KR20100087659A - Radiation sensitive resin composition, and spacer for liquid crystal display device and forming method thereof - Google Patents

Abstract

PURPOSE: A radiation sensitive resin composition, a spacer of a liquid display device, and a method for forming the same are provided to form the spacer of the liquid display device without generating minute concavo-convex parts on a film even when a slit coating method is used. CONSTITUTION: A radiation sensitive resin composition comprises: an alkali soluble resin; a polymerizable unsaturated compound; a radiation sensitive polymerization initiator; and copolymers including a compound which is marked by CH2=CR^1COO-C_α H_2α -C_β F_2β+1, a compound which is marked by CH2=CR^2COO-(C_γ H_2γ-O)_a-R^3, and a polymerizable unsaturated compound including a functional group which is marked by chemical formula 1.

Description

A radiation sensitive resin composition, the spacer of a liquid crystal display element, and its formation method {RADIATION SENSITIVE RESIN COMPOSITION, AND SPACER FOR LIQUID CRYSTAL DISPLAY DEVICE AND FORMING METHOD THEREOF}

This invention relates to a radiation sensitive resin composition, the spacer of a liquid crystal display element, and its formation method.

In liquid crystal display elements, spacer particles such as glass beads and plastic beads having a predetermined particle diameter have been used in order to maintain a constant gap (cell gap) between two substrates. Since these spacer particles are randomly scattered on a transparent substrate such as a glass substrate, when the spacer particles are present in the pixel formation region, reflection phenomenon of the spacer particles occurs, or incident light is scattered and the contrast of the liquid crystal panel is lowered. There was problem to be. Then, in order to solve these problems, the method of forming a spacer in regions other than a pixel region was employ | adopted by photolithography using a radiation sensitive resin composition (patent document 1).

Therefore, in order to keep a cell gap constant in the whole area | region of a liquid crystal display element, high film thickness uniformity is required with respect to a spacer. In particular, in recent years, since the liquid crystal display device has been required to have a high definition of image quality and a high-speed responsiveness (high-speed response) to a high-speed moving image, the demand for film thickness uniformity is required. It is getting more sophisticated.

By the way, with the recent trend of large-screen TV and request for reduction of a process cost, there exists a tendency for the substrate glass size used for manufacture of the board | substrate with a color filter to enlarge. Therefore, in the application | coating process of the radiation sensitive resin composition performed at the time of forming a protective film and a spacer on a board | substrate, it is becoming difficult to employ | adopt the spin coating method conventionally widely performed, and a coating method uses a slit-shaped nozzle for a composition. It changes to what is called the slit coating method discharged from and apply | coats (patent document 2). This slit coating method also has the advantage of reducing the amount of the composition required for coating as compared to the spin coating method, and also helps to reduce the cost of liquid crystal display device manufacturing. However, in such a slit coating method, the coating nozzle is sweeped in a predetermined direction in a state in which the substrate is in close contact with the vacuum suction, and then applied, and then the support pins stored in the holes for vacuum suction are raised. The substrate is lifted and conveyed to the next step from the coating stage. Therefore, in this series of processes, the coating film has a nonuniformity called "stage vacuum adsorption trace" caused by a hole for vacuum adsorption, a nonuniformity called "support pin trace" caused by a support pin, and a sweeping direction of the coating nozzle. Unevenness called "vertical streak spots" which are displayed in a stripe shape may occur, and this hinders the high flatness as described above.

Japanese Patent Laid-Open No. 2001-261761 Japanese Laid-Open Patent Publication No. 2006-184841

This invention is made | formed based on the above circumstances, The objective of this invention is a liquid crystal display element without generating the nonuniformity which consists of minute unevenness | corrugation in a coating film even if the slit coating method is employ | adopted as a coating method. In particular, while maintaining the radiation-sensitive resin composition capable of forming the spacer, the performance required as a spacer of the liquid crystal display device (for example, compression performance and rubbing resistance in combination with high recovery rate and flexibility), particularly high film thickness uniformity There is provided a spacer of a liquid crystal display device having a property and a method of forming the same.

According to this invention, the said objective and advantage of this invention are 1st,

(A) alkali-soluble resin,

(B) a polymerizable unsaturated compound,

(C) a radiation sensitive polymerization initiator, and

(D) (d1) a compound represented by the following general formula (1 ⁰ ) (hereinafter referred to as "compound (d1)"),

(d2) a compound represented by the following general formula (2 ⁰ ) (hereinafter referred to as "compound (d2)"), and

(d3) A copolymer of a polymerizable unsaturated compound containing a polymerizable unsaturated compound (hereinafter referred to as "compound (d3)") having a group represented by the following general formula (3) (hereinafter "copolymer (D)" It is achieved by the radiation sensitive resin composition containing the same).

CH ₂ = CR ¹ COO-C _α H _{2 α} -C _β F _{2β + 1} (1 ⁰ )

(In formula (1 ⁰ ), R ¹ is a hydrogen atom or a methyl group, α is an integer of 0 to 6, and β is an integer of 1 to 20.)

CH ₂ = CR ² COO- (C _γ H _{2 γ} -O) _a -R ³ (2 ⁰ )

(In formula (2 ⁰ ), R ² is a hydrogen atom or a methyl group, R ³ is an alkyl group having 1 to 12 carbon atoms, γ is 2 or 3, a is the number of repeating units, and the number average thereof is 1 to 30). .)

(In formula (3), R <^4> , R <^5> , R <^6> , R <^7> and R <^8> are respectively independently group represented by a C1-C20 alkyl group, a phenyl group, or the following general formula (4), b is an integer of 0 to 3)

(In formula (4), R <^9> , R <^10> and R <^11> is respectively independently a C1-C20 alkyl group or a phenyl group, and c is an integer of 0-3.)

