JP2008158021A - Composition for forming light diffuse reflecting film, light diffuse reflecting film and liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition having a sufficient process margin and proper storage stability, that is superior in adhesion to a substrate, heat resistance and solvent resistance and property of controlling an irregular shape, and capable of easily forming a film for use as a light diffusion reflecting film of a reflecting or semi-transmissive liquid crystal display element. <P>SOLUTION: The composition for forming a light diffusion reflecting film contains [A] a copolymer of (a1) an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride, (a2) a specific oxetanyl group-containing (meth)acrylate and (a3) another olefinically unsaturated compound, and [B] a 1,2-quinonediazide compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a film-forming composition for use in a light diffusive reflective film used for a liquid crystal display or the like, a light diffusive reflective film having a film formed therefrom, and a liquid crystal display element having the light diffusive reflective film.

Since liquid crystal displays require surface illumination that is uniform and has high front luminance, conventionally, those equipped with a backlight unit have been the mainstream. However, in recent years, the adoption of transflective and reflective liquid crystal displays has increased from the viewpoint of power saving due to the spread of portable terminals and the like.
The transflective and reflective liquid crystal displays are provided with a reflector such as an aluminum plate on the lower side of the liquid crystal panel, and obtain luminance by reflecting light from the upper part of the panel. However, according to this method, since the reflecting plate is flat, when the incident direction of incident light from the upper part of the panel is oblique, the direction of the reflected light deviates from the front direction of the panel, and sufficient front luminance cannot be obtained.

In order to improve the above-described drawbacks in the reflective liquid crystal display, a technique using a so-called light diffusing plate has been proposed. This method diffuses the direction of reflected light by giving a fine uneven shape to the surface of the reflector plate, thereby obtaining front luminance.
For example, Patent Document 1 discloses a technique in which a glass substrate is roughened by chemical etching, a metal film is formed, and a reflective plate surface is provided with an uneven shape. According to this method, it is necessary to protect the back surface of the glass substrate from the etching solution, so that the process becomes complicated, and since a corrosive etching solution is used, there is a problem in terms of apparatus and process costs.
Patent Document 2 discloses a film having a concavo-convex shape by utilizing phase separation when a solution-like composition containing a hydrolyzate of a fluorine compound and an alkoxysilane is applied on a substrate to form a coating film. A technique for manufacturing and forming a metal film thereon is disclosed. In this method, it is difficult to control the uneven shape, it is difficult to obtain efficient diffused light, and the adhesion to the substrate is also inferior.
Recently, a method of forming a diffusive reflection film by forming a film having a concavo-convex shape by patterning by photolithography using a photosensitive resin and forming a metal layer on the surface thereof is becoming mainstream. It is difficult to control the shape of the uneven shape with the photosensitive resin, the heat resistance is insufficient, the shape changes due to the heat when sputtering the reflective material, and the solvent resistance when patterning the reflective metal film There was a defect such as lack of.
JP 2000-111886 A JP 2000-193807 A

The present invention has been made in view of the above circumstances, and its purpose is to have sufficient process margin and good storage stability, adhesion to the substrate, heat resistance, solvent resistance, and control of uneven shape. An object of the present invention is to provide an excellent composition capable of easily forming a film for use as a light diffusive reflection film of a reflective or transflective liquid crystal display element.
Another object of the present invention is to provide a light diffusive reflection film having a film formed from the above composition and having an excellent light scattering function.
Still another object of the present invention is to provide a liquid crystal display device having the light diffusive reflective film.

According to the present invention, the above problems are solved by [A] (a1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride (hereinafter also referred to as compound, “compound (a1)”), (a2) general formula (I). ) Or a compound represented by the general formula (II) (hereinafter also referred to as “compound (a2)”),

［ここで、Ｒは水素原子または炭素数１〜４のアルキル基であり、Ｒ¹は水素原子または炭素数１〜４のアルキル基であり、Ｒ²、Ｒ³、Ｒ⁴およびＲ⁵はそれぞれ独立に水素原子、フッ素原子、炭素数１〜４のアルキル基、フェニル基、または炭素数１〜４のパーフロロアルキル基であり、そしてｎは１〜６の整数である。］
で示される単量体、および（ａ３）その他のオレフィン系不飽和化合物（以下化合物「化合物（ａ３）」ともいう。）の共重合体（以下、共重合体［Ａ］ともいう。）並びに
［Ｂ］１，２−キノンジアジド化合物
を含有することを特徴とする光拡散反射膜形成用組成物によって達成される。

Wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ are each It is independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6. ]
And (a3) a copolymer (hereinafter also referred to as copolymer [A]) of (a3) other olefinically unsaturated compound (hereinafter also referred to as “compound (a3)”) and [ B] It is achieved by a composition for forming a light diffusive reflecting film, which contains a 1,2-quinonediazide compound.

The above issues are
Copolymer [A],
[B] It is achieved by a composition for forming a light diffusive reflective film, comprising a 1,2-quinonediazide compound and [C] a heat-sensitive acid generator.

  Furthermore, according to this invention, the said subject is achieved by the light-diffusion reflection film which has the pattern formed from the said composition for light-diffusion reflection film formation, and a liquid crystal display element which has it.

According to the present invention, a reflective or transflective liquid crystal having a sufficient process margin and good storage stability and excellent adhesion to a substrate, heat resistance, solvent resistance, and uneven shape controllability. There is provided a composition capable of easily forming a film for use as a light diffusing reflection film of a display element.
Moreover, the light-diffusion reflection film which is excellent in the light-scattering function which has the film | membrane formed from said composition, and the liquid crystal display element which has the light-diffusion reflection film are provided.

Hereinafter, the composition for forming a light diffusion reflection film of the present invention will be described in detail.
In the present invention, the term “radiation” is used in a concept including ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, γ rays, synchrotron radiation, proton beam rays, and the like.

Copolymer [A]
Copolymer [A] can be produced by radical polymerization of compound (a1), compound (a2) and compound (a3) in the presence of a polymerization initiator in a solvent.

The copolymer [A] used in the present invention preferably contains 5 to 40% by weight, particularly preferably 10 to 35% by weight, of structural units derived from the compound (a1). Copolymers whose constituent units are less than 5% by weight are difficult to dissolve in an alkaline aqueous solution, whereas copolymers exceeding 40% by weight tend to be too soluble in an alkaline aqueous solution.
Examples of the compound (a1) include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid;
Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid; and anhydrides of these dicarboxylic acids;
Mono [(meth) acryloyloxyalkyl] of divalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Esters;
Examples thereof include mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate. Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used from the viewpoints of copolymerization reactivity, solubility in an aqueous alkali solution, and availability. These may be used alone or in combination.

