the columnar spacer is not particularly limited. For example, the curable resin composition of the present invention is applied to a substrate such as glass or a transparent plastic film, dried, and then a coating film is formed. It can be formed by photolithography.

  In development, an aqueous alkali solution is preferably used. Highly sensitive development can be performed with little impact on the environment. As the alkali component, potassium hydroxide, sodium hydroxide, sodium carbonate and the like are preferable. The alkali concentration is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and most preferably 0.03 to 1% by mass. If the alkali concentration is lower than the above range, the solubility of the curable resin may be insufficient. Conversely, if the alkali concentration is high, the dissolving power may be too high and developability may be poor. Further, a surfactant may be added to the alkaline aqueous solution.

In photolithography, for example, a UV aligner (TME-150RNS, manufactured by TOPCON) having a photomask disposed at a distance of about 150 μm from the coating film and equipped with a 2.0 kW ultrahigh pressure mercury lamp has an intensity of 50 mJ / cm ² ( The coating film of the curable resin composition is photocured by irradiating ultraviolet rays at 365 nm illuminance. After UV irradiation, a 0.05% by weight potassium hydroxide aqueous solution is sprayed on the coating film with a spin developing machine for 40 seconds to dissolve and remove the unexposed area, and the remaining exposed area is washed with pure water for 10 seconds. A columnar spacer can be obtained by developing. Then, you may post-bake. The distance to the photomask, UV intensity, development conditions, and the like can be changed as appropriate.

  Examples of the shape of the columnar spacer include a columnar shape, a prismatic shape, a truncated cone shape, and a truncated pyramid shape. In addition, the columnar spacer of the present invention preferably has an elastic recovery rate of compression characteristics described later of 60% or more, more preferably 65% or more, and more preferably 75% or more. By using the columnar spacer having an elastic recovery rate as described above, the problem in manufacturing the liquid crystal cell can be solved.

  The present invention includes a liquid crystal display using the columnar spacer of the present invention. The configuration and materials used for the liquid crystal display are not particularly limited, and any known configuration or material can be used.

  Hereinafter, the present invention will be described in more detail with reference to examples. The examples and comparative examples were evaluated as follows. Moreover, below, a part means a mass part and% means the mass%.

[Evaluation method]
(Weight average molecular weight: Mw)
GPC (HLC-8220GPC, manufactured by Tosoh Corporation) was used as an eluent, and TSKgel SuperHZM-N (manufactured by Tosoh Corporation) was used as a column for the measurement.

(Solid content)
About 0.3 g of the polymer solution was weighed in an aluminum cup, dissolved by adding about 1 g of acetone, and then naturally dried at room temperature. Thereafter, using a hot air dryer (trade name: PHH-101, manufactured by Espec Corp.), the mixture was dried at 140 ° C. for 3 hours, then allowed to cool in a desiccator, and the mass was measured. From the mass loss, the solid content of the polymer solution was calculated.

(Acid value)
About 1.5 g of the polymer solution was precisely weighed, dissolved in a mixed solvent of 90 parts of acetone and 10 parts of water, and titrated with a 0.1N aqueous KOH solution. Titration was performed using an automatic titrator (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value per 1 g of polymer was determined from the solid content concentration (mgKOH / g).

[Example 1-1]
In a monomer dropping tank, 35 parts of benzylmaleimide (BzMI), 114 parts of acrylic acid (AA), 42 parts of acryloylmorpholine (ACMO; manufactured by Kojin Co., Ltd.), ethoxylated o-phenylphenol acrylate (trade name “A-LEN-10” "Shin-Nakamura Chemical Co., Ltd.) 42 parts, t-butyl peroxy-2-ethylhexanoate (" Perbutyl (registered trademark) O ", NOF Corporation; (PBO)) 4.7 parts, propylene glycol methyl A solution obtained by thoroughly stirring and mixing 56 parts of ether acetate (PGMEA) and 84 parts of propylene glycol monomethyl ether (PGME) was added. In a chain transfer agent dropping tank, n-dodecyl mercaptan (n-DM) 2.8 parts, both terminal mercapto-modified polysiloxane (trade name “X-22-167B”; manufactured by Shin-Etsu Silicone) 12 parts, PGMEA 19 parts Then, 29 parts of PGME and well mixed with stirring were added.

  Prepare a separable flask with a cooling tube as a reaction tank, and prepare 142 parts of PGMEA and 214 parts of PGMEA in this reaction tank, replace with nitrogen, and then heat in an oil bath while stirring to 90 ° C. The temperature rose. After the temperature of the reaction tank was stabilized at 90 ° C., dropping of each component was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropwise addition was performed for 180 minutes each while maintaining the flask internal temperature at 90 ° C. After the completion of dropping, the temperature was maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. inside the reaction vessel.

  After maintaining at 115 ° C. for 1.5 hours, 15 parts of PGMEA, 22 parts of PGME, 161 parts of glycidyl methacrylate (GMA), 6-tert-butyl-2,4-xylenol (trade name “Topanol” as a polymerization inhibitor) ”; Tokyo Chemical Industry Co., Ltd.) 0.6 parts, 1.2 parts of dimethylbenzylamine (DMBA) as a catalyst were charged, and nitrogen / oxygen mixed gas (oxygen concentration: 7% by volume) was bubbled for 1 hour at 110 ° C. Then, the mixture was reacted at 115 ° C. for 7 hours. Then, it cooled to room temperature and photosensitive polymer solution No. 3 whose solid content is 39%. 1 was obtained. The polymer had a double bond equivalent of 350 g / equivalent, a weight average molecular weight (Mw) of 14,500, and an acid value of 76 mgKOH / g. The polymer production conditions and the like are shown in Table 1.

[Example 1-2]
[Monomer synthesis]
In a vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube, and dropping funnel, 200 parts of tetrahydrofuran as a solvent, 106 parts of p-hydroxydiphenyl, 1 part of dibutyltin dilaurate as a catalyst, 2,6 as a polymerization inhibitor -While charging 0.1 part of dibutyl-4-methylphenol and bubbling a nitrogen / oxygen mixed gas (oxygen concentration: 7% by volume), from a dropping funnel at 40 ° C, 2-isocyanatoethyl acrylate (trade name "Karenz AOI (registered trademark)" ) ", Manufactured by Showa Denko KK), 88 parts was added dropwise over 1 hour, and then reacted at 60 ° C for 2 hours. Then, the compound (A) was obtained by precipitating the compound (A), which is a synthesized biphenyl group-containing monomer, using hexane, which is a poor solvent.

[Synthesis of polymer]
In a monomer dropping tank, 35 parts of BzMI, 114 parts of AA, 84 parts of the above compound (A), 4.7 parts of PBO, 98 parts of PGMEA and 42 parts of PGME were mixed well. Further, a mixture obtained by thoroughly stirring and mixing 3.5 parts of n-DM, 43 parts of PGMEA and 18 parts of PGME was put into a chain transfer agent dropping tank.

