JP4862990B2 - Method for manufacturing four-color filter - Google Patents

Description

  The present invention relates to a method for manufacturing a four-color filter. More specifically, the present invention relates to a four-color filter having a white pixel used for a color filter for a liquid crystal display element (LCD) and a color filter for a charge coupled device (CCD), and a method for forming a protective film together with the four-color filter.

  The liquid crystal display device has a plurality of pixels including a pixel electrode and red (R), green (G), and blue (B) color filters (hereinafter, each pixel including red, green, and blue color filters is a red pixel) , Green and blue pixels). However, in a general liquid crystal display device that displays one dot based on red, green, and blue color pixels, the color filter disposed in each pixel transmits only a certain portion of incident light. Light efficiency may be low. Therefore, recently, in order to increase the brightness, a liquid crystal panel in which one pixel is composed of four sub-pixels of white (W) in addition to red (R), green (G), and blue (B) has been developed. ing. There are two methods of configuring RGBW sub-pixels with one pixel, the stripe method and the checkerboard method. However, in order to suppress the decrease in the aperture ratio and reduce the cost of the driver IC with respect to the conventional color arrangement, the checker is used. A board system is preferred. For example, one pixel includes a red subpixel (RP), a green subpixel (GP), a blue subpixel (BP), and a white subpixel (WP) arranged in a 2 × 2 matrix. Here, the red and green subpixels (RP, GP) and the blue and white pixels (BP, WP) are arranged adjacent to each other in the row direction, and the red and blue subpixels (RP) are arranged in the column direction. , BP) and a color filter in which green and white sub-pixels (GP, WP) are arranged adjacent to each other have been proposed.

Conventionally, the formation method of the color filter containing the said pixel of 4 colors has been formed by the process of at least following (1)-(4) using the composition for photosensitive colored layer formation.
(1) The process of forming the coating film of the composition for colored layer formation on a board | substrate.
(2) A step of exposing at least a part of the coating film.
(3) The process of developing the coating film after exposure.
(4) The process of heat-processing the coating film after image development.
The steps (1) to (4) are repeated using each colored layer forming composition in which a red, green, or blue pigment is dispersed, and a white forming composition to repeat a red pixel pattern and a green pixel pattern. By forming a blue pixel pattern and a white pixel pattern on the same substrate, a colored layer in which four-color pixel patterns of red, green, blue and white are arranged in a predetermined arrangement is formed on the substrate. be able to.
However, if the number of pixels is increased by one, the number of processes increases accordingly. Therefore, a reduction in the number of processes is required for cost reduction and throughput improvement.
In addition, a protective film is also formed on the pixel pattern. Generally, the protective film is required to flatten a step due to the color filter formed on the base substrate. In forming these pixels, hole filling and flatness are required.

  An object of the present invention is to provide a composition suitable for forming the white pixel, and a method for forming a white pixel or a protective film together with the white pixel.

  Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are as follows.
[A-1] (a1) A polymer unit derived from a polymerizable unsaturated compound having an oxiranyl group or an oxetanyl group, and (a2) the following formula (01)

Here, R is a tertiary alkyl group having 5 or more carbon atoms, a tertiary alkyl group having 4 or more carbon atoms substituted with an alkoxy group having 1 to 4 carbon atoms, oxygen bonded to R in the above-described formula A cycloalkyl group having 3 or more ring carbon atoms bonded to the atom (—O—) with a tertiary carbon atom or a tertiary atom to an oxygen atom (—O—) bonded to R in the above-described formula A lactone ring or a lactam ring of 4 or more members bonded by a carbon atom,
A copolymer comprising polymerized units derived from a polymerizable unsaturated compound having a structure represented by:
And
[A-2] a polymer containing a polymer unit derived from the polymerizable unsaturated compound (a1) but different from the copolymer [A-1], and [A-3] the polymerizable unsaturated compound (a2). ) In combination with a polymer different from the copolymer [A-1],
Of the above copolymer [A-1] ,
And it is used for forming the white sub-pixel in a color filter that constitutes one pixel by four sub-pixels of red (R), green (G), blue (B) and white (W). This is achieved by the resin composition.

According to the present invention, the above objects and advantages of the present invention are secondly,
A method of manufacturing a color filter that forms one pixel by four sub-pixels of white (W) in addition to red (R), green (G), and blue (B). It is achieved by a method for producing a four-color filter, which is formed by an ink jet method using the resin composition of the invention.

In addition, according to the present invention, the above object and advantage of the present invention are thirdly,
This is achieved by a method for producing a four-color filter in which a white subpixel is formed using the resin composition of the present invention and a protective film is simultaneously formed by an inkjet method.

  Hereinafter, each component of the resin composition of this invention is demonstrated.

Copolymer [A-1]
The copolymer [A-1] in the present invention is (a1) a polymer unit derived from a polymerizable unsaturated compound having an oxiranyl group or an oxetanyl group, (a2) a polymer having a structure represented by the above formula (01). A polymerizable unit derived from unsaturation, and optionally further comprising (a3) a polymerized unit derived from another polymerizable unsaturated compound different from the polymerized units of (a1) and (a2) above. .
R in the formula (01) is a tertiary alkyl group having 5 or more carbon atoms, a tertiary alkyl group having 4 or more carbon atoms substituted with an alkoxy group having 1 to 4 carbon atoms, R in the represented formula (01) A cycloalkyl group having 3 or more ring carbon atoms bonded to a bonded oxygen atom (—O—) by a tertiary carbon atom or an oxygen atom bonded to R in the represented formula (01) ( It is a lactone ring or a lactam ring having a 4-membered ring or more which is bonded to -O-) with a tertiary carbon atom.
When R is a tertiary alkyl group having 5 or more carbon atoms or a tertiary alkyl group having 4 or more carbon atoms substituted with an alkoxy group having 1 to 4 carbon atoms, the formula (01) is represented by the following formula (1):

Here, R ¹ and R ² are each independently a C 1-8 alkyl group substituted with a C 1-8 alkyl group or a C 1-4 alkoxyl group, and R ³ Is represented by a C 1-8 alkyl group substituted with a C 2-8 alkyl group or a C 1-4 alkoxy group.
When R is a cycloalkyl group having 3 or more ring carbon atoms, the formula (01) is represented by the following formula (2):

Here, the definition of R ¹ is the same as in the above formula (1), n is an integer of 1 to 8, and R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, or An alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms having an alkoxy group having 1 to 4 carbon atoms at the terminal or side chain of the alkyl group, or an alkoxy group having 1 to 4 carbon atoms, Alternatively, R ⁴ , R ⁵ , R ⁶ and R ⁷ are combined with the carbon atom to which at least two are bonded and the carbon atom to which they are bonded and the carbon atom to which R ¹ is bonded to form a total number of carbon atoms of 7 ˜16 dicycloalkane or tricycloalkane structures may be formed. However, when n = 2 to 8, the plurality of R ⁶ and R ⁷ may be the same or different.
It is represented by
When R is a lactone ring or lactam ring having 4 or more members, the above formula (01) is represented by the following formula (3):

Here, the definition of R ¹ is the same as in the above formula (1), l is 0, 1 or 2, m is an integer of 1 to 4, X is an oxygen atom or a nitrogen atom, and R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a carbon having an alkoxy group having 1 to 4 carbon atoms at the terminal or side chain of the alkyl group. An alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, provided that two R ⁸ and two R ⁹ when l = 2 and a plurality when m is an integer of 2 to 4 R ¹⁰ and the plurality of R ¹¹ may be the same or different.
It is a structure represented by.

R ¹ in the formula (1), (2) or (3) and R ² in the formula (1) are an alkyl group having 1 to 8 carbon atoms, or a terminal group or a side chain of the alkyl group having 1 to 4 carbon atoms. The C1-C8 alkyl group which has the alkoxy group of this is shown. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, (iso) propyl, (iso) butyl, (iso) pentyl, (iso) hexyl, (iso) heptyl, and (iso) octyl. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, (iso) propoxy, (iso) butoxy and the like.
R ³ represents an alkyl group having 2 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms having an alkoxy group having 1 to 4 carbon atoms at the terminal or side chain of the alkyl group. Examples of the alkyl group having 2 to 8 carbon atoms include ethyl, (iso) propyl, (iso) butyl, (iso) pentyl, (iso) hexyl, (iso) heptyl, and (iso) octyl. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, (iso) propoxy, (iso) butoxy and the like.