  The copolymer [A] used in the present invention preferably contains 5 to 60% by weight, particularly preferably 10 to 50% by weight, of structural units derived from the compound (a2). When this structural unit is less than 5% by weight, the heat resistance of the resulting coating film tends to decrease, whereas when it exceeds 60% by weight, the storage stability of the copolymer tends to decrease.

  Examples of the compound (a2) represented by the general formula (I) include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, and 3- (methacryloyloxymethyl) -2-methyloxetane. 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) ) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (Methacryloyloxyethyl) oxetane 3- (methacryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxyethyl) -2 -Pentafluoroethyl oxetane, 3- (methacryloyloxyethyl) -2-phenyloxetane, 2,2-difluoro-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2,2,4-trifluoro Methacrylic acid esters such as oxetane and 3- (methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane;

3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (acryloyloxymethyl) -2,2-difluorooxetane, 3- (acryloyloxymethyl) ) -2,2,4-trifluorooxetane, 3- (acryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -3 -Ethyloxetane, 2-ethyl-3 (Acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -2-trifluoromethyloxetane, 3- (acryloyloxyethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxyethyl) -2-phenyloxetane, 2,2-difluoro-3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (acryloyloxyethyl) -2,2,4,4-tetra And acrylic acid esters such as fluorooxetane.

  Examples of the compound (a2) represented by the general formula (II) include 2- (methacryloyloxymethyl) oxetane, 2-methyl-2- (methacryloyloxymethyl) oxetane, and 3-methyl-2- (methacryloyloxymethyl) oxetane. 4-methyl-2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 2- (methacryloyloxymethyl) -3-trifluoromethyloxetane, 2- (methacryloyloxymethyl) ) -4-trifluoromethyloxetane, 2- (methacryloyloxymethyl) -2-pentafluoroethyl oxetane, 2- (methacryloyloxymethyl) -3-pentafluoroethyloxetane, 2- (methacryloyloxymethyl) -4-pentafuro Ethyl oxetane, 2- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) -3-phenyloxetane, 2- (methacryloyloxymethyl) -4-phenyloxetane, 2,3-difluoro-2- (Methacryloyloxymethyl) oxetane, 2,4-difluoro-2- (methacryloyloxymethyl) oxetane, 3,3-difluoro-2- (methacryloyloxymethyl) oxetane, 3,4-difluoro-2- (methacryloyloxymethyl) Oxetane, 4,4-difluoro-2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -3,3,4-trifluorooxetane, 2- (methacryloyloxymethyl) -3,4,4-tri Fluoroxetane, 2- (me Tacriroyloxymethyl) -3,3,4,4-tetrafluorooxetane,

2- (methacryloyloxyethyl) oxetane, 2- (2- (2-methyloxetanyl)) ethyl methacrylate, 2- (2- (3-methyloxetanyl)) ethyl methacrylate, 2- (methacryloyloxyethyl) -2-methyl Oxetane, 2- (methacryloyloxyethyl) -4-methyloxetane, 2- (methacryloyloxyethyl) -2-trifluoromethyloxetane, 2- (methacryloyloxyethyl) -3-trifluoromethyloxetane, 2- (methacryloyloxy) Ethyl) -4-trifluoromethyloxetane, 2- (methacryloyloxyethyl) -2-pentafluoroethyloxetane, 2- (methacryloyloxyethyl) -3-pentafluoroethyloxetane, 2- (methacryloyloxyethyl) -4- N-tafluoroethyloxetane, 2- (methacryloyloxyethyl) -2-phenyloxetane, 2- (methacryloyloxyethyl) -3-phenyloxetane, 2- (methacryloyloxyethyl) -4-phenyloxetane, 2,3-difluoro- 2- (methacryloyloxyethyl) oxetane, 2,4-difluoro-2- (methacryloyloxyethyl) oxetane, 3,3-difluoro-2- (methacryloyloxyethyl) oxetane, 3,4-difluoro-2- (methacryloyloxy) Ethyl) oxetane, 4,4-difluoro-2- (methacryloyloxyethyl) oxetane, 2- (methacryloyloxyethyl) -3,3,4-trifluorooxetane, 2- (methacryloyloxyethyl) -3,4,4 -Trifluorooxeta , 2- (methacryloyloxyethyl) 3,3,4,4 methacrylic acid esters of tetrafluoroethane oxetane, and the like;

2- (acryloyloxymethyl) oxetane, 2-methyl-2- (acryloyloxymethyl) oxetane, 3-methyl-2- (acryloyloxymethyl) oxetane, 4-methyl-2- (acryloyloxymethyl) oxetane, 2- (Acryloyloxymethyl) -2-trifluoromethyloxetane, 2- (acryloyloxymethyl) -3-trifluoromethyloxetane, 2- (acryloyloxymethyl) -4-trifluoromethyloxetane, 2- (acryloyloxymethyl) 2-Pentafluoroethyl oxetane, 2- (acryloyloxymethyl) -3-pentafluoroethyl oxetane, 2- (acryloyloxymethyl) -4-pentafluoroethyl oxetane, 2- (acryloyloxymethyl) -2-phenyloxet 2- (acryloyloxymethyl) -3-phenyloxetane, 2- (acryloyloxymethyl) -4-phenyloxetane, 2,3-difluoro-2- (acryloyloxymethyl) oxetane, 2,4-difluoro-2 -(Acryloyloxymethyl) oxetane, 3,3-difluoro-2- (acryloyloxymethyl) oxetane, 3,4-difluoro-2- (acryloyloxymethyl) oxetane, 4,4-difluoro-2- (acryloyloxymethyl) ) Oxetane, 2- (acryloyloxymethyl) -3,3,4-trifluorooxetane, 2- (acryloyloxymethyl) -3,4,4-trifluorooxetane, 2- (acryloyloxymethyl) -3,3 , 4,4-tetrafluorooxetane,

2- (acryloyloxyethyl) oxetane, 2- (2- (2-methyloxetanyl)) ethyl methacrylate, 2- (2- (3-methyloxetanyl)) ethyl methacrylate, 2- (acryloyloxyethyl) -2-methyl Oxetane, 2- (acryloyloxyethyl) -4-methyloxetane, 2- (acryloyloxyethyl) -2-trifluoromethyloxetane, 2- (acryloyloxyethyl) -3-trifluoromethyloxetane, 2- (acryloyloxy) Ethyl) -4-trifluoromethyloxetane, 2- (acryloyloxyethyl) -2-pentafluoroethyloxetane, 2- (acryloyloxyethyl) -3-pentafluoroethyloxetane, 2- (acryloyloxyethyl) -4- Pentafluoroethyl Xetane, 2- (acryloyloxyethyl) -2-phenyloxetane, 2- (acryloyloxyethyl) -3-phenyloxetane, 2- (acryloyloxyethyl) -4-phenyloxetane, 2,3-difluoro-2- ( Acryloyloxyethyl) oxetane, 2,4-difluoro-2- (acryloyloxyethyl) oxetane, 3,3-difluoro-2- (acryloyloxyethyl) oxetane, 3,4-difluoro-2- (acryloyloxyethyl) oxetane 4,4-Difluoro-2- (acryloyloxyethyl) oxetane, 2- (acryloyloxyethyl) -3,3,4-trifluorooxetane, 2- (acryloyloxyethyl) -3,4,4-trifluoro Oxetane, 2- (acryloyloxyethyl)- , 3,4,4 acrylic acid esters such as tetrafluoroethane oxetane and the like.