Prepare a separable flask with a cooling tube as a reaction tank, charge 230 parts of PGMEA and 128 parts of PGMEA in this reaction tank, replace with nitrogen, and then heat in an oil bath while stirring to 90 ° C. The temperature rose. After the temperature of the reaction tank was stabilized at 90 ° C., dropping of each component was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropwise addition was performed for 180 minutes each while maintaining the flask internal temperature at 90 ° C. After the completion of dropping, the temperature was maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. inside the reaction vessel.

  After maintaining at 115 ° C. for 1.5 hours, 35 parts of PGMEA, 15 parts of PGME, 161 parts of GMA, 0.6 part of topanol and 1.2 parts of DMBA were charged into the reaction vessel, and a nitrogen / oxygen mixed gas (oxygen concentration: 7% by volume) was added. While bubbling, the reaction was carried out at 110 ° C. for 1 hour and then at 115 ° C. for 7 hours. Then, it cooled to room temperature and photosensitive polymer solution No. 37 whose solid content is 37%. 2 was obtained. The double bond equivalent of the polymer was 350 g / equivalent, Mw was 14,000, and the acid value was 84 mgKOH / g. The polymer production conditions and the like are shown in Table 1.

[Example 1-3]
In a monomer dropping tank, 38 parts of BzMI, 124 parts of AA, 91 parts of A-LEN-10, 5.1 parts of PBO, 106 parts of PGMEA, and 46 parts of PGME were mixed well. A chain transfer agent dropping tank was charged with 3.8 parts of n-DM, 47 parts of PGMEA, and 20 parts of PGME with sufficient stirring and mixing.

  Prepare a separable flask with a cooling tube as a reaction tank, charge 414 parts of PGMEA and 177 parts of PGMEA in this reaction tank, and after replacing with nitrogen, heat in an oil bath while stirring to 90 ° C. The temperature rose. After the temperature of the reaction tank was stabilized at 90 ° C., dropping of each component was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropwise addition was performed for 180 minutes each while maintaining the flask internal temperature at 90 ° C. After the completion of dropping, the temperature was maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. inside the reaction vessel.

  After maintaining at 115 ° C. for 1.5 hours, the reaction vessel was charged with 38 parts of PGMEA, 16 parts of PGME, 175 parts of GMA, 0.6 part of topanol and 1.3 parts of DMBA, and a nitrogen / oxygen mixed gas (oxygen concentration: 7% by volume). While bubbling, the reaction was carried out at 110 ° C. for 1 hour and then at 115 ° C. for 7 hours. Then, it cooled to room temperature and photosensitive polymer solution No. 32 with a solid content of 32%. 3 was obtained. The double bond equivalent of the polymer was 350 g / equivalent, Mw was 15,000, and the acid value was 84 mgKOH / g. The polymer production conditions and the like are shown in Table 1.

[Example 1-4]
In the monomer dropping tank, 35 parts of BzMI, 114 parts of AA, o-phenylphenol glycidyl ether acrylate (trade name “NK ester 401P”; 401P; manufactured by Shin Nakamura Chemical Co., Ltd.) 84 parts, 4.7 parts of PBO, 98 parts of PGMEA and 42 parts of PGME What was stirred and mixed was added. Further, a mixture obtained by thoroughly stirring and mixing 3.5 parts of n-DM, 43 parts of PGMEA and 18 parts of PGME was put into a chain transfer agent dropping tank.

  Prepare a separable flask with a cooling tube as a reaction tank, charge 230 parts of PGMEA and 128 parts of PGMEA in this reaction tank, replace with nitrogen, and then heat in an oil bath while stirring to 90 ° C. The temperature rose. After the temperature of the reaction tank was stabilized at 90 ° C., dropping of each component was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropwise addition was performed for 180 minutes each while maintaining the flask internal temperature at 90 ° C. After the completion of dropping, the temperature was maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. inside the reaction vessel.

  After maintaining at 115 ° C. for 1.5 hours, 35 parts of PGMEA, 15 parts of PGME, 161 parts of GMA, 0.6 part of topanol and 1.2 parts of DMBA were charged into the reaction vessel, and a nitrogen / oxygen mixed gas (oxygen concentration: 7% by volume) was added. While bubbling, the reaction was carried out at 110 ° C. for 1 hour and then at 115 ° C. for 7 hours. Then, it cooled to room temperature and photosensitive polymer solution No. 3 whose solid content is 39%. 4 was obtained. The double bond equivalent of the polymer was 350 g / equivalent, Mw was 13,500, and the acid value was 80 mgKOH / g. The polymer production conditions and the like are shown in Table 1.

[Example 1-5]
A monomer dropping tank was charged with 20 parts of BzMI, 39 parts of AA, 75 parts of A-LEN-10, 2.7 parts of PBO, 56 parts of PGMEA, and 24 parts of PGME. A chain transfer agent dripping tank was charged with 1.3 parts of n-DM, 34 parts of PGMEA and 15 parts of PGMEA with sufficient stirring and mixing.

  Prepare a separable flask with a cooling tube as a reaction tank, charge 128 parts of PGMEA and 55 parts of PGMEA in this reaction tank, replace with nitrogen, and then heat in an oil bath while stirring to 90 ° C. The temperature rose. After the temperature of the reaction tank was stabilized at 90 ° C., dropping of each component was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropwise addition was performed for 180 minutes each while maintaining the flask internal temperature at 90 ° C. After the completion of dropping, the temperature was maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. inside the reaction vessel.

  After maintaining at 115 ° C. for 1.5 hours, a reaction vessel was charged with 8 parts of PGMEA, 2 parts of PGME, 39 parts of GMA, 0.3 part of topanol and 0.5 part of DMBA, and a nitrogen / oxygen mixed gas (oxygen concentration: 7% by volume). While bubbling, the reaction was carried out at 110 ° C. for 1 hour and then at 115 ° C. for 7 hours. Then, it cooled to room temperature and photosensitive polymer solution No. 3 whose solid content is 33%. 5 was obtained. The double bond equivalent of the polymer was 630 g / equivalent, Mw was 10,200, and the acid value was 98 mgKOH / g. The polymer production conditions and the like are shown in Table 1.

[Example 1-6]
To the monomer dropping tank, 18 parts of BzMI, 98 parts of AA, 92 parts of A-LEN-10, 4 parts of PBO, 28 parts of PGMEA, and 12 parts of PGME were mixed well. A chain transfer agent dripping tank was charged with 3 parts of n-DM, 37 parts of PGMEA and 16 parts of PGMEA well stirred and mixed.

