CN101592752A

CN101592752A - Color filter and manufacture method thereof and liquid crystal indicator

Info

Publication number: CN101592752A
Application number: CNA2009102038746A
Authority: CN
Inventors: 山岸庸恭; 黑木信宏; 吉野晴彦
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2008-05-30
Filing date: 2009-05-22
Publication date: 2009-12-02
Also published as: JP2009288656A

Abstract

The invention provides a kind of color filter, it has the resin black matrix of clathrate pattern and the colored pattern of striated pattern at least on substrate, above-mentioned resin black matrix will be divided into a plurality of pixels on the aforesaid substrate, in at least a portion of above-mentioned colored pattern, be provided with continuously on a plurality of pixels that respectively are listed in linearly arrangement of colored pattern and on the resin black matrix between this pixel, and respectively being listed on the resin black matrix with the direction of the direction quadrature of these row of above-mentioned colored pattern has overlapping O _XGroup, and with the resin black matrix of the parallel direction of direction of each row of above-mentioned colored pattern on have overlapping O _YGroup and a pair of pattern edge, when observing pixel in a plurality of pixels of above-mentioned linearly arrangement, draw: overlapping the O adjacent with this pixel _YHeight h with respect to the colored pattern surface in this pixel _YThan overlapping the O adjacent with this pixel _XHeight h with respect to the colored pattern surface in this pixel _XMore than the low 0.1 μ m.

Description

Color filter and manufacture method thereof and liquid crystal indicator

Technical field

The present invention relates to color filter and manufacture method thereof and liquid crystal indicator.

Background technology

Color filter is a component parts indispensable in liquid crystal indicator and the solid-state imager.

For example, LCD is applied to TV gradually, liquid crystal indicator (LCD; LCD) compare with color filter with color filter, monitor with present notebook computer with color filter, require more high-quality image quality.In addition, in order to produce large-scale TV, substrate size enlarges, to the increase in demand of ratio defective product raising and cost cutting.

About the raising of above-mentioned image quality, when making, color filter has following problem: in the boundary member colored pattern projection of black matrix with colored pixels, and color filter unevenness and cause image quality reduction (for example with reference to Japanese patent laid-open 9-113721 communique).The projection of above-mentioned boundary member causes problems such as contrast decline, irregular colour sometimes.

Therefore, at present making the back in pixel grinds or is forming on the pixel protective seam (below be sometimes referred to as " OC layer ") and deal with to the surface of color filter.But if grind or form the OC layer, then the manufacturing process of color filter increases, and cost improves.In addition, when grinding, also can produce drawbacks such as color filter is impaired sometimes, wish to have and to omit the method that grinding step and OC layer form operation.

Be directed to this, attempted solving the problem (for example opening the 2003-161826 communique) of above-mentioned boundary member projection with reference to Japanese patent laid-open 9-113721 communique and Jap.P. spy by the cone angle that reduces black matrix.

Open in the 2003-161826 communique the Jap.P. spy, also only in black matrix frame, give coloured composition by ink-jet method.

But, if adopt the method described in the Japanese patent laid-open 9-113721 communique, then need a large amount of operations to obtain having the black matrix of above-mentioned cone angle, particularly, to deceive matrix forms with photosensitive black composition after coating drying on the substrate, being coated with the eurymeric resist again, regulating the developing powder of this photosensitive black composition and eurymeric resist, is the method that wastes time and energy.And when only regulating cone angle, the inhibition effect of colored pattern projection is insufficient.In addition, this technology is not at large substrate (for example substrate size is the above large substrate of 1m * 1m).

On the other hand, open in the 2003-161826 communique the Jap.P. spy, owing on substrate, give coloured composition by ink-jet method and form colored pattern, therefore be unsuitable for being suppressed at the projection that coating, transfer printing by coloured composition waits the colored pattern of the overlapping overlapping portion of the black matrix that produces when forming colored pattern and colored pattern.Instead at the boundary member of black matrix and colored pixels, black matrix is higher than colored pixels and produces difference in height, and the color filter unevenness produces the problem of same image quality reduction sometimes.

Summary of the invention

The present invention is the invention of In view of the foregoing finishing, and its technical matters is to finish following purpose.

That is, the object of the present invention is to provide the color filter that can suppress the orientation disorder of liquid crystal when being used for liquid crystal indicator and improve contrast, need not to append and grind or be provided with the low and easy method of the available cost of operation such as protective seam and make the color filter manufacture method of this color filter and liquid crystal indicator with high-contrast.

Be used to realize that the concrete grammar of above-mentioned technical matters is as described below.

＜1〉a kind of color filter, it has the resin black matrix that thickness is the clathrate pattern of 0.5 μ m～2.0 μ m at least on substrate, with thickness be the colored pattern of the striated pattern of 1.0 μ m～3.0 μ m, wherein, above-mentioned resin black matrix will be divided into a plurality of pixels on the aforesaid substrate, in at least a portion of above-mentioned colored pattern, the a plurality of pixels that respectively are listed in linearly arrangement (peristome of the grid of above-mentioned black matrix) of colored pattern go up and this pixel between resin black matrix on be provided with continuously, and respectively being listed on the resin black matrix with the direction of the direction quadrature of these row of above-mentioned colored pattern has overlapping O _XGroup, and with the resin black matrix of the parallel direction of direction of each row of above-mentioned colored pattern on have overlapping O _YGroup and a pair of pattern edge, when observing pixel in the pixel groups of above-mentioned linearly arrangement, draw: overlapping the O adjacent with this pixel _YHeight h with respect to the colored pattern surface in this pixel _YThan overlapping the O adjacent with this pixel _XHeight h with respect to the colored pattern surface in this pixel _XMore than the low 0.1 μ m.

＜2〉according to＜1〉described color filter, wherein, above-mentioned overlapping O _YWith the direction of the direction quadrature of above-mentioned row on length be more than the 2 μ m below the 10 μ m.

＜3〉according to＜1〉or＜2〉described color filter, wherein, the cross sectional shape of the end of above-mentioned colored pattern is that rectangle or awl long (taper length) they are the following tapers of 10 μ m.

＜4〉according to＜1 〉～＜3 in each described color filter, wherein, the cross sectional shape of the end of above-mentioned resin black matrix is that rectangle or awl length are the tapers below the 10 μ m.

＜5〉a kind of manufacture method of color filter, it is used to make following color filter,

Described method has: resin black matrix forms operation, forms the resin black matrix of clathrate pattern on substrate; And colored pattern forms operation, it is being formed with on the substrate of above-mentioned resin black matrix, form the photosensitive coloring composition layer with photosensitive coloring composition, the photosensitive coloring composition layer that forms is carried out pattern exposure, to carry out the photosensitive coloring composition layer behind the pattern exposure develops, form colored pattern

Described color filter has thickness at least on substrate be that the resin black matrix and the thickness of the clathrate pattern of 0.5 μ m～2.0 μ m is the colored pattern of the striated pattern of 1.0 μ m～3.0 μ m,

Above-mentioned resin black matrix will be divided into a plurality of pixels on the aforesaid substrate,

In at least a portion of above-mentioned colored pattern, be set up continuously on a plurality of pixels that respectively are listed in linearly arrangement of colored pattern and on the resin black matrix between this pixel, and have overlapping O on the above-mentioned resin black matrix that respectively is listed in the direction of the direction quadrature of these row _XGroup, and with the resin black matrix of the parallel direction of direction of above-mentioned each row on have overlapping O _YGroup and a pair of pattern edge,

When observing pixel in a plurality of pixels of above-mentioned linearly arrangement, draw: overlapping the O adjacent with this pixel _YHeight h with respect to the colored pattern surface in this pixel _YThan overlapping the O adjacent with this pixel _XHeight h with respect to the colored pattern surface in this pixel _XMore than the low 0.1 μ m.

＜6〉manufacture method of basis＜5〉described color filter, wherein, above-mentioned photosensitive coloring composition layer is by forming being formed with on the substrate of above-mentioned resin black matrix coating photosensitive coloring composition and prebake conditions, in the cross section of using the photosensitive coloring composition layer after cutting above-mentioned prebake conditions perpendicular to the pattern edge of above-mentioned resin black matrix and perpendicular to the face of substrate and obtaining, in the above-mentioned photosensitive coloring composition laminar surface, for for the some S of distance substrate point R farthest more close substrate 0.1 μ m on the substrate normal direction, when the position with the above-mentioned pattern edge nearest apart from this S is a benchmark, with the area side that forms resin black matrix is negative, with the area side that does not form resin black matrix is timing, and this S is being parallel to position on the direction of substrate surface in the scope of-2 μ m～+ 10 μ m.

＜7〉a kind of liquid crystal indicator, it has＜1～＜7 in each described color filter.

According to the present invention, can suppress the orientation disorder of liquid crystal in the time of can being provided for liquid crystal indicator and improve contrast color filter, can be with cost low and easy method make the color filter manufacture method of this color filter and liquid crystal indicator with high-contrast.

Description of drawings

Fig. 1 (a) is the vertical view of an example of expression color filter of the present invention, and Fig. 1 (b) is the A-A line sectional view of Fig. 1 (a), and Fig. 1 (c) is the B-B line sectional view of Fig. 1 (a).

Fig. 2 (a) is the vertical view of an example that expression has the substrate of resin black matrix, and Fig. 2 (b) is the A-A line sectional view of Fig. 2 (a), and Fig. 2 (c) is the B-B line sectional view of Fig. 2 (a).

Fig. 3 is the sectional view of taper colored pattern end in the example of color filter of the present invention.

Fig. 4 is the sectional view of the example of expression taper colored pattern end.

Fig. 5 is the sectional view of the example of expression taper colored pattern end.

Fig. 6 is the sectional view of the example of expression rectangle colored pattern end.

Fig. 7 is the sectional view of the example of expression undercutting (under cut) shape colored pattern end.

Fig. 8 is the sectional view of the example of expression undercut colored pattern end.

Fig. 9 is the sectional view of the example of expression undercut colored pattern end.

Figure 10 is the sectional view of the example of the resin black matrix after the approximate rectangular development of expression.

Figure 11 is the sectional view of example of the resin black matrix after the development of expression undercut.

Figure 12 is the sectional view of example of the resin black matrix after the development of expression taper.

Figure 13 is the sectional view of the example of the resin black matrix after the baking processing of expression back.

Figure 14 is illustrated in the sectional view that is formed with the example of colored pattern on the substrate with the resin black matrix after the back baking processing.

Figure 15 is the sectional view of the example of the photosensitive coloring composition layer after the expression prebake conditions.

Embodiment

Below, be that the material of photosensitive coloring composition, resin black matrix of the present invention is that photosensitive black composition and liquid crystal indicator of the present invention describe to the material of color filter of the present invention and manufacture method thereof, colored pattern of the present invention.

" color filter "

Color filter of the present invention is characterised in that, at least the resin black matrix and the thickness that have thickness and be the clathrate pattern of 0.5 μ m～2.0 μ m on substrate are the colored pattern of the striated pattern of 1.0 μ m～3.0 μ m, above-mentioned resin black matrix will be divided into a plurality of pixels on the aforesaid substrate, in at least a portion of above-mentioned colored pattern, be set up continuously on a plurality of pixels that respectively are listed in linearly arrangement of colored pattern and on the resin black matrix between this pixel, and have overlapping O on the above-mentioned resin black matrix that respectively is listed in the direction of the direction quadrature of these row _XGroup, and with the resin black matrix of the parallel direction of direction of above-mentioned each row on have overlapping O _YGroup and a pair of pattern edge, when observing pixel in the pixel groups of above-mentioned linearly arrangement, draw: overlapping the O adjacent with this pixel _YHeight h with respect to the colored pattern surface in this pixel _YThan overlapping the O adjacent with this pixel _XHeight h with respect to the colored pattern surface in this pixel _XMore than the low 0.1 μ m.

Usually, for colored pattern has overlapping portion on black matrix the color filter of structure, under the big situation of the difference in height of this lap, when this color filter was used for liquid crystal indicator, it is disorderly that the orientation of liquid crystal becomes, and contrast descends.

Particularly when colored pattern is the striated pattern, in the difference in height of colored pattern, the influence that is parallel near the part a pair of pattern edge of above-mentioned striped (for example in 4 limits of quadrilateral pixels, being parallel to the part on 2 limits of the pattern edge of colored pattern) is big.

By color filter being made the structure of the invention described above, can reduce overlapping the O approaching with above-mentioned a pair of pattern edge _YDifference in height with the colored pattern of the boundary member of pixel.Therefore, in liquid crystal indicator, use color filter of the present invention, can suppress the orientation disorder of liquid crystal, improve contrast.

In addition, the color filter of the invention described above can adopt need not to be provided with grind and protective seam be provided with etc. the low-cost of operation and simply method make.About the manufacture method of color filter of the present invention, see below and state.

Among the present invention, about the position of patterns such as colored pattern and resin black matrix relation, (wait describe " cross section ") unless otherwise specified represents that all forming the position that the face side observes from the substrate normal directional patterns concerns.

Among the present invention, thickness and height on " thickness " of patterns such as colored pattern and resin black matrix and " highly " expression substrate normal direction.

Among the present invention, " cross section " of patterns such as colored pattern and resin black matrix is meant to be used perpendicular to substrate and the section during perpendicular to the plane cutting pattern of pattern edge.

Among the present invention, the boundary line of the substrate (for example substrate or resin black matrix) of pattern and this pattern of formation when " pattern edge " is meant from the observation of substrate normal directional patterns formation face side.

For example, among Fig. 1 (a), the pattern edge of

colored pattern

20R, 20G, 20B is the line that the straight line of solid line is represented, among Fig. 2 (a), the pattern edge of resin black matrix 12 is lines that the straight line of solid line is represented.

Among the present invention, the pattern upper end is meant at this pattern end cross-sectional place, in patterned surfaces on the substrate normal direction apart from substrate point farthest, promptly be parallel on the direction of substrate surface point (for example, the upper end of the pattern among Fig. 3～Fig. 6 described later T) farthest apart from these pattern central authorities.

The pattern lower end is meant at this pattern end cross-sectional place, the point that joins with substrate in patterned surfaces (for example, the pattern lower end E1 among Fig. 3～Fig. 6 described later).

In addition, when the cross section of pattern end is taper, from the normal direction formation observed pattern edge of face side consistent with the lower end the pattern end cross-sectional (among Fig. 1 (c), the pattern edge of colored pattern 20G is pattern lower end E1 and pattern lower end E2) of substrate.

In the present invention, sometimes will be when the substrate normal directional patterns forms the face side and observes be called " Y direction ", " row (direction) " or " vertically " with the parallel direction (for example arrow Y Fig. 1) that respectively is listed as of colored pattern.In addition, sometimes will be when substrate normal direction colored pattern forms the face side and observes be called " directions X ", " capable (direction) " or " laterally " with the vertical direction (for example arrow X Fig. 1 (a)) that respectively is listed as of colored pattern.

Below, with reference to an example of Fig. 1 (a)～(c) and Fig. 2 (a)～(c) explanation color filter of the present invention.But, the invention is not restricted to following example.

Fig. 1 (a) is the vertical view of of the present invention one routine color filter 100, and Fig. 1 (b) is the A-A line sectional view of Fig. 1 (a), and Fig. 1 (c) is the B-B line sectional view of Fig. 1 (a).

Fig. 2 (a) is the vertical view that has only formed the substrate with resin black matrix 110 of resin black matrix in the stage midway of the color filter 100 of construction drawing 1 (a) on substrate.Fig. 2 (b) is the A-A line sectional view of Fig. 2 (a), and Fig. 2 (c) is the B-B line sectional view of Fig. 2 (a).

Shown in Fig. 1 (a)～(c), in the color filter 100, on substrate 10, be provided with: the resin black matrix 12 of clathrate pattern and the colored pattern of striated pattern (red pattern 20R, green pattern 20G and blue pattern 20B).At this, the thickness of resin black matrix 12 is 0.5 μ m～2.0 μ m, and the thickness of red pattern 20R, green pattern 20G and blue pattern 20B is respectively 1.0 μ m～3.0 μ m.

Above-mentioned resin black matrix 12 will be divided into the clathrate pattern of a plurality of pixels (having the pixel 14 in the substrate 110 of resin black matrix among the dotted line part in the color filter 100 among Fig. 1 (a), Fig. 2 (a)) on the aforesaid substrate 10.That is, above-mentioned resin black matrix 12 forms the clathrate pattern with a plurality of peristomes as pixel 14.

Here, area of the pattern as the clathrate pattern, so long as the zone that comprises by the synthetic zone of the striated pattern of striated pattern of directions X (laterally) (below be also referred to as " horizontal stripe ") and Y direction (vertically) (below be also referred to as " vertical bar ") gets final product, there is not particular restriction.

In the resin black matrix 12 of Fig. 1 (a) and Fig. 2 (a), except that above-mentioned synthetic zone, also possess the TFT shading with pattern 13, its with the striated pattern of the striated pattern of directions X and Y direction in abutting connection with and one jiao position being equivalent to pixel 14 stretch out to the inboard of pixel 14.Therefore, the shape that is shaped as a rectangular corner recess of pixel 14.

Here, the TFT shading is as the counter substrate of color filter 100 and the shading pattern that TFT (thin film transistor (TFT)) shading in the active-matrix substrate that is provided with is used with pattern 13.Wherein, the TFT shading can be omitted according to designs with pattern 13, so the shape of pixel also can be a rectangle.

In addition, in Fig. 1 (a)～(c), observe the row of 1 in the above-mentioned colored pattern (for example green pattern 20G), in above-mentioned a plurality of pixels, be provided with continuously on a plurality of pixels of linearly arrangement and on the resin black matrix between this pixel.Here, "～be provided with continuously " be meant do not have pattern edge and as the state of a pattern setting.

Shown in Fig. 1 (a), green pattern 20G with the resin black matrix of the direction (directions X) of direction (Y direction) quadrature of green pattern 20G on (being on the horizontal stripe) have overlapping O _XGroup, (being on the vertical bar) has overlapping O on the resin black matrix of the direction parallel with the direction of above-mentioned row (Y direction) _YGroup and a pair of pattern edge.

That is, above-mentioned green pattern 20G forms pattern as follows: not only cover 14 whole of above-mentioned pixels, and have overlapping O on resin black matrix 12 _XWith overlapping O _Y, and on resin black matrix, have a pair of pattern edge (pattern lower end E1 and pattern lower end E2)

In color filter 100, other row beyond the above-mentioned green pattern 20G also are same structure.

In the color filter 100 of Fig. 1 (a), dotted line part among the green pattern 20G (part corresponding with the pixel 14 among Fig. 2 (a)) is a green pixel, dotted line part among the red pattern 20R (part corresponding with the pixel 14 among Fig. 2 (a)) is a red pixel, and the dotted line part among the blue pattern 20B (part corresponding with the pixel 14 among Fig. 2 (a)) is a blue pixel.

In this color filter 100, shown in Fig. 1 (a), the bar direction of the length direction of pixel and

colored pattern

20R, 20G, 20B disposes abreast.

Fig. 1 (b) is resin black matrix (i.e. 1 overlapping the O that contains 1 row directions X _X) sectional view.

Shown in Fig. 1 (b), the pattern ends portion of resin black matrix 12 is taper described later, and the upper surface of pattern central portion is (with the reverse side of the face of substrate contacts.Down together) parallel with substrate surface.

On the other hand, green pattern 20G from the pixel on the resin black matrix 12 continuously (not having pattern edge) be provided with.

Resin black matrix 12 (is overlapping O _X) on the surface of green pattern 20G, during the surface observation of the green pattern 20G in pixel, with height h _XProjection.Specifically, surface and overlapping the O of the green pattern 20G in the pixel _XThe part on surface of green pattern 20G all parallel with substrate surface, but the latter only is h with respect to the former height apart from substrate on the substrate normal direction _X

Fig. 1 (c) contains the resin black matrix of 2 row Y directions and the sectional view of the green pattern 20G of 1 row.