The above object and advantages of the present invention are,

The polymerizable (D) copolymer which contains the polymerizable unsaturated compound which has an alkyl group of (d4) C1-C8 further in addition to the said compound (d1), a compound (d2), and a compound (d3). It is achieved by the radiation sensitive resin composition of the said 1st which is a copolymer of an unsaturated compound.

According to this invention, the said objective and advantage of this invention are 3rd,

The (D) copolymer is a polymerizable unsaturated compound having at least two unsaturated bonds in (d5) 1 molecule in addition to the compound (d1), the compound (d2), the compound (d3) and the compound (d4). It is achieved by the radiation sensitive resin composition of the said 2nd which is a copolymer of the polymerizable unsaturated compound containing.

According to this invention, the said objective and advantage of this invention are 4th,

The compound (d1) is a compound represented by the following formula (1),

The compound (d2) is a compound represented by the following formula (2), further

(D) the copolymer,

25-35 mass% of compound (d1),

20-30 mass% of compound (d2),

15-20 mass% of compound (d3),

25-35 mass% of compound (d4), and

1-5 mass% of compound (d5)

It is achieved by the radiation sensitive resin composition of the said 3rd which is a copolymer of the polymerizable unsaturated compound which consists of.

CH ₂ = CR ¹ COOCH ₂ CH ₂ C ₈ F ₁₇ (1)

(In formula (1), R ¹ is as defined in the formula (1 ⁰ ).)

CH ₂ = CR ² COO (C ₂ H ₄ O) _a R ³ (2)

(Formula (2) of, R ² and R ³ are, respectively, the same meanings as defined in the formula ^(20), the number average value of a number of repeating units is 4 to 12).

The above object and advantages of the present invention are,

It is achieved by the formation method of the spacer for liquid crystal display elements containing at least the following processes in the order described below.

(1) process of apply | coating said radiation sensitive resin composition on a board | substrate, and forming a coating film,

(2) exposing to at least part of the coating film;

(3) developing the coating film after exposure; and

(4) The process of heating the coating film after image development.

And the above object and advantages of the present invention, sixth,

It is achieved by the spacer for liquid crystal display elements formed by the above method.

According to the present invention, even when the slit coating method is adopted as the coating method, the radiation-sensitive resin composition and the liquid crystal display element of the liquid crystal display element that can form a spacer of the liquid crystal display element without generating a non-uniform irregularity in the coating film A spacer of a liquid crystal display element having a high film thickness uniformity and a method of forming the same are particularly provided while maintaining the required performance as a spacer (for example, a compression performance in which both a high recovery rate and flexibility are combined, and rubbing resistance).

(Form to carry out invention)

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely.

<(A) alkali-soluble resin>

(A) alkali-soluble resin contained in the radiation sensitive resin composition of this invention will not be specifically limited if it is alkali-soluble resin which has solubility with respect to the developing solution used for the image development process mentioned later preferably an alkali developing solution. As such (A) alkali-soluble resin, alkali-soluble resin which has at least 1 sort (s) chosen from the group which consists of a carboxyl group and a carboxylic anhydride group is preferable,

(a1) at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter referred to as "compound (a1)"),

(a2) Copolymers with unsaturated compounds other than (a1) (hereinafter referred to as "compound (a2)") are preferred.

As a particularly preferable example of such an (A) alkali-soluble resin, a monomer containing [A1] compound (a1) and an unsaturated compound having at least one hydroxyl group in one molecule (hereinafter referred to as "compound (a2-1)") Polymer obtained by reacting an unsaturated isocyanate compound with a copolymer of hereinafter (hereinafter referred to as "copolymer [α]") (hereinafter referred to as "polymer [A]"), [A2] compound (a1) and an epoxy group Copolymer of a monomer containing an unsaturated compound (hereinafter referred to as "compound (a2-2)") (hereinafter referred to as "copolymer [β]"), [A3] compound (a1) and compound (a1) And copolymers of monomers composed of unsaturated compounds (hereinafter referred to as "compound (a2-3)") other than compound (a2-1) and compound (a2-2) (hereinafter referred to as "copolymer [γ]"). ), And the like. When manufacturing copolymer [α], compound (a2-3) can coexist and copolymer [α] can also be made into the copolymer of compound (a1), a compound (a2-1), and a compound (a2-3). In the production of the copolymer [β], the compound (a2-3) is coexisted in addition to the compound (a1) and the compound (a2-2), and the copolymer [β] is compound (a1) and compound (a2-2). ) And a copolymer of the compound (a2-3).

As a compound (a1) used when manufacturing a copolymer [(alpha), a copolymer [(beta)], and a copolymer [(gamma)], monocarboxylic acid, dicarboxylic acid, anhydride of dicarboxylic acid, etc. are mentioned, for example.

Examples of the monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, and 2- Methacryloyloxyethyl hexahydrophthalic acid and the like; As said dicarboxylic acid, For example, maleic acid, fumaric acid, citraconic acid, etc .; As anhydride of the said dicarboxylic acid, anhydride etc. of said dicarboxylic acid are mentioned, respectively.

Among these, acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, or maleic anhydride are preferable from the viewpoint of copolymerization reactivity and solubility in a developing solution of a copolymer obtained.

Compound (a1) can be used individually or in mixture of 2 or more types. In the copolymer [α], the copolymer [β] and the copolymer [γ], the content of the repeating unit derived from the compound (a1) is preferably 5 to 60 mass%, more preferably 7 to 50. It is mass%, Especially preferably, it is 8-40 mass%. When the content rate of the repeating unit derived from a compound (a1) is 5-60 mass%, the radiation sensitive resin composition by which the various characteristics, such as radiation sensitivity, developability, and storage stability, were balanced to a higher level is obtained.