  Prepare a separable flask with a cooling tube as a reaction tank, charge 262 parts of PGMEA and 112 parts of PGMEA in this reaction tank, replace with nitrogen, and then heat in an oil bath with stirring until the temperature of the reaction tank reaches 90 ° C. The temperature rose. After the temperature of the reaction tank was stabilized at 90 ° C., dropping of each component was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropwise addition was performed for 180 minutes each while maintaining the flask internal temperature at 90 ° C. After the completion of dropping, the temperature was maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. inside the reaction vessel.

  After maintaining at 115 ° C. for 1.5 hours, 30 parts of PGMEA, 13 parts of PGME, 138 parts of GMA, 0.5 part of topanol and 1 part of DMBA were charged into the reaction vessel, and a nitrogen / oxygen mixed gas (oxygen concentration: 7% by volume) was bubbled. The reaction was carried out at 110 ° C. for 1 hour and then at 115 ° C. for 7 hours. Then, it cooled to room temperature and photosensitive polymer solution No. 40 whose solid content is 40%. 6 was obtained. The double bond equivalent of the polymer was 350 g / equivalent, Mw was 14,000, and the acid value was 80 mgKOH / g. The polymer production conditions and the like are shown in Table 1.

[Example 1-7]
A monomer dropping tank was charged with 100 parts of AA, 104 parts of A-LEN-10, and 4.1 parts of PBO which were well stirred and mixed. A chain transfer agent dropping tank was charged with 3.1 parts of n-DM, 38 parts of PGMEA, and 16 parts of PGMEA well mixed.

Prepare a separable flask with a cooling tube as a reaction tank, charge 296 parts of PGMEA and 127 parts of PGMEA in this reaction tank, and after purging with nitrogen, heat in an oil bath with stirring until the temperature of the reaction tank reaches 90 ° C. The temperature rose. After the temperature of the reaction tank was stabilized at 90 ° C., dropping of each component was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropwise addition was performed for 180 minutes each while maintaining the flask internal temperature at 90 ° C. After the completion of dropping, the temperature was maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. inside the reaction vessel.

  After maintaining at 115 ° C. for 1.5 hours, 31 parts of PGMEA, 13 parts of PGME, 141 parts of GMA, 0.5 part of topanol and 1 part of DMBA were charged into the reaction vessel, and a nitrogen / oxygen mixed gas (oxygen concentration: 7% by volume) was bubbled. The reaction was carried out at 110 ° C. for 1 hour and then at 115 ° C. for 7 hours. Then, it cooled to room temperature and photosensitive polymer solution No. 3 whose solid content is 39%. 7 was obtained. The double bond equivalent of the polymer was 350 g / equivalent, Mw was 14,500, and the acid value was 81 mgKOH / g. The polymer production conditions and the like are shown in Table 1.

[Example 1-8]
A monomer dropping tank was charged with 30 parts of BzMI, 98 parts of AA, 58 parts of cyclohexyl acrylate (CHA), 20 parts of A-LEN-10, 4 parts of PBO, 84 parts of PGMEA and 36 parts of PGME. A chain transfer agent dripping tank was charged with 3 parts of n-DM, 37 parts of PGMEA and 16 parts of PGMEA well stirred and mixed.

  Prepare a separable flask with a cooling tube as a reaction tank, charge 206 parts of PGMEA and 88 parts of PGME in this reaction tank, replace with nitrogen, and then heat in an oil bath while stirring to 90 ° C. The temperature rose. After the temperature of the reaction tank was stabilized at 90 ° C., dropping of each component was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropwise addition was performed for 180 minutes each while maintaining the flask internal temperature at 90 ° C. After the completion of dropping, the temperature was maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. inside the reaction vessel.

  After maintaining at 115 ° C. for 1.5 hours, 30 parts of PGMEA, 13 parts of PGME, 138 parts of GMA, 0.5 part of topanol and 1 part of DMBA were charged into the reaction vessel, and a nitrogen / oxygen mixed gas (oxygen concentration: 7% by volume) was bubbled. The reaction was carried out at 110 ° C. for 1 hour and then at 115 ° C. for 7 hours. Then, it cooled to room temperature and photosensitive polymer solution No. 40 whose solid content is 40%. 8 was obtained. The double bond equivalent of the polymer was 350 g / equivalent, Mw was 13,000, and the acid value was 80 mgKOH / g. The polymer production conditions and the like are shown in Table 1.

[Example 1-9]
A monomer dropping tank was charged with 30 parts of BzMI, 58 parts of AA, 187 parts of A-LEN-10, 5.5 parts of PBO, 84 parts of PGMEA, and 36 parts of PGME. A chain transfer agent dropping tank was charged with 4.1 parts of n-DM, 50 parts of PGMEA, and 22 parts of PGME with sufficient stirring and mixing.

  Prepare a separable flask with a cooling tube as a reaction tank, charge 155 parts of PGMEA and 66 parts of PGMEA in this reaction tank, replace with nitrogen, and then heat in an oil bath while stirring to 90 ° C. The temperature rose. After the temperature of the reaction tank was stabilized at 90 ° C., dropping of each component was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropwise addition was performed for 180 minutes each while maintaining the flask internal temperature at 90 ° C. After the completion of dropping, the temperature was maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. inside the reaction vessel.

  After maintaining at 115 ° C. for 1.5 hours, 63 parts of PGMEA, 27 parts of PGME, 58 parts of GMA, 0.5 part of topanol and 1 part of DMBA were charged into the reaction vessel, and a nitrogen / oxygen mixed gas (oxygen concentration: 7% by volume) was bubbled. The reaction was carried out at 110 ° C. for 1 hour and then at 115 ° C. for 7 hours. Then, it cooled to room temperature and photosensitive polymer solution No. 41 whose solid content is 41%. 9 was obtained. The double bond equivalent of the polymer was 820 g / equivalent, Mw was 14,000, and the acid value was 83 mgKOH / g. The polymer production conditions and the like are shown in Table 1.

[Example 1-10]
A monomer dropping tank was charged with 30 parts of BzMI, 98 parts of AA, 62 parts of CHA, 15 parts of A-LEN-10, 4.1 parts of PBO, 84 parts of PGMEA and 36 parts of PGME. A chain transfer agent dropping tank was charged with 3.1 parts of n-DM, 38 parts of PGMEA, and 16 parts of PGMEA well mixed.

  Prepare a separable flask with a cooling tube as a reaction tank, and in this reaction tank, charge 214 parts of PGMEA and 92 parts of PGME, purge with nitrogen, and then heat in an oil bath with stirring until the temperature of the reaction tank reaches 90 ° C. The temperature rose. After the temperature of the reaction tank was stabilized at 90 ° C., dropping of each component was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropwise addition was performed for 180 minutes each while maintaining the flask internal temperature at 90 ° C. After the completion of dropping, the temperature was maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. inside the reaction vessel.