Among Fig. 1 (c), the pattern ends portion of 2 resin black matrix 12 is taper, and the upper surface of pattern central portion is parallel with substrate surface.

Green pattern 20G with central part on the pixel, two-end part (is overlapping O on resin black matrix 12 _Y) mode be provided with.In addition, the pattern lower end E1 of the end of green pattern 20G is arranged on the resin black matrix 12 on Fig. 1 (c) right side, and the pattern lower end E2 of the other end of green pattern 20G is arranged on the resin black matrix 12 in Fig. 1 (c) left side.

The surface of green pattern 20G in the pixel is parallel with substrate surface in pixel, but (is overlapping O in resin black matrix 12 _Y) on then be the curved surface shape.

In addition, (be overlapping O on the resin black matrix 12 _Y) green pattern 20G surface, during green pattern 20G surface observation in pixel, with height h _YProjection.Specifically, with respect to the green pattern 20G surface in the pixel, overlapping O _YThe peak on green pattern 20G surface (apart from substrate point farthest.Down together) height apart from substrate on the substrate normal direction only is h _Y

Among the present invention, in the pixel in the pixel groups, overlapping the O adjacent with this pixel _YHeight h with respect to the colored pattern surface in this pixel _YMust be than overlapping the O adjacent with this pixel _XHeight h with respect to the colored pattern surface in this pixel _XMore than the low 0.1 μ m.

That is h, _XAnd h _YBetween satisfy the relation of following formula 1.Here, h _XAnd h _YBe more than the 0 μ m.

h _Y-h _X≤-0.1 μ m ... formula 1

Because h _XAnd h _YSatisfy the relation of above-mentioned formula 1, therefore with overlapping O _YThe difference in height of the colored pattern of adjacency reduces, and when color filter 100 is used for liquid crystal indicator, can suppress the liquid crystal aligning disorder, can improve contrast.

Among the present invention, color filter 100 particularly shown in Figure 1 is such, when the length direction of pixel is parallel with the direction of 1 row colored pattern, at overlapping O of pixel periphery _YThe shared increasing proportion of Y direction composition, thereby can more effectively suppress the orientation disorder of liquid crystal, more effectively improve contrast.

Based on above viewpoint, the shape of pixel preferably is the rectangle or the approximate rectangle (for example shape of rectangular at least 1 corner recess) of length direction with the Y direction, wherein, the ratio [length direction/Width] of preferred length direction (Y direction) and Width (directions X) is rectangle or the approximate rectangle more than 120/100.

More than, with Fig. 1～Fig. 2 an example of color filter of the present invention is illustrated, but color filter of the present invention is not limited to above-mentioned example.

For example, in color filter 100, the color of colored pattern is 3 looks, but the color of colored pattern also can be for monochromatic, double-colored or more than 4 looks.

In addition, to colored pattern is that 1 row and pixel are 1 and are that example is illustrated with green pattern and green pixel, but the pattern of other colors (for example red pattern, blue pattern, red pixel, blue pixel etc.) also can be the shape of above-mentioned green pattern and green pixel.

In addition, for all colored patterns in the color filter, needn't be the such shape of above-mentioned green pattern 20G, the such shape of above-mentioned green pattern 20G of respectively classifying as in the part of colored pattern gets final product.

In addition, the pixel of (by red pixel, green pixel, be green pixel when blue pixel constitutes) is this shape if the high color of visibility, and then contrast is improved the effect height.

Below, colored pattern, resin black matrix, substrate and other are described.

＜colored pattern 〉

Color filter of the present invention has the colored pattern of striated pattern and constitutes.Above-mentioned colored pattern for example can use photosensitive coloring composition described later to form well.

The thickness of colored pattern is necessary for 1.0 μ m～3.0 μ m.

Here so-called " thickness of colored pattern " is meant the thickness of the colored pattern in the pixel.

If this thickness less than 1.0 μ m, then the difference in height with the overlapping pixel periphery of black matrix sharply increases, and produces light leak, has to show uneven tendency.If this thickness surpasses 3.0 μ m, then there is the tendency of the thickness homogeneity decline of large-area chromatograph.

In addition, from reducing overlapping O _YHeight h _Y, making the relation of above-mentioned formula 1 viewpoint such as more effectively set up and set out, the thickness of colored pattern is preferably 1.5 μ m～2.5 μ m.

(overlapping portion)

Figure 3 shows that overlapping the O of Fig. 1 (c) _YNear situation of amplifying.

As shown in Figure 3, green pattern 20G is L in the length that has on the resin black matrix 12 on above-mentioned directions X _oOverlapping O _YThe surface of green pattern 20G is parallel with substrate surface in pixel, but at overlapping O _YThe curve-like projection is through being that pattern upper end T and descend (near substrate) join at pattern lower end E1 and resin black matrix 12 surfaces apart from substrate point farthest.

Among the present invention, overlapping O _YLength L _oBy this overlapping O _YObtain in the distance of directions X between the pattern edge of middle colored pattern and the pattern edge of resin black matrix.Particularly as shown in Figure 3, when the cross sectional shape of the cross sectional shape of colored pattern end and resin black matrix end is taper, as this overlapping O _YDistance between the pattern lower end E1 of middle colored pattern and the pattern lower end of resin black matrix on directions X is obtained.

To overlapping O _YLength L on directions X _oThere is not particular restriction, from reducing height h _Y, make the relation of above-mentioned formula 1 viewpoint such as more effectively set up and set out, be preferably 2 μ m above, below the 10 μ m, more preferably 2 μ m above, below the 8 μ m.

" overlapping O among the present invention _YHeight h with respect to the colored pattern surface in the pixel _Y" overlapping O when being meant the colored pattern surface observation in pixel _YThe peak on colored pattern surface along the height of substrate normal direction." overlapping O _XHeight h with respect to the colored pattern surface in the pixel _X" too.

For example, as shown in Figure 3, as overlapping O _YIn when containing pattern upper end T, above-mentioned height h _YBe the height till the T of upper end from the colored pattern surface in the pixel to colored pattern.

Height h of the present invention _YDo not have particular restriction,, more effectively improve the viewpoint of contrast and set out, be preferably below the 0.6 μ m, more preferably below the 0.5 μ m from more effectively suppressing the orientation disorder of liquid crystal.

(cross sectional shape of pattern end)

In color filter of the present invention, the cross sectional shape of the pattern end of colored pattern there is not particular restriction, can be Any shape such as rectangle, taper, undercut, from reducing height h _Y, make the relation of above-mentioned formula 1 viewpoint such as more effectively set up and set out preferred rectangle or taper.

In addition, colored pattern end cross-sectional more preferably rectangle or awl length is the following tapers of 10 μ m, and more preferably awl length is the following tapers of 10 μ m, and preferred especially awl length is the taper more than the 1 μ m, below the 5 μ m.

Below, " taper ", " awl is long ", " rectangle " and " undercut " are described.

～taper～

Among the present invention, the pattern end cross-sectional is also referred to as positive taper for " taper ", particularly, is meant that the pattern end cross-sectional all satisfies the shape of the arbitrary condition in following 2 conditions.

(condition 1) in the pattern end cross-sectional, observes from the pattern upper end, and the pattern lower end is being parallel to the outside that is positioned at this pattern on the direction of substrate surface (side that departs from from these pattern central authorities).

(condition 2) in the pattern end cross-sectional, and the center section of pattern upper end and pattern lower end is being parallel on the direction of substrate surface all in the pattern upper end between the pattern lower end in the line suitable with patterned surfaces.

Among the present invention, the cross sectional shape of the green pattern 20G end among Fig. 3 comprises taper.The cross sectional shape of green pattern end be taper other examples as shown in Figure 4 and Figure 5.

In addition, when the cross sectional shape of pattern end is taper, suitable from the pattern lower end that the substrate normal directional patterns forms observed pattern edge of face side and the pattern cross section.

Among the present invention, when the cross sectional shape of pattern end is taper, pattern upper end and pattern lower end are called awl length in the distance that is parallel on the direction of substrate surface.

For example, as Fig. 3～shown in Figure 5, in

green pattern

20G, 22G, 24G, bore long L _cFor pattern upper end T between the E1 of pattern lower end in the distance that is parallel on the direction of substrate surface.

The preferable range of awl length as mentioned above.

In addition, in Fig. 3～Fig. 5, bore long L _cThan overlapping O _YLength L _oShort, but the invention is not restricted to this relation, bore long L _cAlso can be than overlapping O _YLength L _oLong.

～rectangle～

Among the present invention, the pattern end cross-sectional is meant that for " rectangle " green pattern 26G as shown in Figure 6 is such, pattern upper end T, pattern lower end E1 and in being equivalent to the line of patterned surfaces, the center section of pattern upper end T and pattern lower end E1 is being parallel to the shape that is positioned at position overlapped on the direction of substrate surface.

When the cross sectional shape of pattern end is rectangle, forms the observed pattern edge of face side from the substrate normal directional patterns and be equivalent to pattern upper end and pattern lower end the pattern cross section.

～undercut～

Among the present invention, the pattern end cross-sectional is also referred to as back taper for " undercut ", is neither to belong to the shape that above-mentioned taper does not belong to rectangle yet.For example, can be set forth in the shape that has the outstanding part of bongrace shape in the pattern end cross-sectional etc.

Fig. 7～Figure 9 shows that green pattern end cross-sectional is the example of " undercut ".

Green pattern 28G among Fig. 7 is in the pattern end cross-sectional, and pattern lower end E1 is positioned at the center side of this pattern in the direction that is parallel to substrate surface when pattern upper end T observes, and does not satisfy above-mentioned " condition 1 ".

Green pattern 30G among Fig. 8 and Fig. 9 and green pattern 32G, pattern lower end E1 is positioned at the outside of this pattern in the direction that is parallel to substrate surface when pattern upper end T observes, and satisfies above-mentioned " condition 1 ".But in being equivalent to the line of patterned surfaces, the part in the center section of pattern upper end T and pattern lower end E1 departs from the pattern upper end between the pattern lower end being parallel on the direction of substrate surface, do not satisfy above-mentioned " condition 2 ".

In addition, the cross sectional shape of pattern end is a undercut, when only satisfying above-mentioned condition 1, forms the observed pattern edge of face side from the substrate normal directional patterns and is equivalent to pattern lower end the pattern cross section.When only not satisfying above-mentioned condition 1 (, when only satisfying above-mentioned condition 2), form the observed pattern edge of face side from the substrate normal directional patterns and be equivalent to pattern upper end the pattern cross section.(look Film Thickness Ratio)

In the present invention, from more effectively reducing above-mentioned height h _YViewpoint set out, " the look Film Thickness Ratio " of following formula 2 expressions is very important sometimes.

Look Film Thickness Ratio (%)=(overlapping O _YThe thickness/pixel of colored pattern in the thickness of colored pattern) * 100... formula 2

In the formula 2, overlapping O _YThe thickness of colored pattern be to overlapping O from colored pattern lower end E1 _YThe peak on colored pattern surface between distance on the substrate normal direction.

Particularly as shown in Figure 3, as overlapping O _YWhen containing colored pattern upper end T, be the distance of upper end T on the substrate normal direction from colored pattern lower end E1 to colored pattern.

From more effectively reducing above-mentioned height h _YViewpoint set out, the look Film Thickness Ratio is preferably 30%～100%, more preferably 50%～90%.

＜resin black matrix 〉

Color filter of the present invention constitutes the resin black matrix with clathrate pattern.

Among the present invention, " resin black matrix " is meant the black matrix that is formed by the material that contains resin.Above-mentioned resin black matrix for example preferably uses the aftermentioned photosensitive black composition to form.

The optical concentration of resin black matrix of the present invention (OD value) does not have particular restriction, be preferably more than 2.0, below 8.0, more preferably more than 3.0, more preferably more than 4.0, below 6.0.When optical concentration is 2.0 when above, can suppress the decline of the display quality of degradation display device under the contrast.

In addition, so-called optical concentration is meant ISO Visual transmission optics concentration here.As the analyzer that can in the mensuration of ISO Visual transmission optics concentration, use, can enumerate for example X-Rite 361T (V) of SAKATAINX ENG. Co., Ltd..

As the live width of resin black matrix of the present invention, can guarantee the viewpoint of brightness to be preferably 5～30 μ m from high aperture.

The thickness of resin black matrix is necessary for 0.5 μ m～2.0 μ m as mentioned above.

If this thickness less than 0.5 μ m then is difficult to improve the OD value, the tendency that exists light-proofness to descend.If this thickness surpasses 2.0 μ m, there is the tendency that causes light leak because of liquid crystal aligning is bad in the inclination steepen on chromatograph surface during then stacked chromatograph.

In addition, from reducing above-mentioned overlapping O of colored pattern _YHeight h _Y, making the relation of above-mentioned formula 1 viewpoint such as more effectively set up and set out, the thickness of resin black matrix is preferably 0.8～1.5 μ m.

In color filter of the present invention, the cross sectional shape of the pattern end of resin black matrix there is not particular restriction, can be Any shape such as rectangle, taper (for example cross sectional shape of 12 ends of the resin black matrix among Fig. 1～Fig. 9), undercut, from reducing height h _Y, make the relation of above-mentioned formula 1 viewpoint such as more effectively set up and set out, be preferably rectangle or taper.

About the cross sectional shape (rectangle, taper, undercut) and the long definition of awl of the pattern end of resin black matrix, identical with the situation of colored pattern.

Among Fig. 1～Fig. 9, L _BThe awl of the pattern end of expression resin black matrix 12 is long.

In addition, from reducing height h _YMaking the relation of above-mentioned formula 1 viewpoint such as more effectively set up sets out, the end cross-sectional of resin black matrix is rectangle or the following taper of the long 10 μ m of awl more preferably, and the following taper of the long 10 μ m of awl more preferably is preferably the taper that the long 2 μ m of awl are above, 8 μ m are following especially.

＜substrate 〉

As substrate of the present invention, the photo-electric conversion element substrate that for example can be set forth in alkali-free glass, soda-lime glass, PYREX (registered trademark) glass, quartz glass that uses in the liquid crystal display cells etc. and the above-mentioned glass that adheres to nesa coating and use in solid-state imager etc. is silicon substrate etc. for example.In addition, can also use plastic base.Wherein, from reagent resistance and stable on heating viewpoint, preferred alkali-free glass.On these substrates, at first form black matrix such as clathrate to isolate each pixel, form colored pixels in the vacancy part of grid (below be also referred to as " peristome " or " pixel ") then.

In addition, on these substrates, can also be provided with as required undercoat with improve and upper layer between adaptation, prevent the material diffusion or make the substrate surface planarization.From the viewpoint of further performance effect of the present invention, substrate is preferably large-scale (Yi Bian being about more than the 1m) substrate.

＜other 〉

Color filter of the present invention can also have ELD (for example ITO film etc.), column spacer, orientation control and will usually constitute with projection pattern etc. is known except that above-mentioned key element (resin black matrix, colored pattern and substrate).

The color of the colored pattern in the above-mentioned color filter (colored pixels) as mentioned above, more preferably more than 3 looks.Wherein, be preferably R (red), G (green), these 3 kinds of colors of B (indigo plant) especially.

Color filter of the present invention can be applicable to televisor, PC, industry with or the display device of various uses such as the carried terminal of medical etc. watch-dog, liquid crystal projection apparatus, game machine, mobile phone etc., digital camera, automobile navigation instrument.

" manufacture method of color filter "

Method as making color filter of the present invention does not have particular restriction, the manufacture method of the color filter of the present invention of preferred following explanation.

That is, the manufacture method of color filter of the present invention is to make the method for the color filter of the invention described above, comprises following operation: the resin black matrix that forms the resin black matrix of clathrate pattern on substrate forms operation; Be formed with on the substrate of above-mentioned resin black matrix, the photosensitive coloring composition layer that forms the photosensitive coloring composition layer with photosensitive coloring composition forms operation; The photosensitive coloring composition layer that forms is carried out the exposure process of pattern exposure; The photosensitive coloring composition layer that will carry out pattern exposure develops and forms the developing procedure of colored pattern.

" resin black matrix formation operation "

It is the operation that forms resin black matrix on substrate that above-mentioned resin black matrix forms operation.

Above-mentioned black matrix forms operation and preferably comprises following operation at least: the photosensitive black composition layer that forms the photosensitive black composition layer with photosensitive black composition on substrate forms operation; Exposure process with above-mentioned photosensitive black composition layer exposure; With the above-mentioned photosensitive black composition layer development after the above-mentioned exposure and the developing procedure of the black matrix pattern of formation.

Resin black matrix forms operation except that above-mentioned each operation, roasting procedure (prebake conditions operation, back roasting procedure) can also be set as required wait other operations.

In addition, in the following description, sometimes " resin black matrix " abbreviated as " black matrix ".-photosensitive black composition layer formation operation-

In this operation, use photosensitive black composition on substrate, to form the photosensitive black composition layer.About substrate, as mentioned above.

As the method that on substrate, forms the photosensitive black composition layer, for example have by coating and wait the method for on substrate, giving photosensitive black composition.

As the method for on substrate, giving photosensitive black composition, can use various adding methods such as slot coated (below be also referred to as " slot coated (method) "), ink-jet method, rotary coating (below be also referred to as " spin coating (method) " or " rotary coating (method) "), curtain coating coating, roller coat cloth, silk screen print method.Wherein, from the viewpoint of precision and speed, preferred slot coated.From improving the viewpoint of coating, preferably before carrying out these coatings, use ultraviolet ray or various cleansing solution washing substrate.

In addition, can also use in advance in the method for the adhering molding transfer by above-mentioned adding method formation on the interim supporter to the substrate.

About printing transferring method, the present invention can preferably use the Jap.P. spy to open the method for making described in paragraph numbering [0023], [0036]～[0051] of 2006-23696 communique or paragraph numbering [0096]～[0108] that the Jap.P. spy opens the 2006-47592 communique.

As the laminating machine that uses in the transfer printing, can preferably use the laminating machine of putting down in writing in the large-scale two ply laminating machine (Japanese original text: Er Ding Stickers ラミネ one ) put down in writing among Figure 24 of WO2006-4225 or the international application no JP2007/069132 communique.Use these lamination functions to obtain high productivity.

Thickness when giving photosensitive black composition on the substrate (for example coating thickness) can be done suitable adjustment according to the design load of the thickness of formed black matrix, generally is preferably 0.5～2.0 μ m, more preferably 0.8 μ m～1.5 μ m.

-exposure process-

In exposure process, will form the photosensitive black composition layer that forms in the operation at above-mentioned photosensitive black composition layer and expose by the mask pattern of stipulating, form pattern (during minus, only making by light-struck coated film partly solidified).As the radioactive ray that can in exposure, use, especially preferably use ultraviolet rays such as g line, h line, i line.Exposure is preferably 5～500mJ/cm ², 10～300mJ/cm more preferably ², most preferably be 10～200mJ/cm ²

Exposure machine can adopt the proximity printing machine, also can adopt mirror surface projection formula exposure machine or step-by-step exposure machine.

-developing procedure-

Then, by carrying out the alkali development treatment, for example when photosensitive black composition is minus, can make in the above-mentioned exposure light not illuminated portion be dissolved in aqueous alkali, the residual light part of solidifying only.

As developer solution, adopt organic base developer solution or inorganic base developer solution or its mixed solution.