As a compound (a2-1) used for manufacture of a copolymer [(alpha)], the hydroxyalkyl ester of (meth) acrylic acid, the hydroxycycloalkyl ester of (meth) acrylic acid, the dihydroxyalkyl ester of (meth) acrylic acid, (6-hydroxyhexanoyloxy) alkyl ester of (meth) acrylic acid, etc. are mentioned. As these specific examples, it is (meth) acrylic acid 2-hydroxyethyl ester, (meth) acrylic acid 3-hydroxypropyl ester, (meth) acrylic acid 4-hydroxybutyl as hydroxyalkyl ester of (meth) acrylic acid, for example. Ester, (meth) acrylic acid 5-hydroxypentyl ester, (meth) acrylic acid 6-hydroxyhexyl ester, etc .; As the hydroxycycloalkyl ester of (meth) acrylic acid, it is (meth) acrylic-acid 4-hydroxy-cyclohexyl ester, (meth) acrylic-acid 4-hydroxymethyl-cyclohexyl methyl ester, (meth) acrylic acid 4-hydroxy, for example. Oxyethyl-cyclohexylethyl ester, etc .;

As the dihydroxyalkyl ester of (meth) acrylic acid, for example, (meth) acrylic acid 1,2-dihydroxyethyl ester, (meth) acrylic acid 2,3-dihydroxypropyl ester, (meth) acrylic acid 1,3 -Dihydroxy propyl ester, (meth) acrylic acid 3,4-dihydroxy butyl ester, etc .; As the (6-hydroxyhexanoyloxy) alkyl ester of (meth) acrylic acid, for example, (meth) acrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester, (meth) acrylic acid 3- (6-hydroxy) (Meth) acrylic acid (6-hydroxyhexanoyloxy) alkyl esters, such as hexanoyloxy) propyl ester and (meth) acrylic acid 4- (6-hydroxyhexanoyloxy) butyl ester, etc. are mentioned, respectively.

Among these compounds (a2-1), acrylic acid 2-hydroxyethyl ester, acrylic acid 3-hydroxypropyl ester, acrylic acid 4-hydroxybutyl ester and methacrylic acid 2- Hydroxyethyl ester, methacrylic acid 3-hydroxypropyl ester, methacrylic acid 4-hydroxybutyl ester, acrylic acid 4-hydroxymethyl cyclohexyl methyl ester, methacrylic acid 4-hydroxymethyl cyclohexyl methyl ester , Acrylic acid 2,3-dihydroxypropyl ester, methacrylic acid 2,3-dihydroxypropyl ester, and (meth) acrylic acid (6-hydroxyhexanoyloxy) alkyl ester are preferable.

In the compound (a2-1), the (meth) acrylic acid (6-hydroxyhexanoyloxy) alkyl ester is particularly preferable from the viewpoint of improving the developability and the compression performance of the spacer formed. Among the (meth) acrylic acid (6-hydroxyhexanoyloxy) alkyl esters, (meth) acrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester is particularly preferable.

As a commercial item of the mixture of methacrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester and methacrylic acid 2-hydroxyethyl ester, PLACCEL®FM1D and FM2D (brand name, produced by Daicel Kagaku Kogyo Co., Ltd.), respectively. Etc. can be mentioned.

In the copolymer [(alpha)], the above compound (a2-1) can be used individually or in mixture of 2 or more types.

In the copolymer [α], the content rate of the repeating unit derived from the compound (a2-1) is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, particularly preferably 5 to 30 mass%. When the content rate of the repeating unit derived from a compound (a2-1) is 1-50 mass%, stability of the copolymer obtained by reaction with an unsaturated isocyanate compound becomes favorable, As a result, the storage of the radiation-sensitive resin composition obtained Stability becomes good.

As an epoxy group in the compound (a2-2) used for manufacture of a copolymer [(beta)], an oxiranyl group (having a 1,2-epoxy structure), an oxetanyl group (having a 1,3-epoxy structure), etc. Can be mentioned.

As an unsaturated compound which has an oxiranyl group, For example, (meth) acrylic-acid oxiranyl (cyclo) alkyl ester, (alpha)-alkylacrylic-acid oxiranyl (cyclo) alkyl ester, the glycidyl ether compound which has an unsaturated bond, etc .;

As an unsaturated compound which has an oxetanyl group, the (meth) acrylic acid ester etc. which have an oxetanyl group are mentioned, for example. As these specific examples, it is (meth) acrylic-acid oxiranyl (cyclo) alkyl ester, For example, (meth) acrylic-acid glycidyl, (meth) acrylic-acid 2-methylglycidyl, 4-hydroxybutyl (meth) acrylate Glycidyl ether, (meth) acrylic acid 3,4-epoxybutyl, (meth) acrylic acid 6,7-epoxyheptyl, (meth) acrylic acid 3,4-epoxycyclohexyl, (meth) acrylic acid 3,4-epoxycyclohexyl Methyl and the like; As (alpha)-alkyl acrylate oxiranyl (cyclo) alkyl ester, For example, (alpha)-ethyl acrylate glycidyl, the (alpha)-n-propyl acrylate glycidyl, the (alpha)-n-butyl acrylate glycidyl, 6, the ethyl ethyl acrylate; 7-epoxyheptyl, alpha -ethylacrylic acid 3,4-epoxycyclohexyl, etc .;

As a glycidyl ether compound which has an unsaturated bond, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, etc. are mentioned, for example;

As (meth) acrylic acid ester which has an oxetanyl group, for example, 3-((meth) acryloyloxymethyl) oxetane, 3-((meth) acryloyloxymethyl) -3-ethyloxetane, 3 -((Meth) acryloyloxymethyl) -2-methyl oxetane, 3-((meth) acryloyloxyethyl) -3-ethyl oxetane, 2-ethyl-3-((meth) acryloyl Oxyethyl) oxetane, 3-methyl- 3- (meth) acryloyl oxymethyl oxetane, 3-ethyl- 3- (meth) acryloyl oxymethyl oxetane, etc. are mentioned, respectively.