  After maintaining at 115 ° C. for 1.5 hours, 31 parts of PGMEA, 13 parts of PGME, 142 parts of GMA, 0.5 part of topanol and 1 part of DMBA were charged into the reaction vessel, and a nitrogen / oxygen mixed gas (oxygen concentration: 7% by volume) was bubbled. The reaction was carried out at 110 ° C. for 1 hour and then at 115 ° C. for 7 hours. Then, it cooled to room temperature and photosensitive polymer solution No. 3 whose solid content is 39%. 10 was obtained. The double bond equivalent of the polymer was 350 g / equivalent, Mw was 15,000, and the acid value was 63 mgKOH / g. The polymer production conditions and the like are shown in Table 1.

[Example 1-11]
Into the monomer dropping tank, 40 parts of BzMI, 93 parts of AA, 133 parts of A-LEN-10, 5.3 parts of PBO, 112 parts of PGMEA and 48 parts of PGME were thoroughly mixed. A chain transfer agent dripping tank was charged with 4 parts of n-DM, 49 parts of PGMEA, and 21 parts of PGMEA with sufficient stirring and mixing.

  Prepare a separable flask with a cooling tube as a reaction tank, and in this reaction tank, 274 parts of PGMEA and 118 parts of PGME were charged, purged with nitrogen, and then heated in an oil bath with stirring until the temperature of the reaction tank reached 90 ° C. The temperature rose. After the temperature of the reaction tank was stabilized at 90 ° C., dropping of each component was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropwise addition was performed for 180 minutes each while maintaining the flask internal temperature at 90 ° C. After the completion of dropping, the temperature was maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. inside the reaction vessel.

  After maintaining at 115 ° C. for 1.5 hours, a reaction vessel was charged with 13 parts of PGMEA, 5 parts of PGME, 158 parts of GMA, 0.6 part of topanol and 1.3 parts of DMBA, and a nitrogen / oxygen mixed gas (oxygen concentration: 7% by volume) Was allowed to react at 110 ° C. for 1 hour and then at 115 ° C. for 7 hours. Then, it cooled to room temperature and photosensitive polymer solution No. with a solid content of 38%. 11 was obtained. The double bond equivalent of the polymer was 380 g / equivalent, Mw was 14,500, and the acid value was 35 mgKOH / g. The polymer production conditions and the like are shown in Table 1.

[Example 1-12]
Into the monomer dropping tank, 25 parts of BzMI, 138 parts of AA, 88 parts of A-LEN-10, 5 parts of PBO, 70 parts of PGMEA and 30 parts of PGME were mixed well. A chain transfer agent dropping tank was charged with 3.8 parts of n-DM, 46 parts of PGMEA, and 19 parts of PGME with sufficient stirring and mixing.

Prepare a separable flask with a cooling tube as a reaction tank, charge 209 parts of PGMEA and 89 parts of PGME to this reaction tank, replace with nitrogen, and then heat in an oil bath with stirring until the temperature of the reaction tank reaches 90 ° C. The temperature rose. After the temperature of the reaction tank was stabilized at 90 ° C., dropping of each component was started from the monomer dropping tank and the chain transfer agent dropping tank. Addition of the flask inside temperature to 9
While maintaining at 0 ° C., each was performed for 180 minutes. After the completion of dropping, the temperature was maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. inside the reaction vessel.

  After maintaining at 115 ° C. for 1.5 hours, 69 parts of PGMEA, 30 parts of PGME, 123 parts of GMA, 0.6 parts of topanol and 1.1 parts of DMBA were charged into the reaction vessel, and a nitrogen / oxygen mixed gas (oxygen concentration: 7% by volume) Was allowed to react at 110 ° C. for 1 hour and then at 115 ° C. for 7 hours. Then, it cooled to room temperature and photosensitive polymer solution No. 41 whose solid content is 41%. 12 was obtained. The double bond equivalent of the polymer was 430 g / equivalent, Mw was 13,000, and the acid value was 168 mgKOH / g. The polymer production conditions and the like are shown in Table 1.

[Example 1-13]
(Α-Hydroxymethyl) methyl acrylate dimer (compound of formula (2); MD) 35 parts, AA 114 parts, A-LEN-10 84 parts, PBO 4.7 parts, PGMEA 98 parts and PGME 42 What was well stirred and mixed was charged. Further, a mixture obtained by thoroughly stirring and mixing 3.5 parts of n-DM, 43 parts of PGMEA and 18 parts of PGME was put into a chain transfer agent dropping tank.

  Prepare a separable flask with a cooling tube as a reaction tank, charge 240 parts of PGMEA and 103 parts of PGMEA in this reaction tank, purge with nitrogen, and then heat in an oil bath while stirring to 90 ° C. The temperature rose. After the temperature of the reaction tank was stabilized at 90 ° C., dropping of each component was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropwise addition was performed for 180 minutes each while maintaining the flask internal temperature at 90 ° C. After the completion of dropping, the temperature was maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. inside the reaction vessel.

  After maintaining at 115 ° C. for 1.5 hours, 35 parts of PGMEA, 15 parts of PGME, 161 parts of GMA, 0.6 part of topanol and 1.2 parts of DMBA were charged into the reaction vessel, and a nitrogen / oxygen mixed gas (oxygen concentration: 7% by volume) Was allowed to react at 110 ° C. for 1 hour and then at 115 ° C. for 7 hours. Then, it cooled to room temperature and photosensitive polymer solution No. 40 whose solid content is 40%. 13 was obtained. The double bond equivalent of the polymer was 350 g / equivalent, Mw was 13,000, and the acid value was 80 mgKOH / g. The polymer production conditions and the like are shown in Table 1.

[Example 1-14]
In a monomer dropping tank, 35 parts of BzMI, 114 parts of AA, 42 parts of ethyl acrylate (EA), 42 parts of A-LEN-10, 4.7 parts of PBO, 98 parts of PGMEA, and 42 parts of PGMEA were charged. Further, a mixture obtained by thoroughly stirring and mixing 3.5 parts of n-DM, 43 parts of PGMEA and 18 parts of PGME was put into a chain transfer agent dropping tank.

  Prepare a separable flask with a cooling tube as a reaction tank, charge 240 parts of PGMEA and 103 parts of PGMEA in this reaction tank, purge with nitrogen, and then heat in an oil bath while stirring to 90 ° C. The temperature rose. After the temperature of the reaction tank was stabilized at 90 ° C., dropping of each component was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropwise addition was performed for 180 minutes each while maintaining the flask internal temperature at 90 ° C. After the completion of dropping, the temperature was maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. inside the reaction vessel.