The cyclic structure in formula (2) represents a cycloalkane structure of n = 1-8. Examples of the cycloalkane include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, and cyclodecane.
R ^{4 to} R ⁷ are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms having an alkoxy group having 1 to 4 carbon atoms at the terminal or side chain of the alkyl group, or the number of carbon atoms 1-4 alkoxy groups are shown. A plurality of R ⁶ and R ⁷ on the cyclic alkane are not necessarily the same when n = 2 or more, but they are not necessarily the same, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a terminal or side chain of the alkyl group Either an alkyl group having 1 to 8 carbon atoms having an alkoxy group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms may be used. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, (iso) propyl, (iso) butyl, (iso) pentyl, (iso) hexyl, (iso) heptyl, (iso) octyl and the like. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, (iso) propoxy, (iso) butoxy and the like.

R ^{4 to} R ⁷ are dicycloalkanes having a total ring carbon number of 7 to 16 together with the carbon atom to which at least two of them are bonded and the carbon atom to which R ¹ is bonded. Alternatively, a tricycloalkane structure can be formed. Examples of the dichlorolucan or tricycloalkane include 2-ethyltricyclo [3.3.1.1 ^3,7 ] decan-2-yl group, 2-methyltricyclo [3.3.1.1 ^{3, 7} ] Decan-2-yl group, 1-ethyltricyclo [3.3.1.1 ^3,7 ] decan-1-yl group, 1-ethyltricyclo [3.3.1.1 ^3,7 ] Examples include a decan-1-yl group and a 3-hydroxytricyclo [3.3.1.1 ^3,7 ] decan-1-yl group.
As R < ⁸ > -R < ¹¹ > in Formula (3), the same group as the group mentioned above about R < ⁴ > -R < ⁷ > can be illustrated.

  Examples of the lactone ring in the formula (3) when X is an oxygen atom include 2-ethyl-γ-butyrolactone-2-yl group, 2-methyl-γ-butyrolactone-2-yl group, and 2-ethyl- γ-butyrolactone-3-yl group, 2-methyl-γ-butyrolactone-3-yl group, 2-ethyl-γ-butyrolactone-4-yl group, 2-methyl-γ-butyrolactone-4-yl group, 2- Ethyl-δ-valerolactone-2-yl group, 2-ethyl-δ-valerolactone-2-yl group, 2-ethyl-δ-valerolactone-3-yl group, 2-ethyl-δ-valerolactone-3 -Yl group, 2-ethyl-δ-valerolactone-4-yl group, 2-ethyl-δ-valerolactone-4-yl group, 2-ethyl-δ-valerolactone-5-yl group and 2-ethyl- δ-valerolactone A 5-yl group etc. can be mentioned.

  Moreover, as a lactam ring in Formula (3) when X is a nitrogen atom, 2-ethyl-γ-butyrolactam-2-yl group, 2-methyl-γ-butyrolactam-2-yl group, 2-ethyl -Γ-butyrolactam-3-yl group, 2-methyl-γ-butyrolactam-3-yl group, 2-ethyl-γ-butyrolactam-4-yl group, 2-methyl-γ-butyrolactam-4-yl group, 2 -Ethyl-δ-valerolactam-2-yl group, 2-ethyl-δ-valerolactam-2-yl group, 2-ethyl-δ-valerolactam-3-yl group and 2-ethyl-δ-valerolactam- 3-yl group, 2-ethyl-δ-valerolactam-4-yl group, 2-ethyl-δ-valerolactam-4-yl group, 2-ethyl-δ-valerolactam-5-yl group and 2-ethyl -Δ-valerolacta Examples thereof include a mu-5-yl group.

In the copolymer [A-1], the polymerizable unsaturated compound (a1) is not particularly limited as long as it has an oxiranyl group or an oxetanyl group and a polymerizable unsaturated group. For example, a polymerizable unsaturated compound containing an oxiranyl group can be used. Examples of the saturated compound include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, methacryl Acid 3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzylglycidyl ether, m -Vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether Tel and the like.
Examples of the oxetanyl group-containing polymerizable unsaturated compound include 3-methyl-3- (meth) acryloxymethyloxetane, 3-ethyl-3- (meth) acryloxymethyloxetane and the like.
Among these, glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether are copolymerized and the protective film obtained or It is preferably used from the viewpoint of increasing the heat resistance and surface hardness of the insulating film.

  In the copolymer [A-1], the polymerizable unsaturated compound (a2) is not particularly limited as long as it is a polymerizable unsaturated compound having the structure of the above chemical formula (1) or (2). (1) Examples of the polymerizable unsaturated polymer having a structure include 1-dimethyl (iso) propyl (meth) acrylate, 1-dimethyl (iso) butyl (meth) acrylate, and 1-dimethyl (iso) octyl (meth). Acrylate, 1-methyl-1-ethylethyl (meth) acrylate, 1-methyl-1-ethyl (iso) propyl (meth) acrylate, 1-methyl-1-ethyl (iso) butyl (meth) acrylate, 1-methyl- 1-ethyl (iso) octyl acrylate, 1-diethyl (iso) propyl (meth) acrylate, 1-diethyl (iso) butyl (meth) acrylate Rate, 1-diethyl (iso) can be mentioned octyl (meth) acrylate.

Examples of the polymerizable unsaturated polymer having the structure of formula (2) include 1-methylcyclopropane (meth) acrylate, 1-methylcyclobutane (meth) acrylate, 1-methylcyclopentyl (meth) acrylate, and 1-methyl. Cyclohexyl (meth) acrylate, 1-methylcycloheptane (meth) acrylate, 1-methylcyclooctane (meth) acrylate, 1-methylcyclononane (meth) acrylate, 1-ethylcyclodecane (meth) acrylate, 1-ethylcyclo Propane (meth) acrylate, 1-ethylcyclobutane (meth) acrylate, 1-ethylcyclopentyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, 1-ethylcycloheptane (meth) acrylate, 1-ethylcyclo Kutan (meth) acrylate, 1-ethylcyclononane (meth) acrylate, 1-ethylcyclodecane (meth) acrylate, 1- (iso) propylcyclopropane (meth) acrylate, 1- (iso) propylcyclobutane (meth) acrylate 1- (iso) propylcyclopentyl (meth) acrylate, 1- (iso) propylcyclohexyl (meth) acrylate, 1- (iso) propylcycloheptane (meth) acrylate, 1- (iso) propylcyclooctane (meth) acrylate 1- (iso) propylcyclononane (meth) acrylate, 1- (iso) propylcyclodecane (meth) acrylate, 1- (iso) butylcyclopropane (meth) acrylate, 1- (iso) butylcyclobutane (meth) Acrylate, -(Iso) butylcyclopentyl (meth) acrylate, 1- (iso) butylcyclohexyl (meth) acrylate, 1- (iso) butylcycloheptane (meth) acrylate, 1- (iso) butylcyclooctane (meth) acrylate, 1 -(Iso) -butylcyclononane (meth) acrylate, 1- (iso) butylcyclodecanyl (meth) acrylate, 1- (iso) pentylcyclopropanyl (meth) acrylate, 1- (iso) pentylcyclobutanyl (Meth) acrylate, 1- (iso) pentylcyclopentyl (meth) acrylate, 1- (iso) pentylcyclohexyl (meth) acrylate, 1- (iso) pentylcycloheptanyl (meth) acrylate, 1- (iso) pentylcyclo Octanyl (meth) acrylate, 1 -(Iso) pentylcyclononanyl (meth) acrylate, 1- (iso) pentylcyclodecanyl (meth) acrylate,
1- (iso) hexylcyclopropanyl (meth) acrylate, 1- (iso) hexylcyclobutanyl (meth) acrylate, 1- (iso) hexylcyclohexyl (meth) acrylate, 1- (iso) hexylcycloheptanyl ( (Meth) acrylate, 1- (iso) hexylcyclooctanyl (meth) acrylate, 1- (iso) hexylcyclononanyl (meth) acrylate, 1- (iso) hexylcyclodecanyl (meth) acrylate,
1- (iso) heptylcyclopropanyl (meth) acrylate, 1- (iso) heptylcyclobutanyl (meth) acrylate, 1- (iso) heptylcycloheptyl (meth) acrylate, 1- (iso) heptylcycloheptyl ( (Meth) acrylate, 1- (iso) heptylcycloheptanyl (meth) acrylate, 1- (iso) heptylcyclooctanyl (meth) acrylate, 1- (iso) heptylcyclononanyl (meth) acrylate, 1- (iso ) Heptylcyclodecanyl (meth) acrylate,
1- (iso) octylcyclopropanyl (meth) acrylate, 1- (iso) octylcyclobutanyl (meth) acrylate, 1- (iso) octylcyclooctyl (meth) acrylate, 1- (iso) octylcyclooctyl ( (Meth) acrylate, 1- (iso) octylcycloheptanyl (meth) acrylate, 1- (iso) octylcyclooctanyl (meth) acrylate, 1- (iso) octylcyclononanyl (meth) acrylate, 1- (iso ) Octylcyclodecanyl (meth) acrylate,
2-ethyltricyclo [3.3.1.1 ^3,7 ] decan-2-yl- (meth) acrylate, 2-methyltricyclo [3.3.1.1 ^3,7 ] decan-2-yl -(Meth) acrylate, 1-ethyltricyclo [3.3.1.1 ^3,7 ] decan-1-yl- (meth) acrylate, 1-ethyltricyclo [3.3.1.1 ^3,7 ] Decan-1-yl- (meth) acrylate 3-hydroxytricyclo [3.3.1.1 ^3,7 ] decan-1-yl- (meth) acrylate and the like.

