JP2009031778A - Photosensitive composition, method, cured product, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition which is suitable for use in the formation of a spacer or the like in liquid crystal display devices such as liquid crystal display, and is excellent in production stability particularly in simultaneous formation of cured products having mutually different height using an identical material by photolithography. <P>SOLUTION: The photosensitive composition is characterized in that, in a percentage residual film-exposure curve obtained by plotting a percentage residual film [t(%)] of exposed area against the logarithm of exposure [logE (mJ/cm<SP>2</SP>)], the γ value of a straight line of the formula (1): t=γlogE+δ formed by connecting a percentage residual film point of 60% to a percentage residual film point of 90% is ≥15 and <45, wherein, when an image is formed through a negative-mask pattern, the percentage residual film t(%) is represented by the following equation: Percentage residual film [t(%)]=ä(height of pattern at each exposure)/(height of pattern at exposure of 1,000 mJ/cm<SP>2</SP>)}×100. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photosensitive composition and the like. More specifically, for example, in a liquid crystal display device such as a liquid crystal display, the present invention relates to a photosensitive composition preferably used for a method of simultaneously forming cured products having different heights such as spacers and ribs with the same material, and the method thereof.

  Conventionally, a photosensitive composition comprising a resin, a photopolymerizable monomer, a photopolymerization initiator, and the like has been used to form a pixel layer, a black matrix, an overcoat, a rib, a spacer, and the like of a liquid crystal display. As such a photosensitive composition, various compositions have been proposed from the viewpoints of developability, pattern accuracy, adhesion, and the like.

  In recent years, liquid crystal displays have become larger and lower in cost, and accordingly, improvement in productivity has been demanded, and the sensitivity of photosensitive compositions used to form various components necessary for display manufacturing has also increased. There is also a need for more efficient production processes. However, on the other hand, since liquid crystal displays are also becoming higher in definition, further manufacturing stability is required. Various compositions and techniques have been studied in order to achieve both manufacturing efficiency and manufacturing stability at a high level.

  As one method for achieving high production efficiency, Patent Documents 1 to 4 disclose a method in which cured products having different heights are simultaneously formed of the same material by a photolithography method.

  According to this method, a cured product having a different height, which has been conventionally formed by a photolithography method of at least two steps, can be formed in one step, so that significant production efficiency can be achieved. As a technique used for these, there is disclosed a method of using an exposure mask having a light shielding portion that blocks light transmission and an opening portion that transmits light as the exposure mask, and the light transmittance of some of the openings is controlled. Has been.

  On the other hand, as one of the indexes representing the properties of the composition, Patent Document 5 proposes a negative blue-violet laser photosensitive composition in which a γ value is defined.

JP 2003-344860 A JP 2004-45757 A JP 2004-240136 A JP 2006-301148 A JP 2005-128508 A

  However, when simultaneously forming cured products with different heights using the same material by photolithography, it has been found that it is very difficult to ensure manufacturing stability even when using a conventionally known photosensitive composition. did. That is, when forming cured products having greatly different heights, a conventional photosensitive composition cannot maintain sufficient height accuracy, and as a result, the height uniformity is significantly impaired. For example, when the cured product is a spacer, height uniformity is an essential performance of the spacer, and if the height uniformity is impaired, it becomes difficult to manufacture a high-definition display. For this reason, the composition and method which can form the hardened | cured material from which height differs simultaneously with the same material, and can achieve the outstanding height precision were calculated | required.

The present invention has been made in view of such circumstances. That is, a main object of the present invention is to provide a photosensitive composition having excellent production stability in a method for simultaneously forming cured products having different heights from the same material by photolithography.
Another object of the present invention is to provide a method for simultaneously forming cured products having different heights using the same material, characterized by using such a photosensitive composition.
Another object of the present invention is to provide a cured product formed by such a photosensitive composition and method.
Still another object of the present invention is to provide a liquid crystal display device comprising a cured product having excellent height uniformity.

As a result of intensive studies on the above problems, the present inventors have completed the present invention by paying attention to the relationship between the exposure amount and the remaining film ratio.
That is, the photosensitive composition of the present invention is a photosensitive composition provided for simultaneously forming cured products having different heights from the same material, and is a logarithm of the exposure amount [log E (mJ / cm ² )]. Γ value of the straight line of the following formula (1) connecting the points of 60% and 90% of the remaining film rate in the remaining film rate-exposure curve in which the remaining film rate [t (%)] of the exposed part is plotted against It is characterized by being 15 or more and less than 45.
t = γlogE + δ (1)
[Here, the remaining film ratio t (%) is expressed below when an image is formed via a negative mask pattern.
Residual film ratio [t (%)] = {(pattern height at each exposure dose) / (pattern height at exposure dose 1000 mJ / cm ² )} × 100]

Here, the double bond equivalent of the photosensitive composition is 300 or less. In the load-unloading test using a microhardness meter, the following (1) is satisfied, and the following (2) and / or (3) It is characterized in that a cured product satisfying the above can be formed.
(1) Deformation amount is 1.4 μm or more (2) Elastic recovery rate is 50% or more (3) Recovery rate is 80% or more

Moreover, in the load-unloading test using a microhardness meter, a cured product satisfying the following (2) and / or (3) and satisfying the following (4) can be formed.
(2) Elastic recovery rate is 50% or more (3) Recovery rate is 80% or more (4) Bottom cross-sectional area is 25 μm ² or less

Furthermore, it is a photosensitive composition provided for simultaneously forming cured products having different heights from the same material, and uses a forming method that includes an exposure process using an exposure mask only once. It is characterized by that.
The exposure mask has a light shielding portion that blocks light transmission and a plurality of openings that transmit light, and the average light transmittance of some openings is smaller than the average light transmittance of other openings. It is characterized by.
On the other hand, the method of simultaneously forming the cured products having different heights of the present invention with the same material, the residual film ratio [t (%)] of the exposed portion with respect to the logarithm of the exposure amount [log E (mJ / cm ² )]. Use a photosensitive composition in which the γ value of the straight line of the following formula (1) connecting the points of 60% and 90% of the remaining film ratio in the plotted remaining film ratio-exposure curve is 15 or more and less than 45. It is a feature.
t = γlogE + δ (1)
[Here, the remaining film ratio t (%) is expressed below when an image is formed via a negative mask pattern.
Residual film ratio [t (%)] = {(pattern height at each exposure dose) / (pattern height at exposure dose 1000 mJ / cm ² )} × 100]
The method is characterized by using the photosensitive composition of the present invention.
The exposure process includes only one exposure process, and the exposure process includes a light-blocking portion that blocks light transmission and a plurality of openings that transmit light, and an average light transmittance of some openings is The exposure is performed using an exposure mask smaller than the average light transmittance of the other openings.

  On the other hand, the present invention is regarded as a cured product, and the cured product of the present invention is characterized by being formed of the photosensitive composition. The cured product of the present invention is formed by the above method. Further, the present invention is regarded as a liquid crystal display device, and the liquid crystal display device of the present invention is characterized by comprising the cured product.

  According to the photosensitive composition of the present invention, excellent manufacturing stability can be realized in a method for simultaneously forming cured products having different heights from the same material by a photolithography method.

  The best mode for carrying out the present invention (hereinafter, an embodiment of the present invention) will be described in detail below. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary. The drawings used are for explaining the present embodiment and do not represent the actual size.

[1] Residual film rate-exposure curve and γ value In the photosensitive composition of the present invention, the residual film rate [t (%)] of the exposed area with respect to the logarithm of the exposure [log E (mJ / cm ² )]. The γ value of the straight line of the following formula (1) connecting the points of 60% and 90% of the remaining film ratio in the remaining film ratio-exposure curve in which is plotted is 15 or more and less than 45.
In the straight line of the following formula (1), the δ value as t when logE = 0 is not particularly meaningful in the present invention. In the present invention, the base of the logarithm is 10 (common logarithm).

t = γlogE + δ (1)
[Here, the remaining film ratio t (%) is expressed below when an image is formed via a negative mask pattern.
Residual film ratio [t (%)] = {(pattern height at each exposure dose) / (pattern height at exposure dose 1000 mJ / cm ² )} × 100]

Here, the residual film rate-exposure curve in which the residual film ratio [t (%)] of the exposed area is plotted against the logarithm of the exposure [log E (mJ / cm ² )] is ideally insufficient. The remaining film rate shows a substantially constant value close to 0% in a small exposure amount region, and the remaining film rate shows a substantially constant value of 90% or more in the exposure amount region above the minimum exposure amount where the remaining film rate is 90% or more. (In the present invention, the “pattern height at an exposure dose of 1000 mJ / cm ² ” measured when calculating the remaining film rate is considered to be given a sufficient exposure dose and ensure a sufficient remaining film rate. This is selected as the pattern height at the exposure amount to be obtained.)
Further, in the intermediate exposure amount region, it is insufficient to form a pattern with a remaining film ratio of 90% or more, but it is an area that exceeds the limit exposure amount that leaves a certain residual film ratio, and rises to the right. Shows a linear slope.
In the present invention, this linear inclination of the intermediate exposure amount region in the remaining film rate-exposure amount curve is regarded as the linear gradient γ of the equation (1) connecting the points of 60% to 90% of the remaining film rate. Stipulates a specific range of values.

The photosensitive composition of the present invention having the above-mentioned specific γ value is suitably used in a method for simultaneously forming cured products having different heights from the same material.
Here, as the cured products having different heights, for example, spacers and sub-spacers, spacers and ribs, spacers and overcoats, ribs and overcoats, spacers and blacks as members used in liquid crystal displays (liquid crystal display devices) and the like. Examples include those formed by combinations of matrices and the like. Among these combinations, a combination in which any one is a spacer is particularly preferable. In the present specification, the “spacer” is formed of a photosensitive composition and refers to a so-called columnar spacer, a photo spacer, or the like. In the present specification, the “sub-spacer” means a spacer having a pattern height slightly lower than that of the spacer. Further, the “rib” means a liquid crystal alignment control protrusion.
Each cured product is appropriately adjusted in size, shape, etc. depending on the specifications of the liquid crystal display used. For example, the spacer has a height of about 2 μm to 7 μm, and the sub-spacer is usually a spacer. The height is lower by about 0.2 μm to 1.5 μm. The rib usually has a height of about 0.5 μm to 2 μm, and the overcoat is usually formed with a thickness of about 0.5 μm to 2 μm. The black matrix usually has a height of about 0.5 μm to 3 μm.

The method of simultaneously forming these cured products having different heights with the same material by photolithography is a method mainly characterized by an exposure mask in the exposure process. For example, a method of using an exposure mask having a light-shielding portion that blocks light transmission and a plurality of openings that allow light to pass, and the average light transmittance of some openings is smaller than the average light transmittance of other openings It has been known.
This has a light-shielding portion (light transmittance 0%) and a plurality of openings, and has the highest average light transmittance (usually an opening having a light transmittance of 100%. ”) With a small average light transmittance (average light transmittance is 0% over 100%, preferably over 5% over 50%. Hereinafter referred to as“ intermediate transmission opening ”. )), Using an exposure mask. By this method, for example, in the case of a negative photosensitive composition, a difference in the residual film rate is caused by a difference in average light transmittance between the intermediate transmission opening and the complete transmission opening, that is, a difference in exposure amount. be able to.
For example, a method of creating the intermediate transmission opening by a matrix-shaped light shielding pattern having a minute polygonal light shielding unit is known. Also known is a method of controlling the light transmittance with a film of a material such as chromium, molybdenum, tungsten, or silicon as the absorber.

When an intermediate transmission opening is formed by arranging a matrix-shaped light-shielding pattern having a minute polygonal light-shielding unit such as a slit in the opening, the average light transmittance of the intermediate transmission opening is A value obtained by multiplying the transmittance of the transmission region and the transmittance of the slit region (region where the transmittance is adjusted) by the area ratio of each region is calculated and compared as the average light transmittance of the opening.
The average light transmittance of the intermediate transmission opening formed by the absorber film is determined by, for example, the absorber film on the substrate of the exposure mask during the step of forming the exposure mask having the intermediate transmission opening. At the stage where is formed, it can be measured using a normal ultraviolet spectrophotometer.
However, according to the study by the present inventors, particularly in the case of such an intermediate transmission opening, particularly when the exposure mask becomes large, due to problems such as the production accuracy of a fine matrix-shaped light shielding pattern and the film thickness accuracy of the absorber. There is a problem that it is difficult to precisely control the light transmittance of the intermediate transmission opening in the exposure mask surface.

Conventionally known photosensitive compositions are susceptible to the light transmittance accuracy of these intermediate transmission openings, and it is difficult to ensure the height accuracy of the resulting cured product, that is, production stability. As a result, it was found that it was difficult to cope with the increase in the size of the exposure mask due to the increase in the size of the liquid crystal display. However, according to the photosensitive composition of the present invention, the cured product corresponding to the intermediate transmission opening can be obtained with high accuracy even when an exposure mask having insufficient in-plane accuracy of the light transmittance of the intermediate transmission opening is used. It is possible to form well. Below, it demonstrates still in detail using a schematic diagram.
FIG. 5 is a schematic diagram showing the relationship between the remaining film ratio and the exposure amount for photosensitive compositions having different γ values. In FIG. 5, the horizontal axis represents the exposure amount E, and is represented by logarithm logE. The vertical axis is the remaining film ratio.
Here, E-1 on the horizontal axis is the exposure amount of the complete transmission opening, and E-2 is the exposure amount of the intermediate transmission opening. R-1 is the remaining film ratio of the completely transmissive opening, R-2 is the remaining film ratio of the intermediate transmissive opening in the photosensitive composition having a small γ value, and R-3 is a medium γ value. The remaining film ratio of the intermediate transmission opening in the photosensitive composition having R-4 is the remaining film ratio of the intermediate transmission opening in the photosensitive composition having a large γ value.
As can be seen from FIG. 5, the difference in the exposure amount when the exposure is performed using the exposure mask having the complete transmission opening and the intermediate transmission opening is the difference between E-1 and E-2. At this time, in the photosensitive composition having a large γ value, the remaining film ratios at E-1 and E-2 are R-1 and R-4, respectively, and are caused by the difference between the exposure amounts E-1 and E-2. The difference in the remaining film ratio, that is, the difference in the height of the cured product is represented by the difference between R-1 and R-4. That is, in the photosensitive composition having a large γ value, the difference in the height of the cured product is greatly caused by the difference in exposure amount. On the other hand, in the photosensitive composition having a small γ value, the remaining film ratios are R-1 and R-2, respectively, and the difference is minute, so that it becomes difficult to form cured products having different heights.
According to the prior art, from such a general tendency, it is considered that a photosensitive composition having a larger γ value is suitable for simultaneously forming cured products having different heights from the same material. . This is because, as described above, a large difference in the remaining film ratio, that is, a difference in the height of the cured product can be caused in accordance with the difference in exposure amount. However, according to the study by the present inventors, if the light transmittance accuracy of the intermediate transmission opening is reduced due to an increase in the size of the exposure mask or the like and the exposure amount E-2 varies, the exposure value E-2 has a large γ value. When the photosensitive composition is used, the residual film ratio R-4 fluctuates greatly even with a slight difference in exposure amount, and as a result, the height accuracy of the cured product formed at the intermediate transmission opening is lowered. It has been found. That is, it has been found that such a photosensitive composition having a large γ value is not suitable for a method of simultaneously forming cured products having different heights from the same material.
On the other hand, when a curable composition having an intermediate γ value, that is, the photosensitive composition of the present invention having a γ value of 15 or more and less than 45, the exposure amount is E-1 and E-2. If there is, the remaining film ratio is R-1 and R-3. This composition is not only useful for forming cured products having different heights with sufficient difference, but also when the light transmittance accuracy of the intermediate transmission opening is lowered, the exposure amount E-2. Since the variation of the remaining film ratio R-3 with respect to the variation of the thickness is small, the cured material formed at the intermediate transmission opening is excellent in height accuracy, and the cured material having different heights, which is the object of the present invention, is the same material. It is very suitable for the method of forming simultaneously.
That is, the present inventors have found that the above-mentioned γ value in the residual film rate-exposure amount curve affects the magnitude of the difference in height and the production stability. It has been found that a photosensitive composition for simultaneously forming cured products having different materials can be appropriately prepared from the same material.
Here, the γ value is usually 15 or more, preferably 20 or more, and usually less than 45, preferably less than 40. When the γ value is smaller than the above, it may be difficult to obtain cured products having greatly different heights, and when the γ value is larger than the above, production stability may be difficult to obtain.
The “height accuracy” means the uniformity of the height of the formed cured product, in other words, the production stability. For example, in the case of a spacer, it is formed by the photosensitive composition of the present invention. The difference between the maximum height value and the minimum height value of the plurality of spacers that should have the same height is usually 0.20 μm or less, preferably 0.15 μm or less.