  After maintaining at 115 ° C. for 1.5 hours, 35 parts of PGMEA, 15 parts of PGME, 161 parts of GMA, 0.6 part of topanol and 1.2 parts of DMBA were charged into the reaction vessel, and a nitrogen / oxygen mixed gas (oxygen concentration: 7% by volume) Was allowed to react at 110 ° C. for 1 hour and then at 115 ° C. for 7 hours. Then, it cooled to room temperature and photosensitive polymer solution No. 3 whose solid content is 39%. 14 was obtained. The double bond equivalent of the polymer was 350 g / equivalent, Mw was 12,500, and the acid value was 63 mgKOH / g. The polymer production conditions and the like are shown in Table 1.

[Comparative Example 1-1]
To the monomer dropping tank, 36 parts of BzMI, 118 parts of AA, 86 parts of CHA, 4.8 parts of PBO, 101 parts of PGMEA, and 43 parts of PGMEA were stirred and mixed. A chain transfer agent dropping tank was charged with 3.6 parts of n-DM, 44 parts of PGMEA, and 19 parts of PGMEA mixed well.

  Prepare a separable flask with a cooling tube as a reaction tank, charge 247 parts of PGMEA and 106 parts of PGME to this reaction tank, replace with nitrogen, and then heat in an oil bath with stirring until the temperature of the reaction tank reaches 90 ° C. The temperature rose. After the temperature of the reaction tank was stabilized at 90 ° C., dropping of each component was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropwise addition was performed for 180 minutes each while maintaining the flask internal temperature at 90 ° C. After the completion of dropping, the temperature was maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. inside the reaction vessel.

  After maintaining at 115 ° C. for 1.5 hours, the reaction vessel was charged with 36 parts of PGMEA, 16 parts of PGME, 166 parts of GMA, 0.6 part of topanol and 1.2 parts of DMBA, and a nitrogen / oxygen mixed gas (oxygen concentration: 7% by volume) Was allowed to react at 110 ° C. for 1 hour and then at 115 ° C. for 7 hours. Then, it cooled to room temperature and photosensitive polymer solution No. 3 whose solid content is 39%. 15 was obtained. The double bond equivalent of the polymer was 350 g / equivalent, Mw was 19,000, and the acid value was 75 mgKOH / g. The polymer production conditions and the like are shown in Table 1.

[Comparative Example 1-2]
In a monomer dropping tank, 7 parts of BzMI, 116 parts of AA, 25 parts of cyclohexyl methacrylate (CHMA), 2.2 parts of PBO, and 30 parts of PGME were mixed well. In addition, a chain transfer agent dropping tank was charged with 3.7 parts of n-DM and 60 parts of PGME well mixed.

  A separable flask equipped with a cooling pipe was prepared as a reaction tank, and 305 parts of PGME were charged into this reaction tank, and after replacing with nitrogen, the temperature of the reaction tank was raised to 90 ° C. by heating with an oil bath while stirring. . After the temperature of the reaction tank was stabilized at 90 ° C., dropping of each component was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropwise addition was performed for 180 minutes each while maintaining the flask internal temperature at 90 ° C. After the completion of dropping, the temperature was maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. inside the reaction vessel.

  After maintaining at 115 ° C. for 1.5 hours, 535 parts of PGMEA, 188 parts of PGME, 184 parts of GMA, 0.5 part of topanol and 1 part of DMBA are charged into the reaction vessel, and a nitrogen / oxygen mixed gas (oxygen concentration: 7% by volume) is bubbled. The reaction was carried out at 110 ° C. for 1 hour and then at 115 ° C. for 7 hours. Then, it cooled to room temperature and photosensitive polymer solution No. 34 whose solid content was 34%. 16 was obtained. The double bond equivalent of the polymer was 260 g / equivalent, Mw was 16,000, and the acid value was 65 mgKOH / g. The polymer production conditions and the like are shown in Table 1.

[Comparative Example 1-3]
In a monomer dropping tank, 36 parts of BzMI, 118 parts of AA, 86 parts of benzyl methacrylate (BzMA), 4.8 parts of PBO, 101 parts of PGMEA, and 43 parts of PGME were charged. A chain transfer agent dropping tank was charged with 3.6 parts of n-DM, 44 parts of PGMEA, and 19 parts of PGMEA mixed well.

Prepare a separable flask with a cooling tube as a reaction tank, charge 247 parts of PGMEA and 106 parts of PGME to this reaction tank, replace with nitrogen, and then heat in an oil bath with stirring until the temperature of the reaction tank reaches 90 ° C. The temperature rose. After the temperature of the reaction tank was stabilized at 90 ° C., dropping of each component was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropwise addition was performed for 180 minutes each while maintaining the flask internal temperature at 90 ° C. After the completion of dropping, the temperature was maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. inside the reaction vessel.

  After maintaining at 115 ° C. for 1.5 hours, the reaction vessel was charged with 36 parts of PGMEA, 16 parts of PGME, 166 parts of GMA, 0.6 part of topanol and 1.2 parts of DMBA, and a nitrogen / oxygen mixed gas (oxygen concentration: 7% by volume) Was allowed to react at 110 ° C. for 1 hour and then at 115 ° C. for 7 hours. Then, it cooled to room temperature and photosensitive polymer solution No. 40 whose solid content is 40%. 17 was obtained. The double bond equivalent of the polymer was 350 g / equivalent, Mw was 15,000, and the acid value was 75 mgKOH / g. The polymer production conditions and the like are shown in Table 1.

(Evaluation of spacer)
Photosensitive polymer solutions 1 to 17 obtained in each Example and Comparative Example, pentaerythritol tetraacrylate (PETA; manufactured by Kyoeisha Chemical Co., Ltd.) as a polyfunctional monomer, and 2-methyl-1- (4- Methylthiophenyl) -2-morpholinopropane-1
-ON (IRGACURE (registered trademark) 907; manufactured by BASF Japan) was mixed so that the solid content of the photosensitive polymer solution was 44 parts, 56 parts of PETA, and 1.75 parts of IRGACURE, and then the resin composition PGMEA was added and dissolved so that the solid content of the product was 35%, and then filtered through a Millipore filter having a pore size of 0.5 μm to prepare a resin composition solution.

(Evaluation of developability of negative resist)
Each resin composition solution was applied onto a 10 cm square glass substrate by a spin coater and dried in an oven at 80 ° C. for 3 minutes. After drying, an intensity of 50 mJ / cm ² by a UV aligner (TME-150RNS, manufactured by TOPCON) equipped with a 2.0 kW ultra high pressure mercury lamp and an 8 μmφ pattern photomask placed at a distance of 150 μm from the coating film (365
Ultraviolet rays were irradiated in terms of nm illuminance. After UV irradiation, 0.05% potassium hydroxide aqueous solution is sprayed on the coating film with a spin developing machine for 40 seconds to dissolve and remove the unexposed area, and the remaining exposed area is washed with pure water for 10 seconds. Developed.