As the alkaline agent that uses in the developer solution, can enumerate for example NaOH, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate, ammoniacal liquor, ethylamine, diethylamide, dimethylethanolamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, choline, pyrroles, piperidines and 1,8-diazabicyclo-[5,4,0]-organic basic compounds such as 7-undecylene preferably is diluted to these alkaline agents 0.001～10 quality %, is preferably the alkaline aqueous solution that 0.01～1 quality % obtains and uses as developer solution with pure water.In addition, when using this developer solution that forms by alkaline aqueous solution, generally after development, wash (rinse) with pure water.

The present invention is behind this developing procedure, before roasting procedure described later, and is preferred so that lower end forms black matrix pattern with respect to the mode that the upper end in the above-mentioned photosensitive black composition layer is positioned at the position of-3.0～+ 3.0 μ m.

Here, " make lower end be positioned at the position of-3.0～+ 3.0 μ m with respect to the upper end in the above-mentioned photosensitive black composition layer " to be meant the black matrix pattern that forms used pattern edge and the face cutting perpendicular to substrate surface perpendicular to this pattern after, the following state in the cross section of an end of this pattern.

Promptly, upper end with this pattern is a benchmark, make this pattern center side for negative, this pattern outside (side that departs from above-mentioned central portion) is timing, and the position of the lower end of the black matrix pattern on the direction parallel with substrate surface is positioned at the scope of-3.0～+ 3.0 μ m.

For example, when above-mentioned when satisfying " condition 1 ", on the occasion of.

The definition of " top " " bottom " of photosensitive black composition layer or black matrix pattern as described later.

The cross sectional shape of cross sectional shape, the particularly end of black matrix pattern can utilize each condition of exposure, development and prebake conditions described later to control.At first, the cross sectional shape to the black matrix pattern end behind the developing procedure is elaborated.

In the formation operation of black matrix, when the photosensitive black composition layer after the exposure is developed, when the surface of photosensitive black composition layer (is referred to not the face with substrate contacts; Below in black matrix address too) and from this surface to thickness (the photosensitive black composition layer is along the length of substrate normal direction) 1/3rd inner (hereinafter referred to as " photosensitive black composition layer top " with interior layer.Similarly will be in black matrix from the surface of black matrix to thickness 1/3rd with interior being called " black matrix top ") develop and the back side to the photosensitive black composition layer (refers to the face with substrate contacts; Below black matrix is called " back side of black matrix " similarly) and 2/3rds inner (hereinafter referred to as " photosensitive black composition layer bottom " with interior layer from this back side to respect to the thickness of photosensitive black composition layer.Being also referred to as " black matrix bottom " at black matrix) when developing for equal extent, the cross sectional shape of photosensitive black composition layer for example is an approximately perpendicular shape (approximate rectangular shape) shown in Figure 10.

Relative therewith, compare with the development that carry out on photosensitive black composition layer top with surface the photosensitive black composition layer, too much sometimes or not enough to the development that carry out the back side and the photosensitive black composition bottom of photosensitive black composition layer.When development is too much, photosensitive black composition layer bottom is etat lacunaire, if will be formed with the Width cutting of the substrate of photosensitive black composition layer (black matrix) along black matrix, then the cross sectional shape of photosensitive black composition layer for example is a undercut (back taper) shown in Figure 11.On the other hand, when underdevelop, photosensitive black composition layer bottom is outstanding state, if will be formed with the Width cutting of the substrate of photosensitive black composition layer (black matrix) along black matrix, then the cross sectional shape of photosensitive black composition layer for example is taper (positive taper) shown in Figure 12.

In addition, behind this developing procedure, before the roasting procedure described later, when back draught shown in Figure 11 was big, in developing procedure, the teat on top was easily damaged, was easy to generate black matrix plane shape defect.Therefore, the size of back draught is preferably below the 3 μ m, and promptly with respect to the upper end in the photosensitive black composition layer, lower end is preferably placed at the position of-3.0～0 μ m.In addition, when positive tapering shown in Figure 12 is big, because it is underdevelop, easily the part that should remove the photosensitive black composition layer residual residue, therefore, the size of positive tapering is preferably below the 3 μ m, and promptly with respect to the upper end in the photosensitive black composition layer, lower end is preferably placed at the position of 0～3.0 μ m.Therefore, most preferred shape is that the end of above-mentioned photosensitive black composition layer shown in Figure 10 is approximately perpendicular shape.Preferably, after development, be approximately perpendicular shape as mentioned above, carry out back baking then and produce the heat limit (Hot ダレ) of collapsing, form circular-arc cross sectional shape.

In fact, there is change in what owing to the unequal of operation, be positioned at the cross sectional shape of position of-3.0～+ 3.0 μ m with respect to upper end just no problem for the lower end that is shaped as of the photosensitive black composition layer after as long as develop, and more preferably lower end is positioned at the cross sectional shape of the position of-2.0～+ 2.0 μ m with respect to upper end.

In order to make the end of above-mentioned photosensitive black composition layer behind this developing procedure, before the aftermentioned roasting procedure is vertical cross-section shape shown in Figure 10, and it is very important suitably to regulate development conditions, by changing development conditions, can regulate cross sectional shape.Roughly,, be back taper, otherwise when under slightly weak condition, developing, be positive taper comparing with development conditions commonly used when developing under the slightly strong condition.

Stronger condition is meant higher temperature, longer time, more flow, higher spray pressure etc., otherwise, more weak condition is meant lower temperature, shorter time, flow still less, lower spray pressure etc., and wherein, the adjusting of temperature and time is particularly important.

Particularly, from regulating the viewpoint of cross sectional shape with good precision, development temperature is preferably 20～35 ℃, more preferably 20～30 ℃.Development time is preferably 20～120 seconds, more preferably 30～70 seconds.

Wherein, as the preferred compositions of development temperature and development time, for example can be set forth in 23 ℃ of developments 40～70 seconds down of temperature, develop 30～60 seconds down for 25 ℃ in temperature.

Press about spray,, be preferably 0.01～0.5MPa, more preferably 0.05～0.3MPa, more preferably 0.1～0.3MPa from preventing the black damaged viewpoint of matrix.

In order to regulate cross sectional shape more subtly, preferably form in the operation and append prebake conditions operation described later at black matrix.

-roasting procedure-

Then, black matrix pattern is implemented to be called the heat treated of baking processing (back baking).Baking is in order to make the heat treated after the completely crued development of photosensitive black composition, to carry out 150～260 ℃ heat curing usually and handle.

Baking temperature is preferably 150～260 ℃, more preferably 180～260 ℃, most preferably is 200～240 ℃.Stoving time is preferably 10～150 minutes, and further preferred 20～120 minutes, most preferably 30～90 minutes.

Behind above-mentioned developing procedure, to the end of the end of above-mentioned photosensitive black composition layer vertical cross-section shape approximate shown in Figure 10, in above-mentioned condition and range, toast, cross sectional shape can be adjusted to approximate shown in Figure 14 circular-arc.This be because, by baking processing the photosensitive black composition after developing is heated, before the photosensitive black composition full solidification, be in low viscosity state, so edge part takes place to curl temporarily under capillary effect, and promptly form above-mentioned shape through overcuring.

The curling easiness at the edge that causes by the heating after this development (below be sometimes referred to as " heat collapse limit ") can with the photonasty black combination form and prebake conditions condition, conditions of exposure or development conditions change.Usually, in the ratio of components of photosensitive black composition, compare with binder polymer described later, the concentration of opacifier is low more, the easy more heat limit of collapsing, and the concentration of opacifier is high more, the difficult more heat limit of collapsing.For example, the thickness after baking is when being 1.4 μ m, and can preferably use OD (optical concentration of black matrix) is 4.1 opacifier concentration.In contrast to this, the thickness after baking is when being 1.0 μ m, is under 4.1 the opacifier concentration at OD, is difficult for taking place the heat limit of collapsing.

Additive method as producing the hot limit of collapsing can be set forth in the method for working hard on the composition of monomer.For example the Jap.P. spy to open the 2004-163917 communique described like that, as monomer, can be preferably with 3 officials can be above monomer mix use with 2 functional monomers.

The prebake conditions temperature is low more, the time is short more, the easy more heat limit of collapsing, and temperature is high more, the time is long more, the difficult more heat limit of collapsing, the weak more easy more heat of the exposure intensity limit of collapsing, the limit and strong more difficult more heat is collapsed, development conditions is weak more, the easy more heat limit of collapsing, the limit and strong more difficult more heat is collapsed.When back lower slightly and time of baking temperature is long, the heat limit of collapsing easily, temperature height and time are difficult for the heat limit of collapsing in short-term.

Figure 13 is an example of the cross sectional shape of the black matrix after the expression baking.

Among Figure 13, will will deceive the clearing end (promptly black matrix lower end) of matrix from the initial point of smooth black matrix surface circular arc (promptly black matrix upper end) as the P point as the Q point.

Distance on the direction that is parallel to substrate surface of ordering from the P point to Q is above-mentioned " awl length ".The preferable range of awl length as mentioned above.

Figure 14 shows that the sectional view when on the substrate of the black matrix that is formed with above-mentioned Figure 13, forming colored pixels.The projection that so can suppress the overlapping portion of black matrix and colored pixels (is above-mentioned high h _Y).

About baking processing, can use heating arrangements such as heating plate, convection oven (heated air circulation type dryer), high frequency heating machine under these conditions, with continous way or batch (-type) the photosensitive black composition layer after developing is carried out baking processing.

-other operations-

Form in the operation at black matrix of the present invention, after above-mentioned photosensitive black composition layer forms operation, before the above-mentioned exposure process, can also add the prebake conditions operation, behind above-mentioned developing procedure, before above-mentioned baking (back baking) operation, can also contain the operation of the black matrix curing that will form as required by exposure.

(prebake conditions operation)

As mentioned above,, form the condition of the exposure imaging in the operation the also preferred prebake conditions condition of suitably regulating in order to regulate black matrix display device movie queen's cross sectional shape except regulating black matrix.Form in the operation at black matrix of the present invention, compare,, then form back taper,, then form taper if at high temperature carry out if carry out at low temperatures with prebake conditions condition commonly used.

Particularly, when carrying out prebake conditions with heating plate, the prebake conditions temperature is preferably 65 ℃～120 ℃.More than 65 ℃ the time, can prevent that the photosensitive black composition layer is peeled off in the developing procedure, below 120 ℃ the time, can make the state of the development of photosensitive black composition layer bottom for progress.More preferably 70 ℃～100 ℃, most preferably be 75 ℃～90 ℃.In addition, stoving time is preferably 50～300 seconds, more preferably 90～200 seconds, most preferably is 100～180 seconds.If carry out prebake conditions under these conditions, then be easy to regulate the cross sectional shape after the photosensitive black composition layer develops.

In addition, prebake conditions also can be carried out in baking oven, and this moment also can be by suitably setting prebake conditions condition same as described above, regulates the cross sectional shape after the development.

＜colored pattern forms operation 〉

Colored pattern formation operation of the present invention is at least with photosensitive coloring composition and is being formed with formation photosensitive coloring composition layer (the photosensitive coloring composition layer forms operation) on the substrate of above-mentioned resin black matrix, the photosensitive coloring composition layer that forms is carried out pattern exposure (dyed layer exposure process), the photosensitive coloring composition layer that will carry out pattern exposure develops (dyed layer developing procedure), forms the operation of the colored pattern of striated pattern.

In addition, from the cross sectional shape of colored pattern end being formed the viewpoint of taper, preferably behind above-mentioned developing procedure, form colored pattern by baking (roasting procedure).

-photosensitive coloring composition layer formation operation-

Form in the operation at the photosensitive coloring composition layer, photosensitive coloring composition is being formed with formation photosensitive coloring composition layer on the substrate of resin black matrix.

As being formed with the method that forms the photosensitive coloring composition layer on the substrate of resin black matrix, can use the method identical with the method that forms the photosensitive black composition layer on substrate is coating process or printing transferring method.

Wherein, from effectively reaching the viewpoint of effect of the present invention, preferably use the method at the substrate front coating photosensitive coloring composition that is being formed with black matrix such as slot coated device.

In order to obtain sufficient Color reproduction zone and to obtain sufficient panel luminance, the bed thickness of photosensitive coloring composition layer is preferably the scope of 1.0～3.0 μ m, more preferably the scope of 1.5～2.5 μ m.

-dyed layer exposure process-

In the dyed layer exposure process, with above-mentioned photosensitive coloring composition layer exposure.

About the exposure-processed of photosensitive coloring composition layer, can similarly carry out with the exposure process of photosensitive black composition layer.When forming the colored pattern of multiple color, the regulation mask pattern by of all kinds exposes by of all kinds, gets final product the photosensitive coloring composition layer of all kinds (solidifying during minus) after pattern forms rayed.

-prebake conditions operation-

Form in the operation at colored pattern, in order to make the photosensitive coloring composition drying, also can after the photosensitive coloring composition layer forms operation, before the dyed layer exposure process, the operation (dyed layer prebake conditions operation) with photosensitive coloring composition layer prebake conditions be set.

The prebake conditions temperature of photosensitive coloring composition layer is preferably 60～140 ℃, more preferably 80 ℃～120 ℃.The prebake conditions time is preferably 30～300 seconds, more preferably 80～200 seconds.

In addition, from reducing above-mentioned high h _Y, make the relation of above-mentioned formula 1 viewpoint such as more effectively set up to set out, the surface configuration of the photosensitive coloring composition layer after the prebake conditions is very important sometimes.

For example, as shown in figure 15, in the cross section that the photosensitive coloring composition layer of using after cutting above-mentioned prebake conditions perpendicular to the pattern edge of above-mentioned resin black matrix 12 and perpendicular to the face of substrate 10 40 obtains, in the above-mentioned photosensitive coloring composition laminar surface 42, with respect to distance substrate 10 point R farthest, the position of the some S of more close substrate 0.1 μ m is very important sometimes on the substrate normal direction.

For example, about this S in the position that is parallel on the direction of substrate surface, as pattern edge E with the resin black matrix nearest apart from this S _BThe position be benchmark (0), resin black matrix forms area side and is negative (-), the non-formation area side of resin black matrix is during for just (+), preferably in the scope of-2 μ m～+ 10 μ m.

This shape for example can be that (more preferably the above 5 μ m of 1 μ m are following) obtains well below the 10 μ m by the awl length that makes resin black matrix.

-dyed layer exposure process-

-dyed layer developing procedure-

In the dyed layer developing procedure, the above-mentioned photosensitive coloring composition layer after the exposure is developed.

About the development treatment of photosensitive coloring composition layer after the exposure, can carry out the operation identical operations described in the explanation with the developing procedure of photosensitive black composition layer, can preferably use at the developer solution described in the above-mentioned developing procedure.

As development conditions, in order to be adjusted in the length and the protruding height of black matrix and the overlapping portion of overlapping generation of colored pixels, preferably under the development conditions of in the explanation of the developing procedure of above-mentioned photosensitive black composition layer, putting down in writing the photosensitive coloring composition layer is developed.

-dyed layer roasting procedure-

In the dyed layer roasting procedure, with the above-mentioned photosensitive coloring composition layer baking after developing.

Method about the baking of the photosensitive coloring composition layer after will developing can adopt the method same with the roasting procedure of above-mentioned photosensitive black composition layer.

In addition, when forming the colored pattern of multiple form and aspect such as RGB3 form and aspect, can carry out the circulation of formation, exposure, development and the baking of photosensitive coloring composition layer by required form and aspect number repeatedly, after also can carrying out formation, exposure and the development of photosensitive coloring composition layer, at last whole form and aspect are toasted together by each form and aspect.Thus, make the color filter of the colored pixels have black matrix and to form by required form and aspect.

Then, photosensitive coloring composition and the photosensitive black composition that uses in the manufacture method to color filter of the present invention describes.

" photosensitive coloring composition "

It is that radiation-ray sensitive composition is (for example during minus that the colored pattern of color filter of the present invention forms with photosensitive coloring composition, be the radiation-ray sensitive composition that under the effect of light, solidifies), preferably contain (A-1) colorant, (B) binder polymer, (C-1) polymerizable compound, (D) Photoepolymerizationinitiater initiater and (E) solvent, can also contain other additives such as macromolecule dispersing agent or surfactant as required.

-(A-1) colorant-

Colorant can suitably be selected from the dye pigment class.As the pigment that colorant uses, can be inorganic pigment, can be organic pigment also, consider when being preferably high-transmission rate the preferred particle size little pigment of trying one's best.Average particle size is preferably 10～100nm, more preferably the scope of 10～50nm.By using macromolecule dispersing agent described later in the photosensitive coloring composition that uses in the present invention, even under the little situation of the size of colorant, pigment-dispersing and dispersion stabilization are also fine, even therefore thickness approaches the colored pixels that also can form the excitation excellence.

Form the inorganic pigment of using colorant as being used as colored pattern (colored pixels), can enumerate metallic compounds such as metal oxide, metal complex, specifically can enumerate composite oxides of metal oxides such as iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and above-mentioned metal etc.

As organic pigment, for example can enumerate

C.I. pigment yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;

C.I. pigment orange 36,38,43,71;

C.I. pigment red 81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270;

C.I. pigment violet 19,23,32,37,39;

C.I. pigment blue 1,2,15,15:1,15:3,15:6,16,22,60,66;

C.I. pigment Green 7,36,37;

C.I. pigment brown 25,28;

C.I. pigment black 1 etc.

The present invention is preferred following pigment further, but there is no particular restriction:

C.I. pigment yellow 11,24,108,109,110,138,139,150,151,154,167,180,185;

C.I. pigment orange 36,71;

C.I. pigment red 122,150,171,175,177,209,224,242,254,255,264;

C.I. pigment violet 19,23,37;

C.I. pigment blue 15: 1,15:3,15:6,16,22,60,66;

C.I. pigment Green 7,36,37.

These organic pigments can use separately or multiple being used in combination in order to improve excitation.The object lesson of combination is as follows.

For example, use pigment as red (R), can use the potpourri of anthraquinone (anthraquinone) class pigment, perylene class pigment, diketopyrrolopyrrolecocrystals (diketopyrrolopyrrole) class pigment or in them at least a kind and bisdiazo class yellow uitramarine, isoindoline (isoindoline) class yellow uitramarine, Kui phthalein ketone (quinophthalone) class yellow uitramarine Huo perylene class red pigment etc. separately.For example, as anthraquinone class pigment, can enumerate C.I. paratonere 177 Zuo Wei perylene class pigment, C.I. paratonere 155, C.I. paratonere 224 can be enumerated,, C.I. paratonere 254 can be enumerated as diketopyrrolopyrroles pigment, from the viewpoint of Color reproduction, preferably with the mixing of C.I. pigment yellow 13 9.In addition, from the viewpoint that obtains sufficient excitation and suppress to depart from mutually from the NTSC aim colour, the mass ratio of red pigment and yellow uitramarine is preferably 100: 5～and 100: 50.As above-mentioned mass ratio, preferred especially 100: 10～100: 30 scope.When being combination between the red pigment, can regulate according to colourity.

Use pigment as green (G), can use halogenated phthalocyanines class pigment separately, or with the potpourri of itself and bisdiazo class yellow uitramarine, Kui phthalein ketone yellow uitramarine, azomethine (azomethine) class yellow uitramarine or isoindoline class yellow uitramarine.For example, as such example, preferred C.I. pigment Green 7,36,37 and the potpourri of C.I. pigment yellow 83, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 180 or C.I. pigment yellow 185.From the viewpoint that obtains sufficient excitation and suppress to depart from mutually from the NTSC aim colour, the mass ratio of viridine green and yellow uitramarine is preferably 100: 5～and 100: 150.As mass ratio, preferred especially 100: 30～100: 120 scope.

Use pigment as blue (B), can use phthalocyanine pigment or itself separately Yu the potpourri of dioxazines violet pigment.For example, preferred C.I. pigment blue 15: 6 with the potpourri of C.I. pigment Violet 23.The mass ratio of blue pigment and violet pigment is preferably 100: 0～and 100: 50, more preferably 100: 5～100: 30.