Among these, methacrylic acid glycidyl, methacrylic acid 2-methylglycidyl, methacrylic acid 3,4- epoxycyclohexyl, methacrylic acid 3,4- epoxycyclohexylmethyl, 3-methacryloyl Oxymethyl- 3-ethyl oxetane, 3-methyl- 3-methacryloyl oxymethyl oxetane, or 3-ethyl- 3-methacryloyl oxymethyl oxetane is preferable from a polymerizable viewpoint.

In manufacture of a copolymer [(beta)], a compound (a2-2) can be used individually or in mixture of 2 or more types.

In the copolymer [β], the content rate of the repeating unit derived from the compound (a2-2) is preferably 0.5 to 70 mass%, more preferably 1 to 60 mass%, particularly preferably 3 to 50 mass%. When the content rate of the repeating unit derived from a compound (a2-2) is 0.5-70 mass%, the sense | storage stability of the radiation sensitive resin composition obtained, the heat resistance of the spacer formed from this, and the compression performance balanced by higher level A radioactive resin composition is obtained.

As a compound (a2-3) used at the time of manufacture of a copolymer [(gamma)], or which can be used arbitrarily at the time of manufacture of a copolymer [(alpha)] and a copolymer [(beta)], it is alkyl (meth) acrylate, for example. (Meth) acrylic acid ester having (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid aryl ester, (meth) acrylic acid aralkyl ester, unsaturated dicarboxylic acid dialkyl ester, oxygen containing hetero 5-membered ring or oxygen containing hetero 6-membered ring And vinyl aromatic compounds, conjugated diene compounds, and other unsaturated compounds.

As these specific examples, it is (meth) acrylic-acid alkylester, for example, methyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, (meth) acrylic acid sec-butyl, t-butyl (meth) acrylate, etc .; As the (meth) acrylic acid cycloalkyl ester, for example, (meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-methylcyclohexyl, (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl, ( Meta) acrylic acid 2- (tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxy) ethyl, (meth) acrylic acid isoboroyl and the like;

As (meth) acrylic-acid aryl ester, For example, phenyl acrylate etc .; As (meth) acrylic-acid aralkyl ester, For example, (meth) acrylic-acid benzyl etc .; As unsaturated dicarboxylic acid dialkyl ester, For example, diethyl maleate, diethyl fumarate, etc .; As (meth) acrylic acid ester which has an oxygen containing hetero 5-membered ring or an oxygen containing hetero 6-membered ring, For example, (meth) acrylic-acid tetrahydrofuran-2-yl, (meth) acrylic-acid tetrahydropyran-2-yl, (meth) Acrylic acid 2-methyltetrahydropyran-2-yl and the like;

As a vinyl aromatic compound, For example, styrene, (alpha) -methylstyrene, p-methoxy styrene;

As a conjugated diene compound, For example, 1, 3- butadiene, isoprene, etc .;

As other unsaturated compounds, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, methacrylic acid 2-methylglycidyl, etc. are mentioned, for example.

Of these compounds (a2-3), from the viewpoint of copolymerization reactivity, n-butyl methacrylate, 2-methylglycidyl methacrylate, benzyl methacrylate, tricyclomethacrylic acid [5.2.1.0 ^2,6 ] Decane-8-yl, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1, 3- butadiene, etc. are preferable.

In the production of the copolymer [α], the copolymer [β] and the copolymer [γ], the compound (a2-3) can be used alone or in combination of two or more thereof.

In the copolymer [α] and the copolymer [β], the content rate of the repeating unit derived from the compound (a2-3) is preferably 10 to 80 mass%, more preferably 20 to 70 mass%, particularly preferably Preferably it is 30-70 mass%. When the content rate of the repeating unit of a compound (a2-3) is 10-80 mass%, the control of the molecular weight of a copolymer becomes easy, and the radiation sensitive resin composition balanced by higher level of developability, radiation sensitivity, etc. Obtained.

The copolymer [α], the copolymer [β] and the copolymer [γ] are preferably produced by polymerizing a mixture of such monomers in a suitable solvent, preferably in the presence of a radical polymerization initiator. As a solvent used for the said superposition | polymerization, a diethylene glycol alkyl ether, a propylene glycol monoalkyl ether acetate, an alkoxy propionic acid alkyl, an acetate ester, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl, for example Methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, cyclohexanol acetate, benzyl Alcohol, 3-methoxy butanol, etc. are mentioned. These solvent can be used individually or in mixture of 2 or more types.

It does not specifically limit as said radical polymerization initiator, For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis- (2, 4- dimethylvaleronitrile), 2,2 ' -Azobis- (4-methoxy-2,4-dimethylvaleronitrile), 4,4'- azobis (4-cyano valeric acid), dimethyl-2,2'- azobis (2-methylprop Azo compounds, such as a cyanate) and 2,2'- azobis (4-methoxy- 2, 4- dimethylvaleronitrile), are mentioned. These radical polymerization initiators can be used individually or in mixture of 2 or more types.

In the copolymer [α], the copolymer [β] and the copolymer [γ], the weight average molecular weight (hereinafter referred to as "Mw") of polystyrene conversion measured by gel permeation chromatography (GPC) is preferably Is 2,000-100,000, More preferably, it is 5,000-50,000. When the Mw of the copolymer [α], the copolymer [β] and the copolymer [γ] is 2,000 to 100,000, a radiation-sensitive resin composition in which heat resistance, developability, radiation sensitivity and the like are balanced at a higher level is obtained.

Polymer [A] can be obtained by reacting an unsaturated isocyanate compound with copolymer [α]. The copolymer [α] obtained as described above may provide the polymerization reaction solution as it is for the production of polymer [A], or may be used to prepare the polymer [A] after separating the copolymer [α] from the solution. It may be.