  As adhesion, the presence or absence of a spacer defect after development was evaluated with a laser microscope (VK-9700, manufactured by Keyence Corporation). No defect, ◎, less than 10% of the defect range, ◯, less than 30% of the defect range, and x for all defects. The evaluation results are shown in Table 2.

  Moreover, the developability of the unexposed part was evaluated by the presence or absence of a residue of the resin composition. ◎ indicates no residue, ○ indicates that a residue can be slightly confirmed in the spacer, and △ indicates that a residue can be slightly confirmed in an unexposed portion. The evaluation results are shown in Table 2.

(Compression rate / elastic recovery rate)
The developed coating film obtained above was heated at 230 ° C. for 30 minutes to obtain a spacer having a bottom diameter of 8 μm and a thickness of 3.5 μm. This spacer was subjected to a compression test using a flat indenter having a diameter of 50 μm using a micro compression tester (MCTW-500, manufactured by Shimadzu Corporation). The compression test conditions were a maximum test force of 80 mN and compression at a speed of 2.28 mN / sec. At this time, a displacement-test force curve was created, and the compression rate was determined by the following formula using the displacement amount when the maximum test force was applied.
Compression rate (%) = 100 × displacement amount at maximum test force load (μm) / measurement spacer thickness (μm)
The elastic recovery rate was determined by performing a load unloading test using the above-described micro compression tester and a flat indenter having a diameter of 50 μm. The load unloading test conditions were as follows. For both unloading and loading, the minimum test force was 0.5 mN, the maximum test force was 80 mN, the speed was 2.28 mN / sec, the holding time was 5 seconds, and the elastic recovery rate was obtained by the following formula.
Elastic recovery rate (%) = 100 × (1−residual displacement after unloading (μm) / maximum displacement during loading (μm))

From Table 2, it can be seen that the curable resin composition of the present invention has a large elastic recovery rate, and the effect of introducing the biphenyl group appears significantly.

  Table 3 below is a table summarizing the composition and evaluation results of the curable resin composition used for each evaluation.

[Example 2-1]
A monomer dropping tank was charged with 30 parts of BzMI, 98 parts of AA, 36 parts of dicyclopentanyl acrylate (DCPA), 36 parts of A-LEN-10, 4 parts of PBO, 84 parts of PGMEA and 36 parts of PGMEA. Further, a well-stirred and mixed solution of 3.0 parts of n-DM, 37 parts of PGMEA and 18 parts of PGMEA was put into a chain transfer agent dropping tank.

  Prepare a separable flask with a cooling tube as a reaction tank, charge 206 parts of PGMEA and 88 parts of PGME in this reaction tank, replace with nitrogen, and then heat in an oil bath while stirring to 90 ° C. The temperature rose. After the temperature of the reaction tank was stabilized at 90 ° C., dropping of each component was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropwise addition was performed for 180 minutes each while maintaining the flask internal temperature at 90 ° C. After the completion of dropping, the temperature was maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. inside the reaction vessel.

  After maintaining at 115 ° C. for 1.5 hours, a reaction vessel was charged with 30 parts of PGMEA, 13 parts of PGME, 138 parts of GMA, 0.5 part of topanol and 1.0 part of DMBA, and a nitrogen / oxygen mixed gas (oxygen concentration 7% by volume). While bubbling, the reaction was carried out at 110 ° C. for 1 hour and then at 115 ° C. for 7 hours. Then, it cooled to room temperature and photosensitive polymer solution No. 3 whose solid content was 38.8%. 18 was obtained. The double bond equivalent of the polymer was 350 g / equivalent, Mw was 20,000, and the acid value was 73 mgKOH / g. The polymer production conditions and the like are shown in Table 4, and the performance evaluation results are shown in Table 5.

[Example 2-2]
A monomer dropping tank was charged with 30 parts of MD, 98 parts of AA, 36 parts of DCPA, 36 parts of A-LEN-10, 4 parts of PBO, 84 parts of PGMEA and 36 parts of PGME. Further, a well-stirred and mixed solution of 3.0 parts of n-DM, 37 parts of PGMEA and 18 parts of PGMEA was put into a chain transfer agent dropping tank.

  Prepare a separable flask with a cooling tube as a reaction tank, charge 206 parts of PGMEA and 88 parts of PGME in this reaction tank, replace with nitrogen, and then heat in an oil bath while stirring to 90 ° C. The temperature rose. After the temperature of the reaction tank was stabilized at 90 ° C., dropping of each component was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropwise addition was performed for 180 minutes each while maintaining the flask internal temperature at 90 ° C. After the completion of dropping, the temperature was maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. inside the reaction vessel.

  After maintaining at 115 ° C. for 1.5 hours, a reaction vessel was charged with 30 parts of PGMEA, 13 parts of PGME, 138 parts of GMA, 0.5 part of topanol and 1.0 part of DMBA, and a nitrogen / oxygen mixed gas (oxygen concentration 7% by volume). While bubbling, the reaction was carried out at 110 ° C. for 1 hour and then at 115 ° C. for 7 hours. Then, it cooled to room temperature and photosensitive polymer solution No. with a solid content of 38.6%. 19 was obtained. The double bond equivalent of the polymer was 350 g / equivalent, Mw was 19,000, and the acid value was 75 mgKOH / g. The polymer production conditions and the like are shown in Table 4, and the performance evaluation results are shown in Table 5.

[Example 2-3]
Into the monomer dropping tank, a mixture of 30 parts of methyl 2-allyloxymethyl acrylate (AMA), 98 parts of AA, 36 parts of DCPA, 36 parts of A-LEN-10, 4 parts of PBO, 84 parts of PGMEA and 36 parts of PGMEA was added. . Further, a well-stirred and mixed solution of 3.0 parts of n-DM, 37 parts of PGMEA and 18 parts of PGMEA was put into a chain transfer agent dropping tank.

  Prepare a separable flask with a cooling tube as a reaction tank, charge 206 parts of PGMEA and 88 parts of PGME in this reaction tank, replace with nitrogen, and then heat in an oil bath while stirring to 90 ° C. The temperature rose. After the temperature of the reaction tank was stabilized at 90 ° C., dropping of each component was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropwise addition was performed for 180 minutes each while maintaining the flask internal temperature at 90 ° C. After the completion of dropping, the temperature was maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. inside the reaction vessel.

