KR20060059203A - Copolymer, resin composition, overcoating film and process for forming the same - Google Patents

Abstract

The composition of the present invention comprises (a1) a polymerizable unsaturated compound having an oxylalanyl group or an oxetanyl group, a polymerized unit derived from a polymerizable unsaturated compound having a specific structure represented by (a2) 1-diethylpropyl methacrylate, and (a3) A copolymer formed by containing a polymerized unit different from the polymerized units (a1) and (a2). This composition can form a cured film having excellent storage stability, high flatness, high transparency and surface hardness, and excellent optical resistance for various resistances such as heat resistance, acid resistance, alkali resistance, sputtering resistance, and etching resistance. Since a protective film is formed, it is used preferably.

Copolymer, resin composition, protective film for optical devices

Description

Copolymer, Resin Composition, Protective Film and Method of Forming Protective Film {Copolymer, Resin Composition, Overcoating Film and Process for Forming the Same}

<Patent Document 1> Japanese Patent Application Laid-Open No. 5-78453

<Patent Document 2> Japanese Patent Application Laid-Open No. 2001-91732

<Patent Document 3> Japanese Patent Application Laid-Open No. 4-218561

The present invention relates to a copolymer, a resin composition, a method of forming a protective film from the composition, and a protective film. More specifically, a composition suitable as a material for forming a protective film for use in a color filter for a liquid crystal display device (LCD) and a color filter for a charge coupled device (CCD), a method of forming a protective film using the composition, and the composition It is about a protective film.

Radiation devices such as LCDs and CCDs are immersed in a display element by a solvent, an acid or an alkaline solution, or the like during its manufacturing process, and when the wiring electrode layer is formed by sputtering, the surface of the element is locally exposed to high temperature. Exposed. Therefore, in order to prevent the element from being deteriorated or damaged by such a treatment, a protective film formed of a thin film resistant to these treatments is provided on the surface of the element.

Such a protective film has a high adhesiveness with respect to the base or lower layer on which the protective film should be formed, and also a layer formed on the protective film, the film itself is smooth and strong, has transparency, high heat resistance and light resistance, The performance which does not cause deterioration, such as coloring, yellowing, whitening, etc. over the long term, and is excellent in water resistance, solvent resistance, acid resistance, and alkali resistance is calculated | required. As a material for forming the protective film which satisfy | fills these various characteristics, the thermosetting composition containing the polymer which has glycidyl group, for example is known (Unexamined-Japanese-Patent No. 5-78453 and Unexamined-Japanese-Patent No. 2001-91732). See publication number).

In addition, when using such a protective film as a protective film of the color filter of a color liquid crystal display device or a charge coupling element, it is generally required to be able to planarize the level | step difference by the color filter formed on the base substrate.

In addition, in a color liquid crystal display device, for example, a color liquid crystal display device of a super twisted nematic (STN) method or a thin film transistor (TFT) method, a bead-shaped spacer is formed on a protective film in order to maintain a uniform cell gap of the liquid crystal layer. After spreading, joining of panels is performed. Thereafter, the liquid crystal cell is sealed by thermocompression bonding of the sealing material. However, the phenomenon that the protective film in the portion where the beads exist is dented by the heat and pressure applied at that time has been a problem, and the cell spacing has become a problem.

In particular, when manufacturing the STN type color liquid crystal display device, the bonding accuracy of the color filter and the opposing substrate must be very strictly performed, and a very high leveling leveling performance and heat resistance resistance performance are required for the protective film.

In recent years, a method of forming a wiring electrode (indium tin oxide: ITO or indium zinc oxide: IZO) on the protective film of the color filter by sputtering and patterning ITO or IZO with a strong acid or strong alkali is also employed. have. For this reason, the surface of a color filter protective film is locally exposed to high temperature at the time of sputtering, or many chemical treatments are performed. Therefore, adhesiveness with wiring electrodes is also required to withstand these treatments and to prevent ITO or IZO from peeling off on the protective film during chemical treatment.

Although it is convenient to use the thermosetting composition which has the advantage of forming the protective film which is excellent in hardness by the easy method for formation of such a protective film, the protective film resin composition for expressing various characteristics as mentioned above forms strong crosslinking. It has a crosslinking group or catalyst having a good reactivity, and thus has a problem that the shelf life of the composition itself is very short, and handling is very difficult. That is, not only the coating performance itself of the composition deteriorated with time, but also frequent maintenance, cleaning, etc. of the coating machine were necessary, and it was complicated at the time of operation.

A material which not only satisfies the general required performance as a protective film such as transparency, but also satisfies various performances as described above, can be easily formed, and a material excellent in storage stability as a composition is not yet known.

In addition, Japanese Patent Laid-Open No. 4-218561 discloses a thermosetting composition containing a latent carboxyl compound used in paints, inks, adhesives, and molded articles, but no disclosure is made regarding the protective film of the color filter. It is not.

The present invention has been made on the basis of the above circumstances, and an object thereof is to form a cured film having a high flatness on the substrate even with a gas having a low surface flatness, high transparency and surface hardness, heat resistance, acid resistance, and resistance to heat. A composition which is preferably used to form a protective film for an optical device that is excellent in various resistances such as alkali resistance, sputtering resistance, and etching resistance, and has excellent storage stability as a composition, a method of forming a protective film using the composition, and from the composition It is to provide the formed protective film.

According to the present invention, the above object of the present invention is, firstly, a polymerized unit derived from a polymerizable unsaturated compound having [A-1] (a1) an oxylalanyl group or an oxetanyl group and (a2) It is achieved by the copolymer characterized by containing the polymerized unit derived from the polymerizable unsaturated compound which has a structure.

Wherein R is a tertiary alkyl group having at least 5 carbon atoms, a tertiary alkyl group having at least 4 carbon atoms substituted with an alkoxy group having 1 to 4 carbon atoms, and bonded as a tertiary carbon atom to an oxygen atom (-O-) bonded to R in the above-described formula It is a 4-membered ring or more lactone ring or lactam ring couple | bonded with the tertiary carbon atom couple | bonded with the cycloalkyl group of reduced carbon number 3 or more, or the oxygen atom (-O-) couple | bonded with R in the said Formula shown.

According to this invention, the said objective of this invention is achieved by the resin composition (henceforth "resin composition ((alpha) 1)") characterized by containing the said copolymer [A-1] of this invention secondly. do.

According to the present invention, the above object of the present invention is thirdly [A-2] a copolymer of the polymerizable unsaturated compound (a1) and the polymerizable unsaturated compound (a3), and [A-3] the polymerizable unsaturated compound It is achieved by the resin composition (henceforth "resin composition ((alpha) 2)") containing the copolymer of (a2) and a polymerizable unsaturated compound (a3).

The said objective of this invention is 4th achieved by the resin composition (henceforth "resin composition ((alpha) 3)") containing the said [A-3] component and a cationically polymerizable compound [B]. do.

The said objective of this invention is fifth, The coating film is formed using each said resin composition ((alpha) 1), resin composition ((alpha) 2), and resin composition ((alpha) 3), and it heat-processes, The protective film of the color filter characterized by the above-mentioned. It is achieved by the formation method of.

The said object of this invention is 6th achieved by the protective film of a color filter formed from the said resin composition.

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

Best Mode for Carrying Out the Invention

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

Copolymer [A-1]

The copolymer [A-1] of the present invention is a polymerized unit derived from a polymerizable unsaturated compound having (a1) an oxylanyl group or an oxetanyl group, and (a2) a polymerizable unsaturated compound having a structure represented by the formula (01). It is formed by containing the polymerization unit derived from (a3), and the polymerization unit derived from a polymerizable unsaturated compound other than the polymerization unit of said (a1) and (a2).

R in the formula (01) is a tertiary alkyl group having 5 or more carbon atoms, a tertiary alkyl group having 4 or more carbon atoms substituted with an alkoxy group having 1 to 4 carbon atoms, and an oxygen atom (-O-) bonded to R in the formula (01) as a tertiary carbon atom. It is a 4-membered or more lactone ring or lactam ring couple | bonded with the cycloalkyl group of 3 or more carbon atoms which are couple | bonded, or the oxygen atom (-O-) couple | bonded with R in the formula (01) shown by the tertiary carbon atom couple | bonded together.

When R is a C4 or more tertiary alkyl group substituted with a C5 or more tertiary alkyl group or a C1 to C4 alkoxy group, Formula 01 is represented by the following Formula (1).

Herein, R ¹ and R ² are each independently an alkyl group having 1 to 8 carbon atoms or an alkyl group having 1 to 8 carbon atoms substituted with an alkoxy group having 1 to 4 carbon atoms, and R ³ is an alkyl group having 2 to 8 carbon atoms or 1 to 4 carbon atoms. It is a C1-C8 alkyl group substituted by the alkoxy group.

When R is a cycloalkyl group having 3 or more carbon atoms, formula 01 is represented by the following formula (2).