The photosensitive composition having a γ value in such a specific range includes other components such as an ethylenically unsaturated compound and a polymerizable monomer contained in the photosensitive composition, and curability of those cured products, This is achieved by a combination of various elements such as alkali solubility, swellability and oxygen barrier properties.
For example, in general, the use of a component having a high surface-curing property tends to increase the γ value, and the use of a component having a low surface-curing property (high internal curing property) tends to decrease the γ value. is there. By combining these properties, the γ value of the photosensitive composition can be appropriately adjusted to 15 or more and less than 45.
For example, when an alkali-soluble or highly swellable ethylenically unsaturated compound or polymerizable monomer is used and a tendency to decrease the γ value is observed, the surface curability has a tendency to increase the γ value. A photopolymerization initiator may be used in combination. Conversely, when an ethylenically unsaturated compound or a polymerizable monomer having low alkali solubility or swellability is used, and a tendency to increase the γ value is observed, an internal curability that tends to decrease the γ value. A high photopolymerization initiator may be used in combination. Thus, the γ value of the photosensitive composition of the present invention can be adjusted by appropriately combining and adjusting the factors that affect the γ value.

  The remaining film rate-exposure curve relating to the photosensitive composition of the present invention is prepared as follows.

[1-1] Creation of Spacer Pattern In creating the residual film rate-exposure curve relating to the photosensitive composition of the present invention, since an accuracy of the curve is required, an exposure mask having an intermediate transmission opening is used. Instead, it is preferable to obtain a curve by creating the remaining film ratio of the composition for each exposure amount by performing exposure with various exposure amounts as follows.
(1) A photosensitive composition is applied onto the ITO film of a glass substrate having an ITO film formed on the surface using a spinner.
(2) A coating film is formed by heating and drying on a hot plate at 80 ° C. for 3 minutes. The dry film thickness is adjusted to 4.3 μm.
(3) The obtained coating film is subjected to an exposure process using a circular pattern mask having an opening diameter of 6.5 μm. The exposure gap (distance between the mask and the coating surface) is 200 μm, and irradiation is performed in the air using ultraviolet light using a high-pressure mercury lamp having an intensity at 365 nm of 32 mW / cm ² as a light source. As the exposure amount, various exposure amounts up to 1000 mJ / cm ² are set.

(4) Next, using a 0.1% aqueous potassium hydroxide solution at 23 ° C., spray development is performed at a development pressure of 0.25 MPa for twice the minimum development time, and further rinsed with pure water. Here, the minimum development time means a time during which the unexposed area is completely dissolved under the same development conditions. By these operations, a pattern from which unnecessary portions are removed can be obtained.
(5) The substrate on which the pattern is formed is heated in an oven at 230 ° C. for 30 minutes to cure the pattern to obtain a substantially cylindrical spacer pattern.

[1-2] Spacer Pattern Shape Measurement For the substantially cylindrical spacer pattern, a vertical cross section passing through the central axis of the spacer pattern is profiled, and the height of the spacer pattern and the cross-sectional diameter of the lower bottom surface are measured. For the measurement, a shape measuring device such as an ultra-deep color 3D shape measuring microscope “VK-9500” manufactured by Keyence Corporation is used.
FIG. 1 is a diagram showing the shape of the substantially cylindrical spacer pattern. In FIG. 1A, a spacer pattern 1 is formed in a convex shape on a glass substrate 2 and has a substantially circular outline in plan view.
FIG. 1B is a cross-sectional view taken along the line XX passing through the central axis 3 of the spacer pattern 1 of FIG. In FIG. 1B, the spacer pattern 1 has a substantially rectangular outline. Such an outline is defined as a profile 4 of the spacer pattern 1, and intersections between the pattern side surface 41 of the profile 4 and the glass substrate 2 are defined as intersections A and A ′. The distance from the surface of the glass substrate 2 to the highest point of the profile 4 is the pattern height H, and the distance between the intersection A and the intersection A ′ is the lower cross-sectional diameter L.

[1-3] Creation of remaining film rate-exposure curve From the results of spacer pattern creation and shape measurement performed based on [1-1] and [1-2], a remaining film rate-exposure curve is obtained. create. By plotting the remaining film rate [t (%)] of the spacer pattern calculated from the pattern height against the logarithm [log E (mJ / cm ² )] of various exposure amounts, a remaining film rate-exposure curve Is obtained.
In the photosensitive composition of the present invention, the γ value (straight line) of the straight line of the following formula (1) connecting the points of 60% and 90% of the remaining film ratio in this curve is 15 or more and less than 45. Become.
t = γlogE + δ (1)
[Here, the remaining film ratio t (%) is expressed below when an image is formed via a negative mask pattern.
Residual film ratio [t (%)] = {(pattern height at each exposure dose) / (pattern height at exposure dose 1000 mJ / cm ² )} × 100]

[2] Double bond equivalent The photosensitive composition of the present invention has a smaller double bond equivalent, that is, the greater the number of double bonds per unit weight, the greater the elastic recovery rate and recovery rate of the resulting cured product. Therefore, it is preferable. A cured product having excellent elastic recovery rate and recovery rate is particularly suitable for a spacer among photosensitive compositions for liquid crystal display devices.
Here, the double bond equivalent of the compound is the weight per mole of the double bond of the compound, calculated by the following formula (2), and the value of the double bond equivalent as the double bond per unit weight increases. Becomes smaller.
Compound double bond equivalent = weight of compound (g) / number of moles containing double bond of compound (2)

On the other hand, the double bond equivalent of the photosensitive composition means the double bond equivalent of the solid content in the composition.
The double bond equivalent of the photosensitive composition is preferably 300 or less, more preferably 250 or less. The lower limit of the double bond equivalent is usually 100 or more. When the double bond equivalent is smaller than this, the curing shrinkage of the double bond is too large, and the adhesion to the substrate may be lowered.
Here, the double bond equivalent of the photosensitive composition can be calculated by the above formula (2) from the charged amount of the compound having an ethylenic double bond when the photosensitive composition is prepared.

  The double bond equivalent of the photosensitive composition is determined by measuring the double bond equivalent of the entire photosensitive composition including the solvent by a known method such as NMR method or titration method, and then the solid content concentration of the photosensitive composition. Can be measured by a known method and calculated by the following formula (3).

Double bond equivalent of photosensitive composition = double bond equivalent of the entire photosensitive composition × solid content concentration
... (3)
The double bond equivalent of the photosensitive composition can be adjusted by adjusting the type and blending ratio of the ethylenically unsaturated compound and polymerizable monomer described later.

[3] Total deformation, elastic recovery rate, recovery rate The photosensitive composition of the present invention satisfies the following (1) in the load-unloading test with a microhardness meter, particularly when used for spacer applications, and It is preferable that a cured product satisfying (2) and / or (3) can be formed.
(1) Deformation amount is 1.4 μm or more (2) Elastic recovery rate is 50% or more (3) Recovery rate is 80% or more

  For example, a spacer used in a liquid crystal display device (hereinafter sometimes referred to as a “panel”) of a large-sized liquid crystal screen television is easily subjected to a load in the manufacturing process of the panel, and the total deformation amount of the spacer is large. Tend to be. In particular, in a large screen panel, the load tends to be uneven in each part. Even in such a case, the photosensitive composition of the present invention is significant in that the cured product (spacer) has a high elastic recovery rate and / or high recovery rate.

Here, the load-unloading test using the micro hardness tester is a spacer pattern created by referring to the spacer pattern creation method and spacer pattern shape measurement method described in the above [1-1] and [1-2] columns. Among these, one pattern having a height of 4 ± 0.3 μm and a bottom cross-sectional area of 200 ± 20 μm ² is performed. Preferably, the test is repeated three times, and the test results of a total of three spacer patterns are averaged to obtain a measured value. Here, the bottom cross-sectional area is obtained from the lower cross-sectional diameter L.

  As the microhardness meter for the load-unloading test, for example, Shimadzu Corp. (Shimadzu dynamic ultra microhardness meter DUH-W201S) is used. The test conditions were a measurement temperature of 23 ° C. and a flat indenter with a diameter of 50 μm. A load was applied to the spacer at a constant speed (0.22 gf / sec). When the load reached 5 gf, the load was held for 5 seconds, and then the same speed. Unload at.

  FIG. 2 is a load-displacement curve in this case. The horizontal axis is displacement H, the vertical axis is weight L, and the relationship between the weight and displacement when a load is applied to the spacer is shown. From the load-displacement curve as shown in FIG. 2, the maximum displacement H [max] and the final displacement H [Last] are measured. The maximum displacement H [max] is defined as the total deformation amount.

  In the present invention, the total deformation amount is preferably 1.4 μm or more, more preferably 1.5 μm or more, preferably 2 μm or less, more preferably 1.8 μm or less.

  If the total deformation amount is too large, the elastic recovery rate and / or the recovery rate tends to deteriorate. On the other hand, if the total deformation amount is too small, the cured product tends to be difficult to cope with load unevenness during panel manufacture.

The elastic recovery rate and recovery rate are calculated by the following formulas (4) and (5), respectively, based on the values measured by the load-unloading test using the micro hardness tester.
Elastic recovery rate (%) = {(maximum displacement H [max] −final displacement H [Last]) / maximum displacement H [max]} × 100 (4)
Recovery rate (%) = {(pattern height before test) −final displacement H [Last]} / (pattern height before test)} × 100 (5)

  The elastic recovery rate is preferably 50% or more, more preferably 60% or more. Further, the recovery rate is preferably 80% or more, and more preferably 85% or more. If the elastic recovery rate and / or the recovery rate is too small, the cured product tends to be difficult to cope with load unevenness during panel manufacture.

[4] Bottom sectional area, elastic recovery rate, recovery rate The photosensitive composition of the present invention can also satisfy the following (2) and / or (3) and form a cured product satisfying the following (4). Is preferred.
(2) Elastic recovery rate is 50% or more (3) Recovery rate is 80% or more (4) Bottom cross-sectional area is 25 μm ² or less

  For example, in a screen panel of a cellular phone, pixels are designed to be small in order to perform high-definition display, but a spacer provided for this needs to have a small bottom area so as not to damage the image. . On the other hand, a product such as a mobile phone is easily subjected to an impact during use, and thus is easily loaded. Even in such a case, the photosensitive composition of the present invention is significant in that the cured product (spacer) has a high elastic recovery rate and / or recovery rate.

In the present invention, the bottom cross-sectional area means that when nine of the spacer patterns having different bottom cross-sectional areas formed as described above are simultaneously formed, the pattern height is 3 μm or more and there are nine. Under the condition that eight or more patterns of the same size spacer pattern are formed (that is, the number of missing patterns among the nine patterns to be formed is one or less), the minimum pattern size Refers to the bottom cross-sectional area. This bottom cross-sectional area can be used as an index of adhesion.
The bottom cross-sectional area is preferably 25 μm ² or less, more preferably 20 μm ² or less, preferably 1 μm ² or more, more preferably 5 μm ² or more. If the bottom cross-sectional area is too large, it may not be suitable for a panel such as a cellular phone having a small pixel. On the other hand, if the bottom cross-sectional area is too small, it may be difficult to obtain a sufficient elastic recovery rate and / or recovery rate.

  The elastic recovery rate and recovery rate are calculated in the same manner as described above based on the values measured by the load-unloading test using the micro hardness tester. The elastic recovery rate is preferably 50% or more, and more preferably Is 60% or more, and the recovery rate is preferably 80% or more, more preferably 85% or more. If the elastic recovery rate and / or recovery rate is too small, the cured product tends to be difficult to cope with a load such as a panel impact.

[5] Photosensitive composition The photosensitive composition of the present invention is not particularly limited, but can be obtained by appropriately blending the following components. Hereinafter, each component will be described.
[5-1] Photopolymerization initiator system [5-2] Amino compound [5-3] Ethylenically unsaturated compound [5-4] Polymerizable monomer [5-5] Other components In the present invention, “( “Meth) acryl” means “acryl and / or methacryl”, and “total solids” means the total amount of components of the photosensitive composition excluding the solvent.

[5-1] Photopolymerization initiator system The photosensitive composition of the present invention contains a photopolymerization initiator and, if necessary, from the viewpoint of effectively expressing the above-mentioned residual film ratio-exposure amount characteristics. It is preferable that a photopolymerization initiator system comprising a hydrogen donating compound and / or a thermal polymerization initiator is included.
The photopolymerization initiator used in the present invention is not particularly limited as long as it is a compound that polymerizes an ethylenically unsaturated group with actinic rays, and a known photopolymerization initiator can be used.

Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.
2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 -Halomethylated triazine derivatives such as ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine;
2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′-benzofuryl) vinyl] -1,3,4-oxa Halomethylated oxadiazole derivatives such as diazole;
2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole dimer, 2- ( Hexaarylbiimidazole derivatives such as 2′-fluorophenyl) -4,5-diphenylimidazole dimer;
Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone;
Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;
2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p -Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl- [ Acetophenone derivatives such as 4- (methylthio) phenyl] -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone;
Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;
benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate;
Acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine;
Phenazine derivatives such as 9,10-dimethylbenzphenazine;
Anthrone derivatives such as benzanthrone;
Dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bis-phenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, Dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadienyl-Ti-2,6-di-fluoro-3- (pyru-1-yl ) -Titanocene derivatives such as phen-1-yl;
Acetophenone oxime-o-acetate, 1,2-octanedione-1- [4- (phenylthio) -2- (o-) described in JP 2000-80068 A, JP 2006-036750 A, etc. Benzoyloxime)], 1- [9-ethyl-6- (2-benzoyl) -9H-carbazol-3-yl] ethanone-1- (o-acetyloxime) and the like.