  After maintaining at 115 ° C. for 1.5 hours, a reaction vessel was charged with 30 parts of PGMEA, 13 parts of PGME, 138 parts of GMA, 0.5 part of topanol and 1.0 part of DMBA, and a nitrogen / oxygen mixed gas (oxygen concentration 7% by volume). While bubbling, the reaction was carried out at 110 ° C. for 1 hour and then at 115 ° C. for 7 hours. Then, it cooled to room temperature and photosensitive polymer solution No. 3 with a solid content of 38.7%. 20 was obtained. The double bond equivalent of the polymer was 350 g / equivalent, Mw was 18,000, and the acid value was 73 mgKOH / g. The polymer production conditions and the like are shown in Table 4, and the performance evaluation results are shown in Table 5.

[Example 2-4]
In the monomer dropping tank, 30 parts of BzMI, 89 parts of AA, 36 parts of ACMO, A-LEN-10
45 parts, 4 parts of PBO, 60 parts of PGMEA, and 60 parts of PGMEA were mixed and mixed well. Moreover, what mixed and mixed 3.0 parts of n-DM, 27 parts of PGMEA, and 27 parts of PGMME well was thrown into the chain transfer agent dripping tank.

  Prepare a separable flask with a cooling tube as a reaction tank, and charge 147 parts of PGMEA and 147 parts of PGMEA in this reaction tank, and after replacing with nitrogen, heat in an oil bath while stirring to 90 ° C. The temperature rose. After the temperature of the reaction tank was stabilized at 90 ° C., dropping of each component was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropwise addition was performed for 180 minutes each while maintaining the flask internal temperature at 90 ° C. After the completion of dropping, the temperature was maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. inside the reaction vessel.

  After maintaining at 115 ° C. for 1.5 hours, a reaction vessel was charged with 22 parts of PGMEA, 22 parts of PGME, 138 parts of GMA, 0.5 part of topanol and 1.0 part of DMBA, and a nitrogen / oxygen mixed gas (oxygen concentration: 7% by volume). While bubbling, the reaction was carried out at 110 ° C. for 1 hour and then at 115 ° C. for 7 hours. Then, it cooled to room temperature and photosensitive polymer solution No. with a solid content of 38.1%. 21 was obtained. The double bond equivalent of the polymer was 350 g / equivalent, Mw was 11,000, and the acid value was 66 mgKOH / g. The polymer production conditions and the like are shown in Table 4, and the performance evaluation results are shown in Table 5.

[Example 2-5]
A monomer dropping tank was charged with 30 parts of MD, 89 parts of AA, 36 parts of ACMO, 45 parts of A-LEN-10, 4 parts of PBO, 60 parts of PGMEA and 60 parts of PGME. Moreover, what mixed and mixed 3.0 parts of n-DM, 27 parts of PGMEA, and 27 parts of PGMME well was thrown into the chain transfer agent dripping tank.

  Prepare a separable flask with a cooling tube as a reaction tank, and charge 147 parts of PGMEA and 147 parts of PGMEA in this reaction tank, and after replacing with nitrogen, heat in an oil bath while stirring to 90 ° C. The temperature rose. After the temperature of the reaction tank was stabilized at 90 ° C., dropping of each component was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropwise addition was performed for 180 minutes each while maintaining the flask internal temperature at 90 ° C. After the completion of dropping, the temperature was maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. inside the reaction vessel.

After maintaining at 115 ° C. for 1.5 hours, the reaction vessel was charged with 22 parts of PGMEA, 22 parts of PGMEA, G
138 parts of MA, 0.5 part of topanol and 1.0 part of DMBA were charged and reacted at 110 ° C. for 1 hour and then at 115 ° C. for 7 hours while bubbling a nitrogen / oxygen mixed gas (oxygen concentration: 7% by volume). Then, it cooled to room temperature and photosensitive polymer solution No. with a solid content of 38.0%. 22 was obtained. The double bond equivalent of the polymer was 350 g / equivalent, Mw was 10,500, and the acid value was 64 mgKOH / g. The polymer production conditions and the like are shown in Table 4, and the performance evaluation results are shown in Table 5.

[Example 2-6]
Into the monomer dropping tank, 30 parts of AMA, 89 parts of AA, 36 parts of ACMO, 45 parts of A-LEN-10, 4 parts of PBO, 60 parts of PGMEA and 60 parts of PGME were charged. Moreover, what mixed and mixed 3.0 parts of n-DM, 27 parts of PGMEA, and 27 parts of PGMME well was thrown into the chain transfer agent dripping tank.

  Prepare a separable flask with a cooling tube as a reaction tank, and charge 147 parts of PGMEA and 147 parts of PGMEA in this reaction tank, and after replacing with nitrogen, heat in an oil bath while stirring to 90 ° C. The temperature rose. After the temperature of the reaction tank was stabilized at 90 ° C., dropping of each component was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropwise addition was performed for 180 minutes each while maintaining the flask internal temperature at 90 ° C. After the completion of dropping, the temperature was maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. inside the reaction vessel.

  After maintaining at 115 ° C. for 1.5 hours, a reaction vessel was charged with 22 parts of PGMEA, 22 parts of PGME, 138 parts of GMA, 0.5 part of topanol and 1.0 part of DMBA, and a nitrogen / oxygen mixed gas (oxygen concentration: 7% by volume). While bubbling, the reaction was carried out at 110 ° C. for 1 hour and then at 115 ° C. for 7 hours. Then, it cooled to room temperature and photosensitive polymer solution No. with a solid content of 38.3%. 23 was obtained. The double bond equivalent of the polymer was 350 g / equivalent, Mw was 11,000, and the acid value was 67 mgKOH / g. The polymer production conditions and the like are shown in Table 4, and the performance evaluation results are shown in Table 5.

[Example 2-7]
A monomer dropping tank was charged with 30 parts of BzMI, 130 parts of AA, 40 parts of A-LEN-10, 4 parts of PBO, 60 parts of PGMEA, and 60 parts of PGME. Further, a mixture obtained by thoroughly stirring and mixing 2.0 parts of n-DM, 26 parts of PGMEA and 26 parts of PGME was put into a chain transfer agent dropping tank.

  Prepare a separable flask with a cooling tube as a reaction tank, and charge 147 parts of PGMEA and 147 parts of PGMEA in this reaction tank, and after replacing with nitrogen, heat in an oil bath while stirring to 90 ° C. The temperature rose. After the temperature of the reaction tank was stabilized at 90 ° C., dropping of each component was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropwise addition was performed for 180 minutes each while maintaining the flask internal temperature at 90 ° C. After the completion of dropping, the temperature was maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. inside the reaction vessel.

  After maintaining at 115 ° C. for 1.5 hours, 65 parts of PGMEA, 65 parts of PGME, 197 parts of GMA, 0.6 parts of topanol and 1.2 parts of DMBA were charged into the reaction vessel, and a nitrogen / oxygen mixed gas (oxygen concentration: 7% by volume) was added. While bubbling, the reaction was carried out at 110 ° C. for 1 hour and then at 115 ° C. for 7 hours. Then, it cooled to room temperature and photosensitive polymer solution No. 3 with a solid content of 39.8%. 24 was obtained. The polymer had a double bond equivalent of 290 g / equivalent, Mw of 23,000, and an acid value of 71 mgKOH / g. The polymer production conditions and the like are shown in Table 4, and the performance evaluation results are shown in Table 5.