  Among these, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, The photosensitive resin composition from which 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane and the like are obtained has a wide process margin and is preferably used from the viewpoint of enhancing the chemical resistance of the obtained light diffusive reflection film. These may be used alone or in combination.

  The copolymer [A] used in the present invention preferably contains 10 to 80% by weight, particularly preferably 20 to 70% by weight, of structural units derived from the compound (a3). When this structural unit is less than 10% by weight, the storage stability of the copolymer [A] tends to be lowered, whereas when it exceeds 80% by weight, the copolymer [A] is hardly dissolved in an alkaline aqueous solution. Become.

Examples of the compound (a3) include methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, and t-butyl methacrylate; acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate; cyclohexyl Methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate (referred to in the art as dicyclopentanyl methacrylate), dicyclopentanyl Methacrylic acid cyclic alkyl esters such as oxyethyl methacrylate and isobornyl methacrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tri Black [5.2.1.0 ^2,6] decan-8-yl acrylate (in the art are said to dicyclopentanyl acrylate as trivial name), dicyclopentanyl oxyethyl acrylate, isobornyl acrylate Acrylic acid cyclic alkyl esters such as phenyl methacrylate and benzyl methacrylate; aryl acrylates such as phenyl acrylate and benzyl acrylate; dicarboxylic acids such as diethyl maleate, diethyl fumarate and diethyl itaconate Diesters; hydroxyalkyl esters such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate;

Bicyclo [2.2.1] hept-2-ene,
5-methylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-hydroxybicyclo [2.2.1] hept-2-ene,
5-carboxybicyclo [2.2.1] hept-2-ene,
5-hydroxymethylbicyclo [2.2.1] hept-2-ene,
5- (2′-hydroxyethyl) bicyclo [2.2.1] hept-2-ene,
5-methoxybicyclo [2.2.1] hept-2-ene,
5-ethoxybicyclo [2.2.1] hept-2-ene,
5,6-dihydroxybicyclo [2.2.1] hept-2-ene,
5,6-dicarboxybicyclo [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,
5,6-dimethoxybicyclo [2.2.1] hept-2-ene,
5,6-diethoxybicyclo [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-carboxy-5-methylbicyclo [2.2.1] hept-2-ene,
5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene,
5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene,
5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene,
5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene,
5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (Hymic acid anhydride),
5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene,
5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene,
5,6-di (t-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene,
Bicyclounsaturated compounds such as 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;

Phenylmaleimide, cyclohexylmaleimide, benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, Dicarbonylimide derivatives such as N- (9-acridinyl) maleimide;

Styrene, α-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid -3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl O-Vinylbenzylglycidylate , M- vinylbenzyl glycidyl ether, p- vinylbenzyl glycidyl ether.

  Among these, styrene, t-butyl methacrylate, dicyclopentanyl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, 1,3-butadiene, glycidyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl Ether, p-vinylbenzylglycidyl ether, phenylmaleimide, cyclohexylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution. These may be used alone or in combination.

The copolymer [A] used in the present invention has a polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”), usually 2 × 10 ^{3 to} 5 × 10 ⁵ , preferably 5 × 10 ³ to 1 × 10. ⁵ is desirable. If the Mw is less than 2 × 10 ^3, developability, lowered and film residual rate, also may the pattern shape, and heat resistance inferior, when the content is higher than 5 × 10 ^5, the sensitivity is lowered The pattern shape may be inferior.

  As described above, the copolymer [A] used in the present invention has a carboxyl group and / or a carboxylic acid anhydride group and an epoxy group, and has appropriate solubility in an alkaline aqueous solution, It can be easily cured by heating without using a special curing agent.

  The radiation-sensitive resin composition containing the above copolymer [A] can easily form a predetermined pattern shape without causing development residue and film slippage during development.

  Examples of the solvent used for the production of the copolymer [A] include alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propio Nates, aromatic hydrocarbons, ketones, esters and the like.

Specific examples thereof include alcohols such as methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, and 3-phenyl-1-propanol;
Ethers such as tetrahydrofuran;
Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
Examples of ethylene glycol alkyl ether acetate include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;
Examples of diethylene glycol include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether.
Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;

As propylene glycol alkyl ether propionate, for example, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate and the like;
As propylene glycol alkyl ether acetate, for example, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc .;
Aromatic hydrocarbons such as toluene, xylene, etc .;
Examples of ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and the like;

Examples of esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxy Ethyl acetate, hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy -3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, propoxy Methyl acetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionic acid Propyl, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate Propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropyl Butyl pionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropionate Examples thereof include esters such as propyl acid, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

    Of these, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, and propylene glycol alkyl ether acetate are preferable, and diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether, and propylene glycol methyl ether acetate are particularly preferable. .

  As the polymerization initiator used for the production of the copolymer [A], those generally known as radical polymerization initiators can be used. For example, 2,2′-azobisisobutyronitrile, 2,2 Azo compounds such as' -azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypi And organic peroxides such as barate, 1,1'-bis- (t-butylperoxy) cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, it may be a redox initiator using the peroxide together with a reducing agent.

  In the production of the copolymer [A], a molecular weight modifier can be used to adjust the molecular weight. Specific examples thereof include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan and thioglycolic acid; dimethylxanthogen Xanthogens such as sulfide and diisopropylxanthogen disulfide; terpinolene, α-methylstyrene dimer and the like.

1,2-quinonediazide compound [B]
As the 1,2-quinonediazide compound [B] used in the present invention, as the 1,2-quinonediazide compound, 1,2-benzoquinonediazidesulfonic acid ester, 1,2-naphthoquinonediazidesulfonic acid ester, 1,2- Examples thereof include benzoquinone diazide sulfonic acid amide and 1,2-naphthoquinone diazide sulfonic acid amide.