In addition, photopolymerization initiators that can be used in the present invention are described in Fine Chemical, March 1, 1991, Vol. 20, no. 4, P16 to P26, JP-A-59-152396, JP-A-61-151197, JP-B-45-37377, JP-A-58-40302, JP-A-10-39503, etc. It is also described in.
As described above, the photopolymerization initiator may be appropriately selected and used according to the γ value required for the photosensitive composition to be prepared.

  One of these photopolymerization initiators may be included alone in the photosensitive composition, or two or more thereof may be included.

  The photopolymerization initiator system used in the present invention may be used in combination with the following hydrogen donating compounds for the purpose of improving sensitivity.

Examples of the hydrogen donating compound include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline. , Β-mercaptonaphthalene, ethylene glycol dithiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate and other mercapto group-containing compounds;
Polyfunctional thiol compounds such as hexanedithiol, trimethylolpropane tristhioglyconate, pentaerythritol tetrakisthiopropionate;
N, N-dialkylaminobenzoic acid ester, N-phenylglycine, N-phenylglycine derivatives such as ammonium salt and sodium salt;
Derivatives such as phenylalanine, ammonium salts and sodium salts of phenylalanine;
And derivatives such as phenylalanine esters. These can be used alone or in combination of two or more.

Among these, from the viewpoint of the sensitivity of the photosensitive composition, mercapto group-containing heterocyclic compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole are preferable.
And from the viewpoint of the rectangularity of the pattern, one or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole, and the hexaarylbiimidazole derivative are combined. Thus, it is suitable for use in the photopolymerization initiator system in the present invention.

In addition, the content of these photopolymerization initiator systems (the total amount when two or more are used) is usually 0.01% with respect to the total solid content of the photosensitive composition of the present invention. % Or more, preferably 0.1% by weight or more, more preferably 0.5% by weight or more, and usually 30% by weight or less, preferably 20% by weight or less. If the content of the photopolymerization initiator system is excessively large, adhesion to the substrate may be reduced. On the other hand, if the amount is too small, curability may be lowered.
Moreover, as a compounding ratio of the photopolymerization initiator system to the ethylenically unsaturated compound described later, the value of (ethylenically unsaturated compound) / (photopolymerization initiator system) (weight ratio) is usually 1/1 to 100. / 1, preferably 2/1 to 50/1. If the blending ratio deviates from the above range, adhesion and curability may be lowered.
Furthermore, you may mix | blend a thermal-polymerization initiator with the photoinitiator system used in this invention. Specific examples of such a thermal polymerization initiator include azo compounds, organic peroxides, hydrogen peroxide, and the like. These can be used alone or in combination of two or more.

[5-2] Amino compound The photosensitive composition of the present invention preferably contains an amino compound from the viewpoint of suppressing thermal shrinkage during the thermosetting process. By adding an amino compound, thermosetting is promoted, and height fluctuation during thermosetting can be suppressed.

  The content of the amino compound is usually 40% by weight or less, preferably 30% by weight or less, based on the total solid content. Moreover, it is 0.5 weight% or more normally, Preferably it is 1 weight% or more. When the content is excessively large, the storage stability of the photosensitive composition may be deteriorated. Moreover, when there is too little content, the thermal contraction inhibitory effect in said thermosetting may become low.

Examples of such an amino compound include an amino compound having at least two methylol groups as functional groups or alkoxymethyl groups obtained by condensation-modifying alcohols having 1 to 8 carbon atoms.
More specifically, for example, a melamine resin obtained by polycondensation of melamine and formaldehyde;
Benzoguanamine resin obtained by polycondensation of benzoguanamine and formaldehyde;
Glycoluril resin obtained by polycondensation of glycoluril and formaldehyde;
Urea resin obtained by polycondensation of urea and formaldehyde;
Examples thereof include a resin obtained by copolycondensation of two or more types such as melamine, benzoguanamine, glycoluril, or urea and formaldehyde, or a modified resin obtained by condensation-modifying alcohol on the methylol group of these resins. These can be used alone or in combination of two or more.

  Among them, in the present invention, a melamine resin and a modified resin thereof are preferable, a modified resin having a methylol group modification ratio of 70% or more is more preferable, and a modified resin of 80% or more is particularly preferable.

Specific examples of the amino compound include melamine resins and modified resins thereof, for example, “Cymel” (registered trademark) 300, 301, 303, 350, 736, 738, 370, 771, 325, 327 manufactured by Mitsui Cytec. , 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, and “Nikarak” (registered trademark) MW-390, MW- manufactured by Sanwa Chemical Co., Ltd. 100LM, MX-750LM, MW-30M, MX-45, MX-302 and the like.
Moreover, as said benzoguanamine resin and its modified resin, "Cymel" (trademark) 1123, 1125, 1128 etc. are mentioned, for example.
Examples of the glycoluril resin and modified resins thereof include “Cymel” (registered trademark) 1170, 1171, 1174, 1172, “Nicarak” (registered trademark) MX-270, and the like.
Examples of the urea resin and its modified resin include “UFR” (registered trademark) 65 and 300 manufactured by Mitsui Cytec Co., Ltd., “Nikarak” (registered trademark) MX-290, and the like.

  Among them, from the viewpoint of reducing the heat shrinkage rate and improving the heat curing rate, in the present invention, “Nikarak” (registered trademark) MW-390, MW-100LM, MX-750LM, MW-30M manufactured by Sanwa Chemical Co., Ltd. , MX-45 and MX-302 are particularly preferably used.

[5-3] Ethylenically unsaturated compound The ethylenically unsaturated compound used in the photosensitive composition of the present invention is the photopolymerization initiator system described above when the photosensitive composition is irradiated with actinic rays. It is a compound having at least one radically polymerizable ethylenically unsaturated bond in the molecule that undergoes addition polymerization by action, and in some cases crosslinks and cures. Specific examples include the following specific ethylenically unsaturated compounds and ethylenically unsaturated group-containing resins.

[5-3-1] Specific ethylenically unsaturated compound In order to achieve the mechanical properties of the cured product, the photosensitive composition of the present invention has an ethylenically unsaturated compound having a double bond equivalent of 400 or less ( Hereinafter, it may be referred to as “specific ethylenically unsaturated compound”).
The smaller the double bond equivalent of the specific ethylenically unsaturated compound used in the present invention and the more double bonds per unit weight, the greater the elastic recovery rate and recovery rate of the resulting cured product. Therefore, the double bond equivalent of the specific ethylenically unsaturated compound used in the present invention is usually 400 or less, preferably 350 or less, and more preferably 300 or less. The lower limit of the double bond equivalent of the specific ethylenically unsaturated compound is usually 100 or more.

  The specific ethylenically unsaturated compound preferably has an acid group. Here, “having an acid group” means having a group giving a value greater than 0 as an acid value determined by titration with KOH (potassium hydroxide). Specifically, it means having a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a phosphoric acid group, etc. Among them, it is particularly preferred to have a carboxyl group.

  Further, the specific ethylenically unsaturated compound is preferably obtained from an epoxy compound as described later.

The weight average molecular weight (Mw) of the specific ethylenically unsaturated compound is preferably 1,000 or more, more preferably 1,500 or more, and particularly preferably 2,000 or more. The weight average molecular weight (Mw) of the specific ethylenically unsaturated compound is usually 100,000 or less, preferably 10,000 or less. If the weight average molecular weight (Mw) of the specific ethylenically unsaturated compound is excessively small, the amount of deformation of the resulting photosensitive composition tends to be small, and if it is excessively large, the photosensitive composition tends to be poorly developed. Tend.
The weight average molecular weight (Mw) is measured as a molecular weight converted to standard polystyrene by GPC (gel permeation chromatography).

  The specific ethylenically unsaturated compound used in the present invention is not particularly limited as long as the double bond equivalent is 400 or less, but is preferably obtained from an epoxy group-containing compound. It is preferable to contain.

  Examples of the specific ethylenically unsaturated compound obtained from such an epoxy group-containing compound include compounds represented by the following general formula (AI).

[In formula (AI), R ¹¹ represents an alkylene group which may have a substituent or an arylene group which may have a substituent. R ¹² represents an ethylenically unsaturated group-containing carbonyloxy group which may have a substituent. R ¹³ and R ¹⁴ each independently represents an arbitrary substituent. n is an integer of 0-10. m is an integer of 1 or more. X represents an arbitrary organic group which may have a substituent. ]

In the general formula (AI), the alkylene group represented by R ¹¹ is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a methylene group, an ethylene group, a propylene group, or a butylene group. Moreover, as an arylene group, a C6-C10 thing is preferable and a phenylene group is still more preferable. Among these, an alkylene group is preferable in the present invention.

Examples of the substituent that the alkylene group or arylene group of R ¹¹ may have include, for example, a halogen atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, and a carbon number. Examples thereof include an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a carboxyl group, a sulfanyl group, a phosphino group, an amino group, and a nitro group.

  N is an integer of 0 to 10, preferably 0 to 5, and more preferably 0 to 3. When n exceeds the above range, when the resulting photosensitive composition is a cured product, there is a tendency that film loss or the like occurs as an image portion during development or heat resistance decreases.

In the general formula (AI), the lower limit of the carbon number of the ethylenically unsaturated group-containing carbonyloxy group which may have a substituent for R ¹² is usually 3, preferably 5, and more preferably 10. The upper limit is not particularly limited, but is preferably 50, more preferably 40, and particularly preferably 35. Whether the carbon number is excessively large or excessively small, the mechanical properties of the cured product formed by the photosensitive composition of the present invention may not be obtained.
As the ethylenically unsaturated group-containing carbonyloxy group which may have a substituent represented by R ¹² , a group represented by the following general formula (A-II) is more preferable.

[In formula (A-II), R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a methyl group, and Q represents an arbitrary divalent group. ]

  In the formula (A-II), Q preferably includes an alkylene group which may have a substituent and / or an arylene group which may have a substituent, and a carbonyloxy group. A divalent group is shown. More preferably, Q is an optionally substituted alkylene group having 1 to 10 carbon atoms and / or an optionally substituted arylene group having 1 to 10 carbon atoms, and And a carbonyloxy group.

In formula (AI), R ¹³ preferably represents a hydrogen atom, a substituent represented by the following general formula (A-IIIa), or a substituent represented by the following general formula (A-IIIb). .

[In the formulas (A-IIIa) and (A-IIIb), R ²¹ and R ²² have an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. A cycloalkyl group which may be substituted, a cycloalkenyl group which may have a substituent or an aryl group which may have a substituent. ]

Here, as the alkyl group for R ²¹ and R ²² , those having 1 to 20 carbon atoms are preferable. Moreover, as an alkenyl group, a C2-C20 thing is preferable. Moreover, as a cycloalkyl group, what is C3-C20 is preferable. Further, as the cycloalkenyl group, those having 3 to 20 carbon atoms are preferable. The aryl group is preferably one having 6 to 20 carbon atoms.

Examples of the substituent that R ²¹ and R ²² may have include, for example, a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and a phenyl group. , Carboxyl group, carbonyl group, sulfanyl group, phosphino group, amino group, nitro group and the like. Among these, R ²¹ preferably has a carboxyl group as a substituent.

Examples of the substituent represented by R ¹⁴ in the compound represented by the aforementioned general formula (A-I), is not particularly limited, for example, there are substituents represented by the following formula (A-IV) .

[In the formula (A-IV), R ¹¹ , R ¹² , R ¹³ and n are as defined in the general formula (AI). ]
Note ^that when ^{R 14} is a substituent represented by the general formula (A-IV), ^R 11 in the formula ^{(A-IV), R 12} , R 13 and n are the general formula (A-I ) May be the same as or different from R ¹¹ , R ¹² , R ¹³ and n. ]

  X in the compound represented by the general formula (AI) described above represents an arbitrary organic group which may have a substituent. This X has a basic function of bonding a double bond-containing group, and serves as a site for bonding an appropriate molecular weight and an appropriate number of substituents so as not to increase the double bond equivalent of the entire compound. There is a function to provide a functional group.

  The molecular weight of X in the compound represented by formula (AI) is usually 14 or more, preferably 28 or more, and usually 1000 or less, preferably 800 or less.

In the present invention, specific examples of the organic group that can be used as X include a linear or cyclic organic group.
Examples of the linear organic group include organic groups derived from alkanes and alkenes; (meth) acrylic acid, (meth) acrylic ester, (meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, vinyl acetate , Organic groups derived from homo- or copolymers such as vinylidene chloride and maleimide; derived from acid-modified epoxy acrylate, polyolefin, polyamide, polyester, polyether, polyurethane, polyvinyl butyral, polyvinyl alcohol, polyvinyl pyrrolidone, acetyl cellulose, etc. An organic group is mentioned.

In addition, as the cyclic organic group, an organic group derived from an alicyclic ring, an aromatic hydrocarbon ring, a heterocyclic ring or the like, or a condensed ring thereof, and these rings are bonded via a linking group. Examples include organic groups derived from things.
Among these, examples of the alicyclic ring include a cyclopentane ring, a cyclohexane ring, a cyclohexene ring, and a tricyclodecane ring.
Examples of the aromatic hydrocarbon ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, azulene ring, fluorene ring, acenaphthylene ring, biphenylene ring, indene ring and the like.
Heterocycles include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, pyridine ring, pyridazine ring, pyrimidine Ring, pyrazine ring and the like.

  Examples of the linking group via the bond of the cyclic organic group include a direct bond or a divalent or higher valent linking group. As the divalent or higher linking group, known ones can be used. For example, alkylene, polyoxyalkylene, amine, O atom, S atom, ketone group, thioketone group, -C (= O) O-, amide , Se, Te, P, As, Sb, Bi, Si, B, and other metals, heterocycles, aromatic rings, heteroaromatic rings, and any combination thereof.

  Examples of the organic group represented by X include an alkylene group having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms; an arylene group having 6 to 10 carbon atoms; and 2 to 50 carbon atoms. , Preferably a polyether having 2 to 30 carbon atoms; bisphenol such as bisphenol A and bisphenol F shown below: trisphenol; residues obtained by removing a hydroxyl group of a polyol compound such as novolak ((X-1 ) To (X-21)).

  In the exemplary formula of the organic group represented by X, z represents an integer of 0 or more. In the exemplified (X-13), (X-15), (X-18), (X-19), and (X-20), * represents a bond. In these exemplary structures, when there are three or more bonds *, the number of bonds as the linking group X covers at least two of these bonds. In this case, the substituent linked to the remaining one or more bonds is not particularly limited and is preferably a group represented by the general formula (A-IV).

  In addition, when the compound represented with the said general formula (AI) has a benzene ring, as a substituent which the benzene ring may have, for example, a C1-C15 alkyl group, carbon C1-C15 alkoxy group, C2-C15 acyl group, C6-C14 aryl group, carboxyl group, hydroxyl group, C1-C16 alkoxycarbonyl group, carboxyl Group, halogen atom and the like. Among these, a C1-C5 alkyl group, a phenyl group, and a halogen atom are still more preferable.