Herein, the definition of R ¹ is the same as that of Chemical Formula 1, n is an integer of 1 to 8, R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, or C1-C8 alkyl group or C1-C4 alkoxy group which has a C1-C4 alkoxy group in the terminal or side chain of an alkyl group, or R <^4> , R <^5> , R <^6> and R <^7> combine two or more To form a dicycloalkane or tricycloalkane structure having a total reduced carbon number of 7 to 16 together with the carbon atom to which they are bonded and the carbon atom to which R ¹ is bonded, provided that when n = 2 to 8, a plurality of R ⁶ and R ⁷ may be the same or different.

In addition, when R is a 4- or more-membered or more lactone ring or lactam ring, Formula 01 is a structure represented by the formula (3).

Herein, the definition of R ¹ is the same as that of Formula 1, l is 0, 1 or 2, m is an integer of 1 to 4, X is an oxygen atom or a nitrogen atom, R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ is independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms having an alkoxy group having 1 to 4 carbon atoms at the end or side chain of the alkyl group, or an alkoxy group having 1 to 4 carbon atoms, provided that two R ⁸ and two R ⁹ when l = 2, And a plurality of R ¹⁰ and a plurality of R ¹¹ when m is an integer of 2 to 4 may be the same or different.

R ¹ in Formula 1, 2 or 3 and R ² in Formula 1 represent an alkyl group having 1 to 8 carbon atoms or an alkyl group having 1 to 8 carbon atoms having an alkoxy group having 1 to 4 carbon atoms at the terminal or side chain of the alkyl group. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, (iso) propyl, (iso) butyl, (iso) pentyl, (iso) hexyl, (iso) heptyl, and (iso) octyl. As a C1-C4 alkoxy group, methoxy, ethoxy, (iso) propoxy, (iso) butoxy, etc. are mentioned, for example.

R <^3> represents a C2-C8 alkyl group or a C1-C8 alkyl group which has a C1-C4 alkoxy group in the terminal or side chain of an alkyl group. Examples of the alkyl group having 2 to 8 carbon atoms include ethyl, (iso) propyl, (iso) butyl, (iso) pentyl, (iso) hexyl, (iso) heptyl, and (iso) octyl. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, (iso) propoxy and (iso) butoxy.

The cyclic structure in the formula (2) represents a cycloalkane structure of n = 1 to 8. Cycloalkanes include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, and cyclodecane. R <^4> -R <^7> represents a hydrogen atom or a C1-C8 alkyl group, or a C1-C8 alkyl group which has a C1-C4 alkoxy group in the terminal or side chain of an alkyl group, or a C1-C4 alkoxy group. When n = 2 or more, R <^6> and R <^7> on a cyclic alkane have two or more, but it does not need to be the same, It has a hydrogen atom or a C1-C8 alkyl group, or a C1-C4 alkoxy group in the terminal or side chain of an alkyl group. Either a C1-C8 alkyl group or a C1-C4 alkoxy group may be sufficient. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, (iso) propyl, (iso) butyl, (iso) pentyl, (iso) hexyl, (iso) heptyl, (iso) octyl, and the like. As a C1-C4 alkoxy group, methoxy, ethoxy, (iso) propoxy, (iso) butoxy, etc. are mentioned, for example.

In addition, R ⁴ to R ⁷ is a dicycloalkane or tricycloalkane structure having a total reduced carbon number of 7 to 16 together with the carbon atoms to which two or more of them are bonded and the carbon atoms to which R ¹ is bonded. It may be formed. Examples of such dicycloalkane or tricycloalkane include 2-ethyltricyclo [3.3.1.1 ^3,7 ] decan-2-yl group and 2-methyltricyclo [3.3.1.1 ^3,7 ] decan-2-yl group. , 1-ethyltricyclo [3.3.1.1 ^3,7 ] decan-1-yl group, 1-methyltricyclo [3.3.1.1 ^3,7 ] decan-1-yl group, 3-hydroxytricyclo [3.3.1.1 ^{3 , 7} ] decane-1-yl group.

As R <^8> -R <^{11> in} General formula (3), the group similar to the group mentioned above with respect to R <^4> -R <^7> can be illustrated.

As a lactone ring in General formula (3) when X is an oxygen atom, 2-ethyl- (gamma) -butyrolactone-2-yl group, 2-methyl- (gamma) -butyrolactone-2-yl group, 2-ethyl- γ-butyrolactone-3-yl group, 2-methyl-γ-butyrolactone-3-yl group, 2-ethyl-γ-butyrolactone-4-yl group, 2-methyl-γ-butyrolactone-4- Diary, 2-ethyl-δ-valerolactone-2-yl group, 2-ethyl-δ-valerolactone-2-yl group, 2-ethyl-δ-valerolactone-3-yl group, 2-methyl-δ- Valerolactone-3-yl group, 2-ethyl-δ-valerolactone-4-yl group, 2-methyl-δ-valerolactone-4-yl group, 2-ethyl-δ-valerolactone-5-yl group and 2-methyl-δ-valerolactone-5-yl group, etc. are mentioned.

 As the lactam ring in the general formula (3) when X is a nitrogen atom, for example, 2-ethyl-γ-butyrolactam-2-yl group, 2-methyl-γ-butyrolactam-2-yl group, 2- Ethyl-γ-butyrolactam-3-yl group, 2-methyl-γ-butyrolactam-3-yl group, 2-ethyl-γ-butyrolactam-4-yl group, 2-methyl-γ-butyrolactam 4-yl group, 2-ethyl-δ-valerolactam-2-yl group, 2-methyl-δ-valerolactam-2-yl group, 2-ethyl-δ-valerolactam-3-yl group and 2-methyl -δ-valerolactam-3-yl group, 2-ethyl-δ-valerolactam-4-yl group, 2-methyl-δ-valerolactam-4-yl group, 2-ethyl-δ-valerolactam-5 -Yl group and 2-methyl- delta-valerolactam-5-yl group, etc. are mentioned.

In the copolymer [A-1], the polymerizable unsaturated compound (a1) is not particularly limited as long as it has an oxiranyl group or an oxetanyl group and a polymerizable unsaturated group. For example, as an oxiranyl-group containing polymerizable unsaturated compound, glycidyl acrylate, glycidyl methacrylate, the glycidyl (alpha)-ethyl acrylate, the glycidyl (alpha) -n-propyl acrylate, alpha-n, for example Glycidyl butyl acrylate, 3,4-epoxy butyl acrylate, methacrylic acid-3,4-epoxy butyl, acrylic acid 6,7-epoxyheptyl, methacrylic acid 6,7-epoxyheptyl, α-ethyl Acrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and the like.

Examples of the oxetanyl group-containing polymerizable unsaturated compound include 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane, and the like.

Of these, methacrylic acid glycidyl, methacrylic acid-6,7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and the like are copolymerized. It is preferably used in view of increasing the reactivity and the heat resistance and surface hardness of the protective film or insulating film to be obtained.

In the copolymer [A-1], the polymerizable unsaturated compound (a2) is not particularly limited as long as it is a polymerizable unsaturated compound having a structure of the general formula (1), (2) or (3). For example, as a polymerizable unsaturated polymer which has a structure of General formula (1), 1-dimethyl (iso) propyl (meth) acrylate, 1-dimethyl (iso) butyl (meth) acrylate, 1-dimethyl ( Iso) octyl (meth) acrylate, 1-methyl-1-ethylethyl (meth) acrylate, 1-methyl-1-ethyl (iso) propyl (meth) acrylate, 1-methyl-1-ethyl (iso) Butyl (meth) acrylate, 1-methyl-1-ethyl (iso) octylacrylate, 1-diethyl (iso) propyl (meth) acrylate, 1-diethyl (iso) butyl (meth) acrylate, 1 -Diethyl (iso) octyl (meth) acrylate, etc. are mentioned.

Moreover, as a polymerizable unsaturated polymer which has a structure of General formula (2), for example, 1-methylcyclopropane (meth) acrylate, 1-methylcyclobutane (meth) acrylate, 1-methylcyclopentyl (meth) acrylate, 1-methylcyclohexyl (meth) acrylate, 1-methylcycloheptane (meth) acrylate, 1-methylcyclooctane (meth) acrylate, 1-methylcyclononane (meth) acrylate, 1-ethylcyclodecane ( Meth) acrylate, 1-ethylcyclopropane (meth) acrylate, 1-ethylcyclobutane (meth) acrylate, 1-ethylcyclopentyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, 1 -Ethylcycloheptane (meth) acrylate, 1-ethylcyclooctane (meth) acrylate, 1-ethylcyclononane (meth) acrylate, 1-methylcyclodecane (meth) acrylate, 1- (iso) propylcyclo Propane (meth) acrylate, 1- (iso) propyl Cyclobutane (meth) acrylate, 1- (iso) propylcyclopentyl (meth) acrylate, 1- (iso) propylcyclohexyl (meth) acrylate, 1- (iso) propylcycloheptane (meth) acrylate, 1- (iso) propylcyclooctane (meth) acrylate, 1- (iso) propylcyclononane (meth) acrylate, 1- (iso) propylcyclodecane (meth) acrylate, 1- (iso) butylcyclopropane (Meth) acrylate, 1- (iso) butylcyclobutane (meth) acrylate, 1- (iso) butylcyclopentyl (meth) acrylate, 1- (iso) butylcyclohexyl (meth) acrylate, 1 -(Iso) butylcycloheptane (meth) acrylate, 1- (iso) butylcyclooctane (meth) acrylate, 1- (iso) -butylcyclononane (meth) acrylate, 1- (iso) butylcyclodeca Ne (meth) acrylate, 1- (iso) pentylcyclopropaneyl (meth) acrylate, 1- (iso) pentylcyclobutanyl (meth) acrylate ) Acrylate, 1- (iso) pentylcyclopentyl (meth) acrylate, 1- (iso) pentylcyclohexyl (meth) acrylate, 1- (iso) pentylcycloheptanyl (meth) acrylate, 1- ( Iso) pentylcyclooctanyl (meth) acrylate, 1- (iso) pentylcyclononanyl (meth) acrylate, 1- (iso) pentylcyclodecanyl (meth) acrylate,