As an unsaturated isocyanate compound, a (meth) acrylic acid derivative etc. are mentioned, for example, As a specific example, 2- (meth) acryloyloxyethyl isocyanate and 3- (meth) acryloyloxypropyl isocyanate, for example. , 4- (meth) acryloyloxybutyl isocyanate, 6- (meth) acryloyloxyhexyl isocyanate, 8- (meth) acryloyloxyoctyl isocyanate, 10- (meth) acryloyloxydecyl isocyanate, ( Meta) acrylic acid 2- (2-isocyanate ethoxy) ethyl, (meth) acrylic acid 2- [2- (2-isocyanate ethoxy) ethoxy] ethyl, (meth) acrylic acid 2- {2- [2- (2- Isocyanate ethoxy) ethoxy] ethoxy} ethyl, (meth) acrylic acid 2- (2-isocyanate propoxy) ethyl, (meth) acrylic acid 2- [2- (2-isocyanate propoxy) propoxy] ethyl, etc. are mentioned. Can be.

As these commercial items, Karenz AOI (manufactured by Showa Denko Co., Ltd.) and 2-methacryloyloxyethyl isocyanate are commercially available products of 2-acryloyloxyethyl isocyanate. As a commercial item of (Showa Denko Co., Ltd.) and methacrylic acid 2- (2-isocyanate ethoxy) ethyl, Kalenz MOI-EG (made by Showa Denko Co., Ltd.) is mentioned, respectively.

Of these unsaturated isocyanate compounds, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 4-methacryloyloxybutyl isocyanate or methacrylic acid 2 from the viewpoint of reactivity with the copolymer [α]. -(2-isocyanate ethoxy) ethyl is preferred.

In manufacture of polymer [A], an unsaturated isocyanate compound can be used individually or in mixture of 2 or more types.

The reaction between the copolymer [α] and the unsaturated isocyanate compound is unsaturated in the presence of a suitable catalyst as necessary, preferably with stirring at room temperature or under heating in a solution of the copolymer [α] containing a polymerization inhibitor. It can carry out by adding an isocyanate compound. Examples of the catalyst include dilauric acid di-n-butyltin (IV) and the like; As said polymerization inhibitor, p-methoxy phenol etc. are mentioned, respectively.

The use ratio of the unsaturated isocyanate compound in producing the polymer [A] is preferably 0.1 to 95 mol%, more preferably relative to the hydroxyl group derived from the compound (a2-1) in the copolymer [α]. 1.0-80 mol%, Especially preferably, it is 5.0-75 mol%. When the use ratio of an unsaturated isocyanate compound is 0.1-95 mol%, the heat resistance and elasticity characteristic of the spacer formed are improved more, and it is preferable.

In the radiation sensitive resin composition of the present invention, the polymer [A], the copolymer [β], and the copolymer [γ] may be used alone, respectively, but the polymer [A] and the copolymer [β] may be used in combination. Or a copolymer [β] and a copolymer [γ] are preferably used together.

By using the polymer [A] and the copolymer [β] together, it is possible to further improve the storage stability of the obtained radiation-sensitive resin composition and the strength and heat resistance of the spacer to be formed, which is preferable. When using a polymer [A] and a copolymer [β] together, as a use ratio of the polymer [A], it is 0.5-50 mass parts with respect to 100 mass parts of copolymers [β], More preferably, 1 It is -30 mass parts, Especially preferably, it is 3-20 mass parts. When the use ratio of the polymer [A] is 0.5-50 mass parts, the radiation sensitive resin composition balanced by the level with high storage stability of the radiation sensitive resin composition and the heat resistance of the spacer formed is obtained.

On the other hand, by using a copolymer [β] and a copolymer [γ] together, the advantage that the storage stability of a radiation sensitive resin composition can be improved more is obtained, and it is preferable. In the case of using the copolymer [β] and the copolymer [γ] in combination, the use ratio of the copolymer [β] is preferably 10 to 150 parts by mass, and more preferably 100 parts by mass of the copolymer [γ]. Is 20-130 mass parts, Especially preferably, it is 30-100 mass parts.

<(B) polymerizable unsaturated compound>

The (B) polymerizable unsaturated compound contained in the radiation sensitive resin composition of this invention is an unsaturated compound which superposes | polymerizes by irradiating a radiation in presence of the (C) radiation sensitive polymerization initiator mentioned later. Although it does not specifically limit as such a polymerizable unsaturated monomer, For example, since the monofunctional, bifunctional, or trifunctional or more (meth) acrylic acid ester has good polymerizability and the strength of the spacer formed is improved. desirable.

As said monofunctional (meth) acrylic acid ester, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, ( 2-acryloyloxyethyl) (2-hydroxypropyl) phthalate, (2-methacryloyloxyethyl) (2-hydroxypropyl) phthalate, ω-carboxy polycaprolactone monoacrylate, etc. are mentioned. . As these commercial items, ARONIX M-101, M-111, M-114, M-5300 (above, Toagosei Co., Ltd. make) are brand names, for example; KAYARAD TC-110S and TC-120S (above, Nippon Kayaku Co., Ltd. product); VISCOAT 158, 2323 (above, Osaka Yuki Kagaku Kogyo Co., Ltd.), etc. are mentioned.

As said bifunctional (meth) acrylic acid ester, for example, ethylene glycol diacrylate, propylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol Diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol di Methacrylate, and the like. As these commercial items, for example, ARONIX M-210, M-240, M-6200 (above, Toagosei Co., Ltd.), KAYARAD®HDDA, HX-220, R-604 (above) , Nippon Kayaku Co., Ltd., VISCOAT 260, East 312, East 335HP (above, Osaka Yukikagaku Kogyo Co., Ltd.), Light acrylate 1,9-NDA (Kyoeisha Kagaku Co., Ltd.) Etc. can be mentioned.