  Specific examples thereof include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone azide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfone. Acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2 , 3,4-Trihydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6 -Trihydroxybenzophenone-1,2-naphthoquinone diazi -5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfone 1,2-naphthoquinone diazide sulfonic acid esters of trihydroxybenzophenone such as acid esters, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinone diazide-8-sulfonic acid ester;

2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5 Sulfonic acid ester, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphtho Quinonediazide-7-sulfonic acid ester, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,3,4,3′-tetrahydroxybenzophenone-1, 2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,3′-tetrahydroxyl Benzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,3′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4,3′- Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,3,4,3′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,3,4,4 '-Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4 , 4'-Tetrahydroxybenzophenone-1,2-naphthoquinonedia Do-6-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2 -Naphthoquinonediazide-8-sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,2'- Tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-6-sulfone Acid ester, 2,3,4,2′-tetrahydroxy-4′-methylbenzophenone-1,2-naphth Toquinonediazide-7-sulfonic acid ester, 2,3,4,2′-tetrahydroxy-4′-methylbenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,3,4,4′-tetra Hydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid Ester, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone -1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,3,4,4′-tetrahi 1,2-naphthoquinonediazide sulfonic acid esters of tetrahydroxybenzophenone such as proxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid esters;

2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphtho Quinonediazide-5-sulfonic acid ester, 2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4,2 ′, 6′-penta Of pentahydroxybenzophenone such as hydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, etc. 1,2-naphthoquinonediazide sulfonic acid esters;

2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone -1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,4, 6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2 -Naphthoquinonediazide-8-sulfonic acid ester, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinonedia Do-4-sulfonic acid ester, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,4,5,3 ′, 4 ', 5'-Hexahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 3,4,5,3', 4 ', 5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-7- 1,2-naphthoquinone diazide sulfonic acid ester of hexahydroxybenzophenone such as sulfonic acid ester, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester Kind;

Bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis ( 2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-6-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-7-sulfonic acid ester, bis (2, 4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-8-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane -1,2-naphthoquinonediazide-5-sulfonic acid Tellurium, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-6-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-7-sulfonic acid ester, bis (p- Hydroxyphenyl) methane-1,2-naphthoquinonediazide-8-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1 , 2-Naphthoquinonediazide-5-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-6-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide- 7-sulfonic acid ester, tri (p-hydride Kishifeniru) methane-1,2-naphthoquinonediazide-8-sulfonic acid ester,

1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide- 5-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-6-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1 , 2-Naphthoquinonediazide-7-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-8-sulfonic acid ester, bis (2,3,4-trihydroxy) Phenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) Tan-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-6-sulfonic acid ester, bis (2,3,4- Trihydroxyphenyl) methane-1,2-naphthoquinonediazide-7-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,2- Bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphtho Quinonediazide-5-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1, -Naphthoquinonediazide-6-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,2-bis (2,3 , 4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-8-sulfonic acid ester,

1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris (2,5- Dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane -1,2-naphthoquinonediazide-6-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-7-sulfonic acid Ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinone Azido-8-sulfonic acid ester, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-sulfone Acid ester, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4, 4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-6-sulfonic acid ester, 4,4 ′-[1 -[4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinone di- Dido-7-sulfonic acid ester, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-8-sulfone Acid esters,

Bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxy Phenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-6-sulfonic acid ester, bis (2,5-Dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-7-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenyl Methane-1,2-naphthoquinonediazide-8-sulfonic acid ester 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′-hexanol-1,2-naphthoquinonediazide-4-sulfone Acid ester 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′-hexanol-1,2-naphthoquinonediazide-5 -Sulfonate ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'-hexanol-1,2-naphthoquinonediazide -6-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'-hexanol-1,2- Naphthoquinonediazide-7-sulfonic acid ester, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiinde -5,6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan -1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonic acid, 2,2, 4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1 2,2-naphthoquinonediazide-7-sulfonic acid, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-8-sulfonic acid, etc. Phenyl) include 1,2-naphthoquinonediazide sulfonic acid esters of alkanoic.
These 1,2-quinonediazide compounds can be used alone or in combination of two or more.

[B] The usage-amount of a component is 5-100 weight part with respect to 100 weight part of copolymers [A], Preferably it is 10-50 weight part.
When this ratio is less than 5 parts by weight, the amount of acid generated by irradiation with radiation is small, so the difference in solubility in an alkaline aqueous solution that is a developer between the irradiated part and the unirradiated part is small, and patterning is difficult. Tend to be. In addition, since the amount of acid involved in the reaction with the copolymer [A] decreases, sufficient heat resistance and solvent resistance may not be obtained. On the other hand, if this ratio exceeds 100 parts by weight, a large amount of unreacted [B] component remains after irradiation for a short time, so that the effect of insolubilization in the alkaline aqueous solution is too high and development is performed. Tend to be difficult.

-Thermal acid generator [C]-
Examples of the thermal acid generator used in the present invention include sulfonium salts (excluding the triarylsulfonium salts), benzothiazonium salts, ammonium salts, and phosphonium salts (excluding the diarylphosphonium salts). ), Sulfonimide compounds, and the like. Of these, sulfonium salts, benzothiazonium salts, and sulfonimide compounds are particularly preferable.

Among the thermal acid generators, as sulfonium salts, for example,
4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexamonate Alkylsulfonium salts such as fluoroantimonate, 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, Benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, etc. Benzylsulfonium salts;

Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, dibenzyl-4-acetoxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3 -Chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate Dibenzylsulfonium salts such as;
4-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-nitro Benzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 2-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium Examples thereof include substituted benzylsulfonium salts such as hexafluoroantimonate.

  Among these sulfonium salts, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium Hexafluoroantimonate, dibenzyl-4-acetoxyphenylsulfonium hexafluoroantimonate, and the like are preferable.

  Examples of the benzothiazonium salts include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- ( Benzylbenzothia such as 4-methoxybenzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate Zonium salts and the like can be mentioned. Of these benzothiazonium salts, 3-benzylbenzothiazonium hexafluoroantimonate is particularly preferable.

Among the commercially available products of thermal acid generators, examples of the alkylsulfonium salts include Adeka Opton CP-66, Adeka Opton CP-77 (manufactured by Asahi Denka Kogyo Co., Ltd.), and the like.
Examples of the benzylsulfonium salts include SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-80L, SI-100L, SI-110L (above, Sanshin). Chemical Industry Co., Ltd.).
Among these commercially available products, SI-80, SI-100, SI-110 and the like are preferable because the obtained protective film has high surface hardness.
The said heat-sensitive acid generator can be used individually or in mixture of 2 or more types.

Among the thermal acid generators, as sulfonium salts, for example,
N- (trifluoromethanesulfonyloxy) succinimide, N- (trifluoromethanesulfonyloxy) phthalimide, N- (trifluoromethanesulfonyloxy) diphenylmaleimide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximide, N- (trifluoromethanesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethane Sulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (trifluoromethanesulfonyloxy) naphthylimide, N- (10-camphorsulfonyloxy) succinimide, N -(10-Camphors Phonyloxy) phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- ( 10-camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] heptane -5,6-oxy-2,3-dicarboximide, N- (10-camphorsulfonyloxy) naphthylimide, N- (p-toluenesulfonyloxy) succinimide, N- (p-toluenesulfonyloxy) phthalimide, N -(P-toluenesulfonyloxy) diphenylmaleimide, N- (p-tolu Sulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5. -Ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (p-toluene) Sulfonyloxy) naphthylimide, N- (2-trifluoromethylbenzenesulfonyloxy) succinimide, N- (2-trifluoromethylbenzenesulfonyloxy) phthalimide, N- (2-trifluoromethylbenzenesulfonyloxy) diphenylmaleimide, N -(2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide N- (4-trifluoromethylbenzenesulfonyloxy) succinimide, N- (4-trifluoromethylbenzenesulfonyloxy) phthalimide, N- (4-trifluoromethylbenzenesulfonyloxy) diphenylmaleimide, N- (4-tri Fluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (4-trifluoromethylbenzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide N- (4-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (4-trifluoromethylbenzenesulfonyloxy) naphthyl Imido, N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (nonafluoro-n-butanesulfonyloxy) phthalimide, N- (nonafluoro-n-butanesulfonyloxy) diphenylmaleimide, N- (nonafluoro-n-butane Sulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3 Dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyl) Oxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) naphthylimide, N- (pentafluorobenzenesulfonyloxy) succinimide N- (pentafluorobenzenesulfonyloxy) phthalimide, N- (pentafluorobenzenesulfonyloxy) diphenylmaleimide, N- (pentafluorobenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N- (pentafluorobenze Sulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (pentafluorobenzenesulfonyloxy) bicyclo [2.2.1] heptane-5 , 6-oxy-2,3-dicarboximide, N- (pentafluorobenzenesulfonyloxy) naphthylimide, N- (perfluoro-n-octanesulfonyloxy) succinimide, N- (perfluoro-n-octanesulfonyloxy) ) Phthalimide, N- (perfluoro-n-octanesulfonyloxy) diphenylmaleimide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imido, N- (perfluoro-n-octanesulfonyloxy) -7-oxa Cyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy- 2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) naphthylimide, N-{(5-methyl-5-carboxymethanebicyclo [2.2.1] hept-2-yl) sulfonyl One or two or more of oxy} succinimide and the like can be mixed and used.

[C] The usage-amount of a component is 0.01-20 weight part with respect to 100 weight part of copolymers [A], Preferably it is 0.1-5 weight part.
When this proportion exceeds 20 parts by weight, precipitates are generated and patterning tends to be difficult. On the other hand, when this proportion is less than 0.01 part by weight, the curing rate during thermosetting tends to be slow and the resolution tends to decrease.

<Other ingredients>
In the radiation sensitive resin composition of the present invention, in addition to the above components [A], [B] and [C], if necessary, a polymerizable compound having at least one ethylenically unsaturated double bond Each component of [D], epoxy resin [E], surfactant [F], and adhesion assistant [G] can be contained.

As the polymerizable compound having at least one ethylenically unsaturated double bond as the component [D], monofunctional (meth) acrylate, bifunctional (meth) acrylate, or trifunctional or higher (meth) acrylate is preferable. Can be used.
Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl. -Hydroxypropyl phthalate and the like are listed, and examples of commercially available products thereof include Aronix M-101, M-111, M-114 (manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S, and TC-120S. (Nippon Kayaku Co., Ltd.), Biscote 158, 2311 (Osaka Organic Chemical Co., Ltd.).

  Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, bisphenoxyethanol full orange acrylate and the like can be mentioned, and commercially available products thereof include, for example, Aronix M-210, M-240, M-6200 (Toagosei ( KAYARAD HDDA, HX-220, R-604 (manufactured by Nippon Kayaku Co., Ltd.), Biscoat 260, 312 and 335HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, and pentaerythritol tetra (meth) acrylate. , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like, and as commercially available products thereof, for example, Aronix M-309, M-400, M-405, M-450, M-7100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 (Japan) Kayaku Co., Ltd.), Biscote 295 The 300, the 360, the GPT, said 3PA, the 400 (manufactured by Osaka Organic Chemical Industry Ltd.) and the like.
These monofunctional, bifunctional, or trifunctional or higher (meth) acrylates can be used alone or in combination.

The proportion of component [D] used is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, based on 100 parts by weight of copolymer [A].
By containing the [D] component at such a ratio, the heat resistance, strength, and the like of the patterned thin film obtained from the radiation-sensitive resin composition can be improved. If this proportion exceeds 50 parts by weight, the compatibility with the copolymer [A] becomes insufficient, and film roughening may occur during coating.

The [E] epoxy resin is not limited as long as the compatibility is not affected, but preferably a bisphenol A type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a cyclic aliphatic epoxy resin, Examples thereof include glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, heterocyclic epoxy resins, and resins obtained by (co) polymerization of glycidyl methacrylate.
Among these, bisphenol A type epoxy resin, cresol novolac type epoxy resin, glycidyl ester type epoxy resin and the like are preferable.

[E] The usage-amount of a component becomes like this. Preferably it is 30 weight part or less with respect to 100 weight part of copolymers [A].
By containing the component [E] at such a ratio, the heat resistance and surface hardness of the protective film or insulating film obtained from the radiation-sensitive resin composition of the present invention can be further improved.
When this ratio exceeds 30 weight part, the compatibility with respect to the alkali-soluble resin which is a copolymer [A] becomes inadequate, and sufficient coating-film formation ability may not be obtained.
When an epoxy group-containing unsaturated compound is used as the compound (a3) when synthesizing the copolymer [A], the copolymer [A] can also be referred to as an “epoxy resin”. [A] is different from the epoxy resin of the [E] component in that it has alkali solubility and is required to have a relatively high molecular weight.

  [F] Surfactant can be used to improve coatability. Examples of the commercially available products include BM-1000, BM-1100 (manufactured by BM CHEMIE), MegaFuck F142D, F172, F173, F183 (manufactured by Dainippon Ink and Chemicals), Florard FC-135, FC-170C, FC-430, FC-431 (manufactured by Sumitomo 3M), 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 (manufactured by Asahi Glass Co., Ltd.), F-top EF301, 303, 352 ( Shin-Akita Kasei Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (manufactured by Toray Silicone Co., Ltd.) Fluorine-based and silicone-based surfactants.

  In addition, [F] component includes polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, etc. Polyoxyethylene aryl ethers; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), ( A meth) acrylic acid copolymer polyflow No. 57, 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.) can be used.

  These surfactants are preferably used in an amount of 5 parts by weight or less, more preferably 2 parts by weight or less based on 100 parts by weight of the copolymer [A]. When the amount of the surfactant is more than 5 parts by weight, there may be a tendency to cause film filming during coating.

  [G] Adhesion aid can also be used to improve the adhesion to the substrate. As such an adhesion assistant, a functional silane coupling agent is preferably used, and examples thereof include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group. Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.

  Such an adhesion assistant is preferably used in an amount of 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the copolymer [A]. When the amount of the adhesion assistant exceeds 20 parts by weight, there may be a case where a development residue is likely to occur.

  The radiation-sensitive resin composition of the present invention is optionally added with the above-mentioned copolymer [A] and [B] components or copolymer [A], [B] and [C] components, and as described above. It is prepared by mixing other ingredients uniformly. The radiation-sensitive resin composition of the present invention is preferably used in a solution state after being dissolved in an appropriate solvent. For example, by mixing the copolymer [A] and [B] components or the copolymer [A], [B] and [C] components, and other components optionally added, in a predetermined ratio, A radiation-sensitive resin composition in a solution state can be prepared.

Solvents used in the preparation of the radiation sensitive resin composition of the present invention include copolymer [A] and [B] components or copolymers [A], [B] and [C] components, and optionally The other components to be blended are uniformly dissolved and do not react with each component.
As such a solvent, the thing similar to what was illustrated as a solvent which can be used in order to manufacture copolymer [A] mentioned above can be mentioned.

Of these solvents, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, esters and diethylene glycol are preferably used from the viewpoints of solubility of each component, reactivity with each component, ease of film formation, and the like. It is done. Among these, for example, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether Propylene glycol monomethyl ether acetate, methyl methoxypropionate, and ethyl ethoxypropionate can be particularly preferably used.
Furthermore, in order to improve the in-plane uniformity of the film thickness together with the solvent, a high boiling point solvent can be used in combination. Examples of the high-boiling solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether. , Dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl Examples include cellosolve acetate. Of these, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.

  When a high boiling point solvent is used in combination as the solvent of the radiation sensitive resin composition of the present invention, the amount used is preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 30%, based on the total amount of the solvent. It can be made into weight% or less. If the amount of the high-boiling solvent used exceeds this amount, the coating film thickness uniformity, sensitivity, and residual film rate may decrease.

When preparing the radiation sensitive resin composition of the present invention in a solution state, components other than the solvent in the solution, that is, the copolymer [A] and [B] components or the copolymers [A], [B] and The proportion of the total amount of the component [C] and other components optionally added can be arbitrarily set according to the purpose of use, the value of the desired film thickness, etc., for example, 5 to 50% by weight, Preferably it is 10 to 40 weight%, More preferably, it is 15 to 35 weight%.
The composition solution prepared as described above can be used after being filtered using a Millipore filter having a pore size of about 0.2 μm.

Formation of light diffusible reflective film will now be described a method of forming a light diffuse reflection layer of the present invention using a light diffuse reflection layer-forming composition of the present invention.
The composition for forming a light diffusive reflection film of the present invention can be formed into a coating film by applying it to the surface of a base substrate and removing the solvent by pre-baking. As a coating method, various methods such as a spray method, a roll coating method, and a spin coating method can be employed.
Moreover, although the conditions of prebaking differ also with the kind of each component, a mixture ratio, etc., the conditions for about 1 to 15 minutes are usually optimal at 70-90 degreeC.
Next, the pre-baked coating film is irradiated with radiation such as ultraviolet rays through a predetermined pattern mask, further developed with a developer, and unnecessary portions are removed to form a predetermined pattern. The developing method may be any of a liquid piling method, a dipping method, a shower method, etc., and the developing time is usually 30 to 180 seconds.
In addition, the conventionally known composition for forming a light diffusive reflective film has a need to strictly control the development time because peeling occurs in the formed pattern when the development time exceeds about 20 to 25 seconds from the optimum value. In the case of the composition for forming a light diffusive reflecting film of the present invention, a good pattern can be formed even when the excess time from the optimum development time is 30 seconds or more, which is advantageous in terms of product yield.

  Examples of the developer include aqueous alkali solutions such as inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; primary amines such as ethylamine and n-propylamine; Secondary amines such as di-n-propylamine; tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; tertiary amines such as dimethylethanolamine, methyldiethanolamine and triethanolamine; pyrrole and piperidine Cyclic tertiary amines such as N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene Pyridine, It can be used tetramethylammonium hydroxide, an aqueous solution of quaternary ammonium salts such as tetraethylammonium hydroxide; lysine, lutidine, aromatic tertiary amines such as quinoline. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant to the alkaline aqueous solution can also be used as a developer.

After the development, washing with running water is performed for 30 to 90 seconds, unnecessary portions are removed, and the pattern is formed by air drying with compressed air or compressed nitrogen. The formed pattern is irradiated with radiation such as ultraviolet rays, and this pattern is then applied to a predetermined temperature, for example, 150 to 250 ° C., for a predetermined time, for example, 5 to 30 minutes on the hot plate, by a heating device such as a hot plate or oven. In the oven, by performing a heat treatment for 30 to 90 minutes, a patterned coating film having a rough surface suitable for a light diffusion reflection film can be obtained.
Next, by performing metal vapor deposition, the light diffusive reflective film of the present invention can be obtained. At this time, the metal used for vapor deposition is not particularly limited, but a metal having a high reflectance in the visible light region is preferably used. From this viewpoint, aluminum, silver, and an alloy containing at least one of these are preferable.

The light diffusive reflecting film formed as described above reflects a rough surface having a pattern before vapor deposition of metal.
At this time, the shape of each unit pattern is preferably a convex lens shape with a flat bottom surface. When the unit pattern is observed from the upper surface, the unit pattern is preferably circular or substantially circular, and the diameter is preferably 1 to 30 μm, and more preferably 5 to 20 μm.
Moreover, it is preferable that the cross-sectional shape of each unit pattern becomes a shape as shown in FIG. 1A, and the height at that time is preferably 0.1 to 5 μm, more preferably 0.2 to 3 μm. is there.

Liquid crystal display element Next, the liquid crystal display element of the present invention will be described.
The liquid crystal display element of the present invention has the light diffusive reflection film formed as described above.
As the structure of the liquid crystal element, an appropriate structure is possible. For example, as shown in FIG. 2, the light diffusion reflection film 23 and the color filter layer 4 of the present invention are formed on the substrate 1, and the alignment film 7, liquid crystal The structure which has the alignment film 9 which opposes via the layer 8, the transparent electrode 10 which opposes, and the opposing board | substrate 11 is mentioned. In this case, as shown in FIG. 2, the transparent electrode 6 may be provided on the lower substrate side, or the metal layer 3 constituting the light diffusion reflection film 23 may have an electrode function. Moreover, you may form the protective film 5 on the polarizing plate 12 or the color filter layer 4 as needed.
As an example of another structure, as shown in FIG. 3, the light diffusion reflection film 23 of the present invention is formed on the substrate 1, the alignment film 7 is opposed to the liquid crystal layer 8, and the transparent film is opposed. A structure having the electrode 10, the color filter layer 4, and the counter substrate 11 can be given. In this case, a structure having the counter transparent electrode 10 below the color filter layer 4 as shown in FIG. 3 or a structure having the counter transparent electrode above the color filter layer 4 may be used. Moreover, you may form the protective film 5 under the polarizing plate 12 or the color filter layer 4 as needed.
In the structure of FIG. 3, the metal layer 3 constituting the light diffusing and reflecting film 23 controls the function of the electrode, but an electrode may be provided separately on the lower substrate side.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In the following, “%” means “% by weight”.

Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 22 parts by weight of methacrylic acid, 38 parts of dicyclopentanyl methacrylate, 40 parts by weight of 3- (methacryloyloxymethyl) -2-phenyloxetane and 1.5 parts of α-methylstyrene dimer were charged and gently stirred while substituting nitrogen. I started. The temperature of the solution was raised to 70 ° C. and heated at this temperature for 4 hours to obtain a polymer solution containing the copolymer [A-1]. The obtained polymer solution had a solid content concentration of 31.8%, a polymer weight average molecular weight of 17,900 and a molecular weight distribution (ratio of weight average molecular weight / number average molecular weight) of 1.8. In addition, a weight average molecular weight and a number average molecular weight are polystyrene conversion average molecular weights measured using GPC (Gel permeation chromatography (HLC-8020 manufactured by Tosoh Corporation)).

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 5 parts by weight of styrene, 22 parts by weight of methacrylic acid, and 45 parts by weight of 3- (methacryloyloxymethyl) -3-ethyloxetane were charged, and the mixture was gently stirred while replacing with nitrogen. The temperature of the solution was raised to 70 ° C. and heated at this temperature for 4 hours to obtain a polymer solution containing the copolymer [A-2]. The obtained polymer solution had a solid content concentration of 31.9%, a weight average molecular weight of 20,200, and a molecular weight distribution of 1.9.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 150 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 20 parts by weight of styrene, 25 parts by weight of methacrylic acid, 20 parts of cyclohexylmaleimide, 35 parts by weight of 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, and 1.5 parts of α-methylstyrene dimer were charged and the nitrogen was replaced. The stirring was started gently. The temperature of the solution was raised to 70 ° C. and heated at this temperature for 4 hours to obtain a polymer solution containing the copolymer [A-3]. The resulting polymer solution had a solid content concentration of 38.7%, the polymer had a weight average molecular weight of 21,500 and a molecular weight distribution of 2.2.

Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 20 parts by weight of styrene, 30 parts by weight of methacrylic acid, 50 parts by weight of 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and 2.0 parts of α-methylstyrene dimer were charged and gently stirred while replacing with nitrogen. It was. The temperature of the solution was raised to 70 ° C. and heated at this temperature for 5 hours to obtain a polymer solution containing the copolymer [A-4]. The obtained polymer solution had a solid content concentration of 31.0%, a weight average molecular weight of 19000, and a molecular weight distribution of 1.7.

Comparative Synthesis Example 1
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol methyl ethyl ether. Subsequently, 23 parts by weight of methacrylic acid, 47 parts of dicyclopentanyl methacrylate, 20 parts by weight of glycidyl methacrylate, and 2.0 parts of α-methylstyrene dimer were charged, and the mixture was gently stirred while replacing with nitrogen. 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-1R]. The resulting polymer solution had a solid content concentration of 32.8%, the polymer had a weight average molecular weight of 24,000 and a molecular weight distribution of 2.3.

Comparative Synthesis Example 2
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol methyl ethyl ether. Subsequently, 25 parts by weight of methacrylic acid, 35 parts of dicyclopentanyl methacrylate, 40 parts by weight of 2-hydroxyethyl methacrylate, and 2.0 parts of α-methylstyrene dimer were charged, and gentle stirring was started while replacing with nitrogen. 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-2R]. The obtained polymer solution had a solid content concentration of 32.8%, a weight average molecular weight of 25,000 and a molecular weight distribution of 2.4.

Example 1
Preparation of radiation sensitive resin composition Polymer solution containing copolymer [A-1] obtained in Synthesis Example 1 (corresponding to 100 parts by weight (solid content) of copolymer [A-1]),
As component [B], 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5 Condensation product with sulfonic acid chloride (2 mol) (4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide -5-sulfonic acid ester) 30 parts by weight, γ-methacryloxypropyltrimethoxysilane 5 parts by weight, triphenylsulfonium trifluoromethanesulfonate (SI-300 manufactured by Sanshin Chemical Co., Ltd.) 1 part by weight was mixed, and the solid content After dissolving in propylene glycol monomethyl ether acetate to a concentration of 30% by weight, Millipore with a pore size of 0.5 μm To prepare a solution of the radiation-sensitive resin composition (S-1) was filtered through a filter.

(I) Formation of rough surface having pattern After applying the above composition solution on a glass substrate using a spinner, prebaking on a hot plate at 90 ° C. for 3 minutes to form a coating film having a thickness of 2.0 μm did.
The coating film obtained above was irradiated with ultraviolet rays having an intensity at 365 nm of 10 mW / cm ² for 10 seconds through a mask having a remaining pattern of 5.0 μm square. Next, after developing with a 0.5% by weight aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 1 minute, it was rinsed with pure water for 1 minute. Furthermore, after irradiating with ultraviolet rays having an intensity at 365 nm of 10 mW / cm ² for 30 seconds, it was heated in an oven at 220 ° C. for 60 minutes to form a rough surface having a pattern.
Further, except that the prebake temperature was set to 100 and 110 ° C., the same operation as described above was performed to form three types of patterned thin films having different prebake temperatures.

(II) Resolution evaluation In the pattern obtained in (I) above, the case where the remaining pattern was resolved was judged good, and the case where the pattern was not resolved was judged as poor. The results are shown in Table 1.

(III) Evaluation of Storage Stability The composition solution was heated in an oven at 40 ° C. for 1 week, and the storage stability was evaluated by the change in viscosity before and after heating. The viscosity change rate at this time is shown in Table 1. When the rate of change is less than 5%, the storage stability is good, and when it is 5% or more, the storage stability is poor.

(IV) Evaluation of pattern cross-sectional shape In (I) above, as a result of observing the cross-sectional shape of the pattern formed at a pre-bake temperature of 90 ° C. with a scanning electron microscope, which of A to C shown in FIG. Are shown in Table 2. As shown in A, the pattern shape is good when the pattern is formed in the shape of a semi-convex lens having a flat bottom surface, and when the pattern edge is formed as a vertical or forward taper like B or C, the pattern is It can be said that the shape is bad.
Further, the diameter and height of the pattern at this time are also shown in Table 2. The pattern diameter and height were evaluated by observing with a scanning electron microscope.

(V) Evaluation of heat resistance In the above (I), the pattern formed at a pre-bake temperature of 90 ° C was heated in an oven at 220 ° C for 60 minutes. The change rate of the film thickness at this time is shown in Table 2. When the absolute value of this value is within 5% before and after heating, it can be said that the heat resistance is good.

(VI) Evaluation of solvent resistance In the above (I), after the pattern formed at a pre-bake temperature of 90 ° C. was immersed in dimethyl sulfoxide controlled at 70 ° C. for 20 minutes, the change in film thickness due to immersion was measured. . The results are shown in Table 2. When the absolute value of this value is less than 5%, the solvent resistance is good.

(VII) Formation of Light Diffuse Reflective Film An aluminum film having a thickness of 1,500 mm was formed on the rough surface formed at the pre-bake temperature of 90 ° C. in the above (I) using a vacuum deposition apparatus. (The substrate thus formed having a light scattering film on a glass substrate and further having an aluminum film thereon is hereinafter referred to as an aluminum vapor deposition substrate.)
In the adhesion test of JIS K-5400 (1900) 8.5, according to the cross-cut tape method of 8.5, 2, 100 cross-cuts were formed on the aluminum vapor-deposited substrate formed above with a cutter knife. An adhesion test was performed. Table 2 shows the number of the remaining grids.

Example 2
In Example 1, a composition solution (S-2) was prepared in the same manner as in Example 1 except that a solution containing the copolymer [A-2] was used instead of the solution containing the copolymer [A-1]. ) Was prepared and evaluated. The results are shown in Tables 1 and 2.

Example 3
In Example 1, the composition solution (S-3) was used in the same manner as in Example 1, except that the solution containing the copolymer [A-3] was used instead of the solution containing the copolymer [A-1]. ) Was prepared and evaluated. The results are shown in Tables 1 and 2.

Example 4
In Example 1, the composition solution (S-4) was used in the same manner as in Example 1 except that the solution containing the copolymer [A-4] was used instead of the solution containing the copolymer [A-1]. ) Was prepared and evaluated. The results are shown in Tables 1 and 2.

Example 5
A polymer solution containing the copolymer [A-1] obtained in Synthesis Example 1 (corresponding to 100 parts by weight (solid content) of the copolymer [A-1]);
As component [B], 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5 Condensation product with sulfonic acid chloride (2 mol) (4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide -5-sulfonic acid ester) (30 parts by weight) and γ-methacryloxypropyltrimethoxysilane (5 parts by weight) were mixed and dissolved in propylene glycol monomethyl ether acetate so that the solid concentration was 30% by weight. A solution (S-5) of the radiation sensitive resin composition was prepared by filtration through a 5 μm Millipore filter and evaluated. The results are shown in Tables 1 and 2.

Comparative Example 1
In Example 1, a composition solution (S-1R) was obtained in the same manner as in Example 1, except that a solution containing the copolymer [A-1R] was used instead of the solution containing the copolymer [A-1]. ) Was prepared and evaluated. The results are shown in Tables 1 and 2.

Comparative Example 2
A solution containing the copolymer [A-2R] obtained in Comparative Synthesis Example 2 (corresponding to 100 parts by weight (solid content) of the copolymer {A-2R]);
As component [B], 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5 Condensation product with sulfonic acid chloride (2 mol) (4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide -5-sulfonic acid ester) 30 parts by weight and γ-methacryloxypropyltrimethoxysilane 5 parts by weight were mixed and dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration was 30% by weight. A radiation sensitive resin composition solution (S-2R) was prepared by filtration through a 0.5 μm Millipore filter and evaluated. The results are shown in Tables 1 and 2.

Example 6
Evaluation of Light Diffusion Properties Using the composition for forming a light scattering film prepared in Example 1, (I) a rough surface forming process having a pattern described in Example 1, and (V) a light diffusing reflective film According to the forming process, a convex lens-like pattern having a bottom surface with a bottom diameter of 10 μm and a height of 0.7 μm and having a flat bottom surface was formed on a glass substrate so as to be in a close-packed arrangement. On top of this, in accordance with the process of forming the (V) light diffusive reflective film described in Example 1, a 1,500 mm aluminum film was formed to obtain a light diffusive reflective film. For the light diffusive reflection film obtained here, using a three-dimensional goniophotometer (manufactured by Murakami Color Research Laboratory Co., Ltd.), the scattering characteristic at 30 ° incidence is changed from -10 ° to 70 °. It was measured. The results are shown in FIG.

It is a schematic diagram which shows the cross-sectional shape of a pattern-form coating film. It is a schematic diagram which shows the structure of a liquid crystal display element. It is a schematic diagram which shows the structure of a liquid crystal display element. 6 is a graph showing light scattering characteristics of the light diffusive reflecting film obtained in Example 6.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Substrate 2 Patterned coating film 3 Metal layer 23 Light diffuse reflection film 4 Color filter layer 5 Protective film 6 Transparent electrode 7 Alignment film 8 Liquid crystal layer 9 Alignment film 10 Transparent electrode 11 Counter substrate 12 Polarizing plate 13 TFT element

Claims (5)

[A] (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (a2) compound represented by general formula (I) or general formula (II),

Wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ are each It is independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6. ]
A monomer represented by
And (a3) a copolymer of other olefinically unsaturated compounds, and [B] a 1,2-quinonediazide compound. [C] The composition for forming a light diffusive reflection film according to claim 1, further comprising a heat-sensitive acid generator. A light diffusion reflection film having a pattern formed from the composition for forming a light diffusion reflection film according to claim 1. The light-diffusion reflection film of Claim 3 whose diameter of the unit pattern formed from the composition for light-diffusion reflection film formation is 1-30 micrometers. A liquid crystal display element having the light diffusing reflective film according to claim 3.

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