About the content of (A-1) colorant (pigment) in the photosensitive coloring composition layer of the present invention's use, the total solid composition (quality) with respect to said composition is preferably 25～75 quality %, more preferably 32～70 quality %.If (A-1) content of colorant (pigment) is in above-mentioned scope, then colour saturation fully also can be guaranteed excellent look characteristic effectively.

-(B) binder polymer-

In order to improve by membrane property and to give developing property etc., above-mentioned photosensitive coloring composition of the present invention preferably contains binder polymer.As binder polymer, can use following alkali soluble resin.

As the alkali soluble resin that the present invention uses, can from wire organic high molecular polymer and molecule (being the molecule of main chain preferably), have in the alkali soluble resin of at least 1 group (for example carboxyl, phosphate, sulfonic group, hydroxyl etc.) that promotes alkali-soluble and suitably select with bases multipolymer, styrene copolymer.

As the preferred example of above-mentioned alkali soluble resin, can enumerate the polymkeric substance that side chain has carboxylic acid, for example the Jap.P. spy opens clear 59-44615 communique, the special public clear 54-34327 communique of Jap.P., the special public clear 58-12577 communique of Jap.P., the special public clear 54-25957 communique of Jap.P., the Jap.P. spy opens clear 59-53836 communique, the Jap.P. spy opens the methacrylic acid copolymer of putting down in writing in each communique of clear 59-71048 communique, acrylic copolymer, itaconic acid copolymer, the butenoic acid multipolymer, maleic acid and partial esterification maleic acid etc., and side chain has the acid cellulose derivant of carboxylic acid, acrylic copolymer with the polymkeric substance of hydroxyl and addition product of acid anhydrides etc.

Acid number is 10～200mgKOH/g, is preferably 30～180mgKOH/g, more preferably the scope of 50～150mgKOH/g.

As the concrete structure unit of alkali soluble resin, preferred especially (methyl) acrylic acid and can with the multipolymer of other monomers of its copolymerization.As above-mentioned can with other monomers of (methyl) acrylic acid copolymer, can enumerate (methyl) alkyl acrylate, (methyl) acrylic acid aryl ester, vinyl compound etc.Here, the hydrogen atom of alkyl and aryl can be substituted the base replacement.

As above-mentioned (methyl) alkyl acrylate and (methyl) acrylic acid aryl ester, can enumerate CH ₂=C (R ¹) (COOR ³) [R here, ¹Expression hydrogen atom or carbon number are 1～5 alkyl, R ³The expression carbon number is that 1～8 alkyl or carbon number are 6～12 aralkyl], specifically can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) 2-ethyl hexyl acrylate, (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) CA, (methyl) acrylic acid naphthalene ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid hydroxyalkyl acrylate (alkyl is that carbon number is 1～8 alkyl), methacrylic acid hydroxyl ethylene oxidic ester, tetrahydrofurfuryl methacrylate etc.

In addition, also preferred molecular side chain has the resin of polyalkylene oxide chain.As above-mentioned polyoxyethylene chain, can adopt polyoxyethylene chain, polypropyleneoxide chain, polytetramethylene glycol chain or they are share, end is the alkyl of hydrogen atom, straight or branched.

The repetitive of polyoxyethylene chain, polypropyleneoxide chain is preferably 1～20, and more preferably 2～12.Have the acrylic copolymer of polyalkylene oxide chain as above-mentioned side chain, for example can enumerate that for example methoxy poly (ethylene glycol) list (methyl) acrylate, ethoxy polypropylene glycol list (methyl) acrylate, single (methyl) acrylate etc. of methoxyl poly-(ethylene glycol and 1,2-propylene glycol) are the acrylic copolymer of copolymer composition with polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylic acid, poly-(ethylene glycol and 1,2-propylene glycol) single (methyl) acrylate etc. and their the terminal OH base compound after by alkyl envelope chain.

As above-mentioned vinyl compound, can enumerate CH ₂=CR ¹R ²[R here, ¹Expression hydrogen atom or carbon number are 1～5 alkyl, R ²The expression carbon number is 6～10 aromatic hydrocarbon ring], specifically can enumerate styrene, α-Jia Jibenyixi, vinyltoluene, vinyl cyanide, vinyl acetate, N-vinyl pyrrolidone, polystyrene macromolecular monomer, polymethylmethacrylate macromonomer etc.

Other monomers of energy copolymerization can use a kind separately, or are used in combination more than 2 kinds.Wherein, the multiple copolymer of preferred especially (methyl) benzyl acrylate/(methyl) acrylic copolymer and (methyl) benzyl acrylate/(methyl) acrylic acid/other monomers formation.

As mentioned above, above-mentioned alkali soluble resin preferably has the acid number of the scope of 10～200mgKOH/g.If acid number is below 200, then the dissolubility in alkali can be not excessive, and the optimum range (development tolerance) that can prevent to develop narrows down.On the other hand, if more than 10, then, can prevent that development time is elongated because the dissolubility in alkali is difficult for reducing.

Weight-average molecular weight Mw (with the polystyrene conversion value of GPC method mensuration) about above-mentioned alkali soluble resin, for the range of viscosities of realizing being easy on operations such as coating photosensitive coloring composition, using, and guarantee film strength, be preferably 2000～100000, more preferably 3000～50000.

In order to improve the cross-linking efficiency of photosensitive coloring composition of the present invention, can use separately at alkali soluble resin to have the resin of polymerizable group or share, can adopt side chain to contain polymkeric substance of aryl, (methyl) propenyl, aryloxy alkyl etc. etc. with the alkali soluble resin that does not contain polymerizable group.Alkali soluble resin with the two keys of polymerism can develop in alkaline developer, also has photo-curable and Thermocurable.These examples of polymkeric substance that contain polymerizable group are as follows, as long as contain alkali-soluble group and carbon-to-carbon unsaturated bonds such as COOH base or OH base in 1 molecule, are not limited to following substances.

(1) make in advance that isocyanate group and OH reaction and residual 1 compound of not sending out the isocyanate group of answering and containing at least 1 (methyl) acryloyl group and the reactive acrylic resin that contains carboxyl obtain urethane-modified contain the two key acryl resins of polymerism,

(2) contain the acryl resin that contains unsaturated group that the reaction of the compound that has epoxy radicals and the two keys of polymerism in the acryl resin of carboxyl and the molecule obtains,

(3) ACID-PENDANT type Epocryl,

(4) acryl resin that contains the OH base reacts the acryl resin that contains the two keys of polymerism that obtains with the dibasic acid anhydride with the two keys of polymerism.

The resin of preferred especially (1) and (2) in the above-mentioned resin.

As object lesson, can use for example acrylic acid-2-hydroxyl ethyl ester with OH base and for example methacrylic acid that contains the COOH base, can have compound that compound compounds such as (for example) the glycidyl acrylates reaction of reactive epoxide ring and carbon carbon unsaturated link obtains etc. to the OH base with containing with the multipolymer of monomers such as the acrylic compounds of their copolymerization or vinylic chemical compound.With the reaction of OH base in, except that epoxide ring, can also use acid anhydrides, have the compound of isocyanate group or acryloyl group.

In addition, can also use the unsaturated carboxylic acid of putting down in writing in Japanese patent laid-open 6-102669 communique, the Japanese patent laid-open 6-1938 communique to react the compound and the saturated or unsaturated multi-anhydride that obtain and react the reactant that obtains by the compound with epoxide ring and acrylic acid and so on.

As the compound of alkali-soluble group that has COOH base and so on concurrently and carbon carbon unsaturated group, for example can enumerate DIANALNR series (Mitsubishi Rayon Co., Ltd's system; Photomer 6173 (the polyurethane acroleic acid oligomer, the Diamond Shamrock Co.Ltd. system that contain the COOH base); VISCOTE R-264, KS resist 106 (being Osaka Organic Chemical Industry Co., Ltd.'s system); CYCLOMER P series, PLACCEL CF200 series (being Daisel chemical industry Co., Ltd's system); Ebecryl 3800 (DAICEL UCB Co., Ltd. system) etc.

As the addition of alkali soluble resin, be preferably the scope of 3～30 quality % in the total solid composition of photosensitive coloring composition layer, more preferably 5～20 quality %.

When the preparation of photosensitive coloring composition, as binder polymer, except that above-mentioned alkali soluble resin, the following epoxy resin of preferred further interpolation.As epoxy resin, can enumerate the compound that has 2 above epoxide rings in bisphenol A type epoxy resin, cresols line style phenol aldehyde type epoxy resin, biphenyl type epoxy resin, the alicyclic epoxy compound equimolecular.

For example, as bisphenol A type epoxy resin, can enumerate EPOTOHTO YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 etc. (more than be Toto Kasei KK's system), DENACOLEX-1101, EX-1102, EX-1103 etc. (more than be Nagase chemical Co., Ltd) system), PLACCEL GL-61, GL-62, G101, G102 (more than be Daisel chemical industry Co., Ltd's system) etc.In addition, as operable epoxy resin, can also enumerate and they similar bisphenol f type epoxy resins, bisphenol-s epoxy resin.

In addition, can also use epoxy acrylates such as Ebecryl 3700,3701,600 (more than be DAICEL UCB Co., Ltd. system).As cresols line style phenol aldehyde type epoxy resin, can enumerate EPOTOHTO YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704 etc. (more than be Toto Kasei KK's system), DENACOL EM-125 etc. (above be the long rapids system of changing into).As biphenyl type epoxy resin, can enumerate 3,5,3 ', 5 '-tetramethyl-4,4 '-diglycidyl biphenyl etc.As the alicyclic epoxy compound, can enumerate CELLOXIDE 2021,2081,2083,2085, EPOLEAD GT-301, GT-302, GT-401, GT-403, EHPE-3150 (above is Daisel chemical industry Co., Ltd's system), SANTOHTO ST-3000, ST-4000, ST-5080, ST-5100 etc. (above is Toto Kasei KK's system), Epiclon430, Epiclon673, Epiclon 695, Epiclon 850S, Epiclon 4032 (above is Dainippon Ink. ﹠ Chemicals Inc's system) etc.In addition, can also use 1,1,2,2-four (to oxidation glycidyl phenyl) ethane, three (to oxidation glycidyl phenyl) methane, triglycidyl group three (hydroxyethyl) isocyanates, phthalic acid diglycidyl ester, terephthalic acid (TPA) diglycidyl ester, as the EPOTOHTO YH-434 and the YH-434L of amine type epoxy resin and in the skeleton of bisphenol A type epoxy resin, carry out dimer acid modified and ethylene oxidic ester of obtaining etc.

Wherein, preferred " quantity of molecular weight/epoxide ring " is more than 100, more preferably 130～500.If " quantity of molecular weight/epoxide ring " little, curable height then, the contraction during curing is big, if excessive, then curable deficiency, less reliable or flatness variation.

As concrete preferred compound, can enumerate EPOTOHTO YD-115,118T, 127, YDF-170, YDPN-638, YDPN-701, PLACCEL GL-61, GL-62,3,5,3 ', 5 '-tetramethyl-4,4 '-diglycidyl biphenyl, CELLOXIDE 2021,2081, EPOLEADGT-302, GT-403, EHPE-3105 etc.

-(C-1) polymerizable compound-

The photosensitive coloring composition that the present invention uses preferably contains (C-1) polymerizable compound.

The polymerizable compound that the present invention can use is from addition polymerization compound with at least 1 ethylenical unsaturated double bonds and have at least 1, preferably select the compound of terminal ethylenic unsaturated bond more than 2.This compound group is widely known by the people in this area, all can not have particular restriction ground in the present invention and uses.They for example can be that monomer, prepolymer are dipolymer, trimer and oligomer or their potpourri and their chemical forms such as multipolymer.Example as monomer and multipolymer thereof, can enumerate unsaturated carboxylic acid (for example acrylic acid, methacrylic acid, itaconic acid, butenoic acid, methacrylate, maleic acid etc.) and ester class thereof, amide-type, preferably use the amide-type of ester class, unsaturated carboxylic acid and the aliphatic polyamine compound of unsaturated carboxylic acid and aliphatic polyol compound.In addition, can also preferably use addition reaction product with the substituent unsaturated carboxylate type of nucleophilicities such as hydroxyl, amino or sulfydryl or amide-type and simple function or polyfunctional isocyanate's class or epoxies and with dehydration condensation product of simple function or polyfunctional carboxylic acids etc.In addition, also preferably have isocyanate group or epoxy radicals etc. and have the addition reaction of the substituent esters of unsaturated carboxylic acids of electrophilicity or amide-type and simple function or multifunctional alcohols, amine, thio-alcohol, and the substituted reactant with the unsaturated carboxylate type of the substituents of leaving away such as halogen, tosyloxy or amide-type and simple function or multifunctional alcohols, amine, thio-alcohol.As other examples, can also use the compound group that above-mentioned unsaturated carboxylic acid is replaced as unsaturated phosphonic acids, styrene, vinyl ether etc. and obtains.

Object lesson as the monomer of the ester of aliphatic polyol compound and unsaturated carboxylic acid, as acrylate, can enumerate glycol diacrylate, triethylene glycol diacrylate, 1, the 3-butanediol diacrylate, the tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentylglycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris (acryloxy propyl group) ether, the trimethylolethane trimethacrylate acrylate, hexanediyl ester, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, the dipentaerythritol diacrylate, dipentaerythritol acrylate, the D-sorbite triacrylate, the D-sorbite tetraacrylate, D-sorbite five acrylate, D-sorbite six acrylate, three (acryloxy ethyl) isocyanuric acid ester, the polyester acrylic ester oligomer, cyamelide EO modification triacrylate etc.

As methacrylate, can enumerate the tetramethylene glycol dimethylacrylate, triethylene glycol dimethacrylate, neopentylglycol dimethacrylate, trimethylol-propane trimethacrylate, the trimethylolethane trimethacrylate methacrylate, ethylene glycol dimethacrylate, the 1,3 butylene glycol dimethylacrylate, hexanediol dimethacrylate, dimethyl pentaerythritol acrylate, pentaerythritol acrylate trimethyl, pentaerythrite tetramethyl acrylate, the dipentaerythritol dimethylacrylate, dipentaerythritol hexamethyl acrylate, the D-sorbite trimethyl acrylic ester, D-sorbite tetramethyl acrylate, two (right-(3-methacryloxy-2-hydroxyl propoxyl group) phenyl) dimethylmethane, two (right-(methacryloxy ethoxy) phenyl) dimethylmethane etc.

As itaconate, can enumerate ethylene glycol bisthioglycolate itaconate, propylene glycol diitaconate, 1,3-butylene glycol diitaconate, 1,4-butylene glycol diitaconate, tetramethylene glycol diitaconate, pentaerythrite diitaconate, D-sorbite four itaconates etc.As butenoate, can enumerate ethylene glycol bisthioglycolate butenoate, tetramethylene glycol dibutene acid esters, pentaerythrite dibutene acid esters, D-sorbite four butenoates etc.As methacrylate, can enumerate glycol ester diisobutylene, pentaerythrite diisobutylene acid esters, D-sorbite tetra methylacrylate etc.As maleate, can enumerate ethylene glycol bisthioglycolate maleate, triethylene glycol dimaleate, pentaerythrite dimaleate, D-sorbite four maleates etc.

As the example of other esters, for example preferably use the special public clear 51-47334 communique of Jap.P., Jap.P. spy open the aliphatic alcohol of putting down in writing in the clear 57-196231 communique be ester class, Jap.P. spy open clear 59-5240 communique, Jap.P. spy open put down in writing in the ester put down in writing in clear 59-5241 communique, the Japanese patent laid-open 2-226149 communique, the Japanese patent laid-open 1-165613 communique with aromatic series pastern bone frame contain amino ester etc.In addition, above-mentioned ester monomer can also use as potpourri.

Object lesson as the monomer of the acid amides of aliphatic polyamine compound and unsaturated carboxylic acid, can enumerate methylene-bisacrylamide, di-2-ethylhexylphosphine oxide Methacrylamide, 1,6-hexa-methylene bisacrylamide, 1, the two Methacrylamides of 6-hexa-methylene, diethylene triamine three acrylamides, xylylene bisacrylamide, the two Methacrylamides of xylylene etc.As the example of other preferred amide-type monomers, can enumerate the acid amides of putting down in writing in the special public clear 54-21726 communique of Jap.P. with cyclohexylidene structure.

In addition, also preferably use the urethanes class addition polymerization compound of the addition reaction manufacturing of isocyanates and hydroxyl, as its object lesson, for example can enumerate the vinyl urethane compounds that contains 2 above polymerism vinyl in 1 molecule that the vinyl monomer addition that contains hydroxyl that the polyisocyanate compounds that has 2 above isocyanate group in 1 molecule of putting down in writing in the special public clear 48-41708 communique of Jap.P. and following general formula (V) represent obtains etc.

CH ₂＝C(R ⁴)COOCH ₂CH(R ⁵)OH (V)

(R ⁴And R ⁵Represent H or CH respectively independently ₃)

Preferred Jap.P. spy opens the urethane compounds class of putting down in writing in the special public clear 58-49860 communique of urethanes esters of acrylic acid, Jap.P. put down in writing in clear 51-37193 communique, the special fair 2-32293 communique of Jap.P., the special fair 2-16765 communique of Jap.P., the special public clear 56-17654 communique of Jap.P., the special public clear 62-39417 communique of Jap.P., the special public clear 62-39418 communique of Jap.P. with ethylene oxide skeleton.In addition, the Jap.P. spy opens clear 63-277653 communique, the Jap.P. spy opens the addition polymerization compounds that has amino structure or sulfide structure in the molecule of putting down in writing in clear 63-260909 communique, the Japanese patent laid-open 1-105238 communique by using, and can obtain the poly-property composition of the extraordinary light of film speed thus.

As other examples, can enumerate the Jap.P. spy and open polyester acrylate class, the epoxy resin put down in writing in each communique of the special public clear 49-43191 communique of clear 48-64183 communique, Jap.P., the special public clear 52-30490 communique of Jap.P. and react polyfunctional acrylic ester and the methacrylates such as epoxy acrylate class that obtains with (methyl) acrylic acid.In addition, can also enumerate the vinyl phosphoric acid compounds put down in writing in the specific unsaturated compound put down in writing in the special public clear 46-43946 communique of Jap.P., the special fair 1-40337 communique of Jap.P., the special fair 1-40336 communique of Jap.P., the Japanese patent laid-open 2-25493 communique etc.In some cases, preferably use the Jap.P. spy to open the structure of putting down in writing in the clear 61-22048 communique that contains perfluoroalkyl.In addition, can also use the photo-curable monomer and the oligomer of record in the will vol.20 of the gluing association of Japan, No.7,300～308 pages (1984).

About the structure of these polymerizable compounds, use separately or share, the detailed content of using method such as addition, can set arbitrarily according to the performance design of final photosensitive material.For example, can select based on following viewpoint.

Aspect sensitivity, preferred many structures of the unsaturated group mass contg of each molecule are more than in most cases preferred 2 official's energy.In order to improve the intensity that rendered image portion is the photosensitive coloring composition layer, can be advisable by above polymerizable compound with 3 officials, in addition, it is very effective to regulate the two method of sensitivity and intensity by the polymerizable compound that share the different polymerizable groups of different functional number (for example acrylate, methacrylate, styrene compound, vinyl ethers compound).From solidifying the viewpoint of sensitivity, the preferred compound that contains (methyl) acrylate structural more than 2 that uses further preferably uses the compound that contains more than 3, most preferably uses the compound that contains more than 4.Viewpoint from the development of solidifying sensitivity and unexposed portion preferably contains EO modification body.From solidifying the viewpoint of sensitivity and exposure portion intensity, preferably contain urethane bonds.