The method for producing the compound represented by the general formula (AI) is not particularly limited as long as the compound has a structure represented by the general formula (AI).
Here, for example, a production method using an epoxy group-containing compound represented by the following general formula (A-V) will be described as an example. That is, a compound obtained by using a compound represented by the following general formula (A-V) as a raw material, forming an ethylenically unsaturated group-containing carbonyloxy group thereon, and then forming this ethylenically unsaturated group-containing carbonyloxy group And a compound represented by the general formula (AI) by reacting with one or more compounds selected from the group consisting of a compound having a polyvalent carboxylic acid and its anhydride and an isocyanate group. it can.

[In formula (A-V), R ¹¹ , X and n are as defined in general formula (AI). R ¹⁸ has the same meaning as R ¹¹ in formula (AI). ]

Examples of the epoxy group-containing compound represented by the general formula (A-V) include (poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, ( Poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) Aliphatic polyepoxy compounds such as sorbitol polyglycidyl ether;
Phenol novolac polyepoxy compound, brominated phenol novolak polyepoxy compound, (o-, m-, p-) cresol novolac polyepoxy compound, bisphenol A polyepoxy compound, bisphenol F polyepoxy compound, bis (hydroxyphenyl) fluorene type poly Aromatic polyepoxy compounds such as epoxy compounds;
And polyepoxy compounds such as heterocyclic polyepoxy compounds such as sorbitan polyglycidyl ether, triglycidyl isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate, and the like.
The epoxy group-containing compound represented by the general formula (A-V) may be used alone or in combination of two or more.

  In addition, the lower limit of the carbon number of the ethylenically unsaturated group-containing carbonyloxy group formed in the epoxy group-containing compound represented by the general formula (A-V) is usually 3, preferably 5, and more preferably 10. . The upper limit is not particularly limited, but is preferably 50, more preferably 40, and particularly preferably 35. When the number of carbon atoms is less than the above range, when the photosensitive composition is cured, the flexibility tends to be insufficient and the adhesion to the substrate tends to be poor. On the other hand, when the carbon number is excessively large, the heat resistance tends to decrease.

  These ethylenically unsaturated group-containing carbonyloxy groups are preferably groups represented by the general formula (A-II).

Here, as a formation method of the ethylenically unsaturated group containing carbonyloxy group represented by the said general formula (A-II), as a result of the reaction which uses the compound represented by the said general formula (AV) as a raw material The method is not particularly limited as long as the ethylenically unsaturated group-containing carbonyloxy group is formed.
Specifically, a method of reacting the compound represented by the general formula (A-V) with an ethylenically unsaturated group-containing carboxylic acid (a); first, a carboxylic acid containing no ethylenically unsaturated group ( Examples thereof include a method of reacting b) and then reacting a compound (c) having a functional group that reacts with a hydroxyl group or a carboxyl group to be produced.

  Examples of the “ethylenically unsaturated group-containing carboxylic acid (a)” used in the above-described method for forming an ethylenically unsaturated group-containing carbonyloxy group include a haloalkyl group, an alkoxyl group, a halogen atom, and a nitro group at the α-position. An unsaturated monocarboxylic acid substituted with a cyano group, etc .; a reaction product of (meth) acrylic acid with a lactone or polylactone; a saturated or unsaturated dicarboxylic acid anhydride and one or more hydroxyl groups in one molecule. And a half ester obtained by reacting a (meth) acrylate derivative with a half ester obtained by reacting a saturated or unsaturated dicarboxylic acid anhydride with an unsaturated group-containing glycidyl compound.

  Here, examples of the unsaturated monocarboxylic acid in which the α-position is substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, a cyano group, etc. include acrylic acid, methacrylic acid, crotonic acid, o-, m- , P-vinylbenzoic acid and the like.

  Examples of the saturated or unsaturated dicarboxylic acid anhydride include succinic anhydride, adipic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride. Examples include acid, methylendomethylenetetrahydrophthalic anhydride, and phthalic anhydride.

  Examples of (meth) acrylate derivatives having one or more hydroxyl groups in one molecule include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and polyethylene glycol mono (meth) acrylate. Glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like.

  Examples of the unsaturated group-containing glycidyl compound include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 8,9-epoxy [bicyclo [4.3.0] non-3-yl] ( And (meth) acrylate, 8,9-epoxy [bicyclo [4.3.0] non-3-yl] oxymethyl (meth) acrylate, and the like.

In the present invention, as the “ethylenically unsaturated group-containing carboxylic acid (a)”, among these, a saturated or unsaturated dicarboxylic acid anhydride and a (meth) acrylate having one or more hydroxyl groups in one molecule A half ester obtained by reacting with a derivative is preferred.
In this case, the saturated or unsaturated dicarboxylic anhydride is preferably succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, or phthalic anhydride. In addition, (meth) acrylate derivatives having one or more hydroxyl groups in one molecule include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and pentaerythritol tri (meth) acrylate. Dipentaerythritol penta (meth) acrylate is preferred.
These ethylenically unsaturated group-containing carboxylic acids (a) may be used alone or in combination of two or more.

  Next, examples of the “carboxylic acids not containing an ethylenically unsaturated group (b)” used in the above-described method for forming an ethylenically unsaturated group-containing carbonyloxy group include hydroxyl group-containing carboxyls such as lactic acid and dihydroxypropionic acid. Examples thereof include acids and anhydrides thereof; saturated or unsaturated dicarboxylic acids such as succinic acid, maleic acid, tetrahydrophthalic acid, phthalic acid, and tartaric acid, and anhydrides thereof.

Examples of the “compound (c) having a functional group reactive with a hydroxyl group or a carboxyl group” used in the above-described method for forming an ethylenically unsaturated group-containing carbonyloxy group include an epoxy group, a carboxyl group, and an isocyanate group. The compound which has is preferable.
Specifically, compounds exemplified in the above-mentioned “ethylenically unsaturated group-containing carboxylic acid (a)”; unsaturated group-containing used for obtaining the “ethylenically unsaturated group-containing carboxylic acid (a)” Examples thereof include, but are not limited to, ethylenically unsaturated group-containing compounds such as glycidyl compounds.
The above-mentioned “carboxylic acid (b) containing no ethylenically unsaturated group” and “compound (c) having a functional group that reacts with a hydroxyl group or a carboxyl group” can be used alone or in combination of two types. You may use the above together.

In addition, as an epoxy group-containing compound represented by the general formula (A-V) as a raw material, an ethylenically unsaturated group-containing carbonyloxy group is formed thereon, and then further reacted as a polyvalent carboxylic acid or an anhydride thereof. Include the following compounds.
For example, saturated or unsaturated dicarboxylic acids such as succinic acid, maleic acid, itaconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, phthalic acid, chlorendic acid, etc. Acids and their acid anhydrides; trimellitic acid and its anhydrides; pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, etc. Examples thereof include tetracarboxylic acids and acid anhydrides thereof.

Among these, as a photosensitive composition, dicarboxylic acids such as oxalic acid, tetrahydrophthalic acid, and phthalic acid, and acid anhydrides thereof, trimellitic acid and acids thereof from the viewpoint of dissolution and removal of non-image areas during alkali development. Preference is given to tetracarboxylic acids such as anhydrides, pyromellitic acid, biphenyltetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, and acid dianhydrides thereof.
Furthermore, among these, acid anhydrides of polycarboxylic acids having an acid dissociation constant (first dissociation constant) of 3.5 or more are preferable. The acid dissociation constant is preferably 3.8 or more, and particularly preferably 4.0 or more. Examples of acid anhydrides of polyvalent carboxylic acids having an acid dissociation constant (first dissociation constant) of 3.5 or more include, for example, acid anhydrides of succinic acid, acid anhydrides of tetrahydrophthalic acid, 1, 2, An acid dianhydride of 3,4-butanetetracarboxylic acid may be mentioned. Of these, succinic acid anhydride and tetrahydrophthalic acid anhydride are particularly preferred.

Here, for the acid dissociation constant, reference can be made to Determination of Organic Structures by Physical Methods, Academic Press, New York, 1955 (Brown, HC, et al.).
Further, from the viewpoint of the storage stability of the photosensitive composition, it is preferable to use dicarboxylic acids such as succinic acid, tetrahydrophthalic acid, and phthalic acid, their acid anhydrides, trimellitic acid, and their acid anhydrides.
The selection of the carboxylic acid and its anhydride is appropriately adjusted according to the required properties of the photosensitive composition.
In the present invention, these polycarboxylic acids and acid anhydrides thereof may be used alone or in combination of two or more.

Moreover, the following compounds are mentioned as a compound which has the isocyanate group made to react after forming an ethylenically unsaturated group containing carbonyloxy group in the epoxy group containing compound represented by the said general formula (AV). It is done.
For example, organic monoisocyanates such as butane isocyanate, 3-chlorobenzene isocyanate, cyclohexane isocyanate, 3-isopropenoyl-α, α-dimethylbenzyl isocyanate;
Aromatic diisocyanates such as paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, tolidine diisocyanate;
Aliphatic diisocyanates such as hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate;
Cycloaliphatic diisocyanates such as isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), ω, ω′-diisocyanate dimethylcyclohexane;
Aliphatic diisocyanates having an aromatic ring such as xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate;
Lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanate phenylmethane), Triisocyanates such as tris (isocyanatophenyl) thiophosphate;
Furthermore, the trimer of the isocyanate compound mentioned above, a water adduct, these polyol adducts, etc. are mentioned.

  Among these, diisocyanate di- or trimer and these polyol adducts are preferable, and trimethylolpropane adduct of tolylene diisocyanate, trimer of tolylene diisocyanate, and trimer of isophorone diisocyanate are most preferable. In addition, the said compound may be used individually by 1 type, or may use 2 or more types together.

  The acid value of the compound represented by formula (AI) used in the present invention is preferably 30 mg-KOH / g to 150 mg-KOH / g, more preferably 40 mg-KOH / g. g to 100 mg-KOH / g.

An example of a specific method for synthesizing the compound represented by formula (AI) used in the present invention is as follows.
For example, based on a conventionally known method described in JP-A-4-355450, an epoxy compound dissolved in an organic solvent and the ethylenically unsaturated group-containing carboxylic acid are mixed with a predetermined catalyst and a thermal polymerization inhibitor. The target compound can be synthesized by performing an addition reaction at a predetermined temperature in the coexistence, and then continuing the reaction by adding a polyvalent carboxylic acid or an anhydride thereof.

Here, examples of the organic solvent include methyl ethyl ketone, ethyl cellosolve acetate, butyl cellosolve acetate and the like.
Examples of the catalyst include tertiary amines such as triethylamine, benzyldimethylamine, and tribenzylamine; fourth catalysts such as tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, and trimethylbenzylammonium chloride. Secondary ammonium salts; Phosphorus compounds such as triphenylphosphine; and stibins such as triphenylstibine.
Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, and the like.

In addition, the ethylenically unsaturated group-containing carboxylic acid is usually 0.8 chemical equivalent to 1.5 chemical equivalents, preferably 0.9 chemical equivalents to 1.1 chemical equivalents per one chemical equivalent of the epoxy group of the epoxy compound. An equivalent amount is added.
The addition reaction of the bis (hydroxyphenyl) fluorene type epoxy compound and the ethylenically unsaturated group-containing carboxylic acid is usually performed at a temperature of 60 ° C to 150 ° C, preferably 80 ° C to 120 ° C.
In addition, the polyvalent carboxylic acid or its anhydride is usually 0.05 chemical equivalent to 1.0 chemical equivalent to 1 chemical equivalent of the hydroxyl group generated by the addition reaction of the epoxy compound and the ethylenically unsaturated group-containing carboxylic acid. It is added in an amount equivalent to an equivalent, preferably 0.5 chemical equivalent.

  In the present invention, the compound represented by the general formula (AI) synthesized in this way is generally affected by the influence of the mixture contained in the raw material and thermal polymerization during the reaction of double bonds. A compound other than the compound represented by the formula (AI) may be included.

  Examples of the specific ethylenically unsaturated compound used in the present invention include compounds represented by the following general formula (A-VI) in addition to the compounds represented by the above general formula (AI).

Wherein ^{(A-VI), R 12} , R 13, R 14 has the same meaning as respective formulas (A-I) definitive meaning. ]

The method for producing the compound represented by the general formula (A-VI) is not particularly limited as long as it is a method capable of obtaining a compound having a structure represented by the general formula (A-VI).
For example, as in the case of the method for producing the compound represented by the general formula (AI) described above, diglycidyl ether is used as a raw material, and an ethylenically unsaturated group-containing carbonyloxy group is formed thereon. Examples thereof include a production method in which one or more compounds selected from a compound having a carboxylic acid and its anhydride and an isocyanate group are reacted.

  In the photosensitive composition of the present invention, the specific ethylenically unsaturated compound having a double bond equivalent of 400 or less can be used alone or as a mixture of two or more.

  The content of the specific ethylenically unsaturated compound in the photosensitive composition of the present invention is usually 25% by weight or more, preferably 35% by weight or more, more preferably 45%, based on the total solid content in the photosensitive composition. % By weight or more. Moreover, it is 70 weight% or less normally. The greater the content of the specific ethylenically unsaturated compound, the greater the total deformation amount of the cured product described later, which is preferable. On the other hand, if the content is excessively small, it tends to be difficult to increase the total deformation amount of the cured product. For example, it may be difficult to sufficiently ensure the function as a spacer.

[5-3-2] Ethylene Unsaturated Group-Containing Resin The photosensitive composition of the present invention comprises ethylene in addition to or in place of the specific ethylenically unsaturated compound of [5-3-1] described above. An unsaturated group-containing resin (hereinafter sometimes simply referred to as a resin) may be contained. As resin mix | blended, 1 type (s) or 2 or more types of resin which has at least 1 ethylenically unsaturated group can be used among resin used for the well-known liquid crystal display device.

Examples of such resins include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride, maleimide, etc. Compound: Acid-modified epoxy acrylate, polyamide, polyester, polyether, polyurethane, polyvinyl butyral, polyvinyl alcohol, polyvinyl pyrrolidone, acetyl cellulose, and the like.
Among these, from the viewpoint of alkali developability and the like, [A-1] a carboxyl group-containing vinyl resin having an ethylenically unsaturated group in the side chain and [A-2] acid-modified epoxy (meth) acrylate are preferable. is there.

[A-1] Carboxyl group-containing vinyl resin having an ethylenically unsaturated group in the side chain [A-1] As a carboxyl group-containing vinyl resin having an ethylenically unsaturated group in the side chain used in the present invention, [A-1-1] Reaction product of carboxyl group-containing vinyl resin and epoxy group-containing unsaturated compound, [A-1-2] Compound having two or more unsaturated groups and unsaturated carboxylic acid or unsaturated compound. A copolymer with a saturated carboxylic acid ester and [A-1-3] E-R-N-T resin are mentioned.

[A-1-1] Reaction product of carboxyl group-containing vinyl resin and epoxy group-containing unsaturated compound As the carboxyl group-containing vinyl resin used in the present invention, specifically, unsaturated carboxylic acid and vinyl Examples include copolymers with compounds.
Here, examples of the unsaturated carboxylic acid include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, and the like.