1- (iso) hexylcyclopropanyl (meth) acrylate, 1- (iso) hexylcyclobutanyl (meth) acrylate, 1- (iso) hexylcyclohexyl (meth) acrylate, 1- ( Iso) hexylcycloheptanyl (meth) acrylate, 1- (iso) hexylcyclooctanyl (meth) acrylate, 1- (iso) hexylcyclononanyl (meth) acrylate, 1- (iso) Hexylcyclodecanyl (meth) acrylate,

1- (iso) heptylcyclopropanyl (meth) acrylate, 1- (iso) heptylcyclobutanyl (meth) acrylate, 1- (iso) heptylcycloheptyl (meth) acrylate, 1- (iso) heptyl Cyclohexyl (meth) acrylate, 1- (iso) heptylcycloheptanyl (meth) acrylate, 1- (iso) heptylcyclooctanyl (meth) acrylate, 1- (iso) heptylcyclononanyl (meth) Acrylate, 1- (iso) heptylcyclodecanyl (meth) acrylate,

1- (iso) octylcyclopropanyl (meth) acrylate, 1- (iso) octylcyclobutanyl (meth) acrylate, 1- (iso) octylcyclooctyl (meth) acrylate, 1- (iso) octyl Cyclohexyl (meth) acrylate, 1- (iso) octylcycloheptanyl (meth) acrylate, 1- (iso) octylcyclooctanyl (meth) acrylate, 1- (iso) octylcyclononanyl (meth) Acrylate, 1- (iso) octylcyclodecanyl (meth) acrylate,

2-ethyltricyclo [3.3.1.1 ^3,7 ] decan-2-yl- (meth) acrylate, 2-methyltricyclo [3.3.1.1 ^3,7 ] decan-2-yl- (meth) acrylate, 1-ethyltricyclo [3.3.1.1 ^3,7 ] decane-1-yl- (meth) acrylate, 1-methyltricyclo [3.3.1.1 ^3,7 ] decane-1-yl- (meth) acrylate, 3-hydroxy tricyclo [3.3.1.1 ^3,7 ] decane-1-yl- (meth) acrylate, etc. are mentioned.

Among these, 1-diethylpropyl (meth) acrylate, 1-ethylcyclopentyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, 1- (iso) propylcyclopentyl (meth) acrylate, 1 -(Iso) propylcyclohexyl (meth) acrylate, 1- (iso) butylcyclopentyl (meth) acrylate, 1- (iso) butylcyclohexyl (meth) acrylate are preferably used, more preferably 1 -Diethylpropyl (meth) acrylate, 1-ethylcyclopentyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, and particularly preferred 1-ethylcyclopentyl (meth) acrylate, 1-ethyl Cyclohexyl (meth) acrylate. These are preferably used in terms of increasing the copolymerization reactivity and the heat resistance and surface hardness of the resulting protective film or insulating film.

Moreover, as a polymerizable unsaturated compound which has a structure of General formula (3), 2-ethyl- (gamma) -butyrolactone-2-yl- (meth) acrylate and 2-methyl- (gamma) -butyrolactone-2-yl, for example. -(Meth) acrylate, 2-ethyl-γ-butyrolactone-3-yl- (meth) acrylate, 2-methyl-γ-butyrolactone-3-yl- (meth) acrylate, 2-ethyl -γ-butyrolactone-4-yl- (meth) acrylate, 2-methyl-γ-butyrolactone-4-yl- (meth) acrylate, 2-ethyl-δ-valerolactone-2-yl -(Meth) acrylate, 2-methyl-δ-valerolactone-2-yl- (meth) acrylate, 2-ethyl-δ-valerolactone-3-yl- (meth) acrylate, 2-methyl -δ-valerolactone-3-yl- (meth) acrylate, 2-ethyl-δ-valerolactone-4-yl- (meth) acrylate, 2-methyl-δ-valerolactone-4-yl Lactones such as-(meth) acrylate, 2-ethyl-δ-valerolactone-5-yl- (meth) acrylate, 2-methyl-δ-valerolactone-5-yl- (meth) acrylate:

2-ethyl-γ-butyrolactam-2-yl- (meth) acrylate, 2-methyl-γ-butyrolactam-2-yl- (meth) acrylate, 2-ethyl-γ-butyrolactam- 3-yl- (meth) acrylate, 2-methyl-γ-butyrolactam-3-yl- (meth) acrylate, 2-ethyl-γ-butyrolactam-4-yl- (meth) acrylate, 2-Methyl-γ-butyrolactam-4-yl- (meth) acrylate, 2-ethyl-δ-valerolactam-2-yl- (meth) acrylate, 2-methyl-δ-valerolactam- 2-yl- (meth) acrylate, 2-ethyl-δ-valerolactam-3-yl- (meth) acrylate, 2-methyl-δ-valerolactam-3-yl- (meth) acrylate, 2-ethyl-δ-valerolactam-4-yl- (meth) acrylate, 2-methyl-δ-valerolactam-4-yl- (meth) acrylate, 2-ethyl-δ-valerolactam- And lactams such as 5-yl- (meth) acrylate and 2-methyl-δ-valerolactam-5-yl- (meth) acrylate.

The copolymer [A-1] may further contain a polymer unit derived from polymerizable unsaturated compounds other than (a3) (a1) and (a2) in addition to (a1) and (a2). As a polymerizable unsaturated compound (a3), for example, (meth) acrylic-acid alkylester, (meth) acrylic-acid cyclic alkylester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, a bicyclo unsaturated compound, and Malay Mid compound, unsaturated aromatic compound, conjugated diene type compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated dicarboxylic acid anhydride, and other unsaturated compounds are mentioned.

As these specific examples, for example, as methacrylic acid alkyl ester, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, di Ethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethyl glycoside, 4-hydroxyphenyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl Methacrylate, sec-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate and the like;

As alkyl acrylate, methyl acrylate, isopropyl acrylate, etc .;

As methacrylic acid cyclic alkyl esters, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, tricyclo [5.2.1.0 ^{2, 6} ] decane-8-yloxyethyl methacrylate, isoboroyl methacrylate and the like;

As acrylic acid cyclic alkylester, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8 -Yloxyethyl acrylate, isoboroyl acrylate and the like;

As methacrylic acid aryl ester, Phenyl methacrylate, benzyl methacrylate, etc .;

As acrylic acid aryl ester, Phenyl acrylate, Benzyl acrylate, etc .;

Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate and the like;

As the bicyclo unsaturated compound, bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene , 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2- N, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dihydrate Roxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2'-hydroxyethyl) Bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept 2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, and the like;

As a maleimide compound, Phenyl maleimide, cyclohexyl maleimide, benzyl maleimide, N-succinimidyl-3- maleimide benzoate, N-succinimidyl-4- maleimide butyrate, N-succinimidyl- 6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (9-acridinyl) maleimide and the like;

As an unsaturated aromatic compound, styrene, (alpha) -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, etc .;

As a conjugated diene type compound, 1, 3- butadiene, isoprene, 2, 3- dimethyl- 1, 3- butadiene, etc .;

As unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, etc .;

As unsaturated dicarboxylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, etc .;

As unsaturated dicarboxylic anhydride, each anhydride of the said unsaturated dicarboxylic acid;

As another unsaturated compound, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, etc. are mentioned.

Among them, styrene, tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, 1,3-butadiene, bicyclo [2.2.1] Hept-2-ene, N-cyclohexylmaleimide, etc. are preferable at the point of copolymerization reactivity, heat resistance, etc.

These are used alone or in combination.

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

As a preferable specific example of copolymer (A-1), for example

Styrene / 1-diethylpropyl methacrylate / methacrylic tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / glycidyl methacrylate copolymer,

Styrene / 1-diethylpropylmethacrylate / N-phenylmaleimide / glycidyl methacrylate copolymer,

Styrene / 1-diethylpropyl methacrylate / N-cyclohexylmaleimide / glycidyl methacrylate copolymer,

Styrene / 1-ethylcyclohexyl methacrylate / methacrylate tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / glycidyl methacrylate copolymer,

Styrene / 1-ethylcyclohexyl methacrylate / N-phenylmaleimide / glycidyl methacrylate copolymer,

Styrene / 1-ethylcyclohexyl methacrylate / N-cyclohexylmaleimide / glycidyl methacrylate copolymer,

Styrene / 1-ethylcyclopentyl methacrylate / methacrylate tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / glycidyl methacrylate copolymer,

Styrene / 1-ethylcyclopentyl methacrylate / N-phenylmaleimide / glycidyl methacrylate copolymer,

Styrene / 1-ethylcyclopentyl methacrylate / N-cyclohexylmaleimide / glycidyl methacrylate copolymer,

Styrene / 1-diethylpropyl methacrylate / methacrylate tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / methacrylic acid glycidyl / methacrylic acid copolymer,

Styrene / 1-diethylpropyl methacrylate / N-phenylmaleimide / methacrylic acid glycidyl / methacrylic acid copolymer,

Styrene / 1-diethylpropylmethacrylate / N-cyclohexylmaleimide / methacrylic acid glycidyl / methacrylic acid copolymer,

Styrene / 1-ethylcyclohexyl methacrylate / methacrylic tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / methacrylic acid glycidyl / methacrylic acid copolymer,

Styrene / 1-ethylcyclohexyl methacrylate / N-phenylmaleimide / methacrylic acid glycidyl / methacrylic acid copolymer,

Styrene / 1-ethylcyclohexyl methacrylate / N-cyclohexylmaleimide / methacrylic acid glycidyl / methacrylic acid copolymer,

Styrene / 1-ethylcyclopentyl methacrylate / methacrylate tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / methacrylic acid glycidyl / methacrylic acid copolymer,

Styrene / 1-ethylcyclopentyl methacrylate / N-phenylmaleimide / methacrylic acid glycidyl / methacrylic acid copolymer,

Styrene / 1-ethylcyclopentyl methacrylate / N-cyclohexyl maleimide / methacrylic acid glycidyl / methacrylic acid copolymer, and the like.

(Co) polymer [A-2]

(Co) polymer [A-2] is a (co) polymer (except copolymer [A-1] mentioned above) obtained by superposing | polymerizing the component containing the said polymerizable unsaturated compound (a1).

The (co) polymer [A-2] can be a copolymer with the polymerizable unsaturated compound (a3) in addition to the polymerizable unsaturated compound (a1).

The (co) polymer [A-2] is a structural unit derived from the polymerizable unsaturated compound monomer, preferably (a1) 5 to 100% by weight and (a3) 0 to 95% by weight, more preferably (a1) 20 to 100% by weight and (a3) 0 to 80% by weight, most preferably (a1) 30 to 90% by weight and (a3) 10 to 70% by weight. In this range, good flattening performance and heat resistance can be realized.

As a preferable specific example of copolymer [A-2], for example

Styrene / 1-diethylpropylmethacrylate / methacrylate tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / methacrylic acid copolymer,

Styrene / 1-diethylpropylmethacrylate / N-phenylmaleimide / methacrylic acid copolymer,

Styrene / 1-diethylpropylmethacrylate / N-cyclohexylmaleimide / methacrylic acid copolymer,

Styrene / 1-ethylcyclohexyl methacrylate / methacrylate tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / methacrylic acid copolymer,

Styrene / 1-ethylcyclohexyl methacrylate / N-phenylmaleimide / methacrylic acid copolymer,

Styrene / 1-ethylcyclohexyl methacrylate / N-cyclohexylmaleimide / methacrylic acid copolymer,

Styrene / 1-ethylcyclopentyl methacrylate / methacrylic tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / methacrylic acid copolymer,

Styrene / 1-ethylcyclopentyl methacrylate / N-phenylmaleimide / methacrylic acid copolymer,

Styrene / 1-ethylcyclopentyl methacrylate / N-cyclohexyl maleimide / methacrylic acid copolymer, etc. are mentioned.

(Co) polymer [A-3]

(Co) polymer [A-3] is a (co) polymer (except copolymer [A-1] mentioned above) obtained by superposing | polymerizing the component containing the said polymerizable unsaturated compound (a2).

The (co) polymer [A-3] can be a copolymer with the polymerizable unsaturated compound (a3) in addition to the polymerizable unsaturated compound (a2).

The (co) polymer [A-3] is a structural unit derived from the polymerizable unsaturated compound monomer, preferably (a2) 5 to 100% by weight and (a3) 0 to 95% by weight, more preferably (a2) 20 to 100% by weight and (a3) 0 to 80% by weight, most preferably 30 to 90% by weight (a2) and 10 to 70% by weight (a3). In this range, good flattening performance and heat resistance can be realized.

As a preferable specific example of copolymer [A-3], for example

Styrene / 1-diethylpropylmethacrylate / methacrylic tricyclo [5.2.1.0 ^2,6 ] decane-8-yl copolymer,

Styrene / 1-diethylpropylmethacrylate / N-phenylmaleimide copolymer,

Styrene / 1-diethylpropylmethacrylate / N-cyclohexylmaleimide copolymer,

Styrene / 1-ethylcyclohexyl methacrylate / tricyclo methacrylate [5.2.1.0 ^2,6 ] decane-8-yl copolymer,

Styrene / 1-ethylcyclohexyl methacrylate / N-phenylmaleimide copolymer,

Styrene / 1-ethylcyclohexyl methacrylate / N-cyclohexylmaleimide copolymer,

Styrene / 1-ethylcyclopentylmethacrylate / methacrylic tricyclo [5.2.1.0 ^2,6 ] decane-8-yl copolymer,

Styrene / 1-ethylcyclopentylmethacrylate / N-phenylmaleimide copolymer,

Styrene / 1-ethylcyclopentyl methacrylate / N-cyclohexylmaleimide copolymer, etc. are mentioned.

Copolymers [A-1], [A-2], and [A-3] were polystyrene equivalent weight average molecular weights (hereinafter referred to as "Mw") measured by gel permeation chromatography (elution solvent: tetrahydrofuran). Preferably it is 1,000-100,000, More preferably, it is 2,000-50,000, Especially preferably, it is 3,000-40,000. In this case, when Mw is less than 1,000, the coating property of a composition may become inadequate, or the heat resistance of the protective film formed may be inadequate, while when Mw exceeds 100,000, planarization performance may become inadequate.

In addition, the molecular weight distribution (Mw / Mn) of the copolymers [A-1], [A-2] and [A-3] is preferably 5.0 or less, and more preferably 3.0 or less.

Such a copolymer is the said polymerizable unsaturated compound (a1) and (a2) in copolymer [A-1], the said polymerizable unsaturated compound (a1) in polymer [A-2], and the polymer [A -3], the polymerizable unsaturated compound (a2) can be synthesized by a known method such as radical polymerization in the presence of a suitable solvent and a suitable polymerization initiator.

Cation Polymerizable  Compound [B]

The cationically polymerizable compound [B] used in the present invention is a compound having two or more oxylanyl groups or oxetanyl groups in the molecule (except the copolymers [A-1] and [A-2] described above). to be. As a compound which has two or more oxylanyl groups or an oxetanyl group in the said molecule, the compound which has two or more epoxy groups in a molecule | numerator, or the compound which has a 3, 4- epoxycyclohexyl group is mentioned, for example.

As a compound which has two or more epoxy groups in the said molecule, For example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogen Of bisphenol compounds such as added bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol S diglycidyl ether Diglycidyl ether;

1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol digly Polyglycidyl ethers of polyhydric alcohols such as cydyl ether;

Polyglycidyl ethers of polyether polyols obtained by adding one or two or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;

Phenol novolac type epoxy resins;

Cresol novolac type epoxy resins;

Polyphenol type epoxy resins;

Diglycidyl esters of aliphatic long chain dibasic acids;

Glycidyl esters of higher fatty acids;

Epoxidized soybean oil, epoxidized linseed oil, etc. are mentioned.

As a commercial item of the compound which has two or more epoxy groups in the said molecule | numerator, it is a bisphenol-A epoxy resin, for example, Epicoat 1001, copper 1002, copper 1003, copper 1004, copper 1007, copper 1009, copper 1010, copper 828 (or more) Japan Epoxy Resin Co., Ltd.);

As bisphenol F type epoxy resin, Epicoat 807 (made by Japan Epoxy Resin Co., Ltd.) etc .;

As a phenol novolak-type epoxy resin, Epicoat 152, Copper 154, Copper 157S65 (above, Japan Epoxy Resin Co., Ltd. product), EPPN201, Copper 202 (above, Nippon Kayaku Co., Ltd. product) etc .;

As a cresol novolak-type epoxy resin, EOCN102, 103S, 104S, 1020, 1025, 1027 (above, Nippon Kayaku Co., Ltd. make), Epicoat 180S75 (made by Japan Epoxy Resin Co., Ltd.), etc .;

As a polyphenol type epoxy resin, Epicoat 1032H60, XY-4000 (above, Japan Epoxy Resin Co., Ltd. product) etc. are mentioned;

As the cyclic aliphatic epoxy resin, CY-175, copper 177, copper 179, araldite CY-182, copper 192, 184 (above, manufactured by Ciba Specialty Chemicals Co., Ltd.), ERL-4234, 4299, 4221, 4206 (above, UCC company), Shodine 509 (Showa Denko Co., Ltd.), epicron 200, copper 400 (above, Dainippon ink, Ltd.), epicoat 871, east 872 (more, Japan Epoxy Resin Co., Ltd.), ED-5661, Copper 5662 (above, manufactured by Ceraniz Coating Co., Ltd.), etc .;

Examples of the aliphatic polyglycidyl ethers include epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Epiol TMP (manufactured by Nippon Yushi Co., Ltd.), 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 and 2- (3,4 -Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methyl Cyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dish Clopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate), lactone modified 3,4-epoxycyclohexylmethyl-3 ' And 4'-epoxycyclohexane carboxylate.

Among these cationic polymerizable compounds [B], phenol novolak type epoxy resins and polyphenol type epoxy resins are preferable.

The amount of the cationically polymerizable compound [B] in the resin composition of the present invention is preferably 100 parts by weight per 100 parts by weight of the total amount of the polymers [A-1], [A-2] and [A-3]. More preferably 5 to 100 parts by weight, in particular 10 to 50 parts by weight. When the usage-amount of a cationically polymerizable compound [B] is more than 200 weight part, a problem may arise in the coating property of a composition, and when it is less than 3 weight part, the hardness of the protective film obtained may be insufficient.

Thermosensitive acid Generator (C)

Examples of the thermosensitive acid generator include sulfonium salts, benzothiazonium salts, ammonium salts, and phosphonium salts. Among these, sulfonium salts and benzothiazonium salts are preferably used.

Specific examples of the sulfonium salts include 4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, and dimethyl-4- (benzyloxycarbonyloxy) phenylsulphur. Phosphorus hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro- Alkylsulfonium salts such as 4-acetoxyphenylsulfonium hexafluoroantimonate;

Benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl- 4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium Benzylsulfonium salts such as hexafluoroarsenate and 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate;

Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, dibenzyl 4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5- dibenzylsulfonium salts such as tert-butylphenylsulfonium hexafluoroantimonate and benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate;

p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chlorobenzyl-4-hydroxyphenyl Methylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoro Substituted benzyl sulfonium salts, such as an antimonate and o-chlorobenzyl-3- chloro-4- hydroxyphenyl methyl sulfonium hexafluoro antimonate, etc. are mentioned.

Among these, 4-acetoxyphenyl dimethyl sulfonium hexafluoro arsenate, benzyl-4-hydroxyphenyl methyl sulfonium hexafluoro antimonate, 4-acetoxy phenyl benzyl methyl sulfonium hexafluoro antimonate, Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, etc. are used preferably.

Examples of the benzothiazonium salts include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, and 3- (p-methoxybenzyl). Benzyl benzothiazo such as benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate A tan salt is mentioned.

Among these, 3-benzyl benzothiazonium hexafluoro antimonate etc. are used preferably.

As a commercial item of the acid generator used preferably as a thermosensitive acid generator, Asahi Denka Kogyo Co., Ltd. brand name: Adeka optone CP-66, CP-77 is mentioned as an alkylsulfonium salt.

Moreover, as a benzyl sulfonium salt, Sanshin Kagaku Kogyo Co., Ltd. brand name: SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-80L, SI-100L, SI -110L may be mentioned.

Among them, SI-80, SI-100, and SI-110 are preferable because the protective film obtained has high surface hardness.

When the resin composition of this invention contains a [C] thermosensitive acid generator, the usage-amount is 100 weight part with respect to the total amount of polymer [A-1], [A-2], and [A-3], Preferably it is 0.05-20 weight part, More preferably, it is 0.1-10 weight part. By setting the amount to be within this range, a protective film having sufficient hardness can be obtained. In addition, the [C] thermosensitive acid generator may be replaced with a radiation sensitive acid generator.

A radiation sensitive acid generator is a compound which can generate an acid by irradiation of visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like.

Diaryl iodonium salts, triarylsulfonium salts, diaryl phosphonium salts, etc. are mentioned as such a radiation sensitive acid generator, These can be used preferably.

Examples of the diaryl iodonium salts include diphenyl iodonium tetrafluoroborate, diphenyl iodonium hexafluorophosphonate, diphenyl iodonium hexafluoroarsenate, and diphenyl iodo. Trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyl Iodonium hexafluorophosphonate, 4-methoxyphenylphenyl iodonium hexafluoroarsenate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodo Trifluoroacetate, 4-methoxyphenylphenyliodonium-p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium tetrafluoroborate, bis (4-tert-butylphenyl) iodo Hexafluoroarsenate, bis (4-t ert-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium trifluoroacetate, bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate Etc. can be mentioned. Among these, diphenyl iodonium hexafluorophosphonate is used preferably.

Examples of the triarylsulfonium salts include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, and triphenylsulfonium trifluoromethanesulfo. Nate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophospho Nitrate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4- Methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyl tetrafluoroborate, 4-phenylthiophenyldiphenyl hexafluorophosphonate, 4-phenylthiophenyldiphenyl Hexafluoroarsenate, 4-phenylthiophenyldiphenyl trifluoromethanesulfonate, 4-phenylthiophenyldiphenyl trifluoroacetate, 4-phenylthiophenyldiphenyl-p-toluenesulfonate, and the like. have. Among these, triphenylsulfonium trifluoromethanesulfonate is used preferably.

As said diaryl phosphonium salt, (1-6- (eta)-cumene) ((eta) -cyclopentadienyl) iron hexafluoro phosphonate, etc. are mentioned.

As a commercially available product of the acid generator used suitably as a radiation sensitive acid generator, it is a diaryl iodonium salt made by Union Carbide brand name: UVI-6950, UVI-6970, UVI-6974, UVI-6990, and Midori. The brand name of Maku-Kaku Corporation: MPI-103, BBI-103, etc. are mentioned.

Moreover, as a triaryl sulfonium salt, Asahi Denka Kogyo Co., Ltd. brand name: Adeka Optoma SP-150, SP-151, SP-170, SP-171, Nihon Soda Co., Ltd. brand name: CI-2481, CI -2624, CI-2639, CI-2064, Midori Kagaku Co., Ltd. brand name: DTS-102, DTS-103, NAT-103, NDS-103, TPS-103, MDS-103, Satoma company brand name: CD -1010, CD-1011, CD-1012, etc. are mentioned.

Moreover, as a diaryl phosphonium salt, Ciba Specialty Chemicals Co., Ltd. brand name: Irgacure-261, Nippon Kayaku Co., Ltd. brand name: PCI-061T, PCI-062T, PCI-020T, PCI-022T Etc. can be mentioned.

Among these, Union Carbide Co., Ltd. Brand Name: UVI-6970, UVI-6974, UVI-6990, Asahi Denka Kogyo Co., Ltd. Brand Name: Adeka Optoma SP-170, SP-171, Satoma Co., Ltd. Brand Name: CD-1012, Midori Since the protective film obtained has a high surface hardness, the Kagaku Co., Ltd. brand name: MPI-103 is preferable.

When the resin composition of this invention contains a radiation sensitive acid generator, the usage-amount is preferably with respect to 100 weight part of total amounts of a polymer [A-1], [A-2], and [A-3]. Is 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight. By setting the amount to be within this range, a protective film having sufficient hardness can be obtained.

[D] adhesion aid

Said [D] adhesion | attachment adjuvant can be added in order to improve the adhesiveness of the protective film formed and a board | substrate.

As such [D] adhesion | attachment adjuvant, the functional silane coupling agent which has a reactive substituent can be used, for example. As said reactive substituent, a carboxyl group, methacryloyl group, an isocyanate group, an epoxy group, etc. are mentioned, for example.

As a specific example of [D] adhesion | attachment adjuvant, for example, trimethoxy silyl benzoic acid, (gamma)-methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, (gamma) -isocyanate propyl triethoxysilane , γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

The adhesive aid [D] is preferably 100 parts by weight or less, more preferably 25 parts by weight or less, per 100 parts by weight of the total amount of the copolymers [A-1], [A-2] and [A-3]. Used in quantity. [D] When the amount of the adhesion assistant exceeds 30 parts by weight, the heat resistance of the protective film obtained may be insufficient.

[E] surfactant

The said surfactant can be added in order to improve the application | coating performance of the resin composition of this invention.

As such surfactant, a fluorochemical surfactant, silicone type surfactant, nonionic surfactant, other surfactant is mentioned, for example.

As said fluorine-type surfactant, BM CHIMIE company brand names: BM-1000, BM-1100, Dainippon Ink & Chemicals Co., Ltd. brand name: Megapack F142D, copper F172, copper F173, copper F183, Sumitomo 3M Manufacture name: Flowride FC-135, East FC-170C, East FC-430, East FC-431, Asahi Glass Co., Ltd. Manufacture Name: Saffron S-112, East S-113, East S-131 Commercial items, such as S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 Can be.

As said silicone type surfactant, Toray Dow Corning Silicone Co., Ltd. brand name: SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190, Shin-Etsu Commercial products, such as Kagaku Kogyo Co., Ltd. brand name: KP341, Shin-Kagawa Kasei Co., Ltd. brand name: F-top EF301, copper EF303, copper EF352, are mentioned.

As said nonionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene dialkyl ester, etc. are mentioned, for example.

As said polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, etc. are mentioned, for example, As polyoxyethylene aryl ether, For example, polyoxyethylene Octyl phenyl ether and polyoxyethylene nonylphenyl ether are mentioned, As a polyoxyethylene dialkyl ester, polyoxyethylene dilaurate, polyoxyethylene distearate, etc. are mentioned, for example.

As said other surfactant, Kyoeisha Chemical Co., Ltd. brand name: (meth) acrylic-acid type copolymer polyflow No. 57, East No. 90 etc. are mentioned.

The addition amount of these [E] surfactants per 100 weight part of total amounts of polymer [A-1], [A-2], and [A-3], Preferably it is 5 weight part or less, More preferably, it is 2 weight part or less. Used as When the quantity of surfactant exceeds 5 weight part, the film roughness of a coating film may become easy in a coating process.

Embodiment of the resin composition

As preferable embodiment of the resin composition of this invention, the following (a)-(c) is mentioned.

(A) The resin composition containing copolymer [A-1], a cationic polymeric compound [B], and a thermosensitive acid generator [C] as needed.

(B) A resin composition containing a copolymer [A-2] and a copolymer [A-3], and optionally a cationic polymerizable compound [B] and a thermosensitive acid generator [C]. In the composition (b), the amount of the copolymer [A-3] is 10 to 90 parts by weight per 100 parts by weight of the total amount of the copolymers [A-2] and [A-3], preferably 20 to 80 parts by weight. Parts by weight. When the amount of the copolymer [A-3] is less than 10 parts by weight, the curing may be insufficient, and when it exceeds 90 parts by weight, the heat resistance may deteriorate.

(C) The resin composition containing a copolymer [A-3] and a cationic polymeric compound [B], and optionally a thermosensitive acid generator [C].

The resin composition of this invention is manufactured by dissolving or disperse | distributing each said component uniformly in a suitable solvent preferably. As a solvent used, what melt | dissolves or disperse | distributes each component of a composition and does not react with each component is used preferably.

As such a solvent, alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate , Aromatic hydrocarbons, ketones, esters and the like.

As these specific examples, For example, as alcohol, methanol, ethanol, benzyl alcohol;

As ether, tetrahydrofuran and the like;

Examples of the glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;

As ethylene glycol alkyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, etc .;

As diethylene glycol monoalkyl ether, Diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, etc .;

As diethylene glycol dialkyl ether, Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .;

As propylene glycol monoalkyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, etc .;

As propylene glycol alkyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc .;

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;

As an aromatic hydrocarbon, toluene, xylene, etc .;

Examples of the ketone include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl isoamyl ketone, and the like;

As the ester, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, and hydroxy Ethyl hydroxy acetate, butyl hydroxy acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxypropionate, butyl 3-hydroxypropionate, 2 Methyl hydroxy-3-methyl butyrate, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate propyl, butyl butyl acetate, ethoxy acetate, ethoxy acetate, ethoxy acetate, ethoxy acetate Methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, butoxya Ethyl acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2 Ethyl ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, 3- Methyl methoxypropionate, 3-methoxy ethylpropionate, 3-methoxy propylpropionate, 3-methoxy propylpropionate, 3-ethoxypropionate methyl, 3-ethoxypropionate, 3-ethoxypropionate, 3-e Butyl oxypropionate, 3-propoxy methyl propionate, 3-propoxy propionate, 3-propoxy propionate, 3-butyl propoxypropionate, 3-butoxy propionate, 3-butoxy propionate, 3-part When there may be mentioned acid profile, such as 3-butoxy-propionic acid butyl, respectively.

Among these, alcohol, diethylene glycol, propylene glycol alkyl acetate, ethylene glycol alkyl ether acetate and diethylene glycol dialkyl ether are preferable, and benzyl alcohol, diethylene glycol ethyl methyl ether, propylene glycol methyl ether acetate and propylene glycol ethyl ether are particularly preferred. Acetate, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether are preferable.

As the usage-amount of a solvent, content of the total solid in the composition of this invention (amount except solvent amount from the total amount of the composition containing a solvent) becomes like this. Preferably it is 1-50 weight%, More preferably, it is 5-40 weight%. It is a range.

A high boiling point solvent can be used together with the said solvent. As a high boiling point solvent which can be used together here, for example, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, and N-methyl Pyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, Diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like.

As a usage-amount when using a high boiling point solvent together, Preferably it is 90 weight% or less with respect to the total amount of solvent, More preferably, it is 80 weight% or less.

The composition prepared as described above may be used after filtration and fractionation using a Millipore filter having a pore size of 0.2 to 3.0 μm, preferably about 0.2 to 0.5 μm, and the like.

Formation of protective film of color filter

Next, the method of forming the protective film of a color filter using the composition of this invention is demonstrated.

After coating the resin composition solution of this invention on the surface of a board | substrate, prebaking and removing a solvent, and forming a coating film, it can heat-process and can form the protective film of the target color filter.

As what can be used as said board | substrate, board | substrates, such as glass, quartz, a silicone, resin, can be used, for example. As resin, resin, such as a ring-opening polymer of polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, and cyclic olefin, and its hydrogenated substance, is mentioned, for example.

As the coating method, for example, a spraying method, a roll coating method, a rotary coating method, a bar coating method, an inkjet method, or the like may be adopted. In particular, a coating method using a spin coater, a spinless coater, and a slit die coater may be employed. Can be preferably used.

Although the conditions of the said prefiring differ also with the kind of each component, a compounding ratio, etc., the conditions of about 1 to 15 minutes can be employ | adopted normally at 70-90 degreeC. The thickness of the coating film is preferably 0.15 to 8.5 mu m, more preferably 0.15 to 6.5 mu m, still more preferably 0.15 to 4.5 mu m. In addition, the thickness of the coating film here should be understood as the thickness after solvent removal.

The heat treatment after coating film formation can be performed by appropriate heating apparatuses, such as a hotplate and a clean oven. As processing temperature, about 150-250 degreeC is preferable, The heating time can employ | adopt the processing time for 5 to 30 minutes when using a hotplate, and 30 to 90 minutes when using an oven.

In addition, when using a radiation sensitive acid generator for a resin composition, after apply | coating the said resin composition to the board | substrate surface, removing a solvent by prebaking and making it into a coating film, the objective is performed by performing a radiation irradiation process (exposure process). A protective film can be formed. If necessary, heat treatment may be further performed after the exposure treatment.

Examples of the radiation that can be used in the irradiation treatment of the radiation include visible light, ultraviolet rays, far ultraviolet rays, electron beams, X rays, and the like, but ultraviolet rays containing light having a wavelength of 190 to 450 nm are preferable.

The exposure dose is usually 100 to 20,000 J / m ² , preferably 150 to 10,000 J / m ² .

The heat treatment may optionally be further performed after irradiation. As heating temperature at this time, about 150-250 degreeC is preferable, and a suitable apparatus, such as a hotplate and a clean oven, can be used as a heating apparatus, for example. Heating time can employ | adopt the processing time for 5 to 30 minutes, when using a hotplate, and 30 to 90 minutes, when using an oven.

Shield of color filter

The protective film thus formed has a film thickness of preferably 0.1 to 8 mu m, more preferably 0.1 to 6 mu m, still more preferably 0.1 to 4 mu m. In addition, when the protective film of the present invention is formed on a substrate having a step of the color filter, the film thickness should be understood as the thickness from the top of the color filter.

As apparent from the following examples, the protective film of the present invention satisfies adhesion, surface hardness, transparency, heat resistance, light resistance, solvent resistance, and the like, and does not dent under load even when heat is applied, and on the base substrate. It is preferable as a protective film for optical devices which is excellent in the performance of flattening the level difference of the color filter formed in the film filter.

In particular, since the protective film of this invention may be exposed to the heating exceeding 250 degreeC in a panel manufacturing process, having sufficient heat resistance even in that case is ensured by having sufficient dimensional stability at 270 degreeC.

According to the present invention, even in a gas having a low surface flatness, a cured film having a high flatness can be formed on the substrate, and transparency and surface hardness are high, and heat resistance pressure resistance, acid resistance, alkali resistance, sputtering resistance, etching resistance, etc. The resin composition which is preferably used in order to form the protective film for optical devices which is excellent in various tolerances, and is excellent in the storage stability as a composition, the formation method of the protective film using this resin composition, and the protective film formed from the said composition are provided.

<Example>

Although a synthesis example and an Example are shown to the following and this invention is demonstrated to it further more concretely, this invention is not limited to a following example.

Preparation of (co) polymer

Synthesis Example 1

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 50 weight part of glycidyl methacrylate and 50 weight part of 1-ethylcyclopentyl methacrylates were added, and nitrogen-substituted, and stirring was gradually started. The solution temperature was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A1-1). Solid content concentration of the obtained polymer solution was 32.9%.

Synthesis Example 2

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer. 40 parts by weight of glycidyl methacrylate, 40 parts by weight of 1-diethylpropylmethacrylate, 10 parts by weight of styrene and 10 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl After nitrogen was replaced, stirring was started slowly. The temperature of the solution was raised to 70 ° C, and this temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A1-2). Solid content concentration of the obtained polymer solution was 33.0%.

Synthesis Example 3

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 40 parts by weight of glycidyl methacrylate, 40 parts by weight of 1-ethylcyclohexyl methacrylate, 10 parts by weight of styrene and 10 parts by weight of cyclohexylmaleimide were added thereto, followed by nitrogen replacement, and stirring was gradually started. The solution temperature was raised to 70 ° C. and maintained at this temperature for 5 hours to obtain a polymer solution containing a copolymer (A1-3). Solid content concentration of the obtained polymer solution was 33.0%.

Synthesis Example 4

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 40 parts by weight of glycidyl methacrylate, 40 parts by weight of 1-ethylcyclopentyl methacrylate, 10 parts by weight of styrene and 10 parts by weight of N-cyclohexylmaleimide were added thereto, followed by nitrogen replacement, and stirring was gradually started. The solution temperature was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A1-4). Solid content concentration of the obtained polymer solution was 32.7%.

Synthesis Example 5

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethylmethyl ether were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 40 parts by weight of glycidyl methacrylate, 40 parts by weight of 1-ethylcyclopentyl methacrylate, 10 parts by weight of methacrylic acid, 5 parts by weight of styrene, and 5 parts by weight of N-cyclohexylmaleimide were added and nitrogen-substituted. After that, stirring was slowly started. The solution temperature was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A1-5). Solid content concentration of the obtained polymer solution was 32.8%.

Synthesis Example 6

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethylmethyl ether were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 40 parts by weight of glycidyl methacrylate, 40 parts by weight of 2-methyl-γ-lactone-4-yl-methacrylate, 10 parts by weight of styrene, and 10 parts by weight of N-cyclohexylmaleimide were substituted for nitrogen. Agitation was started slowly. The solution temperature was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A1-6). Solid content concentration of the obtained polymer solution was 31.9%.

Synthesis Example 7

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 100 weight part of glycidyl methacrylates were added, nitrogen-substituted, and stirring was gradually started. The solution temperature was raised to 70 ° C. and maintained at this temperature for 5 hours to obtain a polymer solution containing a copolymer (A2-1). Solid content concentration of the obtained polymer solution was 33.2%.

Synthesis Example 8

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 80 parts by weight of glycidyl methacrylate and 20 parts by weight of styrene were added thereto, followed by nitrogen replacement, and stirring was gradually started. The solution temperature was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A2-2). Solid content concentration of the obtained polymer solution was 33.3%.

Synthesis Example 9

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 100 weight part of 1-ethylcyclohexyl methacrylates were added, nitrogen-substituted, and stirring was gradually started. The solution temperature was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A3-1). Solid content concentration of the obtained polymer solution was 33.0%.

Synthesis Example 10

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 80 parts by weight of 1-ethylcyclohexyl methacrylate, 10 parts by weight of styrene, and 10 parts by weight of tricyclo methacrylate [5.2.1.0 ^2,6 ] decane-8-yl were added thereto, followed by nitrogen replacement. It was. The solution temperature was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A3-2). Solid content concentration of the obtained polymer solution was 33.3%.

Comparative Synthesis Example 1

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethylmethyl ether were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 25 parts by weight of styrene, 20 parts by weight of methacrylic acid, 45 parts by weight of glycidyl methacrylate, and 10 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl were substituted with nitrogen. Agitation was started slowly. The temperature of the solution was raised to 70 ° C, and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (a-1). Solid content concentration of the obtained polymer solution was 33.0%.

Comparative Synthesis Example 2

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 40 parts by weight of glycidyl methacrylate, 10 parts by weight of styrene, 40 parts by weight of t-butyl methacrylate and 10 parts by weight of cyclohexylmaleimide were added thereto, followed by nitrogen replacement, and stirring was gradually started. The solution temperature was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (a-2). Solid content concentration of the obtained polymer solution was 33.0%.

Preparation and Evaluation of Resin Compositions

Example 1

SH-28PA (Toray Dow) as a solution containing copolymer (A1-1) obtained in Synthesis Example 1 (amount equivalent to 100 parts by weight (solid content) of copolymer (A1-1)) and (E) surfactant 0.1 weight part of Corning Silicone Co., Ltd. was added, and propylene glycol monomethyl ether acetate was further added so that solid content concentration might be 20%, and it filtered with the Millipore filter of 0.5 micrometer of pore diameters, and manufactured the resin composition.

After applying the composition on a SiO ₂ immersed glass substrate using a spinner, the composition was prebaked on a hot plate for 5 minutes at 80 ° C. for 5 minutes, and further heated at 230 ° C. for 60 minutes in an oven to obtain a film thickness of 2.0 μm. A protective film was formed.

Evaluation of the shield

(1) evaluation of transparency

About the board | substrate with a protective film formed as mentioned above, the transmittance | permeability of 400-800 nm was measured using the spectrophotometer (150-20 type double beam (made by Hitachi Seisakusho Co., Ltd.)). The minimum values of transmittance between 400 and 800 nm are shown in Table 1 below. When this value is 95% or more, it can be said that transparency of a protective film is favorable.

(2) Evaluation of heat resistance dimensional stability

About the board | substrate which has a protective film formed as mentioned above, it heated in 250 degreeC on condition of 1 hour in oven, and measured the film thickness before and behind heating. Table 1 shows the heat-resistant dimensional stability calculated according to the following formula. When this value is 95% or more, it can be said that heat-resistant dimensional stability is favorable.

Heat-resistant dimensional stability = (film thickness after heating) / (film thickness before heating) * 100 (%)

(3) Evaluation of heat discoloration resistance

About the board | substrate with a protective film formed as mentioned above, it heated at 250 degreeC in oven for 1 hour, and the transparency before and behind heating was measured as said (1). Table 1 shows the heat discoloration resistance calculated according to the following formula. When this value is 5% or less, it can be said that heat discoloration resistance is favorable.

Heat discoloration resistance = transmittance before heating-transmittance after heating (%)

(4) measurement of surface hardness

About the board | substrate which has a protective film formed as mentioned above, the surface hardness of the protective film was measured by the 8.4.1 pencil scraping test of JISK-5400-1990. This value is shown in Table 1. When this value is 4H or harder, the surface hardness can be said to be good.

(5) Measurement of dynamic microhardness

The substrate having the protective film formed as described above was subjected to the indentation test of a ridge angle 115 ° triangular indenter (Herkovitch type) using Shimadzu dynamic microhardness meter DUH-201 (manufactured by Shimadzu Corporation). By this, the dynamic microhardness of the protective film was measured under measurement conditions of load: 0.1 gf, speed: 0.0145 gf / sec, holding time: 5 seconds, temperature 23 ° C, and 140 ° C. The results are shown in Table 1.

(6) Evaluation of adhesiveness

After the pressure cooker test (120 degreeC, 100% of humidity, 4 hours) was performed with respect to the board | substrate which has the protective film formed as mentioned above, the protective film was adhered by 8.5.3 adhesive lattice tape method of JISK-5400-1990. Adhesion (adhesion to SiO ₂ ) was evaluated. The number of remaining grids among the 100 grids is shown in Table 2 below.

Further, as an evaluation of the adhesion to the Cr, SiO ₂ glass was immersed except that the Cr substrate instead of the substrate forming a protective film of the same thickness of 2.0 ㎛ above, and the same evaluation by the grid tape method. The results are shown in Table 1.

(7) Evaluation of ITO Etch Resistance

With respect to the substrate having the protective film formed as described above, an ITO target (ITO filling rate of 95% or more and In ₂ O ₃ / SnO ₂ = 90/10 weight ratio in a high-speed sputtering apparatus SH-550-C12 manufactured by Nippon Shinjuku Co., Ltd.) ITO sputtering was carried out at 60 ° C. At this time, the atmosphere had a reduced pressure of 1.0 × 10 ⁻⁵ Pa, an Ar gas flow rate of 3.12 × 10 ⁻³ m ³ / h, and an O ₂ gas flow rate of 1.2 × 10 ⁻⁵ m ³ / h. The board | substrate after sputtering was heated in 240 degreeC x 60 minutes in the said clean oven, and it annealed. Next, the board | substrate was set to the spinner, JSR Corporation G-ray positive resist PFR3650-21cp was dripped on the board | substrate, and it coated at 3500 rpm x 30 second. The substrate was warmed on a hot plate at 90 ° C. × 2 minutes to remove the solvent. Subsequently, an ghi line (wavelength ratio of 436 nm, 405 nm, and 365 nm = 2.7: 2.5) using an exposure machine Canon PLA501F (manufactured by Canon Corporation) via a pattern mask of 10 µm / 10 µm. : 4.8) was irradiated with an exposure dose of roughness 23 mW / m ² and 25 mJ / m ² in terms of i-rays, immersed for 60 seconds using 2.4% TMAH aqueous solution at room temperature, and rinsed with ultrapure water for 60 seconds, It was airy. Thereafter, the plate was baked in a clean oven at 150 ° C for 60 minutes. The etchant was used by mixing nitric acid / hydrochloric acid in a weight ratio of 1/3. The substrate was immersed in an etchant, the substrate was taken out every 10 seconds to determine the exact etching time for forming a 10 μm ITO line, and the ITO line width at 1.2 times the correct etching time was measured by an optical microscope. , The results are shown in Table 1. It was said that the higher the retention rate of the 10-micrometer ITO line, the better the ITO etching resistance.

(8) Evaluation of flatness

Pigment-based color resists (trade names "JCR RED 689", "JCR GREEN 706", "CR 8200B", manufactured by JSR Co., Ltd.) were coated on a SiO ₂ immersion glass substrate by a spinner, and then heated to 90 ° C on a hot plate. Prebaking was carried out for 150 seconds to form a coating film. Then, i-line conversion of ghi line (wavelength 436 nm, 405 nm, 365 nm intensity ratio = 2.7: 2.5: 4.8) using the exposure machine Canon PLA501F (made by Canon Co., Ltd.) via a predetermined | prescribed pattern mask. Irradiated with an exposure dose of 2,00 J / m ² , developed using 0.05% potassium hydroxide aqueous solution, rinsed with ultrapure water for 60 seconds, and further heated at 230 ° C. for 30 minutes in an oven to obtain red, green and blue colors. Three color stripe-like color filters (stripe width of 100 mu m) were formed.

It was 1.0 micrometer when the unevenness | corrugation of the surface of the board | substrate with which this color filter was formed was measured with the surface roughness meter "(alpha) -step" (brand name; Tencol company make). However, it measured by the measurement length 2,000 micrometers, the measurement range 2,000 micrometers side, and the measurement score n = 5. That is, the measurement direction is set as two directions of the stripe line short axis direction in the red, green, and blue directions and the stripe line major axis direction of the same color of red, red, green, green, blue, and blue, and n = 5 for each direction. It measured (the n-number of the sum is 10).

After applying the composition for forming a protective film thereon with a spinner, the film is prebaked on a hot plate for 5 minutes at 90 ° C. for 5 minutes, and further heated at 230 ° C. for 60 minutes in an oven to obtain a film thickness from the upper surface of the color filter. A protective film having a thickness of 2.0 μm was formed. However, the film thickness here means the thickness from the uppermost surface of the color filter formed on the substrate.

The surface unevenness | corrugation of the protective film was measured with the contact type film thickness measuring apparatus (alpha) -step (made by Tencol Japan Co., Ltd.) about the board | substrate which has a protective film on the color filter formed as mentioned above. However, it measured by the measurement length 2,000 micrometers, the measurement range 2,000 micrometers side, and the measurement score n = 5. That is, the measurement direction is set as two directions of the stripe line short axis direction in the red, green, and blue directions and the stripe line major axis direction of the same color of red, red, green, green, blue, and blue, and n = 5 for each direction. It measured (the n-number of the sum is 10). Table 1 shows ten average values of the height difference (nm) of the highest part and the lowest part of each measurement. When this value is 300 nm or less, it can be said that planarization property is favorable.

(9) Evaluation of storage stability

The viscosity in the resin composition for protective film formation manufactured in Example 1 was measured using the Tokyo Keiki Co., Ltd. product ELD type viscometer. Thereafter, the solution viscosity at 25 ° C. was measured daily while the composition was left at 25 ° C. The number of days required to thicken 5% based on the viscosity immediately after manufacture was calculated | required, and this day is shown in Table 1. When this number of days is 20 days or more, it can be said that storage stability is favorable.

Examples 2 to 28 and Comparative Examples 1 and 2

The type and amount of each component of the composition were as described in Tables 1 and 2, and were adjusted in the same manner as in Example 1 except that the solids concentrations shown in Tables 1 and 2 were adjusted using the solvents shown in Tables 1 and 2. To prepare a resin composition.

The protective film was formed and evaluated similarly to Example 1 using the resin composition for protective film formation manufactured as mentioned above. The results are shown in Table 1 and Table 2.

Examples 29-32

The resin composition was produced like Example 1 except having set the kind and quantity of each component of a composition as Table 2, and using the solvent of Table 2 to the solid content concentration of Table 2.

The resin composition was produced like Example 1 except having apply | coated using the slit die coater instead of a spin coater, and the protective film was formed and evaluated. The results are shown in Table 2.

In addition, in Table 1 and Table 2, abbreviated-name of a cationically polymerizable compound (B), a thermosensitive acid generator (C), an adhesion | attachment adjuvant (D), and a solvent (S) shows the following, respectively.

B-1: Bisphenol A novolak-type epoxy resin (Japan Epoxy Resin Co., Ltd. make brand name: Epicoat 157S65)

C-1: triphenylsulfonium trifluoromethanesulfonate

D-1: γ-glycidoxypropyltrimethoxysilane

D-2: γ-glycidoxypropyltriethoxysilane

E-1: Silicone type surfactant (Toray Dow Corning Silicone Co., Ltd. make brand name: SH-28PA)

S-1: Propylene Glycol Monomethyl Ether Acetate

S-2: diethylene glycol dimethyl ether

According to the present invention, the composition of the present invention can form a cured film having excellent storage stability and high flatness, high transparency and surface hardness, and various kinds of heat resistance pressure resistance, acid resistance, alkali resistance, sputtering resistance, and etching resistance. The protective film for optical devices excellent in resistance is formed.

Claims (10)

[A-1] (a1) A polymer unit derived from a polymerizable unsaturated compound having an oxylalanyl group or an oxetanyl group and (a2) A polymer unit derived from a polymerizable unsaturated compound having a structure represented by the following formula (01) A copolymer characterized in that it is prepared. <Formula 01>

Wherein R is a tertiary alkyl group having at least 5 carbon atoms, a tertiary alkyl group having at least 4 carbon atoms substituted with an alkoxy group having 1 to 4 carbon atoms, and bonded as a tertiary carbon atom to an oxygen atom (-O-) bonded to R in the above-described formula It is a 4-membered or more lactone ring or lactam ring couple | bonded with the cycloalkyl group of the reduced carbon number 3 or more, or the oxygen atom (-O-) couple | bonded with R in the said Formula shown by the tertiary carbon atom. The copolymer according to claim 1, wherein the structure represented by Formula 01 is a structure represented by Formula 1, a structure represented by Formula 2, or a structure represented by Formula 3 below. <Formula 1>

Herein, R ¹ and R ² are each independently an alkyl group having 1 to 8 carbon atoms or an alkyl group having 1 to 8 carbon atoms substituted with an alkoxy group having 1 to 4 carbon atoms, and R ³ is an alkyl group having 2 to 8 carbon atoms or 1 to 4 carbon atoms. It is a C1-C8 alkyl group substituted by the alkoxy group. <Formula 2>

Herein, the definition of R ¹ is the same as that of Chemical Formula 1, n is an integer of 1 to 8, R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently of each other a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, or C1-C8 alkyl group or C1-C4 alkoxy group which has a C1-C4 alkoxy group in the terminal or side chain of an alkyl group, or R <^4> , R <^5> , R <^6> and R <^7> combine two or more To form a dicycloalkane or tricycloalkane structure having 7 to 16 total carbon atoms, together with the carbon atom to which they are attached and the carbon atom to which R ¹ is bonded, provided that when n = 2 to 8, A plurality of R ⁶ and R ⁷ may be the same or different. <Formula 3>

Herein, the definition of R ¹ is the same as that of Formula 1, l is 0, 1 or 2, m is an integer of 1 to 4, X is an oxygen atom or a nitrogen atom, R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ is independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms having an alkoxy group having 1 to 4 carbon atoms at the end or side chain of the alkyl group, or an alkoxy group having 1 to 4 carbon atoms, provided that Two R <^8> and two R <^9> when l = 2, and some R <^10> and some R <^11> when m is an integer of 2-4 may be same or different. The copolymer [A-1] of Claim 1 is contained, The resin composition characterized by the above-mentioned. [A-2] A polymer obtained by polymerizing a component containing the polymerizable unsaturated compound (a1), and [A-3] a polymer obtained by polymerizing a component containing the polymerizable unsaturated compound (a2) Resin composition characterized by the above-mentioned. The resin composition of Claim 3 or 4 which further contains a [B] cationically polymerizable compound. The [A-3] component of Claim 4, and the [B] component of Claim 5 are contained, The resin composition characterized by the above-mentioned. The resin composition according to any one of claims 3 to 6, further comprising [C] a thermosensitive acid generator. The resin composition according to any one of claims 3 to 7, which is for forming a protective film of a color filter. The coating film of the resin composition of Claim 7 is formed on a board | substrate, and it heat-processes continuously, The formation method of the protective film of a color filter characterized by the above-mentioned. The protective film of a color filter formed from the resin composition of Claim 8.