For with the photosensitive coloring composition layer in intermiscibility, the dispersiveness of other compositions (for example binder polymer, initiating agent, colorant (pigment, dyestuff etc.)), the selection using method of polyaddition compounds is a key factor, for example, by using the low-purity compound or share more than 2 kinds, can improve intermiscibility sometimes.In addition, in order to improve the adaptation with substrate, can also select specific structure.

Based on above viewpoint, can preferably enumerate bisphenol a diacrylate, bisphenol a diacrylate EO modification body, trimethylolpropane triacrylate, trimethylolpropane tris (acryloxy propyl group) ether, the trimethylolethane trimethacrylate acrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, the dipentaerythritol tetraacrylate, dipentaerythritol five acrylate, dipentaerythritol acrylate, the D-sorbite triacrylate, the D-sorbite tetraacrylate, D-sorbite five acrylate, D-sorbite six acrylate, three (acryloxy ethyl) isocyanuric acid ester, tetramethylol methane tetraacrylate EO modification body, dipentaerythritol acrylate EO modification body etc.As commercially available product, preferred urethane ester oligomer UAS-10, UAB-140 (adret state basic policy PULP corporate system), DPHA (Japanese chemical drug metric system), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (common prosperity society system).

Wherein, further preferred bisphenol a diacrylate EO modification body, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol five acrylate, dipentaerythritol acrylate, three (acryloxy ethyl) isocyanuric acid ester, tetramethylol methane tetraacrylate EO modification body, dipentaerythritol acrylate EO modification body etc. and as DPHA (Japanese chemical drug corporate system), UA-306H, UA-306T, UA-306I, AH-600, T-600, the AI-600 (common prosperity society system) of commercially available product.

(C-1) content of polymerizable compound is preferably 5～55 quality % in the total solid composition in the photosensitive coloring composition layer of the present invention, more preferably 10～50 quality %, more preferably 15～45 quality %.

-(D) Photoepolymerizationinitiater initiater-

Photosensitive coloring composition of the present invention preferably contains (D) Photoepolymerizationinitiater initiater.

Above-mentioned Photoepolymerizationinitiater initiater is that the effect at light issues and estrangedly separates and cause and promote above-mentioned (C-1) polymerizable compound polymeric compounds, preferably in the zone of wavelength 300～500nm absorption is arranged.Above-mentioned Photoepolymerizationinitiater initiater can use separately or share more than 2 kinds.

As above-mentioned Photoepolymerizationinitiater initiater, for example can enumerate organohalogen compounds, oxadiazole compound, carbonyls, ketal compound, benzoin compound, acridine compound, organic peroxide, azo-compound, coumarin compound, triazo-compound, metallocene compound, hexa-aryl bi-imidazole compound, organic boronic compound, disulfonic acid compound, oxime ester compound, salt compound, acylphosphanes (oxide) compound.

As organohalogen compounds, specifically can be set forth in if " Bull Chem.Soc Japan " 42 such as woodss, 2924 (1969), No. 3905815 instructions of United States Patent (USP), the special public clear 46-4605 communique of Jap.P., the Jap.P. spy opens clear 48-36281 communique, the Jap.P. spy opens clear 55-32070 communique, the Jap.P. spy opens clear 60-239736 communique, the Jap.P. spy opens clear 61-169835 communique, the Jap.P. spy opens clear 61-169837 communique, the Jap.P. spy opens clear 62-58241 communique, the Jap.P. spy opens clear 62-212401 communique, the Jap.P. spy opens clear 63-70243 communique, the Jap.P. spy opens clear 63-298339 communique, M.P.Hutt " Joumal of HeterocyclicChemistry " 1 (No3), (1970) " compound of record, particularly trihalomethyl group replace De oxazole compound in; the s-triaizine compounds.

As the s-triaizine compounds, more preferably on the s-triazine ring in conjunction with at least 1 one, two or the s-pyrrolotriazine derivatives of three-halogen substituent methyl, particularly, for example can enumerate 2,4,6-three (chloromethyl)-s-triazine, 2,4,6-three (dichloromethyl)-s-triazine, 2,4,6-three (trichloromethyl)-s-triazine, 2-methyl-4, two (the trichloromethyl)-s-triazines of 6-, 2-n-pro-pyl-4, two (the trichloromethyl)-s-triazines of 6-, 2-(α, α, β-three chloroethyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-phenyl-4, two (the trichloromethyl)-s-triazines of 6-, 2-(p-methoxyphenyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(3, the 4-epoxy and phenyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(rubigan)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(1-(p-methoxyphenyl)-2, the 4-butadienyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-styryl-4, two (the trichloromethyl)-s-triazines of 6-, 2-(to methoxyl-styrene)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(to the isopropoxystyrene base)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(p-methylphenyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-methoxyl naphthyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-phenyl sulfo--4, two (the trichloromethyl)-s-triazines of 6-, the 2-dibenzylsulfide is for-4, two (the trichloromethyl)-s-triazines of 6-, 4-(o-bromo-p-N, N-(di ethoxy carbonyl amino)-phenyl)-2,6-two (trichloromethyl)-s-triazine, 2,4,6-three (two bromomethyls)-s-triazine, 2,4,6-three (trisbromomethyl)-s-triazine, 2-methyl-4, two (the trisbromomethyl)-s-triazines of 6-, 2-methoxyl-4, two (the trisbromomethyl)-s-triazines of 6-etc.

Zuo Wei oxadiazole compound, can enumerate 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(cyano styrene base)-1,3,4-oxadiazole, 2-trichloromethyl-5-(naphthalene-1-yl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-styryl) styryl-1,3,4-oxadiazole etc.

As carbonyls, can enumerate benzophenone, michaelis ketone, 2 methyl benzophenone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone, the 2-chlorobenzophenone, 4-bromine benzophenone, benzophenone derivates such as 2-carboxyl benzophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2, the 2-diethoxy acetophenone, the 1-hydroxycyclohexylphenylketone, alpha-hydroxy-2-aminomethyl phenyl acetone, 1-hydroxyl-1-Methylethyl-(p-isopropyl phenyl) ketone, 1-hydroxyl-1-(p-dodecylphenyl) ketone, 2-methyl isophthalic acid-(4 '-(methyl sulfo-) phenyl)-2-morpholino-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1,2,4,6-trimethylbenzene formyl-diphenyl-phosphine oxide, 1,1,1-trichloromethyl-(p-butyl phenyl) ketone, 2-benzyl-2-dimethylamino-acetophenone derivs such as 4-morpholino phenyl propyl ketone, thioxanthones, 2-ethyl thioxanthones, the 2-isopropyl thioxanthone, the 2-clopenthixal ketone, 2,4-dimethyl thioxanthones, 2, the 4-diethyl thioxanthone, 2, thioxanthone derivates such as 4-diisopropyl thioxanthones, p-dimethylaminobenzoic acid ethyl ester, benzoate derivatives such as p-diethylamino ethyl benzoate etc.

As ketal compound, can enumerate benzyl dimethyl ketal, benzyl-'beta '-methoxy ethyl diethyldithiocarbamate ketal etc.

As the benzoin compound, can enumerate a benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, adjacent benzoin methyl benzoate etc.

As the acridine compound, can enumerate the 9-phenylacridine, 9-pyridine radicals acridine, 9-pyrazinyl acridine, 1,2-two (9-acridinyl) ethane, 1,3-two (9-acridinyl) propane, 1,4-two (9-acridinyl) butane, 1,5-two (9-acridinyl) pentane, 1,6-two (9-acridinyl) hexane, 1,7-two (9-acridinyl) heptane, 1,8-two (9-acridinyl) octane, 1,9-two (9-acridinyl) nonane, 1,10-two (9-acridinyl) decane, 1,11-two (9-acridinyl) undecane, 1,12-two (9-acridinyl) dodecane etc. two (9-acridinyl) alkane etc.

As organic peroxide, can enumerate trimethyl hexanone peroxide, acetylacetone peroxide, 1, two (tert-butyl hydroperoxide)-3 of 1-, 3, the 5-trimethylcyclohexanone, 1, two (tert-butyl hydroperoxide) cyclohexanes of 1-, 2, two (tert-butyl hydroperoxide) butane of 2-, tert-butyl peroxide, hydrogen phosphide cumene, the diisopropyl benzene hydrogen peroxide, 2,5-dimethylhexane-2,5-diperoxy hydrogen, 1,1,3, the 3-tetramethyl butyl hydroperoxide, tert-butyl group cumene peroxide, cumyl peroxide, 2,5-dimethylhexane-2,5-two (tert-butyl hydroperoxide) hexane, 2,5-oxanoyl peroxide (オキサノイ Le パ one オキサイ De), succinic acid peroxide, benzoyl peroxide, 2,4-dichloro-benzoyl superoxide, di-isopropyl peroxydicarbonate, peroxy dicarbonate two-2-Octyl Nitrite, peroxy dicarbonate two-2-ethoxy ethyl ester, peroxidating carbonic acid dimethoxy isopropyl ester, peroxy dicarbonate two (3-methyl-3-methoxyl butyl) ester, peroxide acetic acid butyl ester, the peroxidating neopentanoic acid tert-butyl ester, new peroxide tert-butyl caprate, the peroxidation acid tert-butyl ester, the peroxidating lauric acid tert-butyl ester, 3,3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone, 3,3 ', 4,4 '-four (uncle's hexyl peroxidating carbonyl) benzophenone, 3,3 ', 4,4 '-four (p-isopropyl cumenyl peroxidating carbonyl) benzophenone, carbonyl two (tert-butyl hydroperoxide dihydro two phthalic esters), carbonyl two (uncle's hexyl peroxidating dihydro two phthalic esters) etc.

As azo-compound, can enumerate azo-compound of putting down in writing in the Japanese patent laid-open 8-108621 communique etc.

As coumarin compound, can enumerate 3-methyl-5-amino-((s-triazine-2-yl) amino)-3-phenyl cumarin, 3-chloro-5-diethylamino-((s-triazine-2-yl) amino)-3-phenyl cumarin, 3-butyl-5-dimethylamino-((s-triazine-2-yl) amino)-3-phenyl cumarin etc.

As triazo-compound, can be set forth in the organic azide of putting down in writing in No. 2848328 instructions of United States Patent (USP), No. 2852379 instructions of United States Patent (USP) and No. 2940853 instructions of United States Patent (USP), 2, two (4-phenylazide the methylene)-4-ethyl cyclohexanones (BAC-E) of 6-etc.

As metallocene compound, can be set forth in the Jap.P. spy and open clear 59-152396 communique, the Jap.P. spy opens clear 61-151197 communique, the Jap.P. spy opens clear 63-41484 communique, Japanese patent laid-open 2-249 communique, Japanese patent laid-open 2-4705 communique, various two cyclopentadiene titanium compounds of putting down in writing in the Japanese patent laid-open 5-83588 communique are dicyclopentadienyl-Ti-biphenyl for example, dicyclopentadienyl-Ti-two-2,6-two fluorobenzene-1-base, dicyclopentadienyl-Ti-two-2,4-two-fluorobenzene-1-base, dicyclopentadienyl-Ti-two-2,4,6-trifluoro-benzene-1-base, dicyclopentadienyl-Ti-two-2,3,5,6-phenyl tetrafluoride-1-base, dicyclopentadienyl-Ti-two-2,3,4,5,6-phenyl-pentafluoride-1-base, two-methyl cyclopentadienyl-Ti-two-2,6-two fluorobenzene-1-base, two-methyl cyclopentadienyl-Ti-two-2,4,6-trifluoro-benzene-1-base, two-methyl cyclopentadienyl-Ti-two-2,3,5,6-phenyl tetrafluoride-1-base, two-methyl cyclopentadienyl-Ti-two-2,3,4,5,6-phenyl-pentafluoride-1-base, iron-aromatic hydrocarbons complex compound of putting down in writing in Japanese patent laid-open 1-304453 communique and the Japanese patent laid-open 1-152109 communique etc.

As the hexa-aryl bi-imidazole compound, can enumerate the special fair 6-29285 communique of Jap.P., No. the 3479185th, United States Patent (USP), No. the 4311783rd, United States Patent (USP), United States Patent (USP) waits all cpds of putting down in writing in each instructions No. 4622286, specifically can enumerate 2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (o-bromophenyls) 4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (o, the p-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (o-chlorphenyl)-4,4 ', the two imidazoles of 5,5 '-four (m-methoxyphenyls), 2,2 '-two (o, o '-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (o-nitrobenzophenone)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (o-aminomethyl phenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (o-trifluorophenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole etc.

As the organic boronic salt compound, can enumerate the Jap.P. spy and open clear 62-143044 communique, the Jap.P. spy opens clear 62-150242 communique, Japanese patent laid-open 9-188685 communique, Japanese patent laid-open 9-188686 communique, Japanese patent laid-open 9-188710 communique, the Jap.P. spy opens the 2000-131837 communique, the Jap.P. spy opens the 2002-107916 communique, No. 2764769 communique of patent, each communique and Kunz such as the special hope of Jap.P. 2000-310808 communique, the organic borate of record among the Martin " Rad Tech ' 98.Proceeding April 19-22; 1998, Chicago " etc., Japanese patent laid-open 6-157623 communique, Japanese patent laid-open 6-175564 communique, organic boron sulfonium complex compound of putting down in writing in the Japanese patent laid-open 6-175561 communique or organic boron oxygen sulfonium complex compound, Japanese patent laid-open 6-175554 communique, organic boron iodo-complexes of putting down in writing in the Japanese patent laid-open 6-175553 communique, the You Ji Peng Phosphonium complex compound of putting down in writing in the Japanese patent laid-open 9-188710 communique, Japanese patent laid-open 6-348011 communique, Japanese patent laid-open 7-128785 communique, Japanese patent laid-open 7-140589 communique, Japanese patent laid-open 7-306527 communique, organic boron transition metal coordination complexes of putting down in writing in the Japanese patent laid-open 7-292014 communique etc. etc.

As two sulphones, can enumerate the Jap.P. spy and open the middle compounds of putting down in writing such as clear 61-166544 communique, the special 2001-132318 of hope of Jap.P. instructions etc.

As oxime ester compound, can be set forth in J.C.S.Perkin II (1979) 1653-1660, J.C.S.Perkin II (1979) 156-162, Journal of Photopolymer Science andTechnology (1995) 202-232, Jap.P. spy and open the compound put down in writing in the 2000-66385 communique, open the compound put down in writing in 2000-80068 communique, the special table of the Jap.P. 2004-534797 communique etc. the Jap.P. spy.As object lesson, IRGACURE OXE-01, the OXE-02 etc. of preferred Ciba corporate system.

As salt compound, for example can be set forth in S.I.Schlesinger, Photogr.Sci.Eng., 18,387 (1974), T.S.Bal et al, Polymer, the diazo salt of record in 21,423 (1980), No. 4069055 instructions of United States Patent (USP), the ammonium salt of record in the Japanese patent laid-open 4-365049 communique etc., No. 4069055 instructions of United States Patent (USP), record De phosphonium salt in No. 4069056 each instructions such as instructions of United States Patent (USP), No. 104143 instructions of European patent, No. 339049 instructions of United States Patent (USP), each instructions of No. 410201 instructions of United States Patent (USP), Japanese patent laid-open 2-150848 communique, the salt compounded of iodine of putting down in writing in each communique of Japanese patent laid-open 2-296514 communique etc.

The salt compounded of iodine that the present invention can preferably use is diaryl group iodized salt, from the viewpoint of stability, is preferably replaced by donor residuess such as 2 above alkyl, alkoxy, aryloxy group.As the form of other preferred sulfonium salts, 1 substituting group of preferred triarylsulfonium salt has cumarin, anthraquinone ring and the salt compounded of iodine etc. of absorption is arranged more than 300nm.

The sulfonium salt that can preferably use as the present invention, can be set forth in No. 370693 instructions of European patent, No. 390214 instructions of European patent, No. 233567 instructions of European patent, No. 297443 instructions of European patent, No. 297442 instructions of European patent, No. 4933377 instructions of United States Patent (USP), No. 161811 instructions of United States Patent (USP), No. 410201 instructions of United States Patent (USP), No. 339049 instructions of United States Patent (USP), No. 4760013 instructions of United States Patent (USP), No. 4734444 instructions of United States Patent (USP), No. 2833827 instructions of United States Patent (USP), No. 2904626 instructions of Deutsche Bundespatent, No. 3604580 instructions of Deutsche Bundespatent, the sulfonium salt of putting down in writing in each instructions of No. 3604581 instructions of Deutsche Bundespatent, sensitivity based on stability is preferably replaced by electron-withdrawing group.As electron-withdrawing group, Hami paricular value is preferably greater than 0.As preferred electron-withdrawing group, can enumerate halogen atom, carboxylic acid etc.

As other preferred sulfonium salts, a substituting group can enumerating triarylsulfonium salt has cumarin, anthraquinone ring and the sulfonium salt of absorption is arranged more than 300nm.As another preferred sulfonium salt, can also enumerate triarylsulfonium salt and have aryloxy group, arylthio have absorption as substituting group and more than 300nm sulfonium salt.

As salt compound, can be set forth in J.V.Crivello et al, Macromolecules, 10 (6), 1307 (1977), J.V.Crivello et al, J.Polymer Sci., Polymer Chem.Ed., 17, the selenium salt of record in 1047 (1979), at C.S.Wen et al, Teh, Proc.Conf.Rad.Curing ASIA, p478 Tokyo, salt such as the middle record of Oct (1988) De Arsenic salt etc.

As acylphosphanes (oxide) compound, can enumerate IRGACURE819, DAROCURE 4265, DAROCURE TPO of Ciba corporate system etc.

As (D) Photoepolymerizationinitiater initiater; from the viewpoint of exposure sensitivity, be preferably selected from the trihalomethyl group compound in triazine class; the benzyl dimethyl ketal compound; alpha-hydroxyacetone compounds; the alpha-amido ketonic compound; the acylphosphanes compounds; the phosphinoxides compound; metallocene compound; oxime compound; the triarylimidazoles dipolymer; salt compounds; benzothiazole compound; benzophenone compound; acetophenone compounds and derivant thereof; cyclopentadiene-benzene-iron complex and salt thereof; Lu is for Jia oxadiazole compound; compound in the 3-aryl substituted cumarin compound.

More preferably trihalomethyl group compound in triazine class, alpha-amido ketonic compound, acylphosphanes compounds, phosphinoxides compound, oxime compound, triarylimidazoles dipolymer, salt compounds, benzophenone compound, acetophenone compounds most preferably are selected from least a kind of compound in trihalomethyl group compound in triazine class, alpha-amido ketonic compound, oxime compound, triarylimidazoles dipolymer, the benzophenone compound.

(D) content of Photoepolymerizationinitiater initiater with respect to the total solid composition in the photosensitive coloring composition layer, is preferably 0.1～20 quality %, and more preferably 0.5～15 quality % is preferably 1～10 quality % especially.In this scope, can obtain good sensitivity and pattern formation property.

-(E) solvent-

The photosensitive coloring composition that the present invention uses generally can prepare with solvent.