As said trifunctional or more than (meth) acrylic acid ester, a trimethylol propane triacrylate, a trimethylol propane trimethacrylate, a pentaerythritol triacrylate, a pentaerythritol trimethacrylate, a pentaerythritol tetraacrylate, a pentaerythritol, for example Tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate Other than ethylene oxide modified dipentaerythritol hexaacrylate, tri (2-acryloyloxyethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate,

A compound having a linear alkylene group and an alicyclic structure, and also having a compound having two or more isocyanate groups and a compound having one or more hydroxyl groups in the molecule and having three, four or five (meth) acryloyloxy groups is reacted. The polyfunctional urethane acrylate type compound etc. which are obtained are mentioned.

As a commercial item of the (meth) acrylic acid ester more than trifunctional, in a brand name, for example, ARONIX M-309, copper M-400, copper M-405, copper M-450, copper M-7100, copper M-8030, copper M -8060, copper TO-1450 (above, Toagosei Co., Ltd.), KAYARAD TMPTA, copper DPHA, copper DPCA-20, copper DPCA-30, copper DPCA-60, copper DPCA-120, copper DPEA-12 (more Nippon Kayaku Co., Ltd.), VISCOAT 295, Copper 300, Copper 360, Copper GPT, Copper 3PA, Copper 400 (above, manufactured by Osaka Yukikagaku Kogyo Co., Ltd.) and polyfunctional urethane acrylate compounds As a commercial item to contain, NEW FRONTIER R-1150 (made by Daiichi Kogyo Seiyaku Co., Ltd.), KAYARAD DPHA-40H (made by Nippon Kayaku Co., Ltd.), etc. are mentioned.

Among these, in particular, ω-carboxy polycaprolactone monoacrylate, 1,9-nonanediol dimethacrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacryl Commercial products containing latex, dipentaerythritol hexaacrylate, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, ethylene oxide-modified dipentaerythritol hexaacrylate, and polyfunctional urethane acrylate compounds; desirable.

The above-mentioned (B) polymerizable unsaturated compounds can be used individually or in mixture of 2 or more types.

The use ratio of the (B) polymerizable unsaturated monomer in the radiation-sensitive resin composition of the present invention is preferably 30 to 250 parts by mass, more preferably 50 to 100 parts by mass of the (A) alkali-soluble resin. It is -200 mass parts. (B) When the usage-amount of a polymerizable unsaturated monomer is 30-250 mass parts, the intensity | strength of a radiation sensitive resin composition, and the heat resistance and elasticity characteristic of the spacer formed become more favorable.

<(C) radiation sensitive polymerization initiator>

The radiation sensitive polymerization initiator [C] contained in the radiation sensitive resin composition of the present invention is a component that generates active species capable of initiating polymerization of the [B] polymerizable unsaturated compound in response to radiation. As such a [C] radiation sensitive polymerization initiator, an O-acyl oxime compound, an acetophenone compound, a biimidazole compound, a benzophenone compound, etc. are mentioned.

Specific examples of the O-acyl oxime compound include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyl oxime) and 1- [9-ethyl-6-benzoyl-9H-carbazole-3-yl] -octane-1-onoxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-day] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9H-carbazole-3-yl] -ethane-1- Onoxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4- tetrahydrofuranyl benzoyl) -9H-carbazol-3-yl] -1- (O-acetyl Oxime), ethanone-1- (9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyl oxime), ethanone -1-[9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyl oxime) Non-l- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxoranyl) methoxybenzoyl} -9H-carbazole-3-yl] -1- (O-acetyl oxime) etc. are mentioned.

Among them, as preferable O-acyl oxime compounds, ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyl oxime), eta Non-l- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyl oxime) or ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxoranyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyl Oxime).

These O-acyl oxime compounds can be used individually or in mixture of 2 or more types.

As said acetophenone compound, the (alpha)-amino ketone compound and the (alpha)-hydroxy ketone compound are mentioned, for example.

Specific examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2-dimethylamino-2- (4-methylbenzyl) -1 -(4-morpholin-4-yl-phenyl) -butane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, and the like;

As a specific example of an alpha-hydroxy ketone compound, it is 1-phenyl- 2-hydroxy- 2-methyl propane- 1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methyl, for example. Propane-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, and 1-hydroxycyclohexylphenyl ketone.

Among these acetophenone compounds, an α-amino ketone compound is preferable, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one or 2-dimethylamino-2- (4- Methyl benzyl) -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'-ratio Imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichloro Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5, 5'-tetraphenyl- 1,2'- biimidazole etc. are mentioned.

Among these biimidazole compounds, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl -1,2'-biimidazole and 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 preferable.

In the radiation-sensitive resin composition of the present invention, in the case of using a nonimidazole compound as the (C) radiation-sensitive polymerization initiator, an aliphatic or aromatic compound having a dialkylamino group (hereinafter referred to as "amino sensitizer") And at least one selected from thiol compounds.

The amino-based sensitizer is a compound having a function of increasing or decreasing the radiation sensitivity of the biimidazole compound to increase the generation efficiency of imidazole radicals, improving the sensitivity and resolution of the radiation-sensitive resin composition, and forming a spacer or a protective film. It can be added for the purpose of further improving the adhesiveness to the substrate. Examples of such amino sensitizers include N-methyl diethanolamine, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, and ethyl p-dimethylaminobenzoate. and p-dimethylaminobenzoic acid i-amyl etc. are mentioned. Among these amino sensitizers, 4,4'-bis (diethylamino) benzophenone is particularly preferable. These amino sensitizers can be used individually or in mixture of 2 or more types.

The addition amount of an amino-type sensitizer becomes like this. Preferably it is 0.1-50 mass parts with respect to 100 mass parts of biimidazole compounds, More preferably, it is 1-20 mass parts. When the amount of the amino sensitizer added is less than 0.1 part by mass, the effect of improving the sensitivity, the resolution, and the adhesion may be insufficient. On the other hand, when the amount of the amino sensitizer is exceeded, the shape of the spacer to be formed may be damaged.