  Examples of the vinyl compound include styrene, α-methylstyrene, hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl. (Meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl ( (Meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- (meth) acryloylmorpholine, (meta Acrylonitrile, (meth) acrylamide, N- methylol (meth) acrylamide, N, N- dimethyl (meth) acrylamide, N, N- dimethylaminoethyl (meth) acrylamide, vinyl acetate, and the like.

  Among the carboxyl group-containing vinyl resins, a (meth) acrylate- (meth) acrylic acid copolymer and a styrene- (meth) acrylate- (meth) acrylic acid copolymer are preferable. In the (meth) acrylate- (meth) acrylic acid copolymer, a copolymer composed of (meth) acrylate 5 mol% to 80 mol% and (meth) acrylic acid 20 mol% to 95 mol% is prepared. More preferably, a copolymer composed of (meth) acrylate 10 mol% to 90 mol% and (meth) acrylic acid 10 mol% to 90 mol% is particularly preferable.

In the styrene- (meth) acrylate- (meth) acrylic acid copolymer, styrene 3 mol% to 60 mol%, (meth) acrylate 10 mol% to 70 mol%, and (meth) acrylic acid 10 mol. % To 60 mol% is more preferable, styrene 5 mol% to 50 mol%, (meth) acrylate 20 mol% to 60 mol%, and (meth) acrylic acid 15 mol% to 55 mol%. A copolymer consisting of
In addition, the acid value of these carboxyl group-containing vinyl resins is adjusted according to the amount of the epoxy group-containing unsaturated compound to be reacted with these and the acid value required in the resulting reaction product, Usually, it is 50 mg-KOH / g-500 mg-KOH / g. The weight average molecular weight (Mw) in terms of standard polystyrene of the carboxyl group-containing vinyl resin is preferably 1,000 to 300,000.
The weight average molecular weight (Mw) is measured as a molecular weight converted to standard polystyrene by GPC (gel permeation chromatography).
Examples of the epoxy group-containing unsaturated compound include an aliphatic epoxy group-containing unsaturated compound and an alicyclic epoxy group-containing unsaturated compound. Examples of the aliphatic epoxy group-containing unsaturated compound include allyl glycidyl ether. Glycidyl (meth) acrylate, α-ethyl glycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, itaconic acid monoalkyl monoglycidyl ester, fumarate monoalkyl monoglycidyl ester, maleic acid monoalkyl A monoglycidyl ester etc. are mentioned.

  Examples of the alicyclic epoxy group-containing unsaturated compound include 3,4-epoxycyclohexylmethyl (meth) acrylate, 2,3-epoxycyclopentylmethyl (meth) acrylate, 7,8-epoxy [tricyclo [5.2. .1.0] dec-2-yl] oxymethyl (meth) acrylate and the like.

The carboxyl group-containing vinyl resin and the epoxy group-containing unsaturated compound are an epoxy group-containing unsaturated compound having a carboxyl group-containing vinyl resin content of 5 mol% to 90 mol%, preferably about 30 mol% to 70 mol%. The reaction is carried out at a ratio of saturated compounds. The reaction can be carried out by a known method.
The acid value of the reaction product of the [A-1-1] carboxyl group-containing vinyl resin and the epoxy group-containing unsaturated compound is preferably 30 mg-KOH / g to 250 mg-KOH / g. The weight average molecular weight (Mw) in terms of standard polystyrene is preferably 1,000 to 300,000.

[A-1-2] Copolymer of compound having two or more unsaturated groups and unsaturated carboxylic acid or unsaturated carboxylic acid ester [A-1] Carboxyl having ethylenically unsaturated group in side chain Examples of the group-containing vinyl resin also include a copolymer of a compound having two or more unsaturated groups and an unsaturated carboxylic acid or an unsaturated carboxylic ester.
Examples of the compound having two or more unsaturated groups include allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) acrylate, and methallyl (meth) ) Acrylate, N, N-diallyl (meth) acrylamide, vinyl (meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate, vinyl crotonate, vinyl (Meth) acrylamide etc. are mentioned.

Examples of the unsaturated carboxylic acid or unsaturated carboxylic acid ester include (meth) acrylic acid or (meth) acrylic acid ester.
The proportion of the compound having two or more kinds of unsaturated groups in the entire copolymer is about 10 mol% to 90 mol%, preferably about 30 mol% to 80 mol%.
[A-1-2] The acid value of the copolymer of the compound having two or more unsaturated groups and the unsaturated carboxylic acid or unsaturated carboxylic acid ester is preferably 30 mg-KOH / g to 250 mg- KOH / g. The weight average molecular weight (Mw) in terms of standard polystyrene is preferably 1,000 to 300,000.

[A-1-3] E-R-N-T resin The E-R-N-T resin means “(E) component: epoxy group-containing (meth) acrylate” 5 mol% to 90 mol%, “ Component (R): Other radical polymerizable compound that can be copolymerized with component (E) ”is copolymerized with 10 mol% to 95 mol%, and 10 mol% to epoxy group contained in the obtained copolymer. “(N) component: unsaturated monobasic acid” is added to 100 mol%, and “(T) component: polybasic is added to 10 mol% to 100 mol% of the hydroxyl group produced when the (N) component is added. It is a resin obtained by adding an "acid anhydride".

  Here, as the epoxy group-containing (meth) acrylate ((E) component) in the E-R-N-T resin, for example, glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3, 4-epoxycyclohexyl) methyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like. Of these, glycidyl (meth) acrylate is preferred. These (E) components may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

As described above, the copolymerization ratio of the component (E) in the copolymer of the component (E) and the component (R) is usually 5 mol% or more, preferably 20 mol% or more, more preferably 30 mol% or more. It is. Moreover, it is 90 mol% or less normally, Preferably it is 80 mol% or less, More preferably, it is 70 mol% or less. Here, the component (R) is another radical polymerizable compound that can be copolymerized with the component (E).
When the copolymerization ratio of the component (E) is excessively large, the component (R) tends to decrease, and the heat resistance and strength tend to decrease. When the copolymerization ratio of the component (E) is excessively small, the addition amount of the polymerizable component and the alkali-soluble component tends to be insufficient.

  On the other hand, the copolymerization ratio of the (R) component in the copolymer of the (E) component and the (R) component is 10 mol% or more, preferably 20 mol% or more, more preferably 30 mol% or more, as described above. It is. Moreover, it is 95 mol% normally, Preferably it is 80 mol% or less, More preferably, it is 70 mol% or less. When the copolymerization ratio of the component (R) is excessively large, the component (E) tends to decrease and the addition amount of the polymerizable component and the alkali-soluble component tends to be insufficient. Moreover, when the copolymerization ratio of the component (R) is excessively small, heat resistance and strength tend to decrease.

  Here, as the component (R), for example, one or more of mono (meth) acrylates having a partial structure represented by the following formula (13) are preferably used.

(In formula (13), R ^{1d to} R ^6d each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, propyl, etc., and R ^7d and R ^8d are Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, etc. R ^7d and R ^8d may be linked to form a ring. The ring formed by connecting R ^7d and R ^8d is preferably an aliphatic ring, which may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.

  In the above formula (13), mono (meth) acrylate having a structure represented by the following formula (14), formula (15), or formula (16) is preferable. By introducing these partial structures, it is possible to increase the heat resistance and strength of mono (meth) acrylate. In addition, these mono (meth) acrylates may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  As the mono (meth) acrylate having a partial structure represented by the formula (13), various known ones can be used, and those represented by the following formula (17) are particularly preferable.

(In formula (17), R ^9d represents a hydrogen atom or a methyl group, and R ^10d represents the formula (13)).

The content of the mono (meth) acrylate having the partial structure represented by the formula (13) in the copolymer of the component (E) and the component (R) is usually 5 mol% or more, preferably 10 mol. % Or more, more preferably 15 mol% or more. Moreover, it is 90 mol% or less normally, Preferably it is 70 mol% or less, More preferably, it is 50 mol% or less.
When the content of the mono (meth) acrylate represented by the formula (13) in the copolymer of the component (E) and the component (R) is excessively small, the heat resistance tends to be insufficient. Moreover, when there is too much content of the mono (meth) acrylate shown by Formula (13), there exists a tendency for dispersion stability to fall.

Moreover, as (R) component used in this invention, radically polymerizable compounds other than the mono (meth) acrylate which has the partial structure represented by Formula (13) mentioned above are mentioned as shown below.
Specifically, for example, styrene;
Α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives of styrene;
Dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene;
(Meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-iso-propyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid- sec-butyl, tert-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, (meth) acrylic Isobornyl acid, adamantyl (meth) acrylate, (meth) acrylic acid Allyl sulfonate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthraninonyl (meth) acrylate, piperonyl (meth) acrylate, (meth ) Salicyl acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, pyranyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, (meta ) Cresyl acrylate, (meth) acrylic acid-1,1,1-trifluoroethyl, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro (meth) acrylate -Iso-propyl, triphenylmethyl (meth) acrylate, (meth (Meth) acrylic acid esters such as cumyl acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate ;
(Meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, (Meth) acrylic amides such as N-di-iso-propylamide, (meth) acrylic acid anthracenyl amide;
Vinyl compounds such as (meth) acrylic acid anilide, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate;
Unsaturated dicarboxylic acid diesters such as diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconate;
Monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide;
N- (meth) acryloyl phthalimide, etc. are mentioned.

Among these, in order to impart more excellent heat resistance and strength, it is effective to use at least one selected from styrene, benzyl (meth) acrylate and monomaleimide as the (R) component.
In this case, the copolymerization ratio of at least one selected from styrene, benzyl (meth) acrylate and monomaleimide is usually 1 mol% or more, preferably 3 mol% or more, and usually 70 mol% or less, preferably 50 It is less than mol%.

Next, a well-known thing can be used as (N) component (unsaturated monobasic acid) added to the epoxy group contained in the copolymer of (E) component and (R) component. Examples of such unsaturated monobasic acids include unsaturated carboxylic acids having an ethylenically unsaturated double bond.
Specific examples of the unsaturated carboxylic acid having such an ethylenically unsaturated double bond include the ethylenically unsaturated group represented by the general formula (A-II) in the above-mentioned specific ethylenically unsaturated compound section. Examples thereof include “ethylenically unsaturated group-containing carboxylic acid (a)” used for forming the carbonyloxy group. Of these, acrylic acid and / or methacrylic acid are preferred.
These (N) components may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

Furthermore, (N) component is added to the epoxy group contained in the copolymer obtained by the copolymerization reaction of (E) component and (R) component. The amount of the (N) component added to the copolymer is 10 mol%, preferably 30 mol% or more, more preferably 50 mol% or more of the epoxy group contained in the copolymer. When the addition ratio of the component (N) is excessively small, there is a tendency that an adverse effect due to the remaining epoxy group occurs, for example, the stability with time decreases.
In addition, a well-known method is employable as a method of adding (N) component to the copolymer of (E) component and (R) component.

Next, the (T) component (polybasic acid anhydride) is added to the hydroxyl group produced when the (N) component is added to the copolymer of the (E) component and the (R) component. The polybasic acid anhydride is not particularly limited and known ones can be used. As specific examples thereof, as described in the section of the specific ethylenically unsaturated compound, “the epoxy group-containing compound represented by the general formula (A-V) is used as a raw material, and this contains an ethylenically unsaturated group. Examples thereof include a polyvalent carboxylic acid or an anhydride thereof which is further reacted after forming a carbonyloxy group.
In addition, (T) component may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. By adding such components, the nitrogen-free resin can be made alkali-soluble.

The amount of the (T) component added is usually 10 mol% or more, preferably 20% of the hydroxyl group produced when the (N) component is added to the copolymer of the (E) component and the (R) component. The mol% or more, more preferably 30 mol% or more. Moreover, it is 100 mol% or less normally, Preferably, it is 90 mol% or less, More preferably, it is 80 mol% or less.
When the amount of component (T) added is excessively large, the remaining film ratio during development tends to decrease. If the amount of component (T) added is too small, the solubility tends to be insufficient.
In addition, as a method of adding the (T) component to the hydroxyl group generated when the (N) component is added to the copolymer of the (E) component and the (R) component, a known method is arbitrarily adopted. can do.

The E-R-N-T resin is further improved in light sensitivity by adding a glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group to a part of the carboxyl group generated after the addition of the (T) component. Can be improved.
Moreover, developability can also be improved by adding the glycidyl ether compound which does not have a polymerizable unsaturated group to a part of produced | generated carboxyl group after (T) component addition.
Furthermore, you may add both of these after (T) component addition.

Examples of the E-R-N-T resin described above include resins described in JP-A-8-297366 and JP-A-2001-89533.
The average molecular weight of the E-R-N-T resin is not particularly limited, but is usually 3,000 or more, preferably 5,000 as the weight average molecular weight (Mw) converted to standard polystyrene measured by GPC. In addition, it is usually 100,000 or less, preferably 50,000 or less. If the weight average molecular weight (Mw) of the E-R-N-T resin is too small, the heat resistance and the film strength tend to be inferior. When the weight average molecular weight (Mw) of the E-R-N-T resin is excessively large, the solubility in the developer tends to be lowered. The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) is preferably 2.0 to 5.0.

[A-2] Acid-modified epoxy (meth) acrylates The acid-modified epoxy (meth) acrylates used in the present invention include, for example, compounds having the same structure as the specific ethylenically unsaturated compound described above. And compounds obtained from an epoxy group-containing compound and having a double bond equivalent of more than 400.

In the photosensitive composition of the present invention, the content of the ethylenically unsaturated group-containing resin is usually 20% by weight or more, preferably 25% by weight or more, based on the total solid content of the photosensitive composition. Moreover, it is 70 weight% or less normally, Preferably it is 60 weight% or less.
If the content of these resins is too large or too small, the developability, curability, and mechanical properties of the cured product tend to be reduced.

[5-4] Polymerizable monomer The photosensitive composition of the present invention preferably contains a polymerizable monomer separately from the ethylenically unsaturated compound. In the present invention, the term “monomer” means a concept relative to a so-called polymer substance, and in addition to “monomer” in a narrow sense, “dimer”, “trimer”, “oligomer”. Means a concept that also includes

  Examples of the polymerizable monomer include compounds having at least one ethylenically unsaturated group in the molecule. For example, (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid And the like, and alkyl esters thereof, (meth) acrylonitrile, (meth) acrylamide, styrene and the like.

In addition, the polymerizable monomer has two or more ethylenically unsaturated bonds in the molecule from the viewpoints of polymerizability, crosslinkability, and the accompanying difference in developer solubility between exposed and unexposed areas. A compound is preferred, and an acrylate compound whose unsaturated bond is derived from a (meth) acryloyloxy group is particularly preferred.
Examples of the compound having two or more ethylenically unsaturated bonds in the molecule include:
(A) Esters of unsaturated carboxylic acid and polyhydroxy compound (hereinafter sometimes referred to as “ester (meth) acrylates”),
(B) (meth) acryloyloxy group-containing phosphates,
(C) Urethane (meth) acrylates of a hydroxy (meth) acrylate compound and a polyisocyanate compound,
(D) Epoxy (meth) acrylates of (meth) acrylic acid or hydroxy (meth) acrylate compounds and polyepoxy compounds,
Etc. These can be used alone or in combination of two or more.