As solvent, preferred ester class, ethyl acetate for example, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, hydroxy methyl acetate, hydroxyl ethyl acetate, the glycolic acid butyl ester, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate and 3-oxygen base methyl propionate, 3-oxygen base alkyl propionates such as 3-oxygen base ethyl propionate (3-methoxypropionic acid methyl esters for example, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate etc.), 2-oxygen base methyl propionate, 2-oxygen base ethyl propionate, 2-oxygen base alkyl propionates such as 2-oxygen base propyl propionate (2-methoxypropionic acid methyl esters for example, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-oxygen base-2 Methylpropionic acid methyl esters, 2-oxygen base-2 Methylpropionic acid ethyl ester, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester etc.), methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-ketobutyric acid methyl esters, 2-ketobutyric acid ethyl ester, 1,3 butylene glycol diacetate esters etc.;

Ethers, for example diethylene glycol dimethyl ether, tetrahydrofuran, glycol monoethyl ether, ethylene glycol monomethyl ether, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, the propylene glycol monopropyl ether acetic acid esters, diethyl carbitol, the diethylene glycol monoethyl ether acetic acid esters, diethylene glycol monobutyl ether, the diethylene glycol monobutyl ether acetic acid esters, propylene glycol positive propyl ether acetic acid esters, propylene-glycol diacetate, the propylene glycol n-butyl ether acetic acid esters, propylene glycol phenyl ether, propylene glycol phenyl ether acetic acid ester, the dipropylene glycol monomethyl ether acetic acid esters, dipropylene glycol positive propyl ether acetic acid esters, dipropylene glycol n-butyl ether acetic acid esters, the tripropylene glycol mono-n-butyl ether, tripropylene glycol methyl ether acetate etc.;

Ketone, for example acetone, MEK, cyclohexanone, 2-heptanone, 3-heptanone etc.;

Alcohols, for example ethanol, isopropyl alcohol, methyl proxitol, propylene glycol list positive propyl ether, propylene glycol mono-n-butyl ether;

Aromatic hydrocarbon based, for example toluene, dimethylbenzene etc.

Wherein, preferred 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid methyl esters, 2-heptanone, cyclohexanone, ethyl carbitol acetic acid esters, acetate of butyl carbitol, methyl proxitol, methyl proxitol acetate, propylene glycol ethylether acetic acid esters etc.

Solvent may be used alone, two or more kinds can also be used in combination.

-other additives-

In the photosensitive coloring composition that the present invention uses, except that mentioned component, can also use various known adjuvants according to purpose.

Below, such adjuvant is described.

(spreading agent)

Photosensitive coloring composition of the present invention preferably contains macromolecule dispersing agent.This macromolecule dispersing agent is the resin of weight-average molecular weight in 3000～100000 scopes.Preferred acid number is 20～300mg/g.Below abbreviate this specific macromolecule dispersing agent as " dispersion resin " sometimes.

Dispersion resin of the present invention is the compound that spreading agent that the dispersing of pigments agent that can enumerate as above-mentioned (A-1) colorant or the black matrix of aftermentioned form the opacifier (black matrix formation pigment) with photosensitive black composition works.

Dispersion resin must have specific acid number, therefore preferably has the macromolecular compound of acidic groups.

Macromolecular scaffold as this macromolecular compound, be preferably selected from polymer of vinyl monomer or multipolymer, esters polymer, ether polymer, the urethane esters polymer, acylamide polymer, epoxide polymer, silicone based polymkeric substance and their modifier or multipolymer [for example comprise polyethers/polyurethane copolymer, (random copolymerss such as the multipolymer of polyethers/polymer of vinyl monomer, segmented copolymer, in the graft copolymer any)] at least a kind, further be preferably selected from polymer of vinyl monomer or multipolymer, esters polymer, ether polymer, in urethane esters polymer and their modifier or the multipolymer at least a kind, special preferred vinyl polymer of monomers or multipolymer.

As the method that in above-mentioned macromolecular scaffold, imports acidic groups, will contain the method for monomer copolymerization of acidic groups or the method for after above-mentioned macromolecular scaffold polymerization, utilizing high molecular weight reactive to import in the time of for example can being set forth in above-mentioned macromolecular scaffold polymerization.

As the monomer that contains acidic groups, for example can enumerate that (methyl) acrylic acid, butenoic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, acrylic acid dimer, vinyl benzoic acid, styrene sulfonic acid, 2-acrylamide-2-methyl propane sulfonic acid, mono phosphoric acid ester (methyl) acryloyl group ethyl ester or 2-hydroxyethyl methacry-late etc. contain reactions such as cyclic acid anhydrides such as alcohol hydroxyl group monomer and maleic anhydride or fumaric acid anhydride and monomer of obtaining etc.

In addition, the macromolecular compound with acidic groups can also be the compound that is formed by the copolymerization of vinyl monomer composition.

As above-mentioned vinyl monomer, there is not particular restriction, the ester class of for example preferred (methyl) esters of acrylic acid, butenoate class, vinyl ester, maleic acid diester class, dimethyl ester class, itaconic acid diester class, (methyl) acrylic amide, vinyl ethers, vinyl alcohol, phenylethylene, (methyl) vinyl cyanide etc.

As above-mentioned " acidic groups ", can preferably enumerate carboxylic acid group, sulfonic group, a sulfate group, phosphate, Monophosphate base, boronate, further optimization acid's base, sulfonic group, a sulfate group, phosphate, Monophosphate base, special optimization acid's base, sulfonic group, phosphate.

In order to improve dispersiveness, also preferably contain group with basic nitrogen atom.As above-mentioned group, for example can preferably enumerate amino (NH with basic nitrogen atom ₂), substituted imido (NHR ⁸Or-NR ⁹R ¹⁰Here, R ⁸, R ⁹And R ¹⁰Represent independently that respectively carbon number is that 1～20 alkyl, carbon number are that aryl more than 6 or carbon number are the aralkyl more than 7), the guanidine radicals of following chemical formula (a1) expression or the amidino groups of following chemical formula (a2) expression etc.

In the above-mentioned chemical formula (a1), R ¹¹And R ¹²Represent independently that respectively carbon number is that 1～20 alkyl, carbon number are that aryl more than 6 or carbon number are the aralkyl more than 7.

In the above-mentioned chemical formula (a2), R ¹³And R ¹⁴Represent independently that respectively carbon number is that 1～20 alkyl, carbon number are that aryl more than 6 or carbon number are the aralkyl more than 7.

Wherein, amino (NH ₂), substituted imido (NHR ⁸Or-NR ⁹R ¹⁰Here, R ⁸, R ⁹And R ¹⁰Represent independently that respectively carbon number is 1～10 alkyl, phenyl or benzyl), the guanidine radicals of above-mentioned chemical formula (a1) expression [in the chemical formula (a1), R ¹¹And R ¹²Represent independently that respectively carbon number is 1～10 alkyl, phenyl or benzyl], the amidino groups of above-mentioned chemical formula (a2) expression [in the chemical formula (a2), R ¹³And R ¹⁴Represent independently that respectively carbon number is 1～10 alkyl, phenyl or benzyl] etc. also contain by 1～200 hydrogen atom and 0～20 group that sulphur atom forms, they can not replace, and can further have substituting group yet.

(other spreading agents)

The photosensitive coloring composition that the present invention uses also share present known spreading agent (pigment dispersing agent) except that dispersion resin.

As known spreading agent (pigment dispersing agent), can enumerate macromolecule dispersing agent (for example daiamid and salt thereof, high molecular unsaturated acid ester, modified polyurethane, modified poly ester, poly-(methyl) acrylate of modification, (methyl) acrylic copolymer), polyxyethylated phosphate, polyoxyethylene alkyl amine, alkanolamine, pigment derivative etc.

Macromolecule dispersing agent can be further divided into straight chain shape macromolecule, terminal-modified type macromolecule, graft type macromolecule, block type polymer on its structure.

Macromolecule dispersing agent is adsorbed in the surface of pigment, works to prevent aggegation again.Therefore, as preferred construction, can enumerate the terminal-modified type macromolecule, graft type macromolecule, the block type polymer that have at the anchor site of surface of pigments.On the other hand, pigment derivative has by surface of pigments being carried out the effect that modification promotes that macromolecule dispersing agent adsorbs.

The object lesson of the known spreading agent (pigment dispersing agent) that can use as the present invention can be enumerated " the Disperbyk-107 (carboxylate); 130 (polyamide); 161; 162; 163; 164 of BYK Chemie corporate system, 165,166,170 (high-molecular copolymers) "; " EFKA4047 of EFKA corporate system, 4050,4010,4165 (polyurethaness), EFKA4330,4340 (segmented copolymers), 4400,4402 (modified polyacrylates), 5010 (polyesteramides), 6220 (fatty acid polyesters), 6745 (phthalocyanine derivates), 6750 (AZO pigments derivants) "; " the AJISPER PB821 of aginomoto fine chemistry corporate system, PB822 "; " FLOWLEN TG-710 (the urethane ester oligomer) " of chemical company of common prosperity society system; " POLYFLOW No.50E, No.300 (acrylic copolymer) "; nanmu originally changes into " the DISPARLON#7004 (polyether ester) of corporate system, DA-703-50, DA-705, DA-725 "; " EMULGEN920 of KAO. Corp. SA's system, 930,935,985 (polyoxyethylene nonylplenyl ethers) "; " ACETAMIN 86 (octadecane amine acetic acid esters) "; " SOLSPERSE 5000 (phthalocyanine derivates) of Lubrizol Corp.'s system, 22000 (AZO pigments derivants), 13240 (polyesteramines), 3000,17000,27000 (terminal part has the macromolecule of function portion), 24000,28000,32000,38500 (graft type macromolecules) "; " NIKKOLT106 (Tween-81) of day Optical Chemical Company's system, MYS-IEX (polyoxyl 40 stearate) " etc.

Above-mentioned known spreading agent can be as required with respect to dispersion resin be the i.e. uses in the scope of 1/10～1/1 (equivalent) of 10～100 quality %.

(surfactant)

If pigment concentration increases, then the thixotropy of coating fluid generally can become greatly, therefore is prone to the thickness inequality after coating or transfer printing photosensitive coloring composition form photosensitive coloring composition layer (dyed layer is filmed) on the substrate.When particularly forming photosensitive coloring composition layer (dyed layer is filmed) by the slot coated method, it is very important that the formation of photosensitive coloring composition layer forms filming of homogeneous thickness with coating fluid levelling before dry.Therefore, preferably in above-mentioned photosensitive coloring composition, contain suitable surfactant.As above-mentioned surfactant, can preferably enumerate the Jap.P. spy and open disclosed surfactant in 2003-337424 communique, the Japanese patent laid-open 11-133600 communique.

As the surfactant that is used to improve coating, can add non-ionics, fluorine class surfactant, silicone based surfactant etc.

As non-ionics, non-ionics such as for example preferred polyoxyethylene glycol class, polyoxypropylene diols class, polyoxyethylene alkyl ether class, polyoxyethylene alkylaryl ether class, polyxyethylated ester class, polyoxypropylene alkyl ether, polyoxypropylene alkylaryl ethers, polyoxypropylene alkyl esters, sorbitol anhydride alkyl esters, a glycerine alkyl esters.

Particularly, can enumerate polyoxyalkylene diols classes such as polyoxyethylene glycol, polyoxypropylene diols; Polyoxyalkylene alkyl classes such as polyoxyethylene lauryl ether, polyoxypropylene octadecyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as NONIN HS 240, polyoxyethylene polystyrene ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene-propylene polystyrene ether, polyoxyethylene nonylplenyl ether; Polyoxyalkylene dialkyls such as polyoxyethylene dilaurate, polyoxyethylene distearate; Non-ionics such as sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid ester class.

As their object lesson, can enumerate Ai Deke PLURONIC series, Ai Deke NOL series, TETRONIC series (above is Ai Deke Co., Ltd. system), EMULGEN series, RHEODOL series (above is Kao Corp's system), ELEMINOL series, NONIPOL series, OCTAPOL series, DODECAPOL series, NEWPOL series (above is Sanyo Chemical Industries Co., Ltd.'s system), PIONIN series (above is Zhu Ben's Oil Corporation's system), NISSANNONION series (above is NOF Corp's system) etc.Can suitably use their commercially available product.Preferred HLB value is 8～20, more preferably 10～17.

As fluorine class surfactant, the compound that can preferably use endways, the arbitrary at least position in main chain and the side chain has fluoro-alkyl or fluoro alkylidene.

As concrete commercially available product, for example can enumerate MEGAFAC F142D, MEGAFACF172, MEGAFAC F173, MEGAFAC F176, MEGAFAC F177, MEGAFACF183, MEGAFAC 780, MEGAFAC 781, MEGAFAC R30, MEGAFAC R08 (big Japanese ink Co., Ltd. system), FLUORAD FC-135, FLUORAD FC-170C, FLUORAD FC-430, FLUORAD FC-431 (Sumitomo 3M Co., Ltd. system), SURFLONS-112, SURFLON S-113, SURFLON S-131, SURFLON S-141, SURFLONS-145, SURFLON S-382, SURFLON SC-101, SURFLON SC-102, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLONSC-106 (Asahi Glass Co., Ltd's system), EFTOP EF351, EFTOP 352, EFTOP 801, EFTOP 802 (JEMCO Co., Ltd. system) etc.

As silicone based surfactant, for example can enumerate Torey Silicone DC3PA, ToreySilicone DC7PA, Torey Silicone SH11PA, Torey Silicone SH21PA, ToreySilicone SH28PA, Torey Silicone SH29PA, Torey SiliconeSH 30PA, ToreySilicone SH-190, Torey Silicone SH-193, Torey Silicone SZ-6032, ToreySilicone SF-8428, Torey Silicone DC-57, Torey Silicone DC-190 (above is eastern beautiful DOW CORNING organosilicon Co., Ltd. system), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above is organosilicon Co., Ltd. of GE Toshiba system) etc.

The consumption of these surfactants is preferably below 5 mass parts with coating fluid 100 mass parts for forming with respect to the photosensitive coloring composition layer, more preferably below 2 mass parts.When the amount of surfactant is 5 mass parts when following, can suppress the rough surface that coating causes when dry, improve flatness.

For the development of the alkali dissolution that promotes uncured portion, can add organic carboxyl acid, preferred molecular weight is the low-molecular-weight organic carboxyl acid below 1000 with further raising light thermosetting composition.Particularly, for example can enumerate formic acid, acetate, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethacetic acid, enanthic acid (enanthic acid), aliphatics monocarboxylic acid such as sad; Aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, brassylic acid (brasylic acid), methylmalonic acid (methylmalonic acid), ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl succinic acid, citraconic acid; Aliphatics tricarboxylic acids such as the third three acid, aconitic acid, camphoronic acid; Benzoic acid, toluic acid, cumfrey, 2, aromatic series monocarboxylic acids such as 3-mesitylenic acid, sym-trimethyl benzene acid; Aromatic series polybasic carboxylic acids such as phthalic acid, m-phthalic acid, terephthalic acid (TPA), trimellitic acid, trimesic acid, inclined to one side benzene tetracarboxylic acid, Pyromellitic Acid; Other carboxylic acids such as phenylacetic acid, phenoxyacetic acid, methoxybenzene ethoxyacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetate, coumaric acid, umbellic acid.

(alkoxysilane compound containing trialkylsilyl group in molecular structure)

From the viewpoint of raising, in the photosensitive coloring composition that the present invention uses, can use alkoxysilane compound containing trialkylsilyl group in molecular structure, be specially silane coupling agent with the adaptation of substrate.

Silane coupling agent preferably have alkoxysilyl as can with the chemically combined hydrolization group of inorganic material; preferably can interact or become key and show (methyl) acryloyl group, phenyl, sulfydryl, the epoxy radicals silicone hydride of compatibility with organic resin; wherein, more preferably (methyl) acryloyl group propyl trimethoxy silicane.

Addition when using silane coupling agent is preferably the scope of 0.2～5.0 quality % in the total solid composition in the photosensitive coloring composition layer that the present invention uses, more preferably 0.5～3.0 quality %.

(sensitizer altogether)

The photosensitive coloring composition that the present invention uses also preferably contains common sensitizer as required.Altogether sensitizer of the present invention has further raising sensitizing coloring matter or initiating agent to the sensitivity of active radioactive ray or suppress the effects such as polymerization inhibition of oxygen to polymerizable compound.

Example as this common sensitizer; can enumerate for example 3173 pages (1972) of work such as M.R.Sander " Journalof Polymer Society " the 10th volume of amine; the special public clear 44-20189 communique of Jap.P.; the Jap.P. spy opens clear 51-82102 communique; the Jap.P. spy opens clear 52-134692 communique; the Jap.P. spy opens clear 59-138205 communique; the Jap.P. spy opens clear 60-84305 communique; the Jap.P. spy opens clear 62-18537 communique; the Jap.P. spy opens clear 64-33104 communique; the compound of record etc. among No. 33825, the Research Disclosure specifically can be enumerated triethanolamine; the ESCAROL 507 ethyl ester; to the formoxyl xylidin; to methyl sulfo-xylidin etc.

As other examples that are total to sensitizer, can enumerate mercaptan and thioether class, for example the Jap.P. spy opens the mercaptan compound of putting down in writing in clear 53-702 communique, the special public clear 55-500806 communique of Jap.P., the Japanese patent laid-open 5-142772 communique, the disulfide that the Jap.P. spy opens clear 56-75643 communique etc., specifically can enumerate 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-sulfydryl-4 (3H)-quinazoline, β-mercaptonaphthalene etc.

As other examples of sensitizer altogether, can enumerate the sulphur compound put down in writing in the hydrogen donor put down in writing in the organometallics put down in writing in amino-acid compound (for example N-phenylglycine etc.), the special public clear 48-42965 communique of Jap.P. (for example tributyltin acetate (tributyl tin acetate) etc.), the special public clear 55-34414 communique of Jap.P., the Japanese patent laid-open 6-308727 communique (for example trithiane etc.) etc.

Viewpoint from the curing rate that improves polymerization growth rate and chain transfer balance, the content of these common sensitizers is preferably the scope of 0.1～30 quality % of quality of the total solid composition of solidification compound, the more preferably scope of 1～25 quality %, the more preferably scope of 0.5～20 quality 5%.

(polymerization inhibitor)

Among the present invention, in the manufacturing of photosensitive coloring composition or in preserving,, preferably add a spot of hot polymerization inhibitor in order to stop the unnecessary thermal polymerization of compound with olefinic unsaturated double-bond that can polymerization.

The hot polymerization inhibitor that can use as the present invention, can enumerate quinhydrones, p methoxy phenol, BHT, pyrogallol, tert-butyl catechol, benzoquinones, 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), the inferior cerium salt of N-nitroso-phenyl azanol etc.

The addition of hot polymerization inhibitor is preferably with respect to the quality in the photosensitive coloring composition layer and is about 0.01 quality %～about 5 quality %.In addition, can also add the polymerization inhibition to prevent to cause such as senior derivative of fatty acid such as docosanoic acid or docosane acid amides as required, gather surface in the dry run after coating partially in photographic layer by oxygen.The addition of advanced higher fatty acid derivative is preferably about 0.5 quality %～about 10 quality % of total composition.

(plastifier)

Among the present invention,, can add inorganic filler or plastifier, wall, can add sense fat agent etc. for the printing ink that improves the photographic layer surface in order to improve the rerum natura of photosensitive coloring composition layer.

As plastifier, for example can enumerate dioctyl phthalate, phthalic acid two (dodecyl) ester, triethylene glycol dieaprylate, dimethyl glycol phthalic ester, tricresyl phosphate (tricresyl phosphate), dioctyl adipate, dibutyl sebacate, glyceryl triacetate etc., using under the situation of bonding agent, can add gross mass with respect to compound with ethylenical unsaturated double bonds and bonding agent and be the plastifier below the 10 quality %.

By using mentioned component, photosensitive coloring composition of the present invention is good with high sensitivity curing and storage stability.In addition, also show high adaptation to substrate.Therefore, the photosensitive coloring composition that contains above-mentioned various compositions can be preferred for color filter.

From reducing high h _Y, viewpoint that the relation of above-mentioned formula 1 more effectively sets up etc. is set out, the viscosity of photosensitive coloring composition of the present invention is very important sometimes.