The thiol compound is a compound having a function of donating hydrogen radicals to imidazole radicals and, as a result, generating a component having a sulfur radical. Since the polymerization initiation capacity of the imidazole radical generated when the biimidazole compound is cleaved upon irradiation with radiation is moderate and not extremely high, when used as it is for formation of a spacer of a liquid crystal display device, The cross-sectional shape may be an undesirable shape of an inverse taper shape. However, by adding a thiol compound to the imidazole radical, the hydrogen radical is donated from the thiol compound to convert the imidazole radical into a neutral imidazole, and a component having a sulfur radical having a higher polymerization initiation occurs. Therefore, the shape of the spacer can be reliably made a more preferable forward taper shape. As such a thiol compound, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-, for example Aromatic thiol compounds such as 5-methoxybenzimidazole; Aliphatic monothiol compounds such as 3-mercaptopropionic acid, methyl 3-mercaptopropionic acid, ethyl 3-mercaptopropionic acid and octyl 3-mercaptopropionic acid; And bifunctional or higher aliphatic thiol compounds such as 3,6-dioxane-1,8-octanedithiol, pentaerythritol tetra (mercaptoacetate), and pentaerythritol tetra (3-mercaptopropionate). Among these thiol compounds, 2-mercaptobenzothiazole is particularly preferable.

As addition amount of a thiol compound, Preferably it is 0.1-50 mass parts with respect to 100 mass parts of biimidazole compounds, More preferably, it is 1-20 mass parts. When the addition amount of a thiol compound is less than 0.1 mass part, the effect of improving a spacer shape may be inadequate, and when it exceeds 50 mass parts, the shape of the spacer formed may rather be damaged.

In the radiation sensitive resin composition of this invention, when using a biimidazole compound as a (C) radiation sensitive polymerization initiator, it is preferable to add both the said amino type sensitizer and a thiol compound.

As a usage ratio of the (C) radiation sensitive polymerization initiator in this invention, Preferably it is 1-60 mass parts with respect to 100 mass parts of (A) alkali-soluble resin, More preferably, it is 2-50 mass parts More preferably, it is 5-40 mass parts.

As the (C) radiation sensitive polymerization initiator contained in the radiation sensitive resin composition of this invention, it is preferable to contain at least 1 sort (s) chosen from the group which consists of an O-acyl oxime compound and an acetophenone compound, and O-acyl oxime It is more preferable to contain at least 1 sort (s) and a biimidazole compound chosen from the group which consists of a compound and an acetophenone compound.

As the ratio of the O-acyl oxime compound and the acetophenone compound in the radiation sensitive polymerization initiator (C), the total amount thereof is preferably 40% by mass or more relative to the total amount of the radiation sensitive polymerization initiator (C), and more preferably. Preferably it is 45 mass% or more, Especially preferably, it is 50 mass% or more. By using the (C) radiation sensitive polymerization initiator of such a composition, the radiation sensitive resin composition of this invention can form the spacer which has high hardness and adhesiveness even in the case of low exposure amount.

<Copolymer (D)>

The copolymer (D) in the present invention is a copolymer of a polymerizable unsaturated compound containing the compound (d1), the compound (d2) and the compound (d3), and in the resin composition for forming a spacer of the present invention, Even if it is used as a surfactant with a high performance of lowering the surface tension, and even when used in a small proportion, the surface smoothness of the coating film can be improved, whereby the film thickness uniformity of the spacer formed can be remarkably improved.

The copolymer (D) is preferably a polymerizable unsaturated compound having an alkyl group having 1 to 8 carbon atoms in addition to the compound (d1), the compound (d2) and the compound (d3). Compound (d4) "), and more preferably (d5) in addition to the compound (d1), the compound (d2), the compound (d3) and the compound (d4). A copolymer of a polymerizable unsaturated compound containing a polymerizable unsaturated compound having two or more unsaturated bonds (hereinafter referred to as "compound (d5)") in one molecule, and particularly preferably the compound (d1) and a compound It is a copolymer of the polymerizable unsaturated compound which consists of (d2), a compound (d3), a compound (d4), and a compound (d5).

The group -C _α H _{2 α} -in the general formula (1 ⁰ ) is a methylene group, an alkylmethylene group, or a linear or branched alkylene group. When the group —C _α H _{2 α} − is asymmetric, the direction of the bond is irrespective. Carbon number ( _{alpha) of} group -C ( _alpha) H2 _{( alpha)} -becomes like this. Preferably it is 2-4. Specific examples of the group -C _α H _{2 α} -include 1,2-ethylene groups, 1,2-propylene groups, 1,3-propylene groups, 1,4-butylene groups, and the like. A 1, 2- ethylene group or a 1, 3- propylene group is preferable, and a 1, 2- ethylene group is especially preferable.

The group -C _β F _{2β + 1} in the general formula (1 ⁰ ) is a linear or branched fluoroalkylene group, the carbon number β is 1-20, preferably 4-12, and particularly preferably 8 It is preferable that group -C ( _beta) F2 ( _{beta ) +1} is a linear fluoroalkylene group.

As a compound (d1) in this invention, it is preferable that it is a compound represented by following formula (1), and the compound represented by each of following formula (d1-1) and (d1-2) is mentioned as the specific example. Can be.

CH ₂ = CR ¹ COOCH ₂ CH ₂ C ₈ F ₁₇ (1)

(In formula (1), R ¹ is as defined in the formula (1 ⁰ ).)