[Examples 3-1 to 3-9]
Developability, adhesion, compressibility (%), elastic recovery rate in the same manner as above except that the resin solution used and its amount, and the type and amount of polyfunctional acrylate were changed as shown in Table 6. (%) Was evaluated and the results are shown in Table 6. DPHA is dipentaerythritol hexaacrylate (trade name: DPE-6A: manufactured by Kyoeisha Chemical Co., Ltd.) and biscoat # 802 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) is tripentaerythritol octaacrylate.

  From the comparison of Table 3, Table 5, and Table 6, it can be seen that the elastic recovery rate improves as the amount of the polyfunctional acrylate and the number of functional groups increase.

[Examples 4-1 to 4-15]
Into the monomer dropping tank, 15 parts of BzMI, 44.5 parts of AA, 40.5 parts of A-LEN-10, 2 parts of PBO, 42 parts of PGMEA, and 18 parts of PGME were charged. A chain transfer agent dripping tank was charged with 2.0 parts of n-DM, 18 parts of PGMEA, and 8 parts of PGME with sufficient stirring and mixing.

  Prepare a separable flask with a cooling tube as a reaction tank, charge 98 parts of PGMEA and 42 parts of PGME to this reaction tank, replace with nitrogen, and then heat in an oil bath while stirring to 90 ° C. The temperature rose. After the temperature of the reaction tank was stabilized at 90 ° C., dropping of each component was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropwise addition was performed for 180 minutes each while maintaining the flask internal temperature at 90 ° C. After 30 minutes from the completion of the dropping, 0.5 part of PBO was added and maintained at 90 ° C. for 30 minutes, and then the temperature was raised to 115 ° C. inside the reaction vessel.

  After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the reaction vessel, and bubbling of a mixed gas of oxygen / nitrogen = 5/95 (v / v) was started. Next, 69 parts of GMA, 0.3 part of topanol, 0.5 part of DMBA, 16 parts of PGMEA and 6 parts of PGME were charged in the reaction layer and reacted at 110 ° C. for 1 hour and 115 ° C. for 8 hours. Then, it cooled to room temperature and photosensitive polymer solution No. with a solid content of 39.4%. 25 was obtained. The polymer had a double bond equivalent of 350 g / equivalent, a weight average molecular weight (Mw) of 17,200, and an acid value of 55 mgKOH / g. Table 7 shows the polymer production conditions.

(Evaluation of spacer)
Except for using the photosensitive polymer solution 25 and using the aforementioned Tinuvin (registered trademark) 479 (T479) or SEESORB (registered trademark) 707 (SB707) as an ultraviolet absorber. In the same manner as in Examples, a curable resin composition was produced with the formulation shown in Table 8. Further, developability, adhesion, compression rate (%), and elastic recovery rate (%) were evaluated under the following conditions. The results are also shown in Table 8.

(Evaluation of developability of negative resist)
Each resin composition solution was applied onto a 10 cm square glass substrate by a spin coater and dried in an oven at 80 ° C. for 3 minutes. After drying, an intensity of 50 mJ / cm ² by a UV aligner (TME-150RNS, manufactured by TOPCON) equipped with a 2.0 kW ultrahigh pressure mercury lamp with a pattern photomask of 8 μmφ placed at a distance of 100 μm from the coating film (365
Ultraviolet rays were irradiated in terms of nm illuminance. After UV irradiation, 0.05% potassium hydroxide aqueous solution is sprayed on the coating film with a spin developing machine for 40 seconds to dissolve and remove the unexposed area, and the remaining exposed area is washed with pure water for 10 seconds. Developed.
As adhesion, the presence or absence of a spacer defect after development was evaluated with a laser microscope (VK-9700, manufactured by Keyence Corporation). No defect was indicated by ○, partial defect was indicated by Δ, and all defects were indicated by ×.

  Further, the developed spacer was heated on a hot plate at 230 ° C. for 30 minutes, and the spacer diameter and height thereafter were evaluated with the laser microscope.

(Compression rate / elastic recovery rate)
The developed spacer was heated at 230 ° C. for 30 minutes to obtain a spacer having a bottom diameter of 5.9 to 7.7 μm and a height of 3.6 μm. With respect to this spacer, a load of up to 80 mN was applied using a micro compression tester (HM2000, manufactured by Fischer Instruments Co., Ltd.) with a flat indenter having a diameter of 100 μm, with both loading speed and unloading speed set to 4.7 mN / sec. After that, it was unloaded to 0.49 mN. A load-deformation curve at the time of loading and unloading was created, and the compression rate and the elastic recovery rate were obtained using the above formulas.

  The curable resin composition of this invention can be used suitably for manufacture of the columnar spacer of a liquid crystal cell.

Claims (10)

  A curable resin composition for a photospacer used for the production of a columnar spacer of a liquid crystal cell, comprising a monomer capable of introducing an acid group and a monomer containing two or more aromatic rings as essential monomers A photosensitive polymer obtained by reacting a radical polymerizable unsaturated double bond and a compound having a functional group capable of reacting with the acid group of the acid group-containing polymer synthesized from the above, a polyfunctional monomer, A curable resin composition for a photospacer, comprising a photopolymerization initiator.   2. The curable resin composition for a photospacer according to claim 1, wherein a monomer containing two or more aromatic rings is 5 to 70% by mass in 100% by mass of the monomer component.   The curable resin composition for a photospacer according to claim 1 or 2, wherein the monomer containing two or more aromatic rings is a biphenyl group-containing monomer.   The curability for photospacer according to any one of claims 1 to 3, wherein the polyfunctional monomer is 45 mass% to 90 mass% when the total of the photosensitive polymer and the polyfunctional monomer is 100 mass%. Resin composition.   The curable resin composition for a photospacer according to any one of claims 1 to 4, wherein the monomer component further contains a monomer capable of introducing a ring structure into the main chain.   The curable resin composition for a photospacer according to claim 5, wherein the monomer capable of introducing a ring structure into the main chain is an N-substituted maleimide.   The curable resin composition for a photospacer according to any one of claims 1 to 6, further comprising an ultraviolet absorber having a maximum absorption wavelength at a wavelength of 280 to 380 nm.   The curable resin composition for a photospacer according to any one of claims 1 to 7, wherein the acid value of the photosensitive polymer is 20 to 180 mgKOH / g.   A columnar spacer, which is obtained by curing the curable resin composition for a photospacer according to claim 1.   A liquid crystal display using the columnar spacer according to claim 9.