About the preferred viscosities of photosensitive coloring composition, according to the difference of coating process and different, for example when slot coated, the viscosity under preferred 25 ℃ is 1.0 * 10 ^-2Below the Pas.For example when rotary coating, the viscosity under preferred 25 ℃ is 5.0 * 10 ^-2Below the Pas.Viscosity under above-mentioned 25 ℃ is meant the value that records with Toki Sangyo Co., Ltd.'s system E type viscosity meter (RE-80L).

" photosensitive black composition "

The photosensitive black composition that the present invention uses preferably contains (A-2) opacifier, (B) binder polymer, (C-2) polymerizable compound, (D) Photoepolymerizationinitiater initiater and (E) solvent, can also contain other adjuvants such as spreading agent or surfactant as required.

-(A-2) opacifier-

As the ion of (A-2) opacifier, except that above-mentioned (A-1) colorant, can also enumerate that carbon black, titanium are black, the particulate of metal particle, metal oxide, sulfide etc.Wherein, the good carbon black of balance of preferred especially light-proofness and cost.

They can use separately or multiple being used in combination as required.For example, carbon black uses separately, or mixes with organic pigment, and carbon black and organic pigment share etc.

As the shading material, all the time, share at least 2 kinds with the pigment of going up the shielding visible region as black colorant.As these pigment, can enumerate the Jap.P. spy and open the pigment that record in 2005-17521 communique [0080]～[0088] is opened in 2005-17716 communique [0038]～[0040], Jap.P. spy, about using these pigment to form the method for light shield layers, open in Japanese patent laid-open 7-271020 etc.

In order further to strengthen shaded effect, the Jap.P. spy open 2000-147240, Jap.P. spy open 2000-143985, Jap.P. spy open 2005-338328, Jap.P. spy open among the 2006-154849 etc. developed carbon black, titanium is black or desirable light screening material such as graphite.In the present invention, from the viewpoint of light-proofness and cost, carbon black is one of preferred light screening material.

As the example of carbon black, preferred pigments is deceived 7 (carbon blacks).As carbon black, for example can enumerate the carbon black #2400 of Mitsubishi Chemical Ind's system, #2350, #2300, #2200, #1000, #980, #970, #960, #950, #900, #850, MCF88, #650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, #4000, #4010, #55, #52, #50, #47, #45, #44, #40, #33, #32, #30, #20, #10, #5, CF9, #3050, #3150, #3250, #3750, #3950, DIABLACK A, DIABLACKN220M, DIABLACK N234, DIABLACK I, DIABLACK LI, DIABLACKII, DIABLACK N339, DIABLACK SH, DIABLACK SHA, DIABLACK LH, DIABLACK H, DIABLACK HA, DIABLACK SF, DIABLACK N550M, DIABLACK E, DIABLACK G, DIABLACK R, DIABLACK N760M, DIABLACK LP; Carbon black Color Black FW200, the Color BlackFW2 of Degussa corporate system, Color Black FW1, COlor Black FW18, Color Black S170, ColorBlack S160, Special Black6, Special Black5, Special Black4, Special Black4A, Printex U, Printex V, Printex 140U, Printex 140V, Printex 35; The carbon black REGAL 400 of Cabot corporate system, REGAL 400R, REGAL XC72, VULCANXC72R, MOGUL L, MONARCH 1400, MONARCH 1000, BLACK PEARLS1400; Carbon black SUNBLACK900, the SUNBLACK910 of Asahi Carbon corporate system, SUNBLACK930, SUNBLACK960, SUNBLACK970 etc.In order to increase resistance, the above-mentioned carbon black after preferably covering with macromolecular compound.The size of the preferred single-particle of these carbon blacks is 10～100nm, more preferably 10～50nm.

-(C-2) polymerizable compound-

Form with (C-2) polymerizable compound in the photosensitive black composition as black matrix, preferably be set forth in (C-1) polymerizable compound that uses in the above-mentioned photosensitive coloring composition, preferred especially following compound.

As the polymerizable compound in the photosensitive black composition, be preferably and have 2 above ethylenical unsaturated double bonds and the monomer or the oligomer of addition polymerization under the irradiation of light.As such monomer and oligomer, can enumerate that to have at least 1 addition polymerization ethylenically unsaturated group and the boiling point under normal pressure in the molecule be compound more than 100 ℃.As its example, can enumerate monofunctional acrylate or simple function methacrylates such as polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate and phenoxy group ethyl (methyl) acrylate; Polyglycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, the trimethylolethane trimethacrylate acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane diacrylate, neopentyl glycol two (methyl) acrylate, pentaerythrite four (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, hexanediol two (methyl) acrylate, trimethylolpropane tris (acryloxy propyl group) ether, three (acryloxy ethyl) isocyanuric acid ester, three (acryloxy ethyl) isocyanuric acid ester, glycerine three (methyl) acrylate; (methyl) acroleic acid esterification obtains after polyfunctional alcohol such as trimethylolpropane or glycerine and oxirane or the epoxypropane addition polyfunctional acrylic ester or multifunctional methacrylates such as compound.

Acid multifunctional smooth solidity compound also is preferred compound.As the multifunctional smooth solidity compound of acidity, can use (1) by having hydroxyl with dibasic acid anhydride and 3 monomer or oligomer modifications with glazing solidity functional group import the compound that carboxyl obtains, (2) have hydroxyl and 3 with the monomer or the oligomer of glazing solidity functional group and have glycidyl or the additions such as compound of isocyanate group and COOH base import compound that carboxyl obtains or (3) and import compound that sulfonic group obtains etc. by will have 3 aromatics modifications with glazing solidity functional group with the concentrated sulphuric acid or oleum by making.In addition, as the multifunctional smooth solidity compound of acidity, can also use and to contain the oligomer of acid multifunctional smooth solidity compound monomer as repetitive.

As the example of the multifunctional smooth solidity compound of acidity, the compound that preferred following general formula (i), general formula are (ii) represented.In addition, general formula (i) and general formula (ii) in, when T or G were oxyalkylene group, the end of carbon atom side combined with R, X and W.

In the general formula (i), R represents (methyl) acryloxy, X represents-the COOH base or-OPO ₃H ₂Base.T represents oxyalkylene, and here, the carbon number of alkylidene is 1～4.N is 0～20.

General formula (ii) in, W represents R or the X in the general formula (i), among 6 W the W more than 3 being arranged is R.T synonym in G and the general formula (i).Z represents-O-or-OC=ONH (CH ₂) _qNHCOO-.P is 0～20, and q is 1～8.R, T, G, the W of a plurality of existence can be identical respectively in a part, also can be different.

The commercially available product of the acid multifunctional smooth solidity compound of (ii) representing as general formula (i) and general formula for example can be enumerated containing carboxyl 3 functional acrylate TO-756 and containing carboxyl 5 functional acrylate TO-1382 etc. of Toagosei Co., Ltd's system.

In addition, can also enumerate the special public clear 48-41708 communique of Jap.P., the special public clear 50-6034 communique of Jap.P. and Jap.P. spy and open the urethanes esters of acrylic acid of putting down in writing in the clear 51-37193 communique; The Jap.P. spy opens the polyester acrylate class of putting down in writing in clear 48-64183 communique, the special public clear 49-43191 communique of Jap.P. and the special public clear 52-30490 communique of Jap.P.; As polyfunctional acrylic ester and the multifunctional methacrylates such as epoxy acrylate class of epoxy resin with (methyl) acrylic acid reaction product.Wherein, preferred trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, above-mentioned carboxylic 5 functional acrylates etc.In addition, can also preferably enumerate " the polymerizable compound B " that puts down in writing in the Japanese patent laid-open 11-133600 communique.

Form content as black matrix, be preferably 5～50 quality % in the total solid composition of photosensitive black composition layer, more preferably 7～40 quality %, more preferably 10～35 quality % with (C-2) polymerizable compound in the photosensitive black composition.

(B) binder polymer that photosensitive black composition uses, (D) polymerization initiator, (E) solvent, other adjuvants etc. and above-mentioned colored pattern form identical with in the photosensitive coloring composition, and preferred content is also identical.

" liquid crystal indicator "

Liquid crystal indicator of the present invention is the liquid crystal indicator that possesses color filter of the present invention.Therefore, can show high quality image.

Spacer can preferably adopt coating method for making and transfer printing method for making.From the simple viewpoint of operation, preferably be coated with method for making.From the good viewpoint of the homogeneity of spacer height, preferred transfer printing method for making.About the transfer printing method for making, the method for putting down in writing among the special hope of the preferred especially Jap.P. 2007-185797.

About the definition of display device and the explanation of each display device, for example on the books in " electronic console " (the wooden clear husband's work of assistant assistant, Co., Ltd.'s census of manufacturing meeting nineteen ninety distribution), " display " (she blows along chapter work, industry books Co., Ltd., puts down into distribution in the first year) etc.In addition, about liquid crystal indicator, for example on the books in " inferior generation lcd technology " (Uchida Tatsuo edits, Co., Ltd. census of manufacturing can distribution in 1994).Can use liquid crystal indicator of the present invention not have particular restriction, for example can be used for liquid crystal indicator in the variety of way of above-mentioned " inferior generation lcd technology " record.

Wherein, the present invention is effective especially for the liquid crystal indicator of colored TFT mode.About the liquid crystal indicator of colored TFT mode, for example on the books in " colored TFT liquid crystal display " (the upright altogether Co., Ltd. that publishes issued in 1996).In addition, the present invention can also be applicable to liquid crystal indicator, STN, TN, VA, IPS, OCS, FFS and the R-OCR etc. that visual angles such as pixel partitioning scheme such as transverse electric field type of drive, MVA such as IPS enlarge.About these modes, for example on the books in the 43rd page of " the up-to-date trend in EL, PDP, LCD demonstration-technology and market " (department's calendar year 2001 distribution is investigated in eastern beautiful research centre).

Liquid crystal indicator also is made of various parts such as electrode base board, polarizing coating, phase retardation film, backlight, spacer, visual angle guarantee films except that color filter.Band photomask substrate of the present invention goes for the liquid crystal indicator with these known parts formations.

About these parts, for example on the books in " markets of 94 liquid crystal display periphery material chemistry " (island Itou Kentaro, the MC1994 of Co., Ltd. C distribution), " present situation of 2003 liquid crystal relevant markets and vision of the future (last volume) " (distribution in 2003 is always ground by the good Ji of table, Fuji of Co., Ltd.).About backlight, on the books in 25～30 pages (Yagi spark gap is grand bright) in 18～24 pages (the island health is abundant) in SID meeting Digest 1380 (2005) (A.Konno et.al), display monthly magazine in Dec, 2005 number, display monthly magazine in Dec, 2005 number etc.

When the three-wavelength pipe of color filter of the present invention and present known cold-cathode tube makes up, can realize high-contrast, led light source (RGB-LED) by using red, green, blue can provide the high Color reproduction of brightness height and excitation good liquid crystal indicator as backlight.

On the other hand, the desired performance of liquid crystal indicator is the raising of image response speed.In order to improve response speed, the speed of orientation of liquid crystal is improved.On the other hand, consider, want to reduce cost and to reduce the thickness of liquid crystal layer from the structural plane of unit.Reducing another required technology of thickness of liquid crystal layer is to reduce the liquid crystal aligning disorder of the boundary member of colored pixels and black matrix.Therefore, make every effort to reduce projection at the boundary member of colored pixels and black matrix.

Use in the color filter of color filter manufacture method manufacturing of the present invention, because overlapping O _YNear the difference in height of colored pattern is little, therefore when being used for liquid crystal indicator, can suppressing the orientation disorder of liquid crystal, thereby can improve contrast.

As mentioned above, color filter of the present invention can reduce the liquid crystal aligning disorder of above-mentioned overlapping portion, and the visuognosis when image shows also improves.Use color filter of the present invention at liquid crystal indicator of the present invention, can make the overlapping portion flattening of each colored pixels and black matrix, because flatness is good, make the liquid crystal layer attenuation, before laying transparency electrode ITO, need not to grind or give planarization layer, help rationalization and the cost decline and the batch process of operation.

[embodiment]

Below, enumerate embodiment and be described more specifically the present invention.Material shown in the following embodiment, reagent, ratio, instrument, operation etc. are only otherwise depart from the scope of the present invention all and can do suitable change.Therefore, scope of the present invention is not limited to following object lesson.Need to prove, in following embodiment, under the prerequisite of no specified otherwise, " % " and " part " expression " quality % " and " mass parts ", molecular weight is represented weight-average molecular weight.In addition, " wt% " expression " quality % ".

[embodiment 1]

＜1. the preparation of photosensitive black composition 〉

The preparation of-carbon black dispersion liquid (K-1)-

Prepare carbon black dispersion liquid (K-1) by following prescription.

26.7 parts of carbon blacks (Degussa corporate system COLOR BLACK FW2)

Spreading agent (nanmu originally changes into system DISPARLON DA7500 acid number 26 amine values 40)

... 3.3 parts

Benzyl methacrylate/methacrylic acid (=72/28[mol ratio]) multipolymer (50 quality % solution of molecular weight 30000, propylene glycol methyl ether acetate)

... 10 parts

Propylene glycol methyl ether acetate ... 60 parts

Under the condition of 3000rpm, use homogenizer to stir 1 hour above-mentioned each composition.The mixed solution that obtains is implemented 8 hours diffusing processing of differential in the pearl dispersion machine (trade name: DESPERMAT, GETZMANN corporate system) that adopts 0.3mm zirconium pearl, obtain carbon black dispersion liquid (K-1).

The carbon black dispersion liquid that use obtains (K-1) prepares photosensitive black composition coating fluid CK-1 by the prescription of following table 1.Numeric representation mass ratio in the table 1.

[table 1]

The details of each composition is as described below in the table 1.

Resin solution C-2: benzyl methacrylate/methacrylic acid (=85/15 mol ratio) multipolymer (50 quality % solution of Mw10000, propylene glycol methyl ether acetate)

UV curable resin C-3: trade name CYCLOMER P ACA-250 Daisel chemical industry Co., Ltd system [side chain have alicyclic ring, COOH base and acryloyl group acrylic copolymer, propylene glycol methyl ether acetate solution (solid constituent: 50 quality %)]

Polymerizable compound C-5: the potpourri of system KAYARAD DPHA of Nippon Kayaku K. K and the system KAYARAD R-684 of Nippon Kayaku K. K 60 to 40 (mass ratioes)

Initiating agent C-7: trade name " OXE-02 " Ciba corporate system

Surfactant C-8: trade name " MEGAFAC R30 " Dainippon Ink. ﹠ Chemicals Inc's system

Solvent: PGMEA=propylene glycol methyl ether acetate

EEP=3-ethoxyethyl group propionic ester

＜2. coating forms black matrix 〉

-photosensitive black composition layer formation operation-

The photosensitive black composition CK-1 that use obtains, by following operation, on glass substrate, form with Fig. 2 in the black matrix of the same clathrate pattern of resin black matrix 12.

At first, use slit coater (model HC6000, Hirata Spinning Ltd.'s system), regulate spacing between slit and the glass substrate and spray volume so that the thickness after the baking of back is 1.0 μ m, and with coating speed 120mm/ second the glass substrate (MILLENIUM of Coming corporate system, thick 0.7mm) after washing go up the above-mentioned photosensitive black composition CK-1 of coating.

-prebake conditions operation, exposure process-

Then, use heating plate, after heating 120 seconds (prebake conditions processing) under 80 ℃, use proximity printing machine (model LE5565A, Hitachi High Tech. Corp.'s corporate system), with 60mJ/cm ²Carry out pattern exposure.

-developing procedure-

Then, transporting the type developing apparatus with level develops.Promptly, adopt the 1.0% developer solution (dilution that contains CDK-11 mass parts and pure water 99 mass parts of potassium hydroxide class developer solution CDK-1 (Fujiphoto Electronics Materials Co., Ltd system), 24 ℃), set the spray pressure and be 0.15MPa, developed 37 seconds, with pure water washing, the black matrix pattern after obtaining developing.

Here, to with above-mentioned development after formed the sample of the substrate same structure of black matrix pattern, use SEM (scanning electron microscope) to take cross-section photograph (5000 times) and also confirm cross sectional shape, the result is positioned at+taper of 3.0 μ m positions with respect to upper end for lower end.

About the SEM photography,, vertically will deceive matrix pattern with substrate surface and carry out with substrate cutting along direction (Width of black matrix pattern) with the long limit of pixel 2 five equilibriums.

-roasting procedure-

Then, in 220 ℃ cleaning oven, carry out baking processing after 40 minutes, obtained on substrate, forming the black matrix base plate of band of the black matrix of clathrate pattern (with the identical clathrate pattern of resin black matrix 12 among Fig. 2).

The peristome as pixel of the black matrix that obtains is 90 μ m * 200 μ m, and thickness is 1.0 μ m, and the live width of the pattern of the direction parallel with the length direction of pixel is 25 μ m.

Use X-Rite 361T (V) (SAKATA INX ENG.Co., Ltd. system) to measure the optical concentration (OD) of the black matrix that makes, the result is 4.2.

＜3. the preparation of photosensitive coloring composition 〉

The preparation of-3-1. redness (R) usefulness photosensitive coloring composition coating fluid CR-1-

Prepare redness (R) dispersion liquid (R-1) by following prescription.

Paratonere 254 (mean grain size under the SEM observation is 43nm)

... 11 parts

Paratonere 177 (mean grain size under the SEM observation is 58nm)

... 4 parts

Aftermentioned dispersion resin A-3 ... 5 parts

Spreading agent (trade name: Disperbyk-161, BYK Chime corporate system)

(30% solution of propylene glycol methyl ether acetate) ... 3 parts

Alkali soluble resin: benzyl methacrylate/methacrylic acid copolymer (=75/25[mol ratio] multipolymer, molecular weight 30000, propylene glycol methyl ether acetate solution (solid constituent: 50 quality %)) ... 9 parts

Solvent B: propylene glycol methyl ether acetate ... 68 parts

Under the condition of 3000rpm, use homogenizer to stir 1 hour above-mentioned each composition.The mixed solution that obtains is implemented 4 hours diffusing processing of differential in the pearl dispersion machine (trade name: DESPERMAT, GETZMANN corporate system) that adopts 0.3mm zirconium pearl, obtain redness (R) dispersion liquid (R-1).Observe with SEM, mean grain size is 36nm again.

The redness that use obtains (R) prepares redness (R) photosensitive coloring composition coating fluid CR-1 with dispersion liquid (R-1) by following prescription.

Red (R) uses dispersion liquid (R-1) ... 100 parts

Epoxy resin: (trade name EHPE3150 Daicel chemical industrial company system) ... 2 parts

Polymerizable compound: dipentaerythritol five or six acrylate ... 8 parts

Polymerization initiator: 4-(adjacent bromine is right-N, and N-two (ethoxy carbonyl methyl) amino-phenyl)-2,6-two (trichloromethyl)-s-triazine ... 1 part

Polymerization initiator: 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1 ... 1 part

Polymerization initiator: diethyl thioxanthone ... 0.5 part

Polymerization inhibitor: p methoxy phenol ... 0.001 part

Fluorine class surfactant (trade name: the big Japanese ink of Megafac R30 chemical industrial company system)

... 0.01 part

Non-ionics (trade name: Tetronic R150 Chinese mugwort Deco corporate system)

... 0.2 part

Solvent: propylene glycol n-butyl ether acetic acid esters ... 30 parts

Solvent: propylene glycol methyl ether acetate ... 100 parts

Mentioned component is mixed stirring, obtain redness (R) photosensitive coloring composition coating fluid CR-1.

With Toki Sangyo Co., Ltd. system E type viscosity meter (RE-80L), measure the redness (R) that obtains with the viscosity under 25 ℃ of photosensitive coloring composition coating fluid CR-1, the result is 0.3 * 10 ^-2Pas.The preparation of-3-2. green (G) usefulness photosensitive coloring composition coating fluid CG-1-

Prepare green (G) dispersion liquid (G-1) by following prescription.

Pigment green 36 (mean grain size under the SEM observation is 47nm)

... 11 parts

Pigment yellow 150 (mean grain size under the SEM observation is 39nm)

... 7 parts

Aftermentioned dispersion resin A-3 ... 5 parts

Spreading agent (trade name: Disperbyk-161, BYK Chime corporate system 30% solution)

... 3 parts

Alkali soluble resin: benzyl methacrylate/methacrylic acid copolymer (=85/15[mol ratio] multipolymer, molecular weight 30000, propylene glycol methyl ether acetate solution (solid constituent: 50 quality %)) ... 11 parts

Solvent: propylene glycol methyl ether acetate ... 70 parts

Under the condition of 3000rpm, use homogenizer to stir 1 hour above-mentioned each composition.The mixed solution that obtains is implemented 8 hours diffusing processing of differential in the pearl dispersion machine (trade name: DESPERMAT, GETZMANN corporate system) that adopts 0.3mm zirconium pearl, obtain green (G) dispersion liquid (G-1).

The green that use obtains (G) prepares green (G) photosensitive coloring composition coating fluid CG-1 with dispersion liquid (G-1) by following prescription.Observe with SEM, mean grain size is 32nm again.

Green (G) uses dispersion liquid (G-1) ... 100 parts

Epoxy resin (trade name EHPE3150 Daicel chemical industrial company system) ... 2 parts

Polymerizable compound: dipentaerythritol five or six acrylate ... 8 parts

Polymerizable compound: four (ethoxy propylene acid esters) of pentaerythrite

... 2 parts

Polymerization initiator: 1, the two trihalomethyl groups of 3--5-benzo tetrahydrofuran triazine ... 2 parts

Polymerization initiator: diethyl thioxanthone ... 0.5 part

Polymerization inhibitor: p methoxy phenol ... 0.001 part

Fluorine class surfactant (trade name: the big Japanese ink of Megafac R08 chemical industrial company system)

... 0.02 part

Non-ionics (trade name: EMALGNE A-60 KAO. Corp. SA system)

... 0.5 part

Solvent: propylene glycol methyl ether acetate ... 120 parts

Solvent: propylene glycol n-butyl ether acetic acid esters ... 30 parts

Above-mentioned composition is mixed stirring, obtain green (G) photosensitive coloring composition coating fluid CG-1.

With Toki Sangyo Co., Ltd. system E type viscosity meter (RE-80L), measure the green (G) that obtains with the viscosity under 25 ℃ of photosensitive coloring composition coating fluid CR-1, the result is 0.3 * 10 ^-2Pas.The preparation of-3-3. blueness (B) usefulness photosensitive coloring composition coating fluid CB-1-

Prepare blueness (B) dispersion liquid (B-1) by following prescription.

Pigment blue 15: 6 (mean grain size under the SEM observation is 55nm)

... 14 parts

Pigment Violet 23 (mean grain size under the SEM observation is 61nm)

... 1 part

Aftermentioned dispersion resin A-3 ... 5 parts

Spreading agent (trade name: Disperbyk-161, BYK Chemie corporate system 30% solution)

... 3 parts

Alkali soluble resin: benzyl methacrylate/methacrylic acid copolymer (=80/20[mol ratio] multipolymer, molecular weight 30000, propylene glycol methyl ether acetate solution (solid constituent: 50 quality %)) ... 4 parts

Solvent: propylene glycol methyl ether acetate ... 73 parts

Under the condition of 3000rpm, use homogenizer to stir 1 hour above-mentioned each composition.The mixed solution that obtains is implemented 4 hours diffusing processing of differential in the pearl dispersion machine (trade name: DESPERMAT, GETZMANN corporate system) that adopts 0.3mm zirconium pearl, obtain blueness (B) dispersion liquid (B-1).Observe with SEM, mean grain size is 39nm again.

The blueness that use obtains (B) prepares blueness (B) photosensitive coloring composition coating fluid CB-1 with dispersion liquid (B-1) by following prescription.

Blue (B) uses dispersion liquid (B-1) ... 100 parts

Alkali soluble resin: benzyl methacrylate/methacrylic acid copolymer (=80/20[mol ratio] multipolymer, molecular weight 30000, propylene glycol methyl ether acetate solution (solid constituent: 50 quality %)) ... 7 parts

Epoxy resin (trade name CELLOXIDE 2080 Daicel chemical industrial company systems)

... 2 parts

The UV curable resin: (trade name CYCLOMER P ACA-250 Daicel chemical industrial company system) (side chain has acrylic copolymer, the propylene glycol methyl ether acetate solution (solid constituent: 50 quality %)) of alicyclic ring, COOH base and acryloyl group

... 4 parts

Polymerizable compound: dipentaerythritol five or six acrylate ... 12 parts

Polymerization initiator: 1-(9-ethyl-6-(2-toluyl)-9H-carbazole-3-yl)-1-(adjacent acetyl group oxime) ethane ... 3 parts

Polymerization inhibitor: p methoxy phenol ... 0.001 part

... 0.02 part

Non-ionics (trade name: EMALGNE A-60 KAO. Corp. SA system) ... 1.0 parts

Solvent: 3-ethoxyl ethyl propionate ... 20 parts

Solvent: propylene glycol methyl ether acetate ... 150 parts

Mentioned component is mixed stirring, obtain blueness (B) photosensitive coloring composition coating fluid CB-1.

With Toki Sangyo Co., Ltd. system E type viscosity meter (RE-80L), measure the blueness (B) that obtains with the viscosity under 25 ℃ of photosensitive coloring composition coating fluid CB-1, the result is 0.3 * 10 ^-2Pas.

＜4. dispersion resin A-3's is synthetic 〉

(1. chain-transferring agent A3's is synthetic)

With dipentaerythritol six (3-mercaptopropionic acid ester) [DPMP; Sakai Chemical Industry Co., Ltd.'s system] (following compound (33)) 7.83 parts and 4.55 parts of following compounds (m-6) having adsorption site and have a carbon-to-carbon double bond be dissolved in 28.90 parts of the propylene glycol monomethyl ethers, flow down at nitrogen and be heated to 70 ℃.To wherein adding 2,0.04 part of two (2, the 4-methyl pentane nitrile) [V-65, Wako Pure Chemical Industries, Ltd.'s system] of 2 '-azo heated 3 hours.Then, add 0.04 part of V-65, flow down, reacted 3 hours down in 70 ℃ at nitrogen.Be cooled to room temperature, obtain down showing 30% solution of mercaptan compound (chain-transferring agent A3).

(2. dispersion resin A-3's is synthetic)

The mixed solution of 4.66 parts of 1.0 parts of 19.0 parts of 4.99 parts of 30% solution, methyl methacrylates, the methacrylic acids of the above-mentioned chain-transferring agent A3 that obtains and propylene glycol monomethyl ethers flowed down at nitrogen be heated to 90 ℃.Stir on one side this mixed solution, a ray flower dripped 2 in 2.5 hours, the mixed solution that 0.139 part of 2 '-azo-bis-iso-dimethyl [V-601, Wako Pure Chemical Industries, Ltd.'s system], 5.36 parts of propylene glycol monomethyl ethers and propylene glycol methyl ether acetate are 9.40 parts.After dripping end, reacted 2.5 hours down, add the mixed solution of 4.00 parts of 0.046 part of 2,2 '-azo-bis-iso-dimethyl and propylene glycol methyl ether acetates then, reacted again 2 hours at 90 ℃.In reactant liquor, add 21.7 parts of 1.52 parts of propylene glycol monomethyl ethers and propylene glycol methyl ether acetates, be cooled to room temperature, obtain the solution (specific dispersion resin 30 quality %, propylene glycol monomethyl ether 21 quality %, propylene glycol methyl ether acetate 49 quality %) of dispersion resin A-3 (weight-average molecular weight of polystyrene conversion is 24000).

The acid number of this dispersion resin A-3 is 48mg/g.The structure of dispersion resin A-3 is as follows.

The making of＜color filter 〉

-photosensitive coloring composition layer formation operation-

The redness that use obtains (R) photosensitive coloring composition coating fluid CR-1, following operation forms the red pattern (concerning also identical with Fig. 1 (a)～Fig. 1 (c) with the position of resin black matrix) of the striated pattern identical with red pattern 20R among Fig. 1 (a)～Fig. 1 (c).

At first, the black matrix formation face side at the black matrix base plate of above-mentioned band is coated with above-mentioned redness (R) photosensitive coloring composition coating fluid CR-1.Particularly, situation about forming with the photosensitive black composition layer is identical, spacing between the black matrix base plate of adjusting slit and band and spray volume are coated with coating speed 120mm/ so that the bed thickness of the photosensitive coloring composition layer (colored pattern) after the baking of back is about 2.1 μ m second.

-dyed layer prebake conditions operation, dyed layer exposure process-

Then, use heating plate,, use proximity printing machine (model LE5565A, Hitachi High Tech. Corp.'s corporate system) then, at 90mJ/cm 100 ℃ of heating 120 seconds (prebake conditions processing) down ²Under carry out pattern exposure.

In above-mentioned pattern exposure,, make in the red pattern after the following baking along overlapping O about overlapping (the exposure lap) of exposing patterns and black matrix _YThe length L of directions X _oBe 6.0 μ m, set mask pattern and exposure machine.

-dyed layer developing procedure, dyed layer roasting procedure-

Then,, set spray and press, developed 45 seconds, wash with pure water to 0.2MPa with 1.0% developer solution (dilution that contains CDK-11 mass parts and pure water 99 mass parts, 25 ℃) of potassium hydroxide class developer solution CDK-1 (Fujiphoto Electronics Materials Co., Ltd system).

Then, the back baking processing is 30 minutes in 220 ℃ cleaning oven, forms through heat treated red pixel.

Then, except the redness (R) that above-mentioned photosensitive coloring composition layer is formed in operation, dyed layer prebake conditions operation, dyed layer exposure process, dyed layer developing procedure and the dyed layer roasting procedure changes green (G) into the photosensitive coloring composition coating fluid CG-1 with photosensitive coloring composition coating fluid CR-1, same operation forms the green pattern (concerning also identical with Fig. 1 (a)～Fig. 1 (c) with the position of resin black matrix) of the striated pattern identical with green pattern 20G among Fig. 1 (a)～Fig. 1 (c).Then, except changing redness (R) into blueness (B) with the photosensitive coloring composition coating fluid CB-1 with photosensitive coloring composition coating fluid CR-1, same operation forms the blue pattern (concerning also identical with Fig. 1 (a)～Fig. 1 (c) with the position of resin black matrix) of the striated pattern identical with blue pattern 20B among Fig. 1 (a)～Fig. 1 (c), obtains the color filter identical with the color filter 100 shown in Fig. 1 (a)～Fig. 1 (c).

Then, coating green (G) is operated until finishing prebake conditions with above-mentioned color filter is same with photosensitive coloring composition coating fluid CG-1, makes photosensitive coloring composition layer cross section observation sample.

The sample that obtains used perpendicular to the pattern edge of black matrix and perpendicular to the face of substrate cut,, take the SEM photo with scanning electron microscope (5000 times) to this cut surface.The structure of above-mentioned SEM photo is identical with Figure 15.

According to the SEM photo that obtains, obtain the position of comparing the some S of more close substrate 0.1 μ m on the substrate normal direction in the line that is equivalent to green (G) photosensitive coloring composition laminar surface with distance substrate point R farthest.

About a S in the position that is parallel on the direction of substrate surface, as pattern edge E with the resin black matrix nearest apart from this S _BThe position be benchmark (0), resin black matrix forms area side and is negative (-), the non-formation area side of resin black matrix is+2.0 μ m during for just (+).

The making of＜liquid crystal indicator 〉

On the R of the above-mentioned color filter that obtains pixel, G pixel and B pixel and black matrix, further form ITO (Indium Tin Oxide: transparency electrode tin indium oxide) by sputter.Then, be equivalent on the above-mentioned ito transparent electrode black matrix above part column photoinduction spacer is set, the alignment films that is formed by polyimide further is set thereon.

In addition, the active-matrix substrate of preparing to have TFT (thin film transistor (TFT)) forms the face side at TFT the alignment films that is formed by polyimide is set as counter substrate.

Then, on the position that is equivalent to surround the black matrix housing that is provided with around the colored pixels group of color filter, utilize quantitative ejection mode to be coated with the sealant of ultraviolet curable resin, drip TN pattern liquid crystal, under vacuum state, fit with counter substrate.After the substrate of fitting carried out the UV irradiation, thermal treatment made sealant cures.Obtain liquid crystal cells in the manner described above.Paste the polaroid HLC2-2518 that the SANRITZ of Co., Ltd. makes on the two sides of this liquid crystal cells, then, at the backlight that constitutes cold-cathode tube and become the back side one side configuration of the liquid crystal cells that is provided with above-mentioned polaroid, make liquid crystal indicator.

＜measure and estimate

(height h _XWith height h _Y)

Preparation and the test sample that the above-mentioned color filter that obtains is same structure are selected a green pixel at the display frame central portion, measure from the colored pattern surface to overlapping O _YThe height h on colored pattern surface _YThen, to same pixel, measure from the colored pattern surface to overlapping O _XThe height h on colored pattern surface _X

Above-mentioned height h _XWith above-mentioned height h _YMensuration all adopt contact surface roughometer P-10 (KLA Tencor Co., Ltd. system) to carry out.Particularly, about height h _X, along the direction of A-A among Fig. 1 (a), about height h _Y, along the direction of B-B among Fig. 1 (a), mobile respectively contact pilotage is measured.

Measurement result is as shown in table 2.

(bore long L _B, L _CAnd other)

The test sample that preparation and the above-mentioned color filter that obtains are same structure, select a green pixel at the display frame central portion, with test sample being cut with length direction 2 five equilibriums of green pixel and perpendicular to the face of substrate, use scanning electron microscope, take section S EM photo (5000 times) with composition shown in Figure 3.

According to the section S EM photo that photographs, measure thickness, the long L of awl of black matrix _B, green pattern thickness, the awl long L _C, overlapping O _YLength L _OAnd overlapping O _YThickness.Here, overlapping O _YThickness be from colored pattern lower end E1 to colored pattern the upper end T the substrate normal direction on distance.

Measurement result is as shown in table 2.

(contrast evaluation)

To the above-mentioned liquid crystal indicator energising that obtains, brightness and full brightness of deceiving when showing when in the darkroom, using chroma-luminance meter (opening up general health corporate system BM-5A) to measure white full the demonstration respectively.Arbitrary brightness is all measured at the display frame central portion of liquid crystal indicator.

With ratio (brightness during complete white demonstration the/full brightness during black the demonstration) degree as a comparison, estimate contrast according to following evaluation criterion.

～evaluation criterion～

A... contrast is more than 800.

B... contrast is 500 above less thaies 800.

C... contrast is 250 above less thaies 500.

D... the contrast less than 250.

[embodiment 2～embodiment 5, comparative example 2]

Except thickness, the long L of awl with resin black matrix _B, green pattern thickness, the awl long L _CAnd overlapping O _YLength L _OOutside changing shown in the table 2, make color filter and liquid crystal indicator similarly to Example 1, carry out the evaluation identical with embodiment 1.Evaluation result is as shown in table 2.

Specifically, change the thickness of resin black matrix, change the long L of awl by the development time of regulating developing apparatus by the spray volume of regulating the slot coated device _B

In addition, change the thickness of green pattern, change the long L of awl by the development time of regulating developing apparatus by the spray volume of regulating the slot coated device _C, change overlapping O by the time shutter of regulating exposure device _YLength L _O

[comparative example 1]

Except changing green (G) into following green (G) with the photosensitive coloring composition coating fluid CG-A with photosensitive coloring composition coating fluid CG-1, color filter and liquid crystal indicator are made in operation similarly to Example 1, carry out evaluation similarly to Example 1.Evaluation result is as shown in table 2.

(relatively using the preparation of coating fluid CG-A)

Except green (G) among the embodiment 1 changed into the following dispersion resin D-1 with the dispersion resin A-3 in the preparation of photosensitive coloring composition coating fluid CG-1, operate preparation green (G) usefulness photosensitive coloring composition coating fluid CG-A equally with the preparation of CG-1.

With Toki Sangyo Co., Ltd. system E type viscosity meter (RE-80L), measure the green (G) that obtains with the viscosity under 25 ℃ of photosensitive coloring composition coating fluid CG-A, the result is 1.1 * 10 ^-2Pas.

[table 2]

(unit: μ m)

As shown in table 2, at height h _YThan height h _XLow 0.1 μ m is above (to be h _Y-h _X≤-0.1 μ m) among embodiment 1～embodiment 5, liquid crystal indicator obtains high-contrast.

On the other hand, at h _Y-h _XIn the comparative example 1 and comparative example 2 of＞-0.1 μ m, contrast descends.

Claims

1. color filter, wherein,

At least the resin black matrix and the thickness that have thickness and be the clathrate pattern of 0.5 μ m～2.0 μ m on substrate are the colored pattern of the striated pattern of 1.0 μ m～3.0 μ m,

Described resin black matrix will be divided into a plurality of pixels on the described substrate,

In at least a portion of described colored pattern, be provided with continuously on a plurality of pixels that respectively are listed in linearly arrangement of colored pattern and on the resin black matrix between this pixel, and respectively being listed on the resin black matrix with the direction of the direction quadrature of these row of described colored pattern has overlapping O _XGroup, and with the resin black matrix of the parallel direction of direction of each row of described colored pattern on have overlapping O _YGroup and a pair of pattern edge,

When pixel in a plurality of pixels of observing described linearly arrangement, obtain: overlapping the O adjacent with this pixel _YHeight h with respect to the colored pattern surface in this pixel _YThan overlapping the O adjacent with this pixel _XHeight h with respect to the colored pattern surface in this pixel _XMore than the low 0.1 μ m.

2. color filter according to claim 1, wherein,

Described overlapping O _YThe length with on the direction of the direction quadrature of described row be more than the 2 μ m, below the 10 μ m.

3. color filter according to claim 1, wherein,

The cross sectional shape of the end of described colored pattern is that rectangle or awl length are the following tapers of 10 μ m.

4. color filter according to claim 1, wherein,

The cross sectional shape of the end of described resin black matrix is that rectangle or awl length are the following tapers of 10 μ m.

5. the manufacture method of a color filter,

This manufacture method is to make the method for each described color filter in claim 1～claim 4, wherein, comprising:

Resin black matrix forms operation, forms the resin black matrix of clathrate pattern on substrate;

Colored pattern forms operation, be formed with on the substrate of described resin black matrix, form the photosensitive coloring composition layer with photosensitive coloring composition, the photosensitive coloring composition layer that forms is carried out pattern exposure, to carry out the photosensitive coloring composition layer behind the pattern exposure again and develop, form colored pattern.

6. the manufacture method of color filter according to claim 5, wherein,

Described photosensitive coloring composition layer forms being formed with on the substrate of described resin black matrix coating photosensitive coloring composition and prebake conditions,

In the cross section of using the photosensitive coloring composition layer after cutting described prebake conditions perpendicular to the pattern edge of described resin black matrix and perpendicular to the face of substrate and obtaining,

In the described photosensitive coloring composition laminar surface, for for the some S of distance substrate point R farthest more close substrate 0.1 μ m on the substrate normal direction, when the position with the pattern edge of the resin black matrix nearest apart from this S be benchmark, with the area side that forms resin black matrix for negative, be timing with the area side that does not form resin black matrix, the position of this S on being parallel to the direction of substrate surface is in the scope of-2 μ m～+ 10 μ m.

7. liquid crystal indicator,

It has each described color filter in claim 1～claim 4.