  Examples of the (A) ester (meth) acrylates include unsaturated carboxylic acid as described above, ethylene glycol, polyethylene glycol (addition number 2 to 14), propylene glycol, polypropylene glycol (addition number 2 to 14), Aliphatic polyhydroxy compounds such as trimethylene glycol, tetramethylene glycol, hexamethylene glycol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, and their ethylene oxide adducts, propylene oxide adducts, diethanolamine, triethanolamine, etc. And the reaction product.

  More specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tri Methylolpropane ethylene oxide addition tri (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate , Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Sa (meth) acrylate, and the like crotonate, isobutyl crotonate, maleate, itaconate, citraconate, and the like.

  The (A) ester (meth) acrylates include unsaturated carboxylic acids as described above and aromatic polyhydroxy compounds such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, or ethylene oxide adducts thereof. And the reaction product.

More specifically, for example, bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate] and the like;
Reaction product of unsaturated carboxylic acid as described above and heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate: Specifically, for example, di ( (Meth) acrylate, tri (meth) acrylate, etc .;
Reaction product of unsaturated carboxylic acid, polycarboxylic acid and polyhydroxy compound as described above: Specifically, for example, condensate of (meth) acrylic acid, phthalic acid and ethylene glycol, (meth) acrylic acid And a condensate of maleic acid and diethylene glycol, a condensate of (meth) acrylic acid, terephthalic acid and pentaerythritol, a condensate of (meth) acrylic acid, adipic acid, butanediol and glycerin.

  The (B) (meth) acryloyloxy group-containing phosphates are not particularly limited as long as they are phosphate compounds containing a (meth) acryloyloxy group, but those represented by the following general formulas (Ia) to (Ic) Is preferred.

(In the formulas (Ia), (Ib), and (Ic), R ¹⁰ represents a hydrogen atom or a methyl group, and Xa may have an alkylene group or a substituent which may have a substituent. A good arylene group, p and p ′ are each independently an integer of 1 to 25, and q is 1, 2 or 3.)
Here, the alkylene group represented by Xa is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a methylene group, an ethylene group, a propylene group, or a butylene group. Moreover, as an arylene group, a C6-C10 thing is preferable and a phenylene group is still more preferable. Among these, an alkylene group is preferable in the present invention. Examples of the substituent that the alkylene group or arylene group of Xa may have include, for example, a halogen atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, and 2 carbon atoms. ˜C10 alkenyl group, phenyl group, carboxyl group, sulfanyl group, phosphino group, amino group, nitro group and the like.

  Here, p and p 'are preferably 1 to 10, particularly 1 to 4. Specific examples of such compounds include (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, (meth) acryloyloxyethylene glycol phosphate, and the like, manufactured by Kyoeisha Chemical Co., Ltd. Examples include "Ester P-1M", "Light ester P-2M", "Light acrylate P-1A", "Light acrylate P-2A", and "KAYAMER PM-2" and "KAYAMER PM-21" manufactured by Nippon Kayaku Co., Ltd. These may be used alone or as a mixture.

  Examples of the (C) urethane (meth) acrylates include a reaction product of a hydroxy (meth) acrylate compound and a polyisocyanate compound.

  Examples of the hydroxy (meth) acrylate compound include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, tetramethylolethane tri (meth) acrylate, and the like.

Examples of the polyisocyanate compound include aliphatic polyisocyanates such as hexamethylene diisocyanate and 1,8-diisocyanate-4-isocyanate methyloctane;
Cycloaliphatic polyisocyanates such as cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptane triisocyanate;
Aromatic polyisocyanates such as 4,4-diphenylmethane diisocyanate, tris (isocyanatephenyl) thiophosphate;
And heterocyclic polyisocyanates such as isocyanurates.

  As the (C) urethane (meth) acrylates, 4 or more (preferably 6 or more, more preferably 8 or more) urethane bonds [—NH—CO—O—] and 4 in one molecule. A compound having at least (preferably 6 or more, more preferably 8 or more) (meth) acryloyloxy groups is preferable. Such a compound can be obtained, for example, by reacting the following compound (i) with the following compound (ii).

(I) Compound having four or more urethane bonds in one molecule For example, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate is added to a compound having four or more hydroxyl groups in one molecule such as pentaerythritol and polyglycerol. , A compound (i-1) obtained by reacting a diisocyanate compound such as tolylene diisocyanate;
Alternatively, for compounds having two or more hydroxyl groups in one molecule such as ethylene glycol, “Duranate 24A-100”, “Duranate 22A-75PX”, “Duranate 21S-75E”, and “Duranate” manufactured by Asahi Kasei Kogyo Co., Ltd. 18H-70B "and other biuret types," Duranate P-301-75E "," Duranate E-402-90T "," Duranate E-405-80T ", etc. Compound (i-2) obtained by reacting a compound having an isocyanate group of
Examples thereof include a compound (i-3) obtained by polymerizing or copolymerizing isocyanate ethyl (meth) acrylate and the like.
A commercial item can be used as such a compound, for example, "Duranate ME20-100" by Asahi Kasei Kogyo Co., Ltd. is mentioned.

(Ii) Compound having 4 or more (meth) acryloyloxy groups in one molecule, for example, pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipenta Examples thereof include compounds having one or more hydroxyl groups and two or more, preferably three or more (meth) acryloyloxy groups in one molecule, such as erythritol penta (meth) acrylate and dipentaerythritol hexaacrylate.

  Here, the molecular weight of the compound (i) is preferably 500 to 200,000, particularly preferably 1,000 to 150,000. Moreover, as molecular weight of the said (C) urethane (meth) acrylate, it is preferable that it is 600-150,000. Unless otherwise specified, in the present invention, the molecular weight means a weight average molecular weight (Mw) in terms of polystyrene measured using a gel permeation chromatography method (GPC method).

  In addition, such (C) urethane (meth) acrylates are, for example, the above compound (i) and the above compound (ii) in an organic solvent such as toluene or ethyl acetate at 10 ° C to 150 ° C. Can be produced by a method of reacting for about 5 minutes to 3 hours. In this case, the molar ratio of the former isocyanate group to the latter hydroxyl group is preferably set to a ratio of 1/10 to 10/1, and a catalyst such as n-butyltin dilaurate is preferably used as necessary.

  In the present invention, among the (C) urethane (meth) acrylates, those represented by the following general formula (II) are particularly preferably used.

[In the formula (II), Ra represents a group having an alkyleneoxy group or an aryleneoxy group repeating structure and 4 to 20 oxy groups capable of binding to Rb. Rb and Rc each independently represent an alkylene group having 1 to 10 carbon atoms, and Rd represents an organic residue having 1 to 10 (meth) acryloyloxy groups. Ra, Rb, Rc, and Rd may have a substituent. x is an integer of 4 to 20, y is an integer of 0 to 15, and z is an integer of 1 to 15. ]

  Here, examples of the repeating structure of the alkyleneoxy group of Ra in the formula (II) include those derived from propylene triol, glycerin, pentaerythritol and the like. Examples of the repeating structure of the aryleneoxy group of Ra include those derived from pyrogallol, 1,3,5-benzenetriol, and the like.

  Moreover, it is preferable that carbon number of the alkylene group of Rb and Rc is 1-5 each independently. The number of (meth) acryloyloxy groups in Rd is preferably 1-7. It is preferable that x is 4 to 15, y is 1 to 10, and z is 1 to 10.

  Further, as Ra, the following formula [wherein, k is an integer of 2 to 10. It is preferable that Rb and Rc are preferably each independently a dimethylene group, a monomethyldimethylene group, or a trimethylene group. Further, Rd is preferably the following formula.

  Examples of the (D) epoxy (meth) acrylates include a reaction product of a (meth) acrylic acid or hydroxy (meth) acrylate compound and a polyepoxy compound.

Examples of the polyepoxy compound include (poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, and (poly) neo. Aliphatic polyepoxy compounds such as pentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether;
Aromatic polyepoxy compounds such as phenol novolac polyepoxy compounds, brominated phenol novolac polyepoxy compounds, (o-, m-, p-) cresol novolac polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds;
Examples include heterocyclic polyepoxy compounds such as sorbitan polyglycidyl ether, triglycidyl isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate, and the like.

  As epoxy (meth) acrylates of (meth) acrylic acid or hydroxy (meth) acrylate compound and polyepoxy compound, such polyepoxy compounds and the above (meth) acrylic acid or hydroxy (meth) acrylate And a reaction product with a compound.

  Other ethylenically unsaturated compounds include, in addition to the above, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, vinyl group-containing compounds such as divinyl phthalate, ether Examples include thioether bond-containing compounds in which the ether bond of the bond-containing ethylenically unsaturated compound is sulfurized with phosphorus pentasulfide or the like to change to a thioether bond, thereby improving the crosslinking rate.

  Further, for example, polyfunctional (meth) acrylate compounds described in Japanese Patent No. 3164407 and JP-A-9-100111 and silica sols having a particle diameter of 5 nm to 30 nm [for example, isopropanol-dispersed organosilica sol (manufactured by Nissan Chemical Co., Ltd., “ IPA-ST "), methyl ethyl ketone-dispersed organosilica sol (" MEK-ST "manufactured by Nissan Chemical Co., Ltd.), methyl isobutyl ketone-dispersed organosilica sol (" MIBK-ST "manufactured by Nissan Chemical Co., Ltd.))] containing isocyanate groups or mercapto groups Compounds bonded using silane coupling agents (compounds that have improved strength and heat resistance as cured products by reacting and bonding silica sol to ethylenically unsaturated compounds via silane coupling agents) Can be mentioned.

In the present invention, from the viewpoint of the mechanical strength of the cured product, (A) ester (meth) acrylates, (B) (meth) acryloyloxy group-containing phosphates, or (C) urethane (meth) acrylates, among others. And (A) ester (meth) acrylates are more preferable.
Further, among (A) ester (meth) acrylates, an ester containing a polyoxyalkylene group such as polyethylene glycol, polypropylene glycol, or polyethylene oxide adduct of bisphenol A, and containing two or more (meth) acryloyloxy groups ( Particularly preferred are meth) acrylates.

The content of the polymerizable monomer in the photosensitive composition of the present invention is usually less than 80% by weight, preferably less than 70% by weight, preferably 10% by weight or more based on the total solid content. When the content of the polymerizable monomer is outside the above range, it tends to be difficult to obtain an image with a good pattern.
The blending ratio of the polymerizable monomer to the ethylenically unsaturated compound is usually 10/1 to 1/10, preferably (ethylenically unsaturated compound) / (polymerizable monomer) (weight ratio). 5/1 to 1/5.

[5-5] Other components Further, the photosensitive composition of the present invention includes a colorant, a coatability improver, a development improver, an ultraviolet absorber, a polymerization inhibitor, an antioxidant, a silane coupling agent, and an epoxy compound. Other resins and the like can be appropriately blended.

[5-5-1] Colorant As the colorant, known colorants such as pigments and dyes can be used. Further, for example, when a pigment is used, a known dispersant or dispersion aid may be used in combination so that the pigment can be stably present in the photosensitive composition without agglomeration.

[5-5-2] Coating property improver, development improver As the coating property improver or development improver, for example, a known cationic, anionic, nonionic, fluorine-based or silicon-based surfactant is used. Can do. Further, as the development improver, known ones such as organic carboxylic acids or anhydrides thereof can be used. The content thereof is usually 20% by weight or less, preferably 10% by weight or less, based on the total solid content.

[5-5-3] Polymerization inhibitor and antioxidant The photosensitive composition of the present invention includes a polymerization inhibitor such as hydroquinone and methoxyphenol, and 2,6-di-tert. It is preferable to contain a hindered phenolic antioxidant such as -butyl-4-cresol (BHT). The content is usually in the range of 5 ppm to 1000 ppm, preferably 10 ppm to 600 ppm, based on the total solid content. When the content is too small, the stability tends to deteriorate. On the other hand, if it is excessively large, curing may be insufficient, for example, during curing by light and / or heat. In particular, when used in a normal photolithography method, it is necessary to set the optimum amount in view of both the storage stability and sensitivity of the photosensitive composition.

[5-5-4] Silane Coupling Agent It is also preferable to add a silane coupling agent to the photosensitive composition of the present invention in order to improve adhesion to the substrate. Various types of silane coupling agents such as epoxy, methacrylic, amino, and imidazole can be used, and epoxy and imidazole silane coupling agents are particularly preferable. The content thereof is usually 20% by weight or less, preferably 15% by weight or less, based on the total solid content.

[5-5-5] Epoxy Compound It is also preferable to add an epoxy compound to the photosensitive composition of the present invention in order to improve curability and adhesion to the substrate.
As the epoxy compound, constituting a repeating unit of a so-called epoxy resin, a polyglycidyl ether compound obtained by reacting a polyhydroxy compound and epichlorohydrin, a polyglycidyl ester compound obtained by reacting a polycarboxylic acid compound and epichlorohydrin, and Examples include compounds ranging from low molecular weight substances to high molecular weight substances such as polyglycidylamine compounds obtained by reacting polyamine compounds and epichlorohydrin.

  Examples of the polyglycidyl ether compound include diglycidyl ether type epoxy of polyethylene glycol, diglycidyl ether type epoxy of bis (4-hydroxyphenyl), and diglycidyl ether of bis (3,5-dimethyl-4-hydroxyphenyl). Type epoxy, diglycidyl ether type epoxy of bisphenol F, diglycidyl ether type epoxy of bisphenol A, diglycidyl ether type epoxy of tetramethylbisphenol A, diglycidyl ether type epoxy of ethylene oxide-added bisphenol A, diglycidyl ether of fluorene type bisphenol Type epoxy, phenol novolac type epoxy, cresol novolac type epoxy and the like. These polyglycidyl ether compounds may be those obtained by reacting a remaining hydroxyl group with an acid anhydride or a divalent acid compound to introduce a carboxyl group.

  Examples of the polyglycidyl ester compound include diglycidyl ester type epoxy of hexahydrophthalic acid, diglycidyl ester type epoxy of phthalic acid, and the like. Examples of the polyglycidylamine compound include diglycidylamine type epoxy of bis (4-aminophenyl) methane, triglycidylamine type epoxy of isocyanuric acid, and the like.

  The content of the epoxy compound is usually 40% by weight or less, preferably 30% by weight or less, based on the total solid content. When there is too much content, the storage stability of a photosensitive composition may deteriorate.

[5-5-6] Other resins The photosensitive composition of the present invention may contain other resins for adjusting the developability and the mechanical properties of the cured product. Mention may be made of copolymers containing epoxy groups.
Examples of the copolymer containing a carboxyl group and an epoxy group include unsaturated carboxylic acids, unsaturated compounds having an epoxy group, and copolymers with other compounds as necessary. Specifically, for example, alkali-soluble resins used in the composition described in JP-A-11-133600 can be mentioned.

[6] Method of Using Photosensitive Composition The photosensitive composition of the present invention is usually used in a state where the various components described above are dissolved or dispersed in a solvent.
The solvent is not particularly limited. For example, water, diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n -Octane, Valsol # 2, Apco # 18 solvent, diisobutylene, amyl acetate, butyl butyrate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl nonyl ketone, propyl ether, dodecane, Socal solvent No. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, butyl acetate (n, sec, t), hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether , Ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, Amyl formate, cyclohexyl acetate, bicyclohexyl, diethylene glycol monoethyl ether acetate, diethylene glycol mono Chill ether, diethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether, dipentene, methoxymethylpentanol, methyl amyl ketone, methyl isopropyl ketone, propyl propionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, Carbitol, cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene Glycol monoethyl ether, dipropylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3-ethoxypropionic acid, ethyl 3-ethoxypropionate, 3-methoxypropionic acid Methyl, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, dipropylene glycol monomethyl ether, ethylene glycol acetate, methyl carbitol, ethyl carbitol, butyl carbitol, ethylene glycol mono Butyl ether, propylene glycol-t-butyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutane Lumpur, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl acetate, 3-methoxybutyl acetate, the solvent can be specifically exemplified equal.

  The solvent is capable of dissolving or dispersing each component, and is selected according to the method of using the photosensitive composition of the present invention, but a solvent having a boiling point in the range of 60 ° C to 280 ° C is selected. Is preferred. More preferably, it has a boiling point of 70 ° C to 260 ° C. These solvents can be used alone or in combination. These solvents are used so that the ratio of the total solid content in the photosensitive composition of the present invention is usually 10% by weight or more and 90% by weight or less.

The photosensitive composition of the present invention is characterized in that it is applied to a method for simultaneously forming cured products having different heights from the same material. Hereinafter, a case where a spacer and a sub-spacer are formed will be described as an example.
Usually, a photosensitive composition is supplied in a film form by a method such as coating on a substrate on which a spacer is to be provided, and the solvent is dried. Subsequently, pattern formation is performed by a method such as exposure-development photolithography. Then, a spacer is formed on this board | substrate by performing additional exposure and a thermosetting process as needed.

[6-1] Supplying Method to Substrate The photosensitive composition of the present invention is usually supplied onto a substrate in a state where various components are dissolved or dispersed in a solvent. As the supply method, a conventionally known method such as a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like can be used. Above all, the die coating method reduces the amount of coating solution used, and has no influence from mist adhering to the spin coating method. It is preferable from the viewpoint.

The coating amount varies depending on the application. For example, in the case of a spacer, the dry film thickness is usually in the range of 0.5 μm to 10 μm, preferably 1 μm to 9 μm, particularly preferably 1 μm to 7 μm. Further, it is important that the dry film thickness or the height of the finally formed spacer is uniform over the entire area of the substrate. When the variation is large, a nonuniformity defect occurs in the liquid crystal panel. Further, it may be supplied in a pattern by an inkjet method or a printing method.
A known substrate such as a glass substrate can be used as the substrate. The substrate surface is preferably a flat surface.

[6-2] Drying method Drying after supplying the photosensitive composition onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Moreover, you may combine the reduced pressure drying method of drying in a reduced pressure chamber, without raising temperature.
Drying conditions can be appropriately selected according to the type of solvent component, the performance of the dryer used, and the like. The drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 ° C. to 130 ° C., preferably 50 ° C. to 110 ° C., depending on the type of solvent component and the performance of the dryer used. The temperature is selected in the range of 30 seconds to 3 minutes.

[6-3] Exposure Method Exposure is performed by superposing a negative mask pattern on the coating film of the photosensitive composition and irradiating with ultraviolet rays or visible rays through the mask pattern. When exposure is performed using an exposure mask, the exposure mask is placed close to the coating film of the photosensitive composition, or the exposure mask is disposed at a position away from the coating film of the photosensitive composition. Alternatively, a method of projecting exposure light may be used. Further, a scanning exposure method using a laser beam without using a mask pattern may be used. At this time, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, exposure is performed after the formation of an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer or in a deoxygenated atmosphere. Or you may.

The photosensitive composition of the present invention is suitably used in a method for simultaneously forming cured products having different heights from the same material, and as an exposure mask, a light shielding part that blocks light transmission and an opening part that transmits light. A method using an exposure mask in which the average light transmittance of some openings is smaller than the average light transmittance of other openings, that is, having a light shielding portion (light transmittance of 0%) and a plurality of openings. In addition, a method using an exposure mask having a completely transmissive opening and an intermediate transmissive opening can be preferably used.
As a method for forming the intermediate transmission opening, for example, as described in JP-A-2003-344860, by arranging a matrix-shaped light-shielding pattern having a minute polygonal light-shielding unit such as a slit in the opening. Thus, an intermediate transmission opening having an adjusted average light transmittance (small light transmittance with respect to the complete transmission opening) can be formed.

As another method of forming the intermediate transmission opening, there is a method of forming a film of a material such as chromium, molybdenum, tungsten, or silicon as an absorber in the opening.
By using such an exposure mask, a substantial difference in exposure amount is generated in accordance with the transmittance of the opening in one exposure process, and patterns having different heights, for example, a spacer and a sub-spacer are simultaneously formed. Can be made.

The light source used for said exposure is not specifically limited. As the light source, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, a lamp light source, an argon ion laser, a YAG laser, Examples include laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, blue-violet semiconductor laser, and near infrared semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.
The optical filter may be of a type that can control the light transmittance at the exposure wavelength with a thin film, for example, and the material in that case is, for example, a Cr compound (Cr oxide, nitride, oxynitride, fluoride, etc.), Examples include MoSi, Si, W, and Al.

Energy of exposure generally, 1 mJ / cm ² or more, preferably 5 mJ / cm ² or more, more preferably 10 mJ / cm ² or more, usually 300 mJ / cm ² or less, preferably 200 mJ / cm ² or less, more preferably 150 mJ / cm ² or less.
In the case of the proximity exposure method, the distance between the exposure target and the mask pattern is usually 10 μm or more, preferably 50 μm or more, more preferably 75 μm or more, and usually 500 μm or less, preferably 400 μm or less, more preferably 300 μm or less.

[6-4] Development Method After performing the above exposure, an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent. This aqueous solution may further contain a surfactant, an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Machine alkaline compounds. These alkaline compounds may be a mixture of two or more.
Among these, potassium hydroxide is preferably used.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters; Anionic surfactants such as acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts; amphoteric surfactants such as alkylbetaines and amino acids.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used alone or in combination with an aqueous solution.
Although there is no restriction | limiting in particular about the method of image development processing, Usually, it is carried out by methods, such as immersion image development, spray image development, brush image development, and ultrasonic image development, at the image development temperature of 10 to 50 degreeC, Preferably it is 15 to 45 degreeC. .

[6-5] Additional exposure and thermosetting treatment The substrate after development may be subjected to additional exposure by a method similar to the above exposure method, if necessary, or may be subjected to thermosetting treatment. The thermosetting treatment conditions at this time are selected such that the temperature ranges from 100 ° C. to 280 ° C., preferably from 150 ° C. to 250 ° C., and the time ranges from 5 minutes to 60 minutes.

  The photosensitive composition of the present invention is a photosensitive composition suitable for a method of simultaneously forming cured products having different heights by the same material by a photolithography method, and is used in a liquid crystal display device such as a liquid crystal display. It is a photosensitive composition suitably used when forming overcoats, ribs and spacers in various combinations. Further, according to the present invention, a high-quality liquid crystal display device or the like can be provided.

[7] Color Filter Next, the color filter will be described.
FIG. 3 is a schematic diagram illustrating an example of a color filter. As shown in FIG. 3, the color filter 20 has a black matrix 22, a pixel coloring layer 23, and an overcoat layer 24 laminated on a glass substrate 21 as a transparent substrate.
The black matrix 22 blocks external light and improves the quality and contrast of black display. The pixel coloring layer 23 is formed by applying pigments or dyes for displaying three colors of RGB (Red, Green, Blue). The overcoat layer 24 fills the level difference of the pixel coloring layer 23 and flattens it.

Examples of the material having properties equivalent to the glass substrate 21 as the transparent substrate include polyester resins such as polyethylene terephthalate; polyolefin resins such as polypropylene and polyethylene; sheets made of thermoplastic resin such as polycarbonate, polymethyl methacrylate, and polysulfone; Examples thereof include thermosetting resin sheets such as epoxy resins, unsaturated polyester resins, and poly (meth) acrylic resins.
If necessary, the glass substrate 21 as a transparent substrate is subjected to corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as silane coupling agents and urethane resins, etc. to improve surface properties such as adhesion. May be. The thickness of the glass substrate 21 is generally 0.05 mm to 10 mm, preferably 0.1 mm to 7 mm.

The black matrix 22 is formed on the glass substrate 21 using a light-shielding metal thin film or a coloring composition for forming a black matrix.
When a light-shielding metal thin film is used for forming the black matrix 22, a light-shielding metal thin film material may be a chromium compound such as metal chromium, chromium oxide or chromium nitride, nickel and tungsten alloy, and the like. It may be laminated. These light-shielding metal thin film materials are usually formed on the glass substrate 21 by a vapor deposition method or a sputtering method, and then a desired pattern is formed in a film shape by a positive photoresist. Etching solution mixed with ceric ammonium and perchloric acid is used, and other materials are etched using the etching solution according to the material. Finally, the positive photoresist is stripped with a special stripper. By doing so, the black matrix 22 can be formed.

  The black matrix 22 is formed using a photosensitive composition (coloring composition for forming a black matrix) containing a black color material. For example, a black color material such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black or the like, or a red, green, blue or the like appropriately selected from inorganic or organic pigments and dyes The black matrix 22 can be formed in the same manner as the method for forming the red, green, and blue pixel coloring layers 23 by using a photosensitive composition containing a black color material by mixing.

Next, a pixel colored layer 23 of RGB (Red, Green, Blue) three colors is formed on the glass substrate 21 provided with the black matrix 22 with a cured product of the photosensitive composition, and an overcoat layer 24 is further formed. The color filter 20 is manufactured by filling the step of the pixel coloring layer 23 and flattening it.
The photosensitive composition used to form the pixel coloring layer 23 is usually formed on the glass substrate 21 with the photosensitive composition containing at least one pigment or dye of red, green, and blue. It is applied on the resin black matrix forming surface or on the metal black matrix forming surface formed using a chromium compound or other light shielding metal material, and after drying, a photomask is overlaid on the coating film, Then, the pixel colored layer 23 made of a cured product of the photosensitive composition is formed by image exposure, development, and if necessary, heat curing or photocuring. By performing this operation for each of the three colors red, green, and blue, a color filter image can be formed.

The method for supplying the photosensitive composition onto the glass substrate 21, the drying method, the exposure method, the development method, the additional exposure and the thermosetting treatment are the same as the operations and conditions described in the spacer formation method described above. Do.
Here, it is preferable that the color filter is manufactured through a coating process by a die coating method using the photosensitive composition in terms of manufacturing yield and product quality.

[8] Liquid Crystal Display Device Next, a liquid crystal display device will be described.
FIG. 4 is a schematic diagram illustrating an example of a layer configuration of a liquid crystal display device (panel). As shown in FIG. 4, the liquid crystal display device (panel) includes a liquid crystal cell 40 formed by providing a spacer 28 between a color filter 20 having a transparent electrode 25 and a TFT (Thin Film Transistor) array substrate 30. The liquid crystal 29 is filled.

  On the glass substrate 21 of the color filter 20, a black matrix 22, a pixel coloring layer 23, and an overcoat layer 24 are laminated. A transparent electrode 25 made of an ITO film (indium tin oxide) is disposed on the overcoat layer 24. On the transparent electrode 25, a liquid crystal alignment control protrusion (rib) 27 and a spacer 28 are disposed, and an alignment film 26 is laminated thereon. The transparent electrode 25 applies a voltage to the liquid crystal 29 to control the direction of liquid crystal molecules. The alignment film 26 is provided to twist the molecules of the liquid crystal 29 into a special shape.

The TFT array substrate 30 is provided on a glass substrate 31 with a TFT 32 for controlling the display of a liquid crystal display device (panel), an insulating film 33, a transparent electrode 34 made of an ITO film, a liquid crystal alignment control protrusion (rib) 37, The alignment film 35 is sequentially arranged.
A polarizing plate (not shown) is attached to the outside of each of the glass substrates 21 and 31. Further, an illumination device (BL) is provided outside the TFT array substrate 30.

In the color filter 20 of the liquid crystal display device (panel), the pixel coloring layer 23 is formed as a pixel image for displaying RGB (Red, Green, Blue) color using a photosensitive composition.
On the other hand, the liquid crystal alignment control protrusions (ribs) 27 and 37 and the spacer 28 of the liquid crystal display device (panel) can be simultaneously formed of the same material using, for example, the photosensitive composition of the present invention.
The alignment films 26 and 35 are preferably resin films such as polyimide. As a method for forming the alignment films 26 and 35, a gravure printing method, a flexographic printing method, or the like is usually employed, and a curing process is performed by thermal baking. The thickness of the alignment films 26 and 35 is usually several tens of nm.

A liquid crystal display device (panel) is manufactured by the following operation when, for example, a photo spacer and a rib are simultaneously formed of the same material using the photosensitive composition of the present invention.
The color filter 20 forms a black matrix 22 and a pixel coloring layer 23 on a glass substrate 21. Next, the pixel coloring layer 23 is covered with an overcoat layer 24 as necessary, and a transparent electrode 25 is applied. Next, the liquid crystal alignment control protrusion (rib) 27 and the spacer 28 are simultaneously formed of the same material using the photosensitive composition of the present invention. Further, an alignment film 26 is formed on the liquid crystal alignment control protrusions (ribs) 27 and the spacers 28.
In the TFT array substrate 30, a TFT 32, an insulating film 33, a transparent electrode 34, a liquid crystal alignment control protrusion (rib) 37 and an alignment film 35 are formed on a glass substrate 31. Next, the color filter 20 and the TFT array substrate 30 are bonded together with the alignment film 26 of the color filter 20 and the alignment film 35 of the TFT array substrate 30 facing each other to form the liquid crystal cell 40. Then, liquid crystal 29 is injected into the formed liquid crystal cell 40 and connected to a counter electrode (not shown) to manufacture a liquid crystal display device (panel).

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.

(Examples 1-4, Comparative Examples 1-3)
Each component shown in Table 1 was dissolved in propylene glycol monomethyl ether acetate at a blending amount shown in Table 1 (parts by weight in terms of solid content) to prepare a photosensitive composition having a solid content concentration of 30% by weight. The double bond equivalent was calculated from the blending amount of each component and is also shown in Table 1. Using the obtained photosensitive composition, a substantially cylindrical spacer pattern is formed by the method described later, and the γ value, height uniformity of the intermediate transmission opening, total deformation, final displacement, elastic recovery rate, recovery The rate and adhesion (bottom cross-sectional area) were evaluated. The results are also shown in Table 1.