CH ₂ = CHCOOCH ₂ CH ₂ (CF ₂ ) ₇ CF ₃ (d1-1)

CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ (CF ₂ ) ₇ CF ₃ (d1-2)

The group -C _γ H _{2 γ} -in the formula (2 ⁰ ) is a linear or branched alkylene group. When the group -C _γ H _{2 γ} -is asymmetric, the direction of bonding thereof is irrespective. As a specific example of group -C ( _gamma) H2 _{( gamma)} -, a 1,2-ethylene group and a 1,2-propylene group are mentioned, for example, It is preferable that it is a 1,2-ethylene group.

Compound (d2) is a repeating unit number of the value of a in the general formula ⁽²⁰⁾ is used as a mixture of different compounds. The number average value of a is 1-30, Preferably it is 2-20, It is especially preferable that it is 4-12. The value of this a can be calculated | required by calculation from the number average molecular weight of polystyrene conversion measured by the gel permeation chromatography about the compound (d2).

As a compound (d2) in this invention, it is preferable that it is a compound represented by following formula (2).

CH ₂ = CR ² COO (C ₂ H ₄ O) _a R ³ (2)

(Formula (2) of, R ² and R ³ are, respectively, the same meanings as defined in the formula ^(20), the number average value of a number of repeating units is 4 to 12).

As such a compound (d2), a commercial item can be used suitably, For example, NK-ester M-40G, M-90G, AM-90G by Shin-Nakamura Kagaku Co., Ltd .; Niche oil company BLEMMER PME-200, PME-400, PME-550 etc. are mentioned.

In the said General formula (3), when two or more R <^5> and R <^6> exist, each R <^5> may be same or different, and each R <^6> may be same or different. In addition, in the said General formula (4), when two or more R <^10> and R <^11> exist, each R <^10> may be the same or different, and each R <^11> may be the same or different.

As said compound (d3), in said General formula (3), R <^4> , R <^5> and R <^6> are respectively a C1-C20 alkyl group or a phenyl group, and R <^7> and R <^8> are respectively, It is preferable that it is a polymerizable unsaturated compound which has group represented by said formula (4). As compound (d3), It is a compound preferably represented by the following general formula (d3-1).

(In formula (d3-1), R ^Si is a group represented by the general formula (3), R ¹² is a hydrogen atom or a methyl group, and d is an integer of 1 to 3.)

 As a more specific example of a compound (d3), the compound represented by each of following General formula (d3-1-1)-(d3-1-3) is mentioned.

(In the above formula, Me is a methyl group, Ph is a phenyl group, and r, s, and t are each an integer of 0 to 3).

As said compound (d4), the alkyl (meth) acrylate etc. which have a C1-C8 alkyl group are mentioned, for example, Specifically, methyl methacrylate and 2-ethylhexyl acrylate, for example. Etc. can be mentioned.

As a specific example of the said compound (d5), the compound which methacrylated the both ends of tetramethylene glycol, the polyethyleneglycol of the polymerization degrees 1-20, the polypropylene glycol of the polymerization degrees 1-20, etc. are mentioned, for example. As said compound (d5), a commercial item can be used suitably, As a specific example, NK ester 1G, Copper 2G, Copper 3G, Copper 4G, Copper 9G, Copper 14G by Shin-Nakamura Chemical Industries, Ltd., for example. Etc. can be mentioned.

The copolymer (D) in the present invention is a copolymer of a polymerizable unsaturated compound containing a compound (d1), a compound (d2) and a compound (d3) as described above. Here, the use ratio of each compound with respect to all of a polymerizable unsaturated compound is 10-50 mass% in the case of a compound (d1), 10-50 mass% in the case of a compound (d2), and in the case of a compound (d3) It is 5-45 mass%.

Copolymer (D), Preferably, it is a copolymer of the polymerizable unsaturated compound containing compound (d4) other than a compound (d1), a compound (d2), and a compound (d3). At this time, the use ratio of each compound with respect to all of a polymerizable unsaturated compound is 20-50 mass% in the case of a compound (d1), 15-40 mass% in the case of a compound (d2), and in the case of a compound (d3) It is 10-30 mass%, and in the case of a compound (d4), it is 20-35 mass%. Copolymer (D) is more preferably a copolymer of a polymerizable unsaturated compound containing compound (d5) in addition to compound (d1), compound (d2), compound (d3) and compound (d4), Especially preferably, it is a copolymer of the polymerizable unsaturated compound which consists of a compound (d1), a compound (d2), a compound (d3), a compound (d4), and a compound (d5). The use ratio of each compound with respect to all the polymerizable unsaturated compounds at this time is 25-35 mass% in the case of a compound (d1), 20-30 mass% in the case of a compound (d2), and in the case of a compound (d3) 15 It is -20 mass%, in the case of compound (d4), it is 25-35 mass%, and in the case of compound (d5), it is 1-5 mass%.

The weight average molecular weight (Mw) of the copolymer (D) is preferably 5,000 to 25,000, more preferably 10,000 to 25,000, and particularly preferably 15,000 to 25,000. The molecular weight distribution (Mw / Mn) of the copolymer (D) is preferably 1 to 10, and more preferably 2 to 4.

There is no restriction | limiting in particular about the manufacturing method of such a copolymer (D), Based on well-known methods, for example, polymerization mechanisms, such as a radical polymerization method, a cationic polymerization method, and an anion polymerization method, a solution polymerization method and a block shape I) Although it can manufacture by a polymerization method, an emulsion polymerization method, etc., since it is easy to depend on the radical polymerization method in a solution, it is industrially preferable.

As a polymerization initiator used when manufacturing a copolymer (D), For example, peroxides, such as benzoyl peroxide and diacyl peroxide; Azo compounds, such as 2,2'- azobisisobutyronitrile and phenyl azo triphenylmethane, etc. are mentioned.

Although manufacture of a copolymer (D) can be performed in the presence or absence of a solvent, it is preferable to carry out in presence of a solvent from a viewpoint of workability. Examples of the solvent include alcohols, ketones, esters, alkyl esters of monocarboxