JP6278198B2 - Curable resin composition, protective film manufacturing method, liquid crystal display device manufacturing method, and solid-state imaging device manufacturing method - Google Patents

Description

  The present invention relates to a curable resin composition used for forming a protective film for a liquid crystal display element or a protective film for a solid-state imaging element, a protective film formed from the composition, a liquid crystal display element including the protective film, and a solid-state imaging It relates to an element.

  Elements such as liquid crystal display (LCD) and complementary metal oxide semiconductor (CMOS) image sensors are immersed in a solvent, acid or alkali solution during the manufacturing process, and wiring electrode layers are formed by sputtering. When forming, the surface of the element is locally exposed to high temperature. Therefore, in order to prevent the device from being deteriorated or damaged by such treatment, a protective film made of a thin film having resistance to these treatments is provided on the surface of the device.

  Such a protective film has high adhesion to the substrate or lower layer on which the protective film is to be formed, and further to the layer formed on the protective film, the film itself is smooth and tough, transparent It has high heat resistance and light resistance, does not cause deterioration such as coloring, yellowing and whitening over a long period of time, and has excellent water resistance, solvent resistance and alkali resistance. Some performance is required. As a material for forming a protective film satisfying these various properties, for example, a resin composition containing a polymer having a glycidyl group is known (see Patent Document 1 and Patent Document 2).

  In recent years, LCDs and CMOS image sensors using organic compounds have been actively developed. For example, in a liquid crystal cell manufacturing process of an LCD, a silicon-based TFT is used, but research to replace this with an organic TFT is underway. In this manufacturing process, a liquid crystal cell manufacturing process at a low temperature is required to reduce damage to the organic TFT.

  Moreover, although the touch screen panel is provided in the LCD member used for a smart phone, there exists a manufacturing process which forms a touch screen panel after liquid crystal cell preparation. In this manufacturing process, it is desirable to form a touch screen panel at a low temperature in order to reduce damage to organic components such as liquid crystals and color filters.

  Development of a flexible touch panel is also underway. In this case, since an organic polymer film such as PET is introduced instead of a normal glass panel, it is necessary to form a touch screen panel at a low temperature.

  On the other hand, in developing a CMOS image sensor, in order to obtain a more favorable sensor, studies are underway to replace the current silicon photodiode with an organic photoelectric conversion material. This organic photoelectric conversion material has poor heat resistance, and it is generally said that device fabrication at 150 ° C. or lower is necessary (see Non-Patent Document 1).

JP-A-5-78453 JP 2001-91732 A

Satoshi Aihara and one other, “Research Trends of Organic Imaging Devices”, NHK R & D, NHK Broadcasting Technology Laboratory, No. 132, published March 2012, p. 4-11

  However, in order to manufacture elements such as high-performance LCDs and CMOS image sensors that actively incorporate organic materials, not only meet the general required performance as protective films such as transparency and chemical resistance. Although it is necessary to form a protective film that satisfies the required performance and has low sublimation properties at a lower temperature, such a material is not yet known.

  Therefore, some aspects according to the present invention satisfy the general required performance as a protective film such as transparency and chemical resistance by solving the above-mentioned problems, and moreover, a protective film with low sublimation properties. Curable resin composition that can be formed at a low temperature and is suitably used in the manufacture of devices such as LCDs and CMOS image sensors, a protective film formed from the composition, a liquid crystal display device including the protective film, and solid-state imaging An element is provided.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

（上記式（１）中、Ｒ^１は置換もしくは非置換のアリール基、Ｒ^２は置換もしくは非置換のベンジル基、Ｒ^３は炭素数１〜６のアルキル基を表す。Ｘ⁻は非求核性の対アニオンであり、下記式（２）のいずれかを表す。）

（上記式（２）中、Ｒｆはフッ素置換アルキル基であり、ｎは０〜６の整数である。） [Application Example 1]
One aspect of the curable resin composition according to the present invention is:
A curable resin composition comprising a polymer (A) having at least one selected from the group consisting of a radical polymerizable group, a cationic polymerizable group and a hydrolyzed silyl group, and an acid generator (B). There,
The acid generator (B) is a sulfonium salt represented by the following general formula (1),
It is used for the purpose of forming a protective film for a liquid crystal display element or a protective film for a solid-state imaging element.

(In the above formula (1), R ¹ represents a substituted or unsubstituted aryl group, R ² represents a substituted or unsubstituted benzyl group, and R ³ represents an alkyl group having 1 to 6 carbon atoms. X ⁻ represents a non-nucleophilic group. (It represents any one of the following formula (2).)

(In the above formula (2), Rf is a fluorine-substituted alkyl group, and n is an integer of 0-6.)

（上記式（３）中、Ｒ^４およびＲ^５はそれぞれ独立に、炭素数１〜６の直鎖もしくは分岐鎖状アルキル基を表す。Ｒ^６は置換もしくは非置換のベンジル基を表す。）

（上記式（４）中、Ｒ^７は水素原子もしくはアルキルカルボニル基を表す。Ｒ^８は炭素数１〜６の直鎖もしくは分岐鎖状アルキル基を表す。Ｒ^９は置換もしくは非置換のベンジル基を表す。Ｒｆは炭素数１〜４のフッ素置換直鎖状アルキル基を表す。ｎは０〜６の整数を表す。） [Application Example 2]
In the curable resin composition of Application Example 1,
The acid generator (B) may be at least one selected from the group consisting of a compound represented by the following general formula (3) and a compound represented by the following general formula (4).

(In the above formula (3), R ⁴ and R ⁵ each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms. R ⁶ represents a substituted or unsubstituted benzyl group.)

(In the above formula (4), R ⁷ represents a hydrogen atom or an alkylcarbonyl group. R ⁸ represents a linear or branched alkyl group having 1 to 6 carbon atoms. R ⁹ is a substituted or unsubstituted benzyl group. Rf represents a fluorine-substituted linear alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 6.)

[Application Example 3]
One aspect of the protective film for a liquid crystal display device or a solid-state imaging device according to the present invention is:
It is obtained by heat-treating a coating film formed using the curable resin composition of Application Example 1 or Application Example 2 at a temperature of 150 ° C. or lower.

[Application Example 4]
One aspect of the liquid crystal display element according to the present invention is:
A transparent substrate;
A color filter formed on the transparent substrate;
A protective film of Application Example 3 formed between the color filter and the transparent electrode;
It is characterized by including.

[Application Example 5]
One aspect of the solid-state imaging device according to the present invention is:
A pixel electrode formed on a semiconductor substrate on which a signal readout circuit is formed;
An organic photoelectric conversion layer formed on the pixel electrode;
A counter electrode formed on the organic photoelectric conversion layer;
A protective film of Application Example 3 formed on the counter electrode;
It is characterized by including.

According to the curable resin composition of the present invention, it is possible to form a protective film satisfying general required characteristics as a protective film such as transparency and chemical resistance and having a low sublimation property at a lower temperature. . This makes it possible to significantly reduce damage to organic materials such as organic TFTs, liquid crystals, color filters, and organic polymer films in the manufacture of elements such as LCDs and CMOS image sensors.

It is typical sectional drawing which shows the liquid crystal display device which concerns on this Embodiment. It is typical sectional drawing which shows the manufacturing method of the solid-state image sensor which concerns on this Embodiment in order of a process. It is typical sectional drawing which shows the manufacturing method of the solid-state image sensor which concerns on this Embodiment in order of a process. It is typical sectional drawing which shows the solid-state image sensor which concerns on this Embodiment.

  Hereinafter, preferred embodiments according to the present invention will be described in detail. It should be understood that the present invention is not limited only to the embodiments described below, and includes various modifications that are implemented within a scope that does not change the gist of the present invention. In the present specification, “(meth) acrylic acid” is a concept encompassing both “acrylic acid” and “methacrylic acid”. Further, “˜ (meth) acrylate” is a concept encompassing both “˜acrylate” and “˜methacrylate”. As used herein, the term “(meth)” should be construed in the same manner.

1. Curable Resin Composition The curable resin composition according to the present embodiment (hereinafter also simply referred to as “resin composition”) is selected from the group consisting of radically polymerizable groups, cationically polymerizable groups, and hydrolyzed silyl groups. A curable resin composition comprising a polymer (A) having at least one kind and an acid generator (B), wherein the acid generator (B) is a specific acid as described later. It is a generating agent and is used for the purpose of forming a protective film for a liquid crystal display element or a protective film for a solid-state imaging element.

  Hereinafter, each component of the resin composition according to the present embodiment will be described.

1.1. Polymer (A)
The polymer (A) used in the present embodiment is a monomer having at least one selected from the group consisting of a radical polymerizable group, a cationic polymerizable group and a hydrolyzed silyl group (hereinafter referred to as “compound (a1)”. It is a polymer produced through the step of polymerizing.

  Examples of the monomer having a radical polymerizable group include unsaturated carboxylic acid, unsaturated polyvalent carboxylic acid anhydride, (meth) acrylic acid alkyl ester, (meth) acrylic acid alicyclic alkyl ester, and hydroxyl group. (Meth) acrylic acid ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid diester, bicyclounsaturated compound, maleimide compound, vinyl aromatic compound, conjugated diene, acetal of carboxylic acid, ketal of carboxylic acid or carboxylic acid Examples thereof include (meth) acrylic acid esters having a 1-alkylcycloalkyl ester structure. These monomers having a radical polymerizable group may be used alone or in combination of two or more.

  Specific examples of the unsaturated carboxylic acid or unsaturated polyvalent carboxylic acid anhydride include (meth) acrylic acid, crotonic acid, α-ethylacrylic acid, α-n-propylacrylic acid, α-n-butylacrylic acid, Mention may be made of maleic acid, fumaric acid, citraconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, cis-1,2,3,4-tetrahydrophthalic anhydride. Among these unsaturated carboxylic acids or unsaturated polyvalent carboxylic acid anhydrides, acrylic acid, methacrylic acid, and maleic anhydride are particularly preferable.

  Furthermore, (meth) acrylic acid alkyl ester, (meth) acrylic acid alicyclic alkyl ester, (meth) acrylic acid ester having a hydroxyl group, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid diester, bicyclo unsaturated compound, Specific examples of maleimide compounds, vinyl aromatic compounds, and conjugated dienes include (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; (meth) acrylic (Meth) such as methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate Alkyl acrylate; cyclopentyl (meth) acrylate, (meth ) Cyclohexyl acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.02,6] decan-8-yl (meth) acrylate (hereinafter referred to as tricyclo [5.2.1.02, 6) Decan-8-yl is referred to as “dicyclopentanyl”), (meth) acrylic acid alicyclic esters such as (meth) acrylic acid 2-dicyclopentanyloxyethyl, (meth) acrylic acid isobornyl; (Meth) acrylic acid aryl esters such as benzyl acrylate; unsaturated dicarboxylic acid diesters such as diethyl maleate and diethyl fumarate; N-phenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-succinimidyl- 3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate Unsaturated dicarbonylimide derivatives such as; aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene; conjugated dienes such as 1,3-butadiene .

  Further, specific examples of (meth) acrylic acid ester compounds having an acetal, ketal or 1-alkylcycloalkyl ester structure of carboxylic acid include, for example, 1-ethoxyethyl (meth) acrylate, tetrahydro-2H-pyran-2-yl (Meth) acrylate, 1- (cyclohexyloxy) ethyl (meth) acrylate, 1- (2-methylpropoxy) ethyl (meth) acrylate, 1- (1,1-dimethyl-ethoxy) ethyl (meth) acrylate, 1- (Cyclohexyloxy) ethyl (meth) acrylate, 1-methylcyclopropyl (meth) acrylate, 1-methylcyclobutyl (meth) acrylate, 1-methylcyclopentyl (meth) acrylate, 1-methylcyclohexyl (meth) acrylate, 1- Methyl Chloheptyl (meth) acrylate, 1-ethylcyclopropyl (meth) acrylate, 1-ethylcyclobutyl (meth) acrylate, 1-ethylcyclopentyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, 1-ethylcyclooctyl ( And (meth) acrylate.

  Among these, as a monomer having a radical polymerizable group, (meth) acrylic acid hydroxyalkyl ester, methyl methacrylate, t-butyl methacrylate, cyclohexyl acrylate, dicyclopentanyl methacrylate, 2-acrylic acid 2- Methylcyclohexyl, N-phenylmaleimide, N-cyclohexylmaleimide, styrene, p-methoxystyrene, 1-ethoxyethyl methacrylate, tetrahydro-2H-pyran-2-yl methacrylate, 1- (cyclohexyloxy) ethyl methacrylate, 1- (2 -Methylpropoxy) ethyl methacrylate, 1- (1,1-dimethyl-ethoxy) ethyl methacrylate, 1- (cyclohexyloxy) ethyl methacrylate, 1-ethylcyclopentyl (meth) acrylate, 1- Preferably used chill cyclohexyl (meth) acrylate. These monomers having a radically polymerizable group have high copolymerization reactivity and are effective for enhancing the heat resistance and chemical resistance of the resulting protective film.

Examples of the monomer having a cationic polymerizable group include glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, and (meth) acrylic acid. 3,4-epoxybutyl, 3,4-epoxybutyl α-ethyl acrylate, 6,7-epoxyheptyl (meth) acrylate, α-ethyl acrylate 6,7-epoxyheptyl, p-vinylbenzylglycidyl ether, Examples include 3-methyl-3- (meth) acryloxymethyloxetane, 3-ethyl-3- (meth) acryloxymethyloxetane, and the like. These monomers having a cationic polymerizable group may be used alone or in combination of two or more.

  Among these monomers having a cationic polymerizable group, glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, p-vinylbenzyl glycidyl ether, 3-methyl-3- (meth) acryloxymethyloxetane, 3-ethyl-3- (meth) acryloylmethyloxetane and the like are preferably used from the viewpoint of improving the copolymerization reactivity and the heat resistance and chemical resistance of the resulting protective film.

  Examples of the monomer having a hydrolyzed silyl group include vinyloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-trimethoxysilylstyrene, (meth) acrylic acid trimethoxysilane, and (meth) acrylic. Acid triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, Phenyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropylto Silane, .gamma.-hydroxypropyl trimethoxysilane, and the like. These monomers having a hydrolyzed silyl group may be used alone or in combination of two or more.

  The content of the repeating unit derived from the compound (a1) is preferably 10 to 100% by mass, more preferably 20 to 90% by mass, when the total number of repeating units in the polymer (A) is 100% by mass. It is. When the content ratio of the repeating unit derived from the compound (a1) is in the above range, the heat resistance and chemical resistance of the protective film to be formed are good.

  Next, the polymerization method for producing the polymer (A) will be described.

  Polymerization related to a monomer having a radical polymerizable group and / or a monomer having a cationic polymerizable group is performed by, for example, a monomer having a radical polymerizable group and / or a monomer having a cationic polymerizable group, The polymerization can be carried out by polymerization using a radical polymerization initiator in a solvent in the presence of a molecular weight control agent, whereby a polymer (A) having a controlled molecular weight and molecular weight distribution can be obtained.

  As the molecular weight controlling agent used in this polymerization, those having a bis (alkyl mercapto-thiocarbonyl) disulfide or bis (benzyl mercapto-thiocarbonyl) disulfide structure (hereinafter also referred to as “specific molecular weight controlling agent”) are preferable. The polymer (A) produced using the molecular weight control agent is effective for developing good sublimation properties of the protective film. In addition, the molecular weight control agent is stable over time, can synthesize the polymer (A) stably, and as a result, can improve the quality of the resin composition.

  In the polymerization, one or more other molecular weight control agents such as α-methylstyrene dimer and t-dodecyl mercaptan can be used in combination with the specific molecular weight control agent.

  In addition, in the polymerization relating to the monomer having a radical polymerizable group and / or the monomer having a cationic polymerizable group in the presence of a molecular weight control agent, a living radical in which an active radical is formed at the growth terminal of the polymer chain It may take the form of polymerization.

  When the polymerization takes the form of living radical polymerization, a monomer having a radical polymerizable group and / or a monomer having a cationic polymerizable group may have a functional group that may deactivate an active radical such as a carboxyl group. In order to prevent the growth terminal from being deactivated in the case of containing the compound having, the polymer (A) is polymerized by protecting the functional group by, for example, esterification, if necessary, and then deprotecting as necessary. It can also be obtained.

  The radical polymerization initiator is appropriately selected according to the type of monomer used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4 -Dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanovaleric acid), dimethyl-2,2'-azobis (2 -Methyl propionate), azo compounds such as 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), and the like. Among these radical polymerization initiators, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and the like are preferable. The radical polymerization initiators can be used alone or in admixture of two or more.

  In the said polymerization, the usage-amount of a radical polymerization initiator is 0.1-50 mass parts normally with respect to 100 mass parts of monomers, Preferably it is 0.1-20 mass parts.

  Moreover, the usage-amount of the said specific molecular weight control agent is 0.1-50 mass parts normally with respect to a total of 100 mass parts of monomers, Preferably it is 0.2-16 mass parts, More preferably, it is 0.4. -8 parts by mass. In this case, if the amount of the specific molecular weight control agent used is less than the above range, the control effect of the molecular weight and molecular weight distribution tends to be reduced, whereas if it exceeds the above range, a low molecular weight component may be preferentially generated. is there.

  Moreover, the usage-amount of molecular weight control agents other than the said specific molecular weight control agent is 200 mass parts or less normally with respect to 100 mass parts of specific molecular weight control agents, Preferably it is 40 mass parts or less. In this case, when the use ratio of the other molecular weight control agent exceeds the above range, the intended effect of the present invention may be impaired. Moreover, the usage-amount of a solvent is 50-1,000 mass parts normally with respect to a total of 100 mass parts of monomers, Preferably it is 100-500 mass parts. The polymerization temperature is usually 0 to 150 ° C., preferably 50 to 120 ° C., and the polymerization time is usually 10 minutes to 20 hours, preferably 30 minutes to 6 hours.

  Weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) of a polymer (A) obtained by polymerizing a monomer having a radical polymerizable group and / or a monomer having a cationic polymerizable group ( Mw) is preferably 1,000 to 100,000, more preferably 2,000 to 75,000, and the number average molecular weight (Mn) in terms of polystyrene measured by Mw and gel permeation chromatography (GPC). The ratio, that is, the dispersion ratio (Mw / Mn) is preferably 4.5 or less, more preferably 4.0 or less.

  By using such a polymer (A) having Mw and Mw / Mn, a cured film having high heat resistance and chemical resistance can be formed, and the transparency and surface hardness are high. It is possible to form a protective film excellent in various resistances such as resistance and alkali resistance. Moreover, the resin composition excellent in storage stability can be obtained.

On the other hand, the polymerization relating to the monomer having a hydrolyzed silyl group is carried out by the following method or the like. That is, a monomer having a hydrolyzed silyl group is dissolved in an organic solvent, and an inorganic acid such as hydrochloric acid or an organic acid such as acetic acid, maleic anhydride, and p-toluenesulfonic acid is added to adjust the pH to 1 to 4. Then, an appropriate amount of ion-exchanged water is added, and hydrolysis is performed at 30 to 80 ° C. for 1 to 8 hours to obtain an alkoxysilane condensate. Thereafter, cooling and evaporation are performed to remove ion-exchanged water and alcohol generated by hydrolysis condensation. In this way, the polymer (A) obtained by polymerizing the monomer having a hydrolyzed silyl group is obtained.

  The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the polymer (A) obtained by polymerizing the monomer having a hydrolyzed silyl group is preferably 300 to 5,000, More preferably, the ratio is 400 to 2,000, and the ratio of Mw to polystyrene-reduced number average molecular weight (Mn) measured by gel permeation chromatography (GPC), that is, the dispersion ratio (Mw / Mn) is preferably 1. .8 or less, more preferably 1.6 or less.

  By using such a polymer (A) having Mw and Mw / Mn, a cured film having high heat resistance and chemical resistance can be formed, and the transparency and surface hardness are high. It is possible to form a protective film excellent in various resistances such as resistance and alkali resistance. Moreover, the resin composition excellent in storage stability can be obtained.

1.2. Acid generator (B)
Examples of the acid generator (B) used in the present embodiment include sulfonium salts represented by the following general formula (1). According to such an acid generator (B), it becomes possible to form a protective film with low sublimation properties at a lower temperature (specifically, a temperature of 150 ° C. or lower). That is, in the following general formula (1), when R ¹ is a substituted or unsubstituted aryl group, the stability of the compound itself can be maintained. In addition, when R ² is a substituted or unsubstituted benzyl group, the stability of the compound itself can be ensured and cured at a slightly higher temperature than usual. Furthermore, when R ³ is an alkyl group having 1 to 6 carbon atoms, it can be cured at a lower temperature. By using such an acid generator (B), damage to organic materials such as organic TFTs, liquid crystals, color filters, and organic polymer films is greatly reduced by protective films in the manufacture of devices such as LCDs and CMOS image sensors. In addition, since the protective film can be formed at a low temperature, it is possible to significantly reduce thermal damage to the organic material when forming the protective film.

（上記式（１）中、Ｒ^１は置換もしくは非置換のアリール基、Ｒ^２は置換もしくは非置換のベンジル基、Ｒ^３は炭素数１〜６のアルキル基を表す。Ｘ⁻は非求核性の対アニオンであり、下記式（２）のいずれかを表す。）

(In the above formula (1), R ¹ represents a substituted or unsubstituted aryl group, R ² represents a substituted or unsubstituted benzyl group, and R ³ represents an alkyl group having 1 to 6 carbon atoms. X ⁻ represents a non-nucleophilic group. (It represents any one of the following formula (2).)

（上記式（２）中、Ｒｆはフッ素置換アルキル基であり、ｎは０〜６の整数である。）

(In the above formula (2), Rf is a fluorine-substituted alkyl group, and n is an integer of 0-6.)

In the sulfonium salt represented by the general formula (1), R ¹ represents a substituted or unsubstituted aryl group, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, a hydroxy group, Examples thereof include a hydroxyalkyl group, an alkoxy group, a cycloalkoxy group, an acetoxy group, an alkoxycarbonyl group, an alkoxycarbonylalkoxy group, an alkylcarbonylalkoxy group, an alkenyl group, and an alkenyloxy group. Examples of the alkyl group having 1 to 6 carbon atoms include linear hydrocarbon groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group and n-hexyl group; isopropyl group, sec -Branched hydrocarbon groups such as butyl group and tert-butyl group.

R ² represents a substituted or unsubstituted benzyl group, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an alkenyl group, and an alkylcarbonyl group.

R ³ represents an alkyl group having 1 to 6 carbon atoms, for example, a linear hydrocarbon group such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, or an n-hexyl group; Examples thereof include branched hydrocarbon groups such as isopropyl group, sec-butyl group, and tert-butyl group.

  Specific examples of the sulfonium salt represented by the general formula (1) include benzylmethyl (4-tolyl) sulfonium hexafluorophosphate, benzylmethyl (4-hydroxyphenyl) sulfonium hexafluorophosphate, and benzylmethyl (4-acetoxyphenyl). ) Sulfonium hexafluorophosphate, benzylmethyl (4-methoxycarbonyloxyphenyl) sulfonium hexafluorophosphate, methyl (4-hydroxyphenyl) (2-methylbenzyl) sulfonium hexafluorophosphate, methyl (4-acetoxyphenyl) (2-methyl) And sulfonium hexafluorophosphate such as (benzyl) sulfonium hexafluorophosphate.

  Also, benzylmethyl (4-tolyl) sulfonium tetrakis (pentafluorophenyl) borate, benzylmethyl (4-hydroxyphenyl) sulfonium tetrakis (pentafluorophenyl) borate, benzylmethyl (4-acetoxyphenyl) sulfonium tetrakis (pentafluorophenyl) Borate, benzylmethyl (4-methoxycarbonyloxyphenyl) sulfonium tetrakis (pentafluorophenyl) borate, methyl (4-hydroxyphenyl) (2-methylbenzyl) sulfonium tetrakis (pentafluorophenyl) borate, methyl (4-acetoxyphenyl) (2-methylbenzyl) sulfonium tetrakis (pentafluorophenyl) borate and other sulfonium tetrakis (pentafluorophenyl) Cycloalkenyl), and borate.

  In addition, benzylmethyl (4-tolyl) sulfonium bis (trifluoromethanesulfonyl) imide, benzylmethyl (4-hydroxyphenyl) sulfonium bis (trifluoromethanesulfonyl) imide, benzylmethyl (4-acetoxyphenyl) sulfonium bis (trifluoromethanesulfonyl) Imide, benzylmethyl (4-methoxycarbonyloxyphenyl) sulfonium bis (trifluoromethanesulfonyl) imide, methyl (4-hydroxyphenyl) (2-methylbenzyl) bis (trifluoromethanesulfonyl) imide, methyl (4-acetoxyphenyl) ( And sulfonium bis (trifluoromethanesulfonyl) imide such as 2-methylbenzyl) sulfonium bis (trifluoromethanesulfonyl) imide. .

  Among the acid generators (B) exemplified above, at least one compound selected from the group consisting of a compound represented by the following general formula (3) and a compound represented by the following general formula (4) Is preferred.

（上記式（３）中、Ｒ^４およびＲ^５はそれぞれ独立に、炭素数１〜６の直鎖もしくは分岐鎖状アルキル基を表す。Ｒ^６は置換もしくは非置換のベンジル基を表す。）

(In the above formula (3), R ⁴ and R ⁵ each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms. R ⁶ represents a substituted or unsubstituted benzyl group.)

（上記式（４）中、Ｒ^７は水素原子もしくはアルキルカルボニル基を表す。Ｒ^８は炭素数１〜６の直鎖もしくは分岐鎖状アルキル基を表す。Ｒ^９は置換もしくは非置換のベンジル基を表す。Ｒｆは炭素数１〜４のフッ素置換直鎖状アルキル基である。ｎは０〜６の整数を表す。）

(In the above formula (4), R ⁷ represents a hydrogen atom or an alkylcarbonyl group. R ⁸ represents a linear or branched alkyl group having 1 to 6 carbon atoms. R ⁹ is a substituted or unsubstituted benzyl group. Rf is a fluorine-substituted linear alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 6.)

R ⁴ , R ⁵ and R ⁸ in the above formula (3) and the above formula (4) each represent a linear or branched alkyl group having 1 to 6 carbon atoms. For example, a methyl group, an ethyl group, n Linear hydrocarbon groups such as -propyl group, n-butyl group, n-pentyl group and n-hexyl group; branched hydrocarbon groups such as isopropyl group, sec-butyl group and tert-butyl group. .

R ⁶ and R ⁹ in the above formula (3) and the above formula (4) each represent a substituted or unsubstituted benzyl group, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group. , An alkenyl group, an alkylcarbonyl group, and the like.

  Specific examples of the compound represented by the above formula (3) include benzylmethyl (4-acetoxyphenyl) sulfonium tetrakis (pentafluorophenyl) borate, benzylmethyl (4-methoxycarbonyloxyphenyl) sulfonium tetrakis (pentafluorophenyl). Examples thereof include borate and methyl (4-acetoxyphenyl) (2-methylbenzyl) sulfonium tetrakis (pentafluorophenyl) borate.

  Specific examples of the compound represented by the above formula (4) include benzylmethyl (4-hydroxyphenyl) sulfonium hexafluorophosphate, benzylmethyl (4-acetoxyphenyl) sulfonium hexafluorophosphate, benzylmethyl (4-methoxycarbonyloxy). Sulfonium hexafluorophosphate such as phenyl) sulfonium hexafluorophosphate, methyl (4-hydroxyphenyl) (2-methylbenzyl) sulfonium hexafluorophosphate, methyl (4-acetoxyphenyl) (2-methylbenzyl) sulfonium hexafluorophosphate, etc. Can be mentioned.

  The ratio of the acid generator (B) used is preferably 1 part by mass or more, more preferably 1 part by mass or more and 10 parts by mass or less, and particularly preferably 3 parts by mass or more and 10 parts by mass with respect to 100 parts by mass of the polymer (A). It is below mass parts. By making the use ratio of the acid generator (B) 1 part by mass or more, the coating film forming process is excellent in heat resistance and chemical resistance, and a protective film having low sublimation property is made at a lower temperature (specifically, 150 ° C. or less). It is possible to form at a temperature of When the usage-amount of an acid generator (B) is 1 mass part or less, it does not fully harden | cure in a coating-film formation process, and heat resistance and chemical resistance may be impaired.

1.3. Arbitrary additive component The resin composition according to the present embodiment includes, as necessary, optional additive components other than the polymer (A) and the acid generator (B), as long as the effects of the present invention are not impaired. A polyfunctional compound, a radical polymerization initiator, a curing agent, a surfactant, an adhesion assistant, a curing accelerator and the like can be added.

1.3.1. Polyfunctional compound As the polyfunctional compound that can be added to the resin composition according to the present embodiment, a cationic polymerizable compound and / or a polyfunctional (meth) acrylate compound is used. The cationically polymerizable compound is a compound having two or more epoxy groups in the molecule (excluding the aforementioned polymer (A)). Examples of the compound having two or more epoxy groups in the molecule include a compound having two or more epoxy groups in the molecule or a compound having a 3,4-epoxycyclohexyl group.

  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 ether. Hydrogenated bisphenol AD diglycidyl ether; 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol di Polyglycidyl ethers of polyhydric alcohols such as glycidyl ether; ethylene glycol, propylene glycol, glycerin, etc. Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols; phenol novolac type epoxy resins; cresol novolac type epoxy resins; polyphenol type epoxy resins; Examples include diglycidyl esters of chain dibasic acids; glycidyl esters of higher fatty acids; epoxidized soybean oil, epoxidized linseed oil, and the like.

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 (manufactured by Japan Epoxy Resin Co., Ltd.), etc .; Bisphenol F type epoxy resin, Epicoat 807 (Japan Epoxy Resin Co., Ltd.), etc .; Phenol novolac type epoxy resin, Epicoat 152, 154, 157S65 ( As described above, manufactured by Japan Epoxy Resin Co., Ltd., EPPN 201, 202 (manufactured by Nippon Kayaku Co., Ltd.), etc .; As a cresol novolak type epoxy resin, EOCN102, 103S, 104S, 1020, 1025, 1027 , Nippon Kayaku Co., Ltd.) Coat 180S75 (manufactured by Japan Epoxy Resin Co., Ltd.), etc .; as a polyphenol type epoxy resin, Epicoat 1032H60, XY-4000 (above, manufactured by Japan Epoxy Resin Co., Ltd.), etc .; 177, 179, Araldite CY-182, 192, 184 (above, manufactured by Ciba Specialty Chemicals), ERL-4234, 4299, 4221, 4206 (above, manufactured by UC Corporation), Shodyne 509 (manufactured by Showa Denko KK), Epicron 200, 400 (above, Dainippon Ink Co., Ltd.), Epicoat 871, 872 (above, Japan Epoxy Resin Co., Ltd.), ED-5661, 5562 (Celanese Coating Co., Ltd.) etc .; Aliphatic polyglycidyl a Epolight 100MF as Le (manufactured by Kyoeisha Chemical Co.), Epiol TMP (manufactured by NOF Corporation) and the like.

  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) A Le, ethylenebis (3,4-epoxycyclohexane carboxylate), lactone-modified 3,4-epoxycyclohexylmethyl-3 ', may be mentioned 4'-epoxycyclohexane carboxylate. Of such cationically polymerizable compounds, phenol novolac type epoxy resins and polyphenol type epoxy resins are preferred.

On the other hand, examples of the polyfunctional (meth) acrylate compound include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol (meth) acrylate, and tetraethylene glycol diester. (Meth) acrylate, bisphenoxyethanol full orange acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, triacryloyloxypentaerythritol succinic acid {also known as: 3-acryloyloxy- , 2-bisacryloyloxymethyl-propyl) ester}, diacryloyloxypentaerythritol succinic acid {also known as: 3-acryloyloxy-2-acryloyloxymethyl-propyl) ester}, pentaacryoyloxydipentaerythritol succinic acid { Also known as: [3- (3-acryloyloxy-2,2-bis-acryloyloxymethyl-propyl) -2,2-bis-acryloyloxymethyl-propyl] ester}, tetraaclioyloxydipentaerythritol succinic acid { Another name: [3- (3-acryloyloxy-2,2-bis-acryloyloxymethyl-propyl) -2-acryloyloxymethyl-propyl] ester} and the like. As the commercial product, for example, Aronix M-210, M-240, M-6200, M-309, M-400, M-402, M-405, M-450, M -7100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, HX-220, R-604, TMPTA, DPHA, DPCA-20, DPCA-30 DPCA-60, DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), Biscote 260, 312, 335HP, 295, 300, 360, GPT, 3PA, 4
00 (manufactured by Osaka Organic Industry Co., Ltd.).

  These may be used alone or in combination. Among these polyfunctional (meth) acrylate compounds, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate are preferable.

  The use ratio of the polyfunctional compound is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, with respect to 100 parts by mass of the polymer (A). When the use ratio of the polyfunctional compound is in the above range, a protective film having excellent heat resistance and solvent resistance can be formed.

1.3.2. Radiation-sensitive radical polymerization initiator A radiation-sensitive resin composition can be obtained by adding a radical polymerization initiator to the resin composition according to the present embodiment. In particular, when the polymer (A) is a polymer having a hydrolyzed silyl group, it is preferable to add a radical polymerization initiator to obtain a radiation-sensitive resin composition. By using a radiation sensitive resin composition, a fine and elaborate pattern can be easily formed.

  The “radiation” of the “radiation-sensitive resin composition” in the present specification is a concept including visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams and the like.

  As the radiation-sensitive radical polymerization initiator, for example, an O-acyloxime compound, an acetophenone compound, a biimidazole compound, a benzophenone compound, or the like can be used.

  Specific examples of the O-acyloxime compound include 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), ethanone-1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like.

Among these, preferable O-acyloxime compounds include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], and ethanone-1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) or ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime). These O
-An acyl oxime compound can be used individually or in mixture of 2 or more types.

  Examples of the acetophenone compound include an α-aminoketone compound and an α-hydroxyketone compound.

  Specific examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and the like can be mentioned.

  Specific examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane-1- ON, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone and the like.

Of these acetophenone compounds, α-aminoketone compounds are preferred, such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one or 2-dimethylamino-2- (4-methylbenzyl). ) -1- (4-morpholin-4-yl-phenyl) -butan-1-one is particularly preferred.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 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, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 Examples include '-biimidazole.

  Among these biimidazole compounds, 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 or 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5 '-Tetraphenyl-1,2'-biimidazole is preferred, especially 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole Is preferred.

  The use ratio of the radiation sensitive radical polymerization initiator is preferably 1 to 40 parts by mass, more preferably 3 to 30 parts by mass with respect to 100 parts by mass of the polymer (A). When the proportion of the radical polymerization initiator used is in the above range, it effectively prevents contamination of a baking furnace, photomask, etc. due to sublimation of the radical polymerization initiator, and has a high sensitivity and excellent adhesion. Can be formed.

1.3.3. Curing Agent A curing agent is added to improve the heat resistance and hardness of the protective film to be formed. Examples of the curing agent include a polymer of a polymerizable unsaturated compound having an acid anhydride group and an olefinically unsaturated compound (excluding the polymer (A)), or a polyvalent carboxylic acid anhydride.

Examples of the polymerizable unsaturated compound having an acid anhydride group include itaconic anhydride, citraconic anhydride, maleic anhydride, and cis 1,2,3,4-tetrahydrophthalic anhydride.

  Examples of the olefinically unsaturated compound include styrene, p-methylstyrene, p-methoxystyrene, methyl methacrylate, t-butyl methacrylate, and tricyclo [5.2.1.02,6] decane-8 methacrylate. -Yl, 2-methylcyclohexyl acrylate, phenylmaleimide, cyclohexyl and the like.

  The copolymerization ratio of the polymerizable unsaturated compound having an acid anhydride group in 100 parts by mass of the copolymer of the polymerizable unsaturated compound having an acid anhydride group and the olefinically unsaturated compound is preferably 1 to 80 mass. Parts, more preferably 10 to 60 parts by mass. By using such a copolymer, a protective film with lower sublimation property can be obtained.

  Preferable examples of the copolymer of the polymerizable unsaturated compound having an acid anhydride group and the olefinically unsaturated compound include maleic anhydride copolymer / styrene, citraconic anhydride / tricyclomethacrylate [5.2.1]. .02,6] decan-8-yl copolymer and the like.

  The polystyrene-converted weight average molecular weight of the copolymer of the polymerizable unsaturated compound having an acid anhydride group and the olefinically unsaturated compound is preferably 500 to 50,000, more preferably 500 to 10,000. is there. By using a copolymer having such a molecular weight range, a protective film having a lower sublimation property can be obtained.

  Examples of the polycarboxylic acid anhydride include itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbanilic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and hymic anhydride. Aliphatic dicarboxylic anhydrides such as acids; alicyclic polycarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride and cyclopentanetetracarboxylic dianhydride; phthalic anhydride And aromatic polyvalent carboxylic anhydrides such as pyromellitic anhydride, trimellitic anhydride, and benzophenone tetracarboxylic anhydride; and ester group-containing acid anhydrides such as ethylene glycol bistrimellitic anhydride and glycerin tris anhydrous trimellitate. . Of these, aromatic polycarboxylic anhydrides, particularly trimellitic anhydride and hexahydrophthalic anhydride are preferred in that a cured film having high heat resistance can be obtained.

  The use ratio of the curing agent is preferably 40 parts by mass or less, more preferably 30 parts by mass or less with respect to 100 parts by mass of the polymer (A). When the use ratio of the curing agent is 30 parts by mass or less, the storage stability of the resin composition is good, and a protective film excellent in heat resistance and solvent resistance can be formed.

1.3.4. Surfactant A surfactant is added to improve the applicability of the composition. Examples of such surfactants include fluorine-based surfactants and silicone-based surfactants.

  Examples of commercially available fluorosurfactants include BM-1000 and BM-1100 (manufactured by BM CHIMID); Megafuck F142D, Megafuck F172, Megafuck F173, Megafuck F183, Megafuck R08- MH (above, Dainippon Ink & Chemicals, Inc.); Fluorard FC-135, Fluorard FC-170C, Fluorard FC-430, Fluorard FC-431 (above, Sumitomo 3M Ltd.); 251, 222F, FTX-218 (manufactured by Neos Co., Ltd.) and the like.

  Examples of the silicone surfactant include SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (above, Toray Dow Corning Silicone Co., Ltd. KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); Ftop DF301, Ftop DF303, Ftop DF352 (above, Shin-Akita Kasei Co., Ltd.) and the like.

  Furthermore, as a commercial item of surfactants other than those described above, Polyflow No. 1 which is a (meth) acrylic acid copolymer. 57 and polyflow no. 90 (manufactured by Kyoeisha Chemical Co., Ltd.).

  The use ratio of the surfactant is preferably 5 parts by mass or less, more preferably 2 parts by mass or less, with respect to 100 parts by mass of the polymer (A).

1.3.5. Adhesion aid An adhesion aid is added to improve the adhesion between the protective film to be formed and the substrate. As such an adhesion assistant, for example, a silane coupling agent having a reactive group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, or an epoxy group is preferable.

  Specific examples of the adhesion assistant include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxy. Examples thereof include silane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

  The use ratio of the adhesion assistant is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, with respect to 100 parts by mass of the polymer (A).

1.3.6. Curing accelerator The curing accelerator includes 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 2,4-diamino-6- [2'-methylimidazolyl- (1 ' )]-Ethyl-S-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]-ethyl-S-triazine, 2,4-diamino-6- [2'-ethyl -4'-methylimidazolylundecylimidazolyl- (1 ')]-ethyl-S-triazine, 2-phenyl-4,5-dihydroxymethylimidazole and the like.

  The use ratio of the curing accelerator is preferably 0.0001 to 10 parts by mass, preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the polymer (A) from the viewpoint of heat resistance and storage stability. Part.

1.4. Solvent The resin composition according to the present embodiment 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.

  Examples of such a solvent include propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, and ketone.

Examples of the propylene glycol alkyl ether acetate include propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate and the like. Examples of the propylene glycol alkyl ether propionate include propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate and the like. Examples of the ketone include cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl isoamyl ketone, and the like.

  Among these, propylene glycol alkyl acetate and propylene glycol alkyl ether propionate are preferable, and propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, methyl-3-methoxypropionate and the like are more preferable.

  As the use ratio of the solvent, the total solid content in the resin composition according to the present embodiment (the amount obtained by removing the amount of the solvent from the total amount of the composition including the solvent) is preferably 1 to 50% by mass More preferably, it is the range which becomes 5-40 mass%.

  A high boiling point solvent can be used in combination with the above solvent. Examples of the high boiling point solvent that can be used together here include N-methylpyrrolidone and γ-butyrolactone.

  The amount of the high-boiling solvent used in combination is preferably 90% by mass or less, more preferably 80% by mass or less, when the total amount of the solvent is 100% by mass.

  The resin composition prepared as described above is preferably filtered after using a filter having a pore size of 0.2 μm or less, more preferably a pore size of 0.05 μm or less, and then used.

2. Protective film A protective film according to an embodiment of the present invention is a protective film for a liquid crystal display element or a solid-state imaging element, and a coating film formed using the curable resin composition is 150 ° C or lower. It is obtained by heat treatment at a temperature.

  Hereinafter, a liquid crystal display element and a solid-state image sensor provided with a protective film formed using the resin composition according to the present embodiment will be specifically described.

2.1. Liquid crystal display element The liquid crystal display device according to the present embodiment is formed using the above resin composition between a transparent substrate, a color filter formed on the transparent substrate, and the color filter and the transparent electrode. And a protective film. FIG. 1 is a schematic cross-sectional view showing a liquid crystal display device according to the present embodiment. As shown in FIG. 1, the liquid crystal display device 100 includes a transparent substrate 12 provided with a polarizing plate 10, a transparent electrode 18 a, a transparent insulating film 24, and a TFT element 28, and a back surface provided with an alignment film 20 thereon. A color filter 14, a protective film 16 and a transparent electrode 18b are provided on the substrate and the transparent substrate 12 provided with the polarizing plate 10, an alignment film 20 is provided thereon, and a front substrate facing the back substrate; A sealing material 30 provided between the substrates, and a liquid crystal layer 22 sealed in a sealing region surrounded by the front substrate, the rear substrate, and the sealing material 30 are provided.

The material of the transparent substrate 12 is not particularly limited as long as it is substantially transparent, and glass, ceramics, plastics, and the like can be used. Examples of plastic substrates include cellulose derivatives such as cellulose, triacetyl cellulose, diacetyl cellulose, polycycloolefin derivatives, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polypropylene, and polyethylene. Polyolefin, polycarbonate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyamide, polyimide, polyimide amide, polystyrene, polyacrylate, polymethyl methacrylate, polyethersulfone, polyarylate, and glass fiber-epoxy resin Inorganic-organic composite materials such as glass fiber and acrylic resin can be used.

  In the back substrate, the TFT element 28 and the transparent electrode 18a are provided on the transparent substrate 12 on which the polarizing plate 10 is provided. These are manufactured by a normal array process. A transparent insulating film 24 and an alignment film 20 are provided thereon to obtain a back substrate. The transparent insulating film 24 is a film for protecting the TFT element 28. Usually, a nitride film (SiNx), an oxide film (SiOx) or the like is formed by a chemical vapor deposition (CVD) technique or the like.

  The alignment film 20 is a film having a function of aligning liquid crystals, and a polymer material such as polyimide is usually used. As the coating solution, an alignment agent solution composed of a polymer material and a solvent is used. Since the alignment film 20 may hinder the adhesive force with the sealing material, a pattern is applied in the sealing region. For the application, a printing method such as a flexographic printing method or a droplet discharge method such as an ink jet is used. The applied alignment agent solution is crosslinked and cured by baking after the solvent is evaporated by temporary drying. Thereafter, an alignment process is performed to provide an alignment function. A rubbing method is usually used for the alignment treatment. The polymer film formed as described above is rubbed in one direction using a rubbing cloth made of fibers such as rayon, thereby producing liquid crystal alignment ability.

  On the other hand, the front substrate is provided with the color filter 14, the protective film 16, the transparent electrode 18 b, and the alignment film 20 on the transparent substrate 12 on which the polarizing plate 10 is provided. The color filter 14 is produced by a pigment dispersion method, an electrodeposition method, a printing method, a dyeing method, or the like. Taking the pigment dispersion method as an example, a color resin solution in which a pigment (for example, red) is uniformly dispersed is applied onto the transparent substrate 12, and after baking and curing, a photoresist is applied thereon and prebaked. After the photoresist is exposed through a mask pattern, development is performed and patterning is performed. Thereafter, the photoresist layer is peeled off and baked again to complete the (red) color filter 14. There is no particular limitation on the order of colors to be produced. Similarly, the green color filter 14 and the blue color filter 14 are formed.

  Here, the protective film 16 is generally classified into two types, that is, a protective film formed from a non-radiation sensitive resin composition and a protective film formed from a radiation sensitive resin composition. Explained.

  When the protective film 16 is a protective film formed from a non-radiation sensitive resin composition, first, the above-described resin composition is applied to the surface of the transparent substrate 12 to form a coating film. As a coating method, for example, an appropriate method such as a spray method, a roll coating method, a spin coating method, a bar coating method, an ink jet method, or the like can be adopted. Can be suitably used.

Next, the coating film is heat-treated at a temperature of 150 ° C. or lower. 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 treatment temperature is preferably 150 ° C. or lower, more preferably 130 ° C. or lower, and particularly preferably 120 ° C. or lower. By using the resin composition described above, it is possible to form a protective film with low sublimation properties at a low temperature of 150 ° C. or lower. This makes it possible to significantly reduce damage to organic materials such as organic TFTs, liquid crystals, color filters, and organic polymer films when the protective film 16 is formed in the production of a liquid crystal display element. As the heating time, a processing time of 1 to 30 minutes can be employed when using a hot plate, and 30 to 90 minutes when using an oven.

  The thickness of the protective film 16 is preferably 0.15 to 8.5 μm, more preferably 0.15 to 6.5 μm, and particularly preferably 0.15 to 4.5 μm. In addition, the thickness of a protective film here should be understood as the thickness after solvent removal.

  The protective film 16 formed as described above satisfies general required characteristics as a protective film such as transparency, hardness, adhesion, and chemical resistance, and is excellent in sublimation.

  Specifically, the sublimation property of the protective film according to the present embodiment is preferably 1.0 μg or less, more preferably 0.9 μg or less, and more preferably 0.8 μg or less. In addition, the sublimation property measuring method shall be based on the method ((7) Evaluation of the sublimate volatilization amount at the time of forming the protective film) described in Examples described later.

  The protective film according to this embodiment is suitable as a protective film for a liquid crystal display element having low sublimation property even in a state where heat is applied.

On the other hand, when the protective film 16 is a protective film formed from a radiation sensitive resin composition, the protective film can be formed through the following steps (1) to (4).
(1) The process of forming the coating film of the above-mentioned resin composition on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) a step of developing the coating film irradiated with radiation in step (2), and (4) a step of heating the coating film developed in step (3).

  In the step (1), after the above resin composition is applied on the substrate, the solvent is removed by preferably heating (pre-baking) the coating surface to form a coating film.

  The method for applying the resin composition is not particularly limited. For example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, or a bar coating method can be employed. Among these coating methods, a spin coating method or a slit die coating method is particularly preferable. Prebaking conditions vary depending on the type of each component, the blending ratio, and the like, but can be preferably set at 50 to 100 ° C. for about 1 to 10 minutes.

  In step (2), at least a part of the coating film formed in step (1) is exposed. Usually, when exposing a part of coating film, it exposes through the photomask which has a predetermined pattern. As radiation used for exposure, visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like can be used, for example. Among these radiations, radiation having a wavelength in the range of 190 to 450 nm is preferable, and radiation containing ultraviolet light of 365 nm is particularly preferable.

The exposure amount in this step is preferably 10 to 1,000 mJ / cm ² , more preferably 20 to 700 mJ, as a value obtained by measuring the intensity of radiation at a wavelength of 365 nm with an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.). / Cm ² .

In step (3), the coated film after exposure is developed to remove unnecessary portions (non-irradiated portions of radiation) and form a predetermined pattern. Thus, since the above-mentioned resin composition removes the non-irradiated part of the radiation, it is a negative radiation sensitive composition. The developer used in the development step is preferably an aqueous solution of an alkali (basic compound). Examples of alkalis include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. be able to.

  In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to such an alkaline aqueous solution. As a developing method, for example, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time varies depending on the composition of the resin composition, but is preferably about 10 to 180 seconds. Subsequent to such development processing, for example, washing with running water can be performed for 30 to 90 seconds to form a desired pattern.

  In step (4), the patterned thin film is heated by using a heating device such as a hot plate or an oven, thereby promoting the condensation reaction of the polymer (A) having a hydrolyzed silyl group and reliably curing the cured product. Can be obtained. The heating temperature is preferably 150 ° C. or lower, more preferably 130 ° C. or lower, and particularly preferably 120 ° C. or lower. Although heating time changes with kinds of heating apparatus, for example, when performing a heating process on a hotplate, it can be set to 30 to 90 minutes when performing a heating process in an oven. The step baking method etc. which perform a heating process 2 times or more can also be used. In this manner, a patterned thin film corresponding to the target protective film or interlayer insulating film can be formed on the surface of the substrate.

  The thickness of the protective film 16 thus formed is preferably 0.15 to 8.5 μm, more preferably 0.15 to 6.5 μm.

  The protective film formed from the above resin composition has excellent properties such as surface hardness, transparency, heat-resistant transparency, and crack resistance as well as high resolution, as will be apparent from the following examples. Therefore, a highly accurate pattern having the property can be formed. Therefore, the said protective film is used suitably for display elements, such as a touchscreen of a liquid crystal display element.

  Next, the transparent electrode 18 b is provided on the protective film 16. The transparent electrode 18b preferably has a high transmittance and preferably has a low electrical resistance. The transparent electrode 18b is formed of an oxide film such as ITO by a sputtering method or the like. The alignment film 20 is the same as the alignment film described above.

  Next, the back substrate is bonded to the front substrate on which the sealing material 30 is applied and the liquid crystal is dropped. Specifically, the front substrate and the rear substrate are adsorbed on a stage having a mechanism for adsorbing a substrate such as an electrostatic chuck, and the alignment film 20 on the front substrate and the alignment film 20 on the rear substrate face each other. It arrange | positions in the position (distance) where the sealing material 30 and another board | substrate do not contact | connect. In this state, the system is depressurized. After the decompression is completed, the positions of both substrates are adjusted while confirming the bonding position between the front substrate and the rear substrate (alignment operation). When the adjustment of the bonding position is completed, the substrate is brought close to a position where the sealing material on the front substrate is in contact with the rear substrate. In this state, the system is filled with an inert gas, and the pressure is gradually returned to normal pressure while releasing the reduced pressure. At this time, the front substrate and the rear substrate are bonded together by atmospheric pressure, and a cell gap is formed at the height position of the column spacer. In this state, the sealing material 30 is irradiated with ultraviolet rays to cure the sealing material, thereby forming a liquid crystal cell. Thereafter, a heating step is added in some cases to promote curing of the sealing material. A heating process is often added to enhance the adhesive strength of the sealing material and improve the reliability of electrical characteristics.

2.2. Solid-state imaging device The solid-state imaging device according to the present embodiment includes a pixel electrode formed on a semiconductor substrate on which a signal readout circuit is formed, an organic photoelectric conversion layer formed on the pixel electrode, and the organic photoelectric conversion. It includes a counter electrode formed on the layer and the above-described protective film formed on the counter electrode. Hereinafter, a method for manufacturing a solid-state imaging device according to the present embodiment will be described with reference to the drawings.

  2A to 2C are schematic cross-sectional views illustrating the method of manufacturing the solid-state imaging device according to the present embodiment in the order of steps. 3A and 3B are schematic cross-sectional views illustrating the method of manufacturing the solid-state imaging device according to the present embodiment in the order of steps, and illustrate the subsequent step of FIG. FIG. 4 is a schematic cross-sectional view showing the solid-state imaging device according to the present embodiment.

  In the method of manufacturing the solid-state imaging device 200 according to the present embodiment, first, as shown in FIG. 2A, the first circuit is formed on the substrate 112 on which the signal readout circuit 140 and the counter electrode voltage supply unit 142 are formed. A circuit board 111 (CMOS substrate) on which an insulating layer 114 provided with one connecting portion 144, a second connecting portion 146, and a wiring layer 148 is prepared. In this case, as described above, the first connecting portion 144 and the signal readout circuit 140 are connected, and the second connecting portion 146 and the counter electrode voltage supply portion 142 are connected.

  A titanium oxynitride (TiNxOx) film is formed on the surface 114a of the insulating layer 114 of the circuit board 111 by using, for example, a sputtering method. Next, a titanium oxynitride film is patterned in the pattern of the pixel electrode 116 to form the pixel electrode 116.

  Next, the electron blocking layer 152 is transferred to a film formation chamber (not shown) through a predetermined transfer path, and as shown in FIG. 2B, all pixels except the second connection portion 146 are used. An electron blocking material 152 is formed by depositing an electron blocking material through a metal mask so as to cover the electrode 116 under a predetermined vacuum using, for example, a vapor deposition method. As the electron blocking material, for example, a carbazole derivative, more preferably a bifluorene derivative is used.

  Next, the organic photoelectric conversion layer 150 is transferred to a film formation chamber (not shown) of the organic photoelectric conversion layer 150 through a predetermined transfer path, and the organic photoelectric conversion layer 150 is formed on the surface 152a of the electron blocking layer 152 as shown in FIG. Is formed under a predetermined vacuum using a vapor deposition method, for example, through a metal mask. As the photoelectric conversion material, for example, a p-type organic semiconductor material and fullerene or a fullerene derivative are used. Thereby, the organic photoelectric conversion layer 150 is formed, and the photoelectric conversion unit 118 is formed.

  Next, after transporting to a deposition chamber (not shown) of the counter electrode 120 through a predetermined transport path, as shown in FIG. 3A, the photoelectric conversion unit 118 is covered, and the second connection unit 146 is covered. The counter electrode 120 is formed through a metal mask with a pattern formed thereon, for example, under a predetermined vacuum using a sputtering method. When forming the counter electrode 120, for example, ITO is used as a transparent conductive oxide.

  Next, the sealing layer 122 is transferred to a film formation chamber (not shown) through a predetermined transfer path, and as shown in FIG. 3B, the surface 114a of the insulating layer 114 is covered so as to cover the counter electrode 120. Further, a stacked film having a three-layer structure of a silicon oxynitride film, an alumina film, and a silicon oxynitride film is formed as the sealing layer 122. In this case, for example, the silicon oxynitride film is formed using a sputtering method or a CVD method, and the alumina film is formed using an ALCVD method under a predetermined vacuum. The sealing layer 122 may be a single layer film.

  Next, the color filter 126, the partition wall 128, and the light shielding layer 129 are formed on the surface 122a of the sealing layer 122 by using, for example, a photolithography method. As the color filter 126, the partition wall 128, and the light shielding layer 129, known ones used for organic solid-state imaging devices are used. The formation process of the color filter 126, the partition wall 128, and the light shielding layer 129 may be under a predetermined vacuum or under a non-vacuum.

  Next, the protective film 130 is formed so as to cover the color filter 126, the partition wall 128, and the light shielding layer 129. The protective film 130 is formed using the above resin composition. The formation process of the protective film 130 may be under a predetermined vacuum or non-vacuum. In this way, the solid-state imaging device 200 according to the present embodiment can be formed. Note that a specific method of forming the protective film 130 is the same as that of the protective film 16 of the liquid crystal display device 100 described above, and thus description thereof is omitted.

  The protective film formed as described above satisfies general required characteristics as a protective film such as transparency, hardness, adhesion, and chemical resistance, and is excellent in sublimation.

  Specifically, the sublimation property of the protective film according to this embodiment is preferably 1.0 μg or less, more preferably 0.9 μg or less. In addition, the sublimation property measuring method shall be based on the method ((7) Evaluation of the sublimate volatilization amount at the time of forming the protective film) described in Examples described later.

  The protective film according to the present embodiment is suitable as a protective film for a CMOS image sensor that is excellent in performance with low sublimation property even in a heated state.

3. EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. “Part” and “%” in Examples and Comparative Examples are based on mass unless otherwise specified.

3.1. Production of polymer (A) 3.1.1. Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 0.8 parts by mass of 2,2′-azobis-isobutyronitrile and 200 parts by mass of methyl-3-methoxypropionate. Subsequently, 80 parts by mass of glycidyl methacrylate and 20 parts by mass of styrene were charged, and after nitrogen substitution, stirring was started gently. The solution temperature was raised to 95 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-1). The solid content concentration of the obtained polymer solution was 31.8% by mass. This polymer had Mw = 27,000 and Mw / Mn = 1.9.

3.1.2. Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 2 parts by mass of 2,2′-azobis-isobutyronitrile and 200 parts by mass of methyl-3-methoxypropionate. Subsequently, 79 parts by mass of glycidyl methacrylate, 1 part by mass of methyl methacrylate, and 20 parts by mass of styrene were charged, and after the atmosphere was replaced with nitrogen, stirring was started gently. The solution temperature was raised to 95 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-2). The solid content concentration of the obtained polymer solution was 30.5% by mass. This polymer had Mw = 10,000 and Mw / Mn = 1.8.

3.1.3. Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 0.6 parts by mass of 2,2′-azobis-isobutyronitrile and 200 parts by mass of methyl-3-methoxypropionate. Subsequently, 50 parts by mass of dicyclopentanyl methacrylate and 50 parts by mass of glycidyl methacrylate were charged, and after substituting with nitrogen, stirring was started gently. The solution temperature was raised to 95 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-3). The solid content concentration of the obtained polymer solution was 38.7% by mass. This polymer had Mw = 74,000 and Mw / Mn = 4.0.

3.1.4. Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 0.6 parts by mass of 2,2′-azobis-isobutyronitrile and 200 parts by mass of methyl-3-methoxypropionate. Subsequently, 38 parts by mass of t-butyl methacrylate and 62 parts by mass of glycidyl methacrylate were charged, and after substituting with nitrogen, stirring was started gently. The solution temperature was raised to 95 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-4). The solid content concentration of the obtained polymer solution was 31.8% by mass. This polymer had Mw = 63,000 and Mw / Mn = 3.3.

3.1.5. Synthesis example 5
In a vessel equipped with a stirrer, 24 parts by mass of propylene glycol monomethyl ether was charged, followed by 25 parts by mass of methyltrimethoxysilane (MTMS) and 75 parts by mass of p-trimethoxysilylstyrene (StTMS). Heated to 60 ° C. After the solution temperature reached 60 ° C., 0.2 part by weight of maleic anhydride and 19 parts by weight of ion-exchanged water were charged, heated to 75 ° C. and held for 2 hours. After cooling to 45 ° C., evaporation was performed to remove ion-exchanged water and methanol generated by hydrolysis condensation. Thus, polysiloxane (A-5) was obtained. Polysiloxane (A-5) had a solid content concentration of 40% by mass, a weight average molecular weight (Mw) of 610, and a dispersity (Mw / Mn) of 1.1.

3.1.6. Synthesis Example 6
In a vessel equipped with a stirrer, 24 parts by mass of propylene glycol monomethyl ether was charged, followed by 70 parts by mass of methyltrimethoxysilane (MTMS) and 30 parts by mass of p-trimethoxysilylstyrene (StTMS). Heated to 60 ° C. After the solution temperature reached 60 ° C., 0.2 part by weight of maleic anhydride and 19 parts by weight of ion-exchanged water were charged, heated to 75 ° C. and held for 2 hours. After cooling to 45 ° C., evaporation was performed to remove ion-exchanged water and methanol generated by hydrolysis condensation. Thus, polysiloxane (A-6) was obtained. Polysiloxane (A-6) had a solid content concentration of 40% by mass, a weight average molecular weight (Mw) of 900, and a dispersity (Mw / Mn) of 1.3.

3.2. Example 1 (Preparation example of non-radiation sensitive protective film)
3.2.1. Preparation of Resin Composition Acid generator for the solution containing polymer (A-1) obtained in Synthesis Example 1 above (amount corresponding to 100 parts by mass (solid content) of polymer (A-1)). As (B), 1 part by mass of methyl (4-acetoxyphenyl) (2-methylbenzyl) sulfonium tetrakis (pentafluorophenyl) borate (indicated as “B-1” in Table 1) is added, and the solid content concentration is 12 masses. Then, methyl-3-methoxypropionate was added so as to be%, and then filtered through a Millipore filter having a pore size of 0.5 μm to prepare a resin composition.

3.2.2. Production of Non-Radiosensitive Protective Film After applying the resin composition obtained above using a spin coater onto a silicon wafer or glass substrate, the film was baked on a hot plate at 140 ° C. for 5 minutes to obtain a film thickness of 4 A protective film of 0.0 μm was formed.

3.2.3. Evaluation of Non-Radiosensitive Protective Film (1) Transparency Evaluation Regarding the glass substrate having the non-radiosensitive protective film obtained as described above, a spectrophotometer (manufactured by Hitachi, Ltd., model “150-20”). 400-800 nm transmittance was measured using a "type double beam"). Table 1 shows the minimum transmittance of 400 to 800 nm. When this value is 95% or more, it can be judged that the transparency of the protective film is good.

(2) Measurement of pencil hardness About the glass substrate which has the non-radiation sensitive protective film obtained by making it above, "JIS"
The surface hardness of the non-radiation sensitive protective film was measured according to “K-5400-1990 8.4.1 Pencil Scratch Test”. This value is shown in Table 1. When this value is 4H or higher, it can be judged that the surface hardness is good.

(3) Evaluation of adhesion After performing a pressure cooker test (120 ° C., humidity 100%, 4 hours) on the glass substrate having the non-radiation sensitive protective film obtained as described above, “JIS K- According to “5400-1990 8.5.3 Adhesive cross-cut tape method”, the adhesion (adhesion to SiO ₂ ) of the non-radiation sensitive protective film was evaluated. Table 1 shows the number of remaining grids out of 100 grids.

(4) Evaluation of cracks Whether or not the glass substrate having the non-radiosensitive protective film obtained as described above is left to stand at 23 ° C. for 24 hours and cracks are generated on the surface of the non-radiosensitive protective film. These were evaluated using a laser microscope (VK-8500 manufactured by Keyence) according to the following criteria.
<Criteria>
A: There is no crack at all.
○: There are 1 to 3 cracks.
Δ: There are 4 to 10 cracks.
X: There are 10 or more cracks.

(5) Evaluation of sublimate volatilization amount at the time of protective film formation The resin composition was apply | coated with the spin coater on the silicon substrate, respectively, and the coating film with a coating film thickness of 1.0 micrometer was formed. About this coating film, head space gas chromatography / mass spectrometry (head space sampler: manufactured by Nippon Analytical Industries, model name “JHS-100A”; gas chromatography / mass spectrometer: manufactured by Nippon Analytical Industries, Ltd., “ JEOL JMS-AX505W type mass spectrometer "). The purge area was set to 100 ° C./10 min, and the peak area A related to generation of volatile components in the cured film was determined. Using n-octane (specific gravity: 0.701; injection amount: 0.02 μL) as a standard substance, using the peak area as a reference, the sublimate volatilization amount in terms of n-octane is calculated from the following formula, and the results are shown It was shown in 1.
Sublimate volatilization amount (μg) = A × (amount of n-octane (μg)) / (peak area of n-octane)
When the sublimate volatilization amount is 1.0 μg or less, it can be said that the sublimate from the protective film is small. If the amount of sublimation is more than 1.0 μg, it may be a difficult material to use because it causes inconveniences in terms of contamination in the baking furnace and photomask during exposure.

(6) Evaluation of chemical resistance The silicon substrate having the non-radiation sensitive protective film obtained as described above was immersed in the chemicals shown in Table 1 for 5 minutes at room temperature and then sufficiently spin-dried on a spin coater. The film thickness after the measurement was measured using an optical interference type film thickness measuring device (manufactured by Dainippon Screen, model “VM-2200”). The chemical resistance was evaluated by the residual rate of the non-radiation sensitive protective film calculated based on the following formula. The values are shown in Table 1.
Chemical resistance = ((film thickness after chemical immersion) / (film thickness before chemical immersion)) × 100 (%)

3.3. Examples 2-14 and Comparative Examples 1-4
A resin composition was prepared in the same manner as in Example 1 except that the type and amount of each component of the resin composition were as described in Table 1. Further, a non-radiation sensitive protective film was formed and evaluated in the same manner as in Example 1 except that the resin composition thus obtained was used. The results are shown in Table 1.

3.4. Example 15 (Example of producing radiation-sensitive protective film)
3.4.1. Preparation of Resin Composition Acid generator (B) is added to a solution containing polysiloxane (A-5) obtained in Synthesis Example 5 (amount corresponding to 100 parts by mass (solid content) of polysiloxane (A-5)). As methyl (4-acetoxyphenyl) (2-methylbenzyl) sulfonium tetrakis (pentafluorophenyl) borate 5 parts by weight, as a radiation sensitive radical polymerization initiator (C) 1,2-octanedione-1- [4- ( Phenylthio) phenyl] -2- (o-benzoyloxime) 10 parts by mass, dipentaerythritol hexa (meth) acrylate (component (D)) 10 parts by mass, fluorine-containing nonionic surfactant as nonionic surfactant (E) 0.1 parts by mass of an agent (manufactured by Neos Co., Ltd., FX-218) is mixed to make the radiation-sensitive polysiloxane composition a solid content concentration of 12% by mass. After addition of sea urchin propylene glycol monomethyl ether and then filtered through Millipore filter having a pore size of 0.5μm resin composition was prepared.

3.4.2. Preparation of radiation-sensitive protective film The radiation-sensitive polysiloxane composition obtained above was applied to a Si substrate using a clean track made by Tokyo Electron, and then pre-baked on a hot plate at 50 ° C. for 1 minute. Formed. Subsequently, using the Nikon i line | wire stepper, the obtained coating film was exposed with the exposure amount of 100-1,000mJ / cm < ² > through the mask for pattern formation. Subsequently, development was performed at 25 ° C. for 60 seconds with a 2.38 mass% tetramethylammonium hydroxide aqueous solution, followed by washing with pure water for 1 minute and further heating in an oven at 230 ° C. for 2 minutes. A polysiloxane pattern having a thickness of 5 μm was formed.

3.4.3. Evaluation of Radiation Sensitive Protective Film Transparency, pencil hardness, adhesion, cracks, sublimate volatilization amount when forming the protective film, and chemical resistance were carried out in the same manner as the evaluation of the non-radiosensitive protective film. For the radiation-sensitive protective film, in addition to these evaluations, “patterning property” and “development residue” were also evaluated.

(1) Evaluation of patterning property About the board | substrate which carried out the exposure development processing above, the patterning property was confirmed using length measurement SEM (Hitachi S-9260) with the following criteria.
<Criteria>
(Double-circle): The pattern of less than 5 micromLS is resolved satisfactorily.
○: A pattern of 5 μmLS or more is resolved well.
Δ: The pattern is resolved, but the shape is not good.
X: The pattern is not resolved.

(2) Evaluation of developability of unexposed area About the substrate exposed and developed as described above, the developability of a predetermined unexposed area was confirmed visually and with a laser microscope (VK-8500 manufactured by Keyence) according to the following criteria.
<Criteria>
○: The unexposed area is completely developed and no coating film component is observed.
X: A coating film component is observed on an unexposed part.

3.5. Examples 15-20 and Comparative Examples 5-8
A resin composition was prepared in the same manner as in Example 15 except that the type and amount of each component of the resin composition were as described in Table 2. Moreover, the radiation sensitive protective film was formed and evaluated similarly to Example 15 except having used the resin composition obtained in this way. The results are shown in Table 2.

3.6. Evaluation results Table 1 shows the compositions of the resin compositions used in Examples 1 to 14 and Comparative Examples 1 to 4, and the results of each evaluation test. In Table 2, the composition of the resin composition used in Examples 15-20 and Comparative Examples 5-8 and the result of each evaluation test are shown.

In addition, the abbreviation of each component in Table 1 and Table 2 represents the following, respectively.
<Polymer (A)>
A-1: Polymer obtained in Synthesis Example 1 A-2: Polymer obtained in Synthesis Example 2 A-3: Polymer obtained in Synthesis Example 3 A-4: Polymer obtained in Synthesis Example 4 A-5: Polymer obtained in Synthesis Example 5 A-6 Polymer obtained in Synthesis Example 6 <Acid generator (B)>
B-1: Methyl (4-acetoxyphenyl) (2-methylbenzyl) sulfonium tetrakis (pentafluorophenyl) borate B-2: Benzylmethyl (4-acetoxyphenyl) sulfonium tetrakis (pentafluorophenyl) borate 3: benzylmethyl (4-hydroxyphenyl) sulfonium hexafluorophosphate B-4: benzylmethyl (4-hydroxyphenyl) sulfonium tetrakis (pentafluorophenyl) borate B-5: dimethyl (4-hydroxyphenyl) sulfonium hexafluoro Phosphate B-6: Benzylmethyl (4-hydroxyphenyl) sulfonium trifluoromethanesulfonate B-7: Dimethyl (4-acetoxyphenyl) sulfonium hexafluorophosphate Fate B-8: Dimethyl (4-hydroxyphenyl) sulfonium tetrakis (pentafluorophenyl) borate The acid generators are B-1, B-2, B-3, B- in order of decreasing activation temperature. 4, B-5, B-6, B-7, and B-8.
<Radical polymerization initiator>
C-1: 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime)
<Polyfunctional compound (D)>
D-1: Dipentaerythritol hexa (meth) acrylate <nonionic surfactant (E)>
E-1: Fluorine-containing nonionic surfactant (manufactured by Neos Co., Ltd., FX-218)
<Chemicals used for chemical resistance>
* TMAH: Tetramethylammonium hydroxide * PGMEA: Propylene glycol monomethyl ether acetate * EL: Ethyl lactate * GBL: [gamma] -butyrolactone

  According to the resin compositions of Examples 1 to 14, a protective film that satisfies general required performance as a non-radioactive protective film such as transparency, hardness, adhesion, and chemical resistance, and has low sublimation properties. It was found that can be formed at lower temperatures. On the other hand, in the resin compositions of Comparative Examples 1 to 4, because the activation temperature of the acid generator is high, curing proceeds at a temperature closer to 140 ° C., which is the firing temperature, and the cause is large shrinkage of the cured film after firing. It has been found that possible poor adhesion of the film occurs.

  According to the resin composition of Examples 15-20, it turned out that general performance requirements as a radiation sensitive protective film, such as patternability, developability of an unexposed part, and crack tolerance, are satisfy | filled. On the other hand, in the resin compositions of Comparative Examples 5 to 8, because the activation temperature of the acid generator is high, the curing proceeds at a temperature closer to 140 ° C., which is the baking temperature, and the cause is that the film has a large curing shrinkage after baking. It has been found that possible film cracking occurs.

  As described above, the resin composition of the present invention is a device using an organic material such as an LCD or a CMOS image sensor in order to satisfy general performance requirements as a protective film regardless of whether it is non-radiosensitive or radiation-sensitive. It turned out that it can be used conveniently for manufacture.

  The present invention is not limited to the above-described embodiments, and various modifications can be made. For example, the present invention includes substantially the same configuration (for example, a configuration having the same function, method, and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment. In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that achieves the same effect as the configuration described in the embodiment or a configuration that can achieve the same object. In addition, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

DESCRIPTION OF SYMBOLS 10 ... Polarizing plate, 12 ... Transparent substrate, 14 ... Color filter, 16 ... Protective film, 18a ... Transparent electrode (ITO electrode), 18b ... Transparent electrode (ITO electrode), 20 ... Alignment film, 22 ... Liquid crystal layer, 24 ... Transparent insulating film, 26 ... resin spacer, 28 ... TFT element, 30 ... sealing material, 100 ... liquid crystal display element, 111 ... circuit substrate (CMOS substrate), 112 ... substrate, 114 ... insulating layer, 114a ... (of insulating layer) Surface 116, pixel electrode 118, photoelectric conversion unit 120, counter electrode 122, sealing layer 122 a, surface (of sealing layer) 126 color filter 128, partition wall 129, light shielding layer 130 Protective film, 140 ... signal readout circuit, 142 ... counter electrode voltage supply unit, 144 ... first connection unit, 146 ... second connection unit, 148 ... wiring layer, 150 ... organic photoelectric conversion layer, 152 ... electricity Blocking layer, 152a ... (electron blocking layer) surface, 200 ... solid-state imaging device

Claims (5)

A curable resin composition comprising a polymer (A) having at least one selected from the group consisting of a radical polymerizable group, a cationic polymerizable group and a hydrolyzed silyl group, and an acid generator (B). There,
The acid generator (B) is a compound represented by the following general formula (3) ,
A curable resin composition used for forming a protective film for a liquid crystal display device or a protective film for a solid-state imaging device.

(In the above formula (3), R ⁴ and R ⁵ each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms. R ⁶ represents a substituted or unsubstituted benzyl group.) The curable resin composition according to claim 1, wherein the polymer (A) has a hydrolyzed silyl group. A protective film for a liquid crystal display device or a solid-state imaging device , comprising a step of heat-treating a coating film formed using the curable resin composition according to claim 1 or 2 at a temperature of 150 ° C. or lower . Manufacturing method . Forming a color filter on a transparent substrate;
A step of forming a coating film using the curable resin composition according to claim 1 or 2 between the color filter and the transparent electrode ;
Heating the coating film at a temperature of 150 ° C. or lower to form a protective film;
The manufacturing method of a liquid crystal display element containing this. Forming a pixel electrode on a semiconductor substrate on which a signal readout circuit is formed;
Forming an organic photoelectric conversion layer on the pixel electrode;
Forming a counter electrode on the organic photoelectric conversion layer;
Forming a coating film on the counter electrode using the curable resin composition according to claim 1 or 2,
Heating the coating film at a temperature of 150 ° C. or lower to form a protective film;
The manufacturing method of a solid-state image sensor containing this.

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