A1:
By reacting 118 parts by weight of succinic anhydride with 596 parts by weight of commercially available pentaerythritol triacrylate at 85 ° C. for 5 hours in the presence of 2.5 parts by weight of triethylamine and 0.25 parts by weight of hydroquinone, A polyfunctional acrylate mixture having an acid value of 92.7 consisting of 66% polyfunctional acrylate having one carboxyl group and two or more acryloyl groups and 34% pentaerythritol tetraacrylate was obtained. (Ethylenically unsaturated group-containing carboxylic acid mixture AA1).
In a 1000 ml four-necked flask, 231 g of diglycidyl etherified product (epoxy equivalent 231) of 9,9-bis (4′-hydroxyphenyl) fluorene, 605 g of the above ethylenically unsaturated group-containing carboxylic acid mixture (AA1), triethyl Charge 6.06 g of benzylammonium chloride, 0.15 g of p-methoxyphenol and 170 g of propylene glycol monomethyl ether acetate, heat and dissolve at 70 ° C. to 80 ° C., and gradually raise the temperature to 85 ° C. while the solution is cloudy The solution, which was completely dissolved and subsequently became transparent and viscous, was heated and stirred for 8 hours until the acid value reached 3.0 KOH mg / g to obtain a colorless and transparent reaction product. Propylene glycol monomethyl ether acetate was added to the obtained reaction product to adjust the solid content to 50%.
Subsequently, 8.7 g of 1,2,3,6-tetrahydrophthalic anhydride was added to 100 g of the obtained 50% solid solution, and the temperature was gradually raised and reacted at 80 ° C. to 85 ° C. for 3 hours. A solution of compound (A1) was obtained. The obtained compound had a solid content acid value of 55 KOH mg / g and a weight average molecular weight (Mw) of 2,500 (double bond equivalent 216). [5-3] Corresponds to ethylenically unsaturated compound.

A2:
Nippon Kayaku Co., Ltd. TCR1286, acid value 101 (double bond equivalent 315). [5-3] Corresponds to ethylenically unsaturated compound.
A3:
180 parts of propylene glycol monomethyl ether acetate and 7.3 parts of an azo polymerization initiator (“V-59” manufactured by Wako Pure Chemical Industries, Ltd.) were charged into a reaction vessel, heated to 80 ° C. in a nitrogen atmosphere, and 4 parts of methyl methacrylate. Then, 70 parts of methacrylic acid and 31 parts of isobornyl methacrylate were added dropwise and further stirred for 4 hours.
Next, the inside of the reaction vessel was purged with air, and 0.1 part of paramethoxyphenol, 103.8 parts of glycidyl methacrylate and 4.2 parts of tetraethylammonium chloride were added, and the reaction was continued at 85 ° C. for 10 hours.
Propylene glycol monomethyl ether acetate was added to the obtained reaction solution to obtain a solution having a solid content concentration of 50% by weight.
The obtained ethylenically unsaturated compound (A3) had a solid content acid value of 22 mgKOH / g and a weight average molecular weight (Mw) of 16,000 (double bond equivalent 286). [5-3] Corresponds to ethylenically unsaturated compound.
A4:
90 parts of propylene glycol monomethyl ether acetate was charged into a reaction vessel, heated to 80 ° C. in a nitrogen atmosphere, monomethacrylate having 2.6 parts of styrene, 66.1 parts of glycidyl methacrylate and tricyclodecane skeleton (manufactured by Hitachi Chemical Co., Ltd.). A solution prepared by dissolving 7 parts of an azo polymerization initiator (“V-59” manufactured by Wako Pure Chemical Industries, Ltd.) in 2.2 parts of “FA-513M”) was added dropwise over 3 hours and further stirred for 4 hours.
Subsequently, the inside of the reaction vessel was purged with air, 0.05 parts of paramethoxyphenol, 33.5 parts of acrylic acid and 1.5 parts of triphenylphosphine were added, and the reaction was continued at 80 ° C. for 12 hours.
Thereafter, 7.6 parts of tetrahydrophthalic anhydride was added and reacted at 85 ° C. for 4 hours.
Propylene glycol monomethyl ether acetate was added to the obtained reaction solution to obtain a solution having a solid content concentration of 50% by weight.
The ethylenically unsaturated compound (A4) obtained had a solid content acid value of 24.3 mgKOH / g and a weight average molecular weight (Mw) of 9,100 (solid content double bond equivalent was 250). [5-3] Corresponds to ethylenically unsaturated compound.

B1:
“BCIM” manufactured by Hodogaya Chemical Co., Ltd. 4,4 ′, 5,5′-tetraphenylbiimidazole. [5-1] Corresponds to the photopolymerization initiator system.
B2:
2-mercaptobenzothiazole manufactured by Tokyo Chemical Industry Co., Ltd. [5-1] Corresponds to the photopolymerization initiator system.
B3:
“Irgacure 907” manufactured by Ciba Specialty Chemicals. [5-1] Corresponds to the photopolymerization initiator system.
B4:
“Irgacure 369” manufactured by Ciba Specialty Chemicals. [5-1] Corresponds to the photopolymerization initiator system.

C:
“Nikarak MW-30M” manufactured by Sanwa Chemical Co., Ltd. Melamine resin. [5-2] Corresponds to amino compound.
D1:
“KAYARAD DPHA” manufactured by Nippon Kayaku. Dipentaerythritol hexaacrylate. (Double bond equivalent 100) [5-4] Corresponds to polymerizable monomer.
D2:
“KAYAMER PM-21” manufactured by Nippon Kayaku Co., Ltd. (Double bond equivalent 292) Corresponds to [5-4] polymerizable monomer.
F:
“FC430” manufactured by Sumitomo 3M Limited. Surfactant. [5-5] Corresponds to other components.

[Evaluation of γ value]
A residual film rate-exposure curve was created with reference to the method described in the embodiment of the present invention, and a γ value was calculated. Evaluation was made according to the following criteria.
○: γ value is 15 or more and less than 45 ×: γ value is less than 15 or 45 or more

[Evaluation of height uniformity of intermediate transmission opening]
The said photosensitive composition was supplied on this ITO film | membrane of the glass substrate (10 cm x 10 cm substantially square-shaped board | substrate) which formed the ITO film | membrane on the surface. After forming the coating film by the photosensitive composition using the spinner, it heated on the hotplate at 80 degreeC for 3 minutes, and dried the coating film. The dry film thickness of the coating film was 4.3 μm.
Next, the obtained coating film was exposed through a circular pattern mask having a diameter of 20 μm with a light transmittance at 365 nm of 20 ± 2% by providing a thin film of chromium oxide in the opening, and the exposed coating film was Formed. The mask installation position was a position 200 μm away from the coating film surface. The exposure was performed using an ultraviolet ray having an intensity at 365 nm of 32 mW / cm ² and a high-pressure mercury lamp as a light source so that the exposure amount at a portion where the light transmittance was 100% was 50 mJ / cm ² . At this time, ultraviolet irradiation was performed under air.
Next, the exposed coating film was subjected to development treatment and further subjected to heat treatment to obtain a spacer pattern. Development is performed by using a 0.1% aqueous potassium hydroxide solution (developer), performing shower development at 23 ° C. with a water pressure of 0.25 MPa, stopping development with pure water, and rinsing with water spray. Was used. Here, the shower development time was set to twice the minimum development time. On the other hand, the heat treatment was a heat treatment at 230 ° C. for 30 minutes.

On the surface of the glass substrate, about 24 spacer patterns existing on the circumference having a radius of 2.5 cm from the center point position, the center axis of the spacer pattern is measured using Keyence Corporation's ultra-deep color 3D shape measurement microscope “VK-9500”. The vertical cross section was profiled and the height of the spacer pattern was measured. Based on the obtained pattern height data of 24 points, the following criteria were used for evaluation.
Height uniformity (maximum-minimum)
A: Among the pattern heights of 24 points, the difference between the maximum height value and the minimum height value is 0.15 μm or less. ○: The difference exceeds 0.15 μm and is 0.20 μm or less. Over 20μm

[Load-unloading test with micro hardness tester (total deformation, elastic recovery rate, recovery rate)]
A load-unloading test was performed with a microhardness meter, and the total deformation, elastic recovery rate, and recovery rate were determined by the method described in [3] above, and evaluated according to the following criteria.
Total deformation amount ◎: Total deformation amount is 1.4 μm or more ○: Total deformation amount is 1.0 μm or more and less than 1.4 μm ×: Total deformation amount is less than 1.0 μm Elastic recovery rate ◎: Elastic recovery rate is 60% or more ○: Elastic recovery rate is 50% or more and less than 60% ×: Elastic recovery rate is less than 50% Recovery rate ◎: Recovery rate is 85% or more ○: Recovery rate is 80% or more and less than 85% ×: Recovery rate is 80 %Less than

[Evaluation of adhesion (bottom cross-sectional area)]
For the spacer patterns having different bottom cross-sectional areas prepared as described above, the adhesion (bottom cross-sectional area) was determined by the method described in [4] above, and evaluated according to the following criteria.
Adhesion (bottom cross-sectional area)
◎: Bottom cross-sectional area is 20 μm ² or less ○: Bottom cross-sectional area is over 20 μm ² , 25 μm ² or less ×: Bottom cross-sectional area is over 25 μm ²

[Method of simultaneously forming cured products with different heights from the same material]
The said photosensitive composition was apply | coated using the spinner on this ITO film | membrane of the glass substrate which formed the ITO film | membrane on the surface. Then, it was heated and dried on a hot plate at 80 ° C. for 3 minutes to form a coating film. The dry film thickness was 4.3 μm.
The obtained coating film was subjected to exposure treatment using an exposure mask having a circular transmission pattern having a circular pattern with a diameter of 6.5 μm and an intermediate transmission opening having a circular pattern with a diameter of 20 μm. The intermediate transmission opening is a Cr oxide thin film having a light transmittance of 20 ± 2% at a wavelength of 365 nm. The exposure gap (distance between the mask and the coated surface) was 200 μm. Further, ultraviolet rays having an intensity at 365 nm of 32 mW / cm ² were used. The exposure amount was 50 mJ / cm ² . Moreover, ultraviolet irradiation was performed under air. Next, spray development was carried out using a 0.1% potassium hydroxide aqueous solution at 23 ° C. for twice the minimum development time, and further rinsed with pure water.

By these operations, a pattern from which unnecessary portions were removed was obtained. The substrate on which the pattern was formed was heated in an oven at 230 ° C. for 30 minutes to cure the pattern to obtain a substantially cylindrical spacer pattern.
The height and lower cross-sectional diameter L of the obtained spacer pattern were determined and shown in Table 1. Table 1 shows the difference (ΔH) between the height of the spacer pattern in the complete transmission opening and the height of the spacer pattern in the intermediate transmission opening. It was judged that the difference in height was obtained when ΔH was 0.2 μm or more.

From the results of Table 1, according to the photosensitive composition of the present invention, even when an exposure mask with insufficient in-plane accuracy of light transmittance of the intermediate transmission opening is used, the height corresponding to the intermediate transmission opening. It can be seen that a cured product with high accuracy can be obtained, and is useful for a method of simultaneously forming cured products having different heights from the same material.
Although the invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application (Japanese Patent Application No. 2007-169766) filed on June 27, 2007, which is incorporated by reference in its entirety.

It is a figure for demonstrating the shape of the spacer pattern obtained using the photosensitive composition of this invention. It is a schematic diagram which shows the load-displacement curve in the load-unloading test of a spacer. It is the schematic which shows an example of a color filter. It is the schematic which shows an example of the laminated constitution of a liquid crystal display device (panel). It is the schematic diagram showing the relationship between the film remaining rate and exposure amount about the photosensitive composition from which (gamma) value differs.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Spacer pattern, 2, 21, 31 ... Glass substrate, 3 ... Medium axis, 4 ... Profile, 20 ... Color filter, 22 ... Black matrix, 23 ... Pixel coloring layer, 24 ... Overcoat layer, 25, 34 ... Transparent electrode , 26, 35 ... alignment film, 27, 37 ... liquid crystal alignment control protrusion (rib), 28 ... spacer, 29 ... liquid crystal, 30 ... TFT array substrate, 32 ... TFT, 33 ... insulating film, 40 ... liquid crystal cell, A, A '... intersection, H ... pattern height, L ... lower cross-sectional diameter

Claims (14)

A photosensitive composition provided for simultaneously forming cured products having different heights from the same material, and the remaining film ratio [t of the exposed area with respect to the logarithm of the exposure amount [log E (mJ / cm ² )] (%)] Is plotted, and the γ value of the straight line of the following formula (1) connecting the points of 60% and 90% of the remaining film ratio in the remaining film ratio-exposure curve is 15 or more and less than 45. A photosensitive composition.
t = γlogE + δ (1)
[Here, the remaining film ratio t (%) is expressed below when an image is formed via a negative mask pattern.
Residual film ratio [t (%)] = {(pattern height at each exposure dose) / (pattern height at exposure dose 1000 mJ / cm ² )} × 100]   The photosensitive composition according to claim 1, wherein the double bond equivalent of the composition is 300 or less. The load-unloading test with a microhardness meter can form a cured product that satisfies the following (1) and satisfies the following (2) and / or (3). Photosensitive composition.
(1) Deformation amount is 1.4 μm or more (2) Elastic recovery rate is 50% or more (3) Recovery rate is 80% or more The load-unloading test with a microhardness meter can form a cured product that satisfies the following (2) and / or (3) and satisfies the following (4). 2. The photosensitive composition according to item 1.
(2) Elastic recovery rate is 50% or more (3) Recovery rate is 80% or more (4) Bottom cross-sectional area is 25 μm ² or less   A photosensitive composition provided for simultaneously forming cured products having different heights from the same material, and using a forming method that includes an exposure step using an exposure mask only once in the formation. The photosensitive composition according to claim 1, wherein the composition is a photosensitive composition.   The exposure mask has a light-blocking portion that blocks light transmission and a plurality of openings that transmit light, and the average light transmittance of some openings is smaller than the average light transmittance of other openings. The photosensitive composition according to claim 5. The points of 60% and 90% of the remaining film rate in the remaining film rate-exposure curve in which the remaining film rate [t (%)] of the exposed portion is plotted against the logarithm of the exposure amount [log E (mJ / cm ² )]. A method of simultaneously forming cured products having different heights using the same material, wherein a photosensitive composition having a γ value of the straight line of the following formula (1) connecting 15 is 15 or more and less than 45 is used.
t = γlogE + δ (1)
[Here, the remaining film ratio t (%) is expressed below when an image is formed via a negative mask pattern.
Residual film ratio [t (%)] = {(pattern height at each exposure dose) / (pattern height at exposure dose 1000 mJ / cm ² )} × 100]   The method according to claim 7, wherein the photosensitive composition according to claim 2 is used.   9. The method according to claim 7, wherein the exposure step is included only once.   An exposure process includes an exposure mask having a light shielding portion that blocks light transmission and a plurality of openings that allow light to pass, and an average light transmittance of some openings is smaller than an average light transmittance of other openings. The method according to claim 9, wherein the method is performed.   Hardened | cured material formed with the photosensitive composition of any one of Claims 1 thru | or 6.   The cured product according to claim 11, wherein the cured product is a cured product having different heights formed simultaneously from the same material.   A cured product formed by the method according to claim 7. A liquid crystal display device comprising the cured product according to claim 11.

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