  Among these, 1-diethylpropyl (meth) acrylate, 1-ethylcyclopentyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, 1- (iso) propylcyclopentyl (meth) acrylate, 1- (iso) propylcyclohexyl It is preferable to use (meth) acrylate, 1- (iso) butylcyclopentyl (meth) acrylate, 1- (iso) butylcyclohexyl (meth) acrylate, more preferably 1-diethylpropyl (meth) acrylate, 1-ethyl. Cyclopentyl (meth) acrylate and 1-ethylcyclohexyl (meth) acrylate are preferable, and 1-ethylcyclopentyl (meth) acrylate and 1-ethylcyclohexyl (meth) acrylate are particularly preferable. These are preferably used from the viewpoint of enhancing the copolymerization reactivity, the heat resistance and surface hardness of the protective film or insulating film to be obtained.

Examples of the polymerizable unsaturated compound having the structure of formula (3) include 2-ethyl-γ-butyrolactone-2-yl- (meth) acrylate and 2-methyl-γ-butyrolactone-2-yl- (meth). Acrylate, 2-ethyl-γ-butyrolactone-3-yl- (meth) acrylate, 2-methyl-γ-butyrolactone-3-yl- (meth) acrylate, 2-ethyl-γ-butyrolactone-4-yl- (meth) ) Acrylate, 2-methyl-γ-butyrolactone-4-yl- (meth) acrylate, 2-ethyl-δ-valerolactone-2-yl- (meth) acrylate, 2-ethyl-δ-valerolactone-2-yl -(Meth) acrylate, 2-ethyl-δ-valerolactone-3-yl- (meth) acrylate, 2-ethyl-δ-valerolactone-3- Ru- (meth) acrylate, 2-ethyl-δ-valerolactone-4-yl- (meth) acrylate, 2-ethyl-δ-valerolactone-4-yl- (meth) acrylate, 2-ethyl-δ-valero Lactones such as lactone-5-yl- (meth) acrylate and 2-ethyl-δ-valerolactone-5-yl- (meth) acrylate:
2-ethyl-γ-butyrolactam-2-yl- (meth) acrylate, 2-methyl-γ-butyrolactam-2-yl- (meth) acrylate, 2-ethyl-γ-butyrolactam-3-yl- (meth) acrylate 2-methyl-γ-butyrolactam-3-yl- (meth) acrylate, 2-ethyl-γ-butyrolactam-4-yl- (meth) acrylate, 2-methyl-γ-butyrolactam-4-yl- (meth) Acrylate, 2-ethyl-δ-valerolactam-2-yl- (meth) acrylate, 2-ethyl-δ-valerolactam-2-yl- (meth) acrylate, 2-ethyl-δ-valerolactam-3-yl -(Meth) acrylate, 2-ethyl-δ-valerolactam-3-yl- (meth) acrylate, 2-ethyl-δ-valerolactam-4 -Yl- (meth) acrylate, 2-ethyl-δ-valerolactam-4-yl- (meth) acrylate, 2-ethyl-δ-valerolactam-5-yl- (meth) acrylate, 2-ethyl-δ- Mention may be made of lactams such as valerolactam-5-yl- (meth) acrylate.

  In addition to (a1) and (a2), copolymer [A-1] can further contain polymerized units derived from polymerizable unsaturated compounds other than (a3), (a1) and (a2). The polymerizable unsaturated compound (a3) includes, for example, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, and bicyclo unsaturated compounds. And maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other unsaturated compounds.

Specific examples of these include, for example, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, and alkylmethacrylate. -Methacryloxyethylglycoside, 4-hydroxyphenyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl Methacrylate, etc .;
Methyl acrylate, isopropyl acrylate, etc. as alkyl acrylate ester;
As cyclic alkyl esters of methacrylic acid, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane. -8-yloxyethyl methacrylate, isobornyl methacrylate and the like;
As cyclic alkyl ester of acrylic acid, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane -8-yloxyethyl acrylate, isobornyl acrylate, etc .;
As methacrylic acid aryl ester, phenyl methacrylate, benzyl methacrylate, etc .;
As acrylic acid aryl ester, phenyl acrylate, benzyl acrylate, etc .;
As unsaturated dicarboxylic acid diesters, diethyl maleate, diethyl fumarate, diethyl itaconate, etc .;

Bicyclo unsaturated compounds include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept. 2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2. 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] hept-2-ene 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2 '-Hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5 Hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [ 2.2.1] hept-2-ene and the like;
As maleimide compounds, phenylmaleimide, cyclohexylmaleimide, benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3- Maleimide propionate, N- (9-acridinyl) maleimide and the like;
Examples of unsaturated aromatic compounds include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, and the like;
As conjugated diene compounds, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like;
As unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, etc .;
As unsaturated dicarboxylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like;
As unsaturated dicarboxylic acid anhydrides, the anhydrides of the above unsaturated dicarboxylic acids;
Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

Of these, styrene, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, 1,3-butadiene, bicyclo [2.2.1. Hept-2-ene, N-cyclohexylmaleimide and the like are preferable from the viewpoints of copolymerization reactivity and heat resistance.
These may be used alone or in combination.

  The copolymer [A-1] is preferably a structural unit derived from a polymerizable unsaturated compound monomer (a1) 5 to 95% by weight, (a2) 5 to 95% by weight, and (a3) 0 to 90%. %, More preferably (a1) 20-80%, (a2) 20-80%, and (a3) 0-60%, most preferably (a1) 30-60%, (a2) 30 -60 wt% and (a3) 10-40 wt%. When the content falls within this range, good planarization performance and heat resistance can be realized.

As a preferable specific example of the copolymer (A-1), for example,
Styrene / 1-diethylpropyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate / glycidyl methacrylate copolymer,
Styrene / 1-diethylpropyl methacrylate / N-phenylmaleimide / glycidyl methacrylate copolymer,
Styrene / 1-diethylpropyl methacrylate / N-cyclohexylmaleimide / glycidyl methacrylate copolymer,
Styrene / 1-ethylcyclohexyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / glycidyl methacrylate copolymer,
Styrene / 1-ethylcyclohexyl methacrylate / N-phenylmaleimide / glycidyl methacrylate copolymer,
Styrene / 1-ethylcyclohexyl methacrylate / N-cyclohexylmaleimide / glycidyl methacrylate copolymer,
Styrene / 1-ethylcyclopentyl methacrylate / tricyclomethacrylate [5.2.1.0 ^2,6 ] decan-8-yl / glycidyl methacrylate copolymer,
Styrene / 1-ethylcyclopentyl methacrylate / N-phenylmaleimide / glycidyl methacrylate copolymer,
Styrene / 1-ethylcyclopentyl methacrylate / N-cyclohexylmaleimide / glycidyl methacrylate copolymer,
Styrene / 1-diethylpropyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / glycidyl methacrylate / methacrylic acid copolymer,
Styrene / 1-diethylpropyl methacrylate / N-phenylmaleimide / glycidyl methacrylate / methacrylic acid copolymer,
Styrene / 1-diethylpropyl methacrylate / N-cyclohexylmaleimide / glycidyl methacrylate / methacrylic acid copolymer,
Styrene / 1-ethylcyclohexyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / glycidyl methacrylate / methacrylic acid copolymer,
Styrene / 1-ethylcyclohexyl methacrylate / N-phenylmaleimide / glycidyl methacrylate / methacrylic acid copolymer,
Styrene / 1-ethylcyclohexyl methacrylate / N-cyclohexylmaleimide / glycidyl methacrylate / methacrylic acid copolymer,
Styrene / 1-ethylcyclopentyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / glycidyl methacrylate / methacrylic acid copolymer,
Styrene / 1-ethylcyclopentyl methacrylate / N-phenylmaleimide / glycidyl methacrylate / methacrylic acid copolymer,
Examples thereof include styrene / 1-ethylcyclopentyl methacrylate / N-cyclohexylmaleimide / glycidyl methacrylate / methacrylic acid copolymer.

(Co) polymer [A-2]
The (co) polymer [A-2] is a (co) polymer obtained by polymerizing the component containing the polymerizable unsaturated compound (a1) (excluding the above-mentioned copolymer [A-1]). It is.
The (co) polymer [A-2] can be made into a copolymer with the polymerizable unsaturated compound (a3) in addition to the polymerizable unsaturated compound (a1).
The (co) polymer [A-2] is preferably a structural unit derived from a polymerizable unsaturated compound monomer (a1) 5 to 100% by weight, and (a3) 0 to 95% by weight, more preferably ( a1) 20 to 100% by weight, and (a3) 0 to 80% by weight, most preferably (a1) 30 to 90% by weight, and (a3) 10 to 70% by weight. When the content falls within this range, good planarization performance and heat resistance can be realized.

As a preferable specific example of the copolymer [A-2], for example,
Styrene / 1-diethylpropyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl / methacrylic acid copolymer,
Styrene / 1-diethylpropyl methacrylate / N-phenylmaleimide / methacrylic acid copolymer,
Styrene / 1-diethylpropyl methacrylate / N-cyclohexylmaleimide / methacrylic acid copolymer,
Styrene / 1-ethylcyclohexyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / methacrylic acid copolymer,
Styrene / 1-ethylcyclohexyl methacrylate / N-phenylmaleimide / methacrylic acid copolymer,
Styrene / 1-ethylcyclohexyl methacrylate / N-cyclohexylmaleimide / methacrylic acid copolymer,
Styrene / 1-ethylcyclopentyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / methacrylic acid copolymer,
Styrene / 1-ethylcyclopentyl methacrylate / N-phenylmaleimide / methacrylic acid copolymer,
Examples thereof include styrene / 1-ethylcyclopentyl methacrylate / N-cyclohexylmaleimide / methacrylic acid copolymer.

(Co) polymer [A-3]
(Co) polymer [A-3] is a (co) polymer obtained by polymerizing the component containing the polymerizable unsaturated compound (a2) (excluding the above-mentioned copolymer [A-1]). It is.
The (co) polymer [A-3] can be made into a copolymer with the polymerizable unsaturated compound (a3) in addition to the polymerizable unsaturated compound (a2).
The (co) polymer [A-3] is preferably a structural unit derived from a polymerizable unsaturated compound monomer (a2) 5 to 100% by weight, and (a3) 0 to 95% by weight, more preferably ( a2) 20 to 100 wt%, and (a3) 0 to 80 wt%, most preferably (a2) 30 to 90 wt%, and (a3) 10 to 70 wt%. When the content falls within this range, good planarization performance and heat resistance can be realized.

As a preferable specific example of the copolymer [A-3], for example,
Styrene / 1-diethylpropyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl copolymer,
Styrene / 1-diethylpropyl methacrylate / N-phenylmaleimide copolymer,
Styrene / 1-diethylpropyl methacrylate / N-cyclohexylmaleimide copolymer,
Styrene / 1-ethylcyclohexyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl copolymer,
Styrene / 1-ethylcyclohexyl methacrylate / N-phenylmaleimide copolymer,
Styrene / 1-ethylcyclohexyl methacrylate / N-cyclohexylmaleimide copolymer,
Styrene / 1-ethylcyclopentyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl copolymer,
Styrene / 1-ethylcyclopentyl methacrylate / N-phenylmaleimide copolymer,
Examples thereof include styrene / 1-ethylcyclopentyl methacrylate / N-cyclohexylmaleimide copolymer.

Copolymers [A-1], [A-2] and [A-3] may be referred to as polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”) measured by gel permeation chromatography (elution solvent tetrahydrofuran). .) Is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and particularly preferably 3,000 to 40,000. In this case, if the Mw is less than 1,000, the coating property of the composition may be insufficient, or the heat resistance of the protective film to be formed may be insufficient. On the other hand, if the Mw exceeds 100,000, the composition may be flat. In some cases, the conversion performance becomes insufficient.
Furthermore, the molecular weight distribution (Mw / Mn) of the copolymers [A-1], [A-2] and [A-3] is preferably 5.0 or less, more preferably 3.0 or less.
Such a copolymer includes the polymerizable unsaturated compounds (a1) and (a2) in the copolymer [A-1], and the polymerizable unsaturated compound (a-2) in the polymer [A-2]. In the polymer [A-3], the polymerizable unsaturated compound (a2) can be synthesized by a known method such as radical polymerization in the presence of a suitable solvent and a suitable polymerization initiator. .

Cationic polymerizable compound [B]
The cationically polymerizable compound [B] used in the present invention is a compound having two or more oxiranyl groups or oxetanyl groups in the molecule (excluding the above-mentioned copolymers [A-1] [A-2]. ). Examples of the compound having two or more oxiranyl groups or oxetanyl groups in the molecule include compounds having two or more epoxy groups in the molecule, or compounds having 3,4-epoxycyclohexyl groups.

Examples of the compound having two or more epoxy groups in the molecule include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hydrogenated bisphenol F diglycidyl. Diglycidyl ethers of bisphenol compounds such as ether, hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether;
Polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether Glycidyl ethers;
Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;
Phenol novolac type epoxy resin;
Cresol novolac type epoxy resin;
Polyphenol type epoxy resin;
Diglycidyl esters of aliphatic long-chain dibasic acids;
Glycidyl esters of higher fatty acids;
Examples include epoxidized soybean oil and epoxidized linseed oil.

Commercially available compounds having two or more epoxy groups in the molecule include, for example, Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, and the like as bisphenol A type epoxy resins. 828 (above, manufactured by Japan Epoxy Resin Co., Ltd.) and the like;
As bisphenol F type epoxy resin, Epicoat 807 (manufactured by Japan Epoxy Resin Co., Ltd.) and the like;
As a phenol novolac type epoxy resin, Epicoat 152, 154, 157S65 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPPN 201, 202 (above, manufactured by Nippon Kayaku Co., Ltd.), etc .;
As cresol novolac type epoxy resin, EOCN102, 103S, 104S, 1020, 1025, 1027 (above, manufactured by Nippon Kayaku Co., Ltd.), Epicoat 180S75 (manufactured by Japan Epoxy Resin Co., Ltd.) and the like;
As a polyphenol type epoxy resin, Epicoat 1032H60, XY-4000 (above, manufactured by Japan Epoxy Resin Co., Ltd.) and the like;
As cycloaliphatic epoxy resins, CY-175, 177, 179, Araldite CY-182, 192, 184 (above, manufactured by Ciba Specialty Chemicals Co., Ltd.), ERL-4234, 4299, 4221, 4206 ( As described above, manufactured by U.C.C. Co., Ltd., Shodyne 509 (manufactured by Showa Denko KK), Epicron 200, 400 (above, manufactured by Dainippon Ink Co., Ltd.), Epicoat 871, 872 (above, Japan Epoxy) Resin Co., Ltd.), ED-5661, 5562 (above, Celanese Coating Co., Ltd.), etc .;
Examples of the aliphatic polyglycidyl ether include Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.) and Epiol TMP (manufactured by Nippon Oil & Fats Co., Ltd.).

Examples of the compound having two or more 3,4-epoxycyclohexyl groups in the molecule include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxy Cyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3, 4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-ethylene glycol) Epoxycyclohexylmethyl) ether, Chirenbisu (3,4-epoxycyclohexane carboxylate), lactone-modified 3,4-epoxycyclohexylmethyl-3 ', may be mentioned 4'-epoxycyclohexane carboxylate.
Of such cationically polymerizable compounds [B], phenol novolac type epoxy resins and polyphenol type epoxy resins are preferred.

  The amount of the cationic polymerizable compound [B] used in the resin composition of the present invention is preferably 3 per 100 parts by weight of the total amount of the polymers [A-1], [A-2] and [A-3]. It is -200 weight part, More preferably, it is 5-100 weight part, Especially 10-50 weight part. When the amount of the cationically polymerizable compound [B] used is more than 200 parts by weight, there may be a problem in the coating property of the composition. On the other hand, when it is less than 3 parts by weight, the resulting film has insufficient hardness. There is.

Thermosensitive acid generator [C]
Examples of the thermal acid generator include sulfonium salts, benzothiazonium salts, ammonium salts, phosphonium salts, etc. Among these, sulfonium salts and benzothiazonium salts are preferably used.

Specific examples of the sulfonium salts include 4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl- Alkylsulfonium salts such as 4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate;
Benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, Such as benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, etc. Benzylsulfonium salt;
Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3 -Chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-tert-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate Dibenzylsulfonium salts such as;
p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, p-nitro Benzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium Examples thereof include substituted benzylsulfonium salts such as hexafluoroantimonate.

  Among these, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate Nate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate and the like are preferably used.

Examples of the benzothiazonium salts include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, and 3- (p-methoxybenzyl). Benzylbenzothiazonium salts such as benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate It is done.
Of these, 3-benzylbenzothiazonium hexafluoroantimonate and the like are preferably used.

Examples of commercially available acid generators that can be suitably used as thermal acid generators include, as alkylsulfonium salts, trade names: Adeka Opton CP-66 and CP-77 manufactured by Asahi Denka Kogyo Co., Ltd.
Moreover, as a benzyl sulfonium salt, the Sanshin Chemical Co., Ltd. product name: SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-80L, SI-100L, SI-110L can be mentioned.
Of these, SI-80, SI-100, and SI-110 are preferred because the resulting protective film has a high surface hardness.

When the resin composition of the present invention contains a [C] heat-sensitive acid generator, the amount used is 100 weights of the total amount of the polymers [A-1], [A-2] and [A-3]. Preferably it is 0.05-20 weight part with respect to part, More preferably, it is 0.1-10 weight part. By setting the amount used within this range, a film having sufficient hardness can be obtained.
[C] The heat-sensitive acid generator can be replaced with a radiation-sensitive acid generator.
A radiation-sensitive acid generator is a compound capable of generating an acid upon irradiation with radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray.
Examples of such a radiation sensitive acid generator include diaryl iodonium salts, triaryl sulfonium salts, diaryl phosphonium salts, and the like, which can be preferably used.

  Examples of the diaryliodonium salts include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, 4 -Methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoro Cetate, 4-methoxyphenylphenyl iodonium-p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium tetrafluoroborate, bis (4-tert-butylphenyl) iodonium hexafluoroarsenate, bis (4-tert- Examples thereof include butylphenyl) iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium trifluoroacetate, and bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate. Of these, diphenyliodonium hexafluorophosphonate is preferably used.

Examples of the triarylsulfonium salts include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium- p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4- Methoxyphenyl diphenyl Rufonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsenate, Examples include 4-phenylthiophenyl diphenyl trifluoromethane sulfonate, 4-phenyl thiophenyl diphenyl trifluoroacetate, 4-phenyl thiophenyl diphenyl-p-toluene sulfonate, and the like. Of these, triphenylsulfonium trifluoromethanesulfonate is preferably used.
Examples of the diarylphosphonium salts include (1-6-η-cumene) (η-cyclopentadienyl) iron hexafluorophosphonate.

Commercially available products of acid generators preferably used as radiation-sensitive acid generators are diaryl iodonium salts manufactured by Union Carbide, Inc. Trade names: UVI-6950, UVI-6970, UVI-6974, UVI-6990, Midori Chemical Product name: MPI-103, BBI-103, etc. can be mentioned.
Moreover, as a triarylsulfonium salt, Asahi Denka Kogyo Co., Ltd. product name: Adeka optomer SP-150, SP-151, SP-170, SP-171, Nippon Soda Co., Ltd. product name: CI-2481, CI-2624, CI-2639, CI-2064, manufactured by Midori Chemical Co., Ltd. Trade names: DTS-102, DTS-103, NAT-103, NDS-103, TPS-103, MDS-103, manufactured by Sartomer : CD-1010, CD-1011, CD-1012 and the like.

Moreover, Ciba Specialty Chemicals Co., Ltd. brand name: Irgacure 261, Nippon Kayaku Co., Ltd. brand name: PCI-061T, PCI-062T, PCI-020T, PCI-022T, etc. are mentioned as diarylphosphonium salts. be able to.
Among these, Union Carbide make brand name: UVI-6970, UVI-6974, UVI-6990, Asahi Denka Kogyo Co., Ltd. trade name: Adeka optomer SP-170, SP-171, Sartomer brand name: CD-1012, manufactured by Midori Chemical Co., Ltd., trade name: MPI-103 is preferred because the resulting protective film has a high surface hardness.
When the resin composition of the present invention contains a radiation sensitive acid generator, the amount used is 100 parts by weight of the total amount of the polymers [A-1], [A-2] and [A-3]. The amount is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight. By setting the amount used within this range, a film having sufficient hardness can be obtained.

[D] Adhesion aid The above [D] adhesion aid can be added to improve the adhesion between the film to be formed and the substrate.
As such [D] adhesion assistant, for example, a functional silane coupling agent having a reactive substituent can be used. Examples of the reactive substituent include a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group.
[D] Specific examples of the adhesion assistant include, for example, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ- Examples thereof include glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.
Such [D] adhesion assistant is preferably 30 parts by weight or less, more preferably 25 parts per 100 parts by weight of the total amount of the copolymers [A-1], [A-2] and [A-3]. It is used in an amount of parts by weight or less. [D] When the amount of the adhesion assistant exceeds 30 parts by weight, the heat resistance of the resulting film may be insufficient.

[E] Surfactant The above surfactant can be added to improve the coating performance of the resin composition of the present invention.
Examples of such surfactants include fluorine surfactants, silicone surfactants, nonionic surfactants, and other surfactants.
Examples of the fluorine-based surfactant include, for example, BM CHIMIE product names: BM-1000, BM-1100, Dainippon Ink and Chemicals, Inc. product names: Megafax F142D, F172, F173, F183, Product name: FLORARD FC-135, FC-170C, FC-430, FC-431, manufactured by Asahi Glass Co., Ltd. Product names: Surflon S-112, S-113, S- 131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106, etc. Can be mentioned.

As said silicone type surfactant, for example, Toray Dow Corning Silicone Co., Ltd. trade name: SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC- 190, Shin-Etsu Chemical Co., Ltd. product name: KP341, Shin-Akita Kasei Co., Ltd. product name: Ftop EF301, EF303, EF352, and other commercial products.
Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene dialkyl esters, and the like.

  Examples of the polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether. Examples of polyoxyethylene aryl ethers include polyoxyethylene octylphenyl. Examples include ether and polyoxyethylene nonylphenyl ether. Examples of polyoxyethylene dialkyl esters include polyoxyethylene dilaurate and polyoxyethylene distearate.

As said other surfactant, Kyoeisha Chemical Co., Ltd. brand name: (meth) acrylic acid type copolymer polyflow No. 57, no. 90 etc. can be mentioned.
The addition amount of these [E] surfactants is preferably 5 parts by weight or less, more preferably 100 parts by weight or less, more preferably 100 parts by weight of the total amount of the polymers [A-1], [A-2] and [A-3]. Used in 2 parts by weight or less. When the amount of the surfactant exceeds 5 parts by weight, the coating film may be easily roughened in the coating process.

Preferred embodiments of the resin composition in the form present invention embodiment of the resin composition, and (b) of the following (a) to (b).
(A) A resin composition containing a copolymer [A-1] and, optionally, a cationic polymerizable compound [B] and a heat-sensitive acid generator [C].
(B) A resin composition containing the polymer [A-2] and the polymer [A-3] and optionally a cationic polymerizable compound [B] and a heat-sensitive acid generator [C]. In the composition (b), the amount of the polymer [A-3] used is 10 to 90 parts by weight per 100 parts by weight of the total amount of the polymers [A-2] and [A-3]. The amount is preferably 20 to 80 parts by weight. When the amount of the copolymer [A-3] is less than 10 parts by weight, curing may be insufficient, and when it exceeds 90 parts by weight, heat resistance may be deteriorated.
The resin composition of the present invention is prepared by uniformly dissolving or dispersing each of the above components in an appropriate solvent. As the solvent to be used, a solvent in which each component of the composition is dissolved or dispersed and does not react with each component is preferably used.

[D] Solvent having a boiling point of 180 ° C. or higher at normal pressure The solvent in the present invention is a solvent having a boiling point (hereinafter simply referred to as “boiling point”) of 180 ° C. or higher at normal pressure (1 atm) (hereinafter referred to as “high boiling solvent”). "[D].). The boiling point of the high-boiling solvent is preferably 200 ° C. or higher. Further, the upper limit of the boiling point of the high boiling point solvent is not particularly limited as long as the color filter can be produced by the inkjet method from the radiation-sensitive resin composition for the inkjet method in the present invention. From the viewpoint of operability in the preparation process and the color filter manufacturing process, a high boiling point solvent having a boiling point of 290 ° C. or less, preferably 280 ° C. or less and a liquid having a relatively low viscosity at room temperature (20 ° C.) is desirable. Therefore, the preferable boiling point range of the high boiling point solvent in the present invention is specifically 180 to 290 ° C, more preferably 200 to 280 ° C.

As a high boiling point solvent, for example,
Diethylene glycol dialkyl ether solvent represented by the formula R ¹² —O (CH ₂ CH ₂ O) ₂ —R ¹³ (wherein R ¹² and R ¹³ each independently represents an alkyl group having 2 to 10 carbon atoms). Triethylene glycol dialkyl represented by the formula R ¹⁴ —O (CH ₂ CH ₂ O) ₃ —R ¹⁵ (wherein R ¹⁴ and R ¹⁵ independently represent an alkyl group having 1 to 10 carbon atoms); Ether solvents;
Wherein _{^{R 16 -O (CH 2 CH 2}} O) i -R 17 ( ^{where, R 16} and ^{R 17} represents an alkyl group having 1 to 10 carbon atoms independently of one another, i is an integer of 2 to 30. Polyethylene glycol dialkyl ether solvents represented by:
Propylene glycol dialkyl ether solvent represented by the formula R ¹⁸ —OCH (CH ₃ ) CH ₂ O—R ¹⁹ (wherein R ¹⁸ and R ¹⁹ each independently represents an alkyl group having 2 to 10 carbon atoms). ;
Ethylene glycol monoalkyl ethers such as ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether;
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monobutyl ether acetate;
Diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether;
Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl ether acetate, diethylene glycol mono-n-butyl ether acetate;
Propylene glycol alkyl ether acetates such as propylene glycol butyl ether acetate;
Other ethers such as ethylene glycol monophenyl ether acetate, diethylene glycol diethyl ether, benzyl ethyl ether, dihexyl ether;
Alcohols such as 1-octanol, 1-nonanol and benzyl alcohol;
Ketones such as acetonylacetone and isophorone;
Carboxylic acids such as caproic acid and caprylic acid;
Butyl lactate, ethyl benzoate, n-butyl benzoate, diethyl oxalate, diethyl maleate, di-n-butyl maleate, glycerol triacetate, di-n-butyl fumarate, dimethyl phthalate, diethyl phthalate, phthalic acid Examples thereof include ester solvents such as di-n-propyl, di-i-propyl phthalate, di-n-butyl phthalate, i-amyl salicylate, γ-butyrolactone, ethylene carbonate, and propylene carbonate.

As a specific example of a preferable high boiling point solvent in the present invention,
Ethylene glycol monobutyl ether acetate, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol, propylene glycol butyl ether acetate, diethylene glycol di-n-butyl ether, tetraethylene glycol dimethyl ether, pentaethylene glycol dimethyl ether, hexaethylene glycol Examples thereof include dimethyl ether, propylene glycol di-n-butyl ether, and butyl lactate.
The high boiling point solvents can be used alone or in admixture of two or more.

The amount of the high-boiling solvent used is preferably 10 to 10,000 parts by weight, more preferably 50 to 5,000 parts by weight, still more preferably 100 to 2,000 parts per 100 parts by weight of the copolymer [A]. Parts by weight.
When the amount used is within this range, a composition having good controllability of the drying rate of the discharged resin composition and excellent coating properties can be obtained.

  In the present invention, the following effects can be obtained by using a high boiling point solvent.

(1) When forming a white part or a protective film with the white part by an inkjet method, the part forming resin composition is discharged to remove the solvent, and then heated to form the part film. The evaporation rate of the high boiling point solvent is low and the discharged resin composition does not change abruptly when the solvent is removed or heated, so that the work margin when forming the part is improved.
(2) When the part is formed by the inkjet method, the part-forming resin composition gradually becomes viscous due to evaporation of the solvent, but if the boiling point of the solvent is low, it becomes difficult to control the viscosity change, Adopt a high-boiling solvent, while the degree of change in the resin composition discharged onto the substrate at the initial and final stages of the formation process of the part increases and hinders the formation of the part. This makes it possible to control this change in viscosity within an appropriate range, and it becomes easy to form the desired portion.
(3) It is possible to prevent clogging due to drying of the composition in the ink jet head part which discharges the resin composition for forming the part, and it is also possible to prevent flight bending at the time of discharging the composition, and good straightness Since it can ensure, the utilization efficiency of the said part composition and the cleaning efficiency of a manufacturing apparatus improve.
In the present invention, a solvent having a boiling point of less than 180 ° C. (hereinafter referred to as “low boiling point solvent”) may be used in combination with the high boiling point solvent.

As such a low boiling point solvent, for example,
Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether;
Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate;
Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate;
Other ethers such as diethylene glycol dimethyl ether and tetrahydrofuran;
Propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether;
Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate;
Alcohols such as methanol and ethanol;
Aromatic hydrocarbons such as toluene and xylene,
Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, 2-heptanone, 3-heptanone, methyl isoamyl ketone;
And methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxy- Methyl 2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butylhydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, methyl 3-hydroxypropionate, 3-hydroxypropionate Ethyl acetate, propyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate Propyl ethoxy acetate, methyl propoxyacetate, ethyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, Methyl 2-butoxypropionate, ethyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-propoxypropionate, 3 -Esters such as ethyl propoxypropionate, methyl 3-butoxypropionate, and ethyl 3-butoxypropionate.

Of these, diethylene glycols, propylene glycol monoalkyl ethers, propylene glycol alkyl acetates, and esters are preferred, and in particular, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether. Acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl lactate and ethyl lactate are preferred.
These low-boiling solvents can be used alone or in admixture of two or more.

The use ratio of the low boiling point solvent is preferably 90% by weight or less, more preferably 50% by weight or less, based on the total of the high boiling point solvent and the low boiling point solvent. In this case, if the use ratio of the low boiling point solvent exceeds 90% by weight, the desired effect due to the use of the high boiling point solvent may be impaired.
The composition prepared as described above can be used after being filtered using a Millipore filter having a pore size of 0.2 to 3.0 μm, preferably about 0.2 to 0.5 μm. .

4 color filter formation
Method for Forming Color Filter Next, using a radiation-sensitive composition for forming a colored layer (hereinafter also simply referred to as “colored layer forming composition”), three colors R, G, and B are used in the color filter. A method of forming will be described.

The method for forming R, G, and B color filters includes at least the following steps (1) to (4).
(1) The process of forming the coating film of the composition for colored layer formation on a board | substrate.
(2) A step of exposing at least a part of the coating film.
(3) The process of developing the coating film after exposure.
(4) The process of heat-processing the coating film after image development.

  Hereinafter, these steps will be sequentially described.

-Step (1)-
First, on the surface of the substrate, if necessary, a light shielding layer is formed so as to partition the pixel forming portion, and after applying the colored layer forming composition on this substrate, vacuum baking is performed under reduced pressure. To remove the solvent by evaporation to form a coating film.
Examples of the substrate used in this step include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, polyethersulfone, cyclic olefin ring-opening polymer, and hydrogenated products thereof. be able to.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

A method for applying the colored layer forming composition to the substrate is not particularly limited, but a method using a slit nozzle such as a slit-and-spin coating method or a spinless coating method (hereinafter referred to as “slit nozzle coating method”). ") Is preferred.
In the slit nozzle coating method, the conditions differ depending on the size of the slit-and-spin coating method, the spinless coating method, and the coated substrate. For example, the fifth generation glass substrate (1,100 mm × 1,250 mm) by the spinless coating method Is applied, the discharge amount of the composition for forming a colored layer from the slit nozzle is usually 500 to 2,000 microliters / second, preferably 800 to 1,500 microliters / second, and the coating speed Is usually 500 to 1,500 mm / second, preferably 700 to 1,200 mm / second.
The solid content of the colored layer forming composition is usually 10 to 20%, preferably 13 to 18%.
The vacuum baking conditions are such that the degree of vacuum is usually about 0.1 to 1.0 torr, preferably about 0.2 to 0.5 torr, and the temperature is usually about 60 to 120 ° C., preferably about 70 to 110 ° C. The baking time is usually about 1 to 5 minutes, preferably about 2 to 4 minutes.
The thickness of the coating film to be formed is usually 0.1 to 10 μm, preferably 0.2 to 8.0 μm, particularly preferably 0.2 to 6.0 μm as the film thickness after removal of the solvent.

-Step (2)-
Thereafter, at least a part of the formed coating film is exposed. When exposing a part of the coating film, it is usually exposed through a photomask having an appropriate pattern.
As the radiation used for the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable.
Exposure of radiation is usually, 10~10,000J / ^{m 2} approximately.

-Step (3)-
Then, it develops using a developing solution and melt | dissolves and removes the unexposed part of a coating film.
Examples of the developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo. -An alkaline developer composed of an aqueous solution such as [4.3.0] -5-nonene is preferable.
For example, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be employed.
The development conditions are preferably about 5 to 300 seconds at room temperature.

-Step (4)-
Then, a colored layer can be formed on the substrate by heat treatment (hereinafter referred to as “post-bake”).
The post-baking conditions are preferably 180 to 230 ° C. and about 20 to 40 minutes.
In the method for forming a color filter of the present invention, the steps (1) to (4) are repeated using each colored layer forming composition in which a red, green, or blue pigment is dispersed to obtain a red pixel pattern. By forming the green pixel pattern and the blue pixel pattern on the same substrate, a colored layer in which the pixel patterns of the three primary colors of red, green, and blue are arranged in a predetermined arrangement can be formed on the substrate. However, in the present invention, the order of forming the pixel patterns of the respective colors is not particularly limited.
The film thickness of the pixel thus formed is usually 0.5 to 5.0 μm, preferably 1.0 to 3.0 μm.
It is also possible to form a coating film by coating the substrate surface with an ink jet apparatus and then heating (pre-baking) the coated surface.
The radiation-sensitive composition for forming a colored layer includes (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a photopolymerization initiator, and (E) a solvent as essential components. (E) The solvent contains 5 to 40% by weight of dipropylene glycol dimethyl ether. Specific examples of particularly preferred compositions are as follows (a) to (e).

(A) Component (B) contains carboxyl group-containing copolymer (II), and (D) component contains at least one selected from the group of acetophenone compounds, biimidazole compounds and triazine compounds. Radiation sensitive composition.

(B) The component (B) contains a carboxyl group-containing copolymer (II), and the acetophenone compound in the component (D) is 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone -1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 and 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime ), And the biimidazole compound in component (D) is 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1, 2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and 2,2'-bis (2, 4,6- (Trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, and at least one selected from the group (D) is a triazine compound in 2- (2- The radiation-sensitive composition for forming a colored layer according to (i) above, which comprises (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine.

  (C) The carboxyl group-containing copolymer (II) in component (B) is (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / Polymethyl (meth) acrylate macromonomer copolymer, (meth) acrylic acid / N-phenylmaleimide / styrene / benzyl (meth) acrylate copolymer, (meth) acrylic acid / N-phenylmaleimide / α-methylstyrene / Benzyl (meth) acrylate, (meth) acrylic acid / N-cyclohexylmaleimide / styrene / benzyl (meth) acrylate copolymer, (meth) acrylic acid / N-cyclohexylmaleimide / α-methylstyrene / benzyl (meth) acrylate Polymer, (meth) acrylic acid / succinic acid NO [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / styrene / allyl (meth) acrylate copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N- Phenylmaleimide / styrene / benzyl (meth) acrylate copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / styrene / allyl (meth) acrylate copolymer, (Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / styrene / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / glycerol mono (Meth) acrylate copolymer, (meth) Acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer , (Meth) acrylic acid / styrene / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) Acrylic acid / 2-hydroxyethyl (meta Acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide / styrene / phenyl (meth) acrylate / polystyrene macromonomer Copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide / styrene / phenyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / N-phenyl Maleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, and (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-phenylmale The radiation-sensitive composition for forming a colored layer according to the above (a) or (b), which comprises at least one selected from the group of amide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer.

(D) The colored layer of (i), (b) or (c), wherein the component (C) contains at least one selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate. Radiation sensitive composition for forming.

(E) The radiation-sensitive composition for forming a colored layer according to (a), (b), (c) or (d), wherein the component (A) contains an organic pigment and / or carbon black.

Method for forming white portion or protective film The white portion of the color filter can be suitably applied by the ink jet method using the resin composition of the present invention.
A component of a color filter having a partition wall 102 and a large number of light transmission regions 105 on a substrate 101 as shown in FIG.
Next, as shown in FIG. 1B, the resin composition of the present invention is ejected from the inkjet head 10 to each light transmission region 105, and the upper surface of the resin composition is raised from the upper end of the partition wall 102. As described above, the resin composition reservoir layers 21, 22,... In addition, 20 has illustrated the state in the middle of discharge of a resin composition. In this case, the discharge speed of the resin composition is, for example, about 0.01 to 100 m / second. Thereafter, as shown in FIG. 1 (c), the resin composition forming each reservoir layer is heat-treated to evaporate the solvent, thereby drying the resin composition to form a white pixel pattern having a predetermined thickness. To do. Note that the volume of each reservoir is reduced by such processing.

The conditions for pre-baking after coating vary depending on the types and blending ratios of the components, but conditions of 70 to 90 ° C. for about 1 to 15 minutes can be preferably employed. The thickness of the coating film is preferably 0.15 to 8.5 μm, more preferably 0.15 to 6.5 μm, and still more preferably 0.15 to 4.5 μm. In addition, the thickness of a coating film here should be understood as thickness after solvent removal.
The heat treatment after the coating film is formed can be carried out by an appropriate heating device such as a hot plate or a clean oven. The processing temperature is preferably about 150 to 250 ° C., and the heating time can be 5 to 30 minutes when using a hot plate, and 30 to 90 minutes when using an oven.

When a radiation sensitive acid generator is used for the resin composition, the resin composition is applied to the substrate surface, the solvent is removed by pre-baking to form a coating film, and then a radiation irradiation treatment (exposure treatment). The desired white portion can be formed by applying. In this case, if necessary, a heat treatment may be further performed after the exposure processing.
Examples of the radiation that can be used in the radiation irradiation treatment include visible light, ultraviolet light, far ultraviolet light, electron beams, X-rays, and the like, and ultraviolet light including light having a wavelength of 190 to 450 nm is preferable.

Energy of exposure generally 100~20,000J / ^{m 2,} preferably 150~10,000J / ^{m 2.}
A heat treatment may be optionally further performed after irradiation. As heating temperature at this time, about 150-250 degreeC is preferable, and appropriate apparatuses, such as a hotplate and a clean oven, can be used as a heating apparatus, for example. As the heating time, a processing time of 5 to 30 minutes can be employed when using a hot plate, and 30 to 90 minutes when using an oven.

After the four color filters are formed, a protective film can be formed by an inkjet method as necessary. At this time, a white coating solution, a separately prepared coating solution, or a commercially available coating solution can be used. The protective film can be formed by a conventional method such as spin coating or slit coating. Furthermore, the formation of white pixels and the formation of a protective film and a single inkjet application, or a plurality of inkjet applications can also be performed.
For example, as shown in FIG. 1D following FIG. 1C, the protective film 103 is formed so as to cover each pixel pattern.

Color filter protective film The protective film formed as described above preferably has a thickness of 0.1 to 8 μm, more preferably 0.1 to 6 μm, and still more preferably 0.1 to 4 μm. In addition, when the protective film of this invention is formed on the board | substrate which has the level | step difference of a color filter, said film thickness should be understood as the thickness from the uppermost part of a color filter.
Formation of the protective film satisfies adhesion, surface hardness, transparency, heat resistance, light resistance, solvent resistance, etc., and does not dent even under a load under heat, and is formed on the base substrate. It is suitable as a protective film for optical devices having excellent performance for flattening the level difference of the color filter.
In particular, since the protective film of the present invention may be exposed to heating exceeding 250 ° C. in the panel manufacturing process, sufficient dimensional stability at 270 ° C. has sufficient heat resistance even in that case. Guaranteed by having.

  The present invention will be described more specifically with reference to synthesis examples and examples. However, the present invention is not limited to the following examples.

(Co) polymer production synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, after 50 parts by weight of glycidyl methacrylate and 50 parts by weight of 1-ethylcyclopentyl methacrylate were charged and purged with nitrogen, stirring was started gently. The solution temperature was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A1-1). The solid content concentration of the obtained polymer solution was 32.9%.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 40 parts by weight of glycidyl methacrylate, 40 parts by weight of 1-diethylpropyl methacrylate, 10 parts by weight of styrene, and 10 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged. After the replacement, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A1-2). The solid content concentration of the obtained polymer solution was 33.0%.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 40 parts by weight of glycidyl methacrylate, 40 parts by weight of 1-ethylcyclohexyl methacrylate, 10 parts by weight of styrene, and 10 parts by weight of cyclohexylmaleimide were charged, and the mixture was purged with nitrogen. The solution temperature was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A1-3). The solid content concentration of the obtained polymer solution was 33.0%.

Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 40 parts by weight of glycidyl methacrylate, 40 parts by weight of 1-ethylcyclopentyl methacrylate, 10 parts by weight of styrene, and 10 parts by weight of N-cyclohexylmaleimide were charged and the mixture was purged with nitrogen. The solution temperature was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A1-4). The solid content concentration of the obtained polymer solution was 32.7%.

Synthesis example 5
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 40 parts by weight of glycidyl methacrylate, 40 parts by weight of 1-ethylcyclopentyl methacrylate, 10 parts by weight of methacrylic acid, 5 parts by weight of styrene, and 5 parts by weight of N-cyclohexylmaleimide were charged, and the mixture was gently stirred. The solution temperature was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A1-5). The resulting polymer solution had a solid content concentration of 32.8%.

Synthesis Example 6
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 40 parts by weight of glycidyl methacrylate, 40 parts by weight of 2-methyl-γ-lactone-4-yl-methacrylate, 10 parts by weight of styrene, and 10 parts by weight of N-cyclohexylmaleimide were charged with nitrogen, and then gently stirred. It was. The solution temperature was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A1-6). The solid content concentration of the obtained polymer solution was 31.9%.

Synthesis example 7
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, after 100 parts by weight of glycidyl methacrylate was charged and purged with nitrogen, stirring was started gently. The solution temperature was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A2-1). The resulting polymer solution had a solid content concentration of 33.2%.

Synthesis Example 8
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, after 80 parts by weight of glycidyl methacrylate and 20 parts by weight of styrene were charged and purged with nitrogen, stirring was started gently. The solution temperature was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A2-2). The solid content concentration of the obtained polymer solution was 33.3%.

Synthesis Example 9
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 100 parts by weight of 1-ethylcyclohexyl methacrylate was charged and purged with nitrogen, and then gently stirred. The solution temperature was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A3-1). The solid content concentration of the obtained polymer solution was 33.0%.

Synthesis Example 10
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 80 parts by weight of 1-ethylcyclohexyl methacrylate, 10 parts by weight of styrene, and 10 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged, and the mixture was purged with nitrogen, followed by gentle stirring. I started. The solution temperature was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A3-2). The solid content concentration of the obtained polymer solution was 33.3%.

Comparative Synthesis Example 1
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 25 parts by weight of styrene, 20 parts by weight of methacrylic acid, 45 parts by weight of glycidyl methacrylate, and 10 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged, and after the nitrogen substitution, Stirring was started. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (a-1). The solid content concentration of the obtained polymer solution was 33.0%.

Comparative Synthesis Example 2
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 40 parts by weight of glycidyl methacrylate, 10 parts by weight of styrene, 40 parts by weight of t-butyl methacrylate, and 10 parts by weight of cyclohexylmaleimide were charged, and the mixture was purged with nitrogen. The solution temperature was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (a-2). The solid content concentration of the obtained polymer solution was 33.0%.

Preparation and Evaluation of Resin Composition Example 1
<Preparation of composition>
A solution containing the copolymer (A1-1) obtained in Synthesis Example 1 (an amount corresponding to 100 parts by weight (solid content) of the copolymer (A1-1)) and (E) SH- After adding 0.1 parts by weight of 28PA (made by Toray Dow Corning Silicone Co., Ltd.) and further adding diethylene glycol monobutyl ether acetate as a high boiling point solvent so that the solid content concentration becomes 20%, the pore diameter is 0.5 μm. A resin composition was prepared by filtration through a Millipore filter.
The composition solution was applied into a hole on a glass substrate on which a three-color pixel corner pattern of 100 μm × 100 μm × 2 μm and a hole of 100 μm × 100 μm × 2 μm were formed using an inkjet device, and then heated to 90 ° C. This was pre-baked for 3 minutes on a heated hot plate, and further post-baked for 20 minutes on a hot plate heated to 220 ° C. to form a 2.0 μm white pixel portion.
Using the contact-type film thickness measuring device α-step (trade name: manufactured by Tencor), the unevenness of the surface of this coating film was measured at n = 5, and the difference in height between the highest and lowest portions of the white pixel portion was The average value was obtained. The results are shown in Table 1. When this value is 500 nm or less, it can be said that the inkjet coating property is good.

Example 2-6, Comparative Example 1-2
Synthesis Example 2-6, and except for using the copolymer obtained in Comparative Synthesis Example 1-2 was a resin composition prepared in the same manner as in Example 1. In addition, a white pixel portion of 2.0 μm was formed by the same method as in Example 1. Further, in the same manner as in Example 1, the average value of the height difference between the highest portion and the lowest portion of the white pixel portion was obtained. The results are shown in Table 1.

Explanatory drawing for demonstrating the manufacturing method of a color filter.

Claims (6)

[A-1] (a1) A polymer unit derived from a polymerizable unsaturated compound having an oxiranyl group or an oxetanyl group, and (a2) the following formula (01)

Here, R is a tertiary alkyl group having 5 or more carbon atoms, a tertiary alkyl group having 4 or more carbon atoms substituted with an alkoxy group having 1 to 4 carbon atoms, oxygen bonded to R in the above-described formula A cycloalkyl group having 3 or more ring carbon atoms bonded to the atom (—O—) with a tertiary carbon atom or a tertiary atom to an oxygen atom (—O—) bonded to R in the above-described formula A lactone ring or a lactam ring of 4 or more members bonded by a carbon atom,
A copolymer comprising a polymerized unit derived from a polymerizable unsaturated compound having a structure represented by in
Or Rannahli,
And it is used for forming the white sub-pixel in a color filter that constitutes one pixel by four sub-pixels of red (R), green (G), blue (B) and white (W). A resin composition.
The resin composition according to claim 1, further comprising (B) a cationically polymerizable compound. The resin composition according to claim 1 or 2, further comprising (C) a heat-sensitive acid generator. (D) The resin composition according to any one of claims 1 to 3, which is in a solution state in which a boiling point at 1 atm is dissolved in a solvent having a temperature of 180 ° C or higher. A method of manufacturing a color filter that constitutes one pixel by four sub-pixels of white (W) in addition to red (R), green (G), and blue (B), wherein the white sub-pixel is claimed. Item 5. A method for producing a four-color filter, wherein the resin composition according to any one of Items 1 to 4 is formed by an inkjet method. A method for producing a four-color filter, wherein a protective film is simultaneously formed by an inkjet method when a white subpixel is formed using the resin composition according to any one of claims 1 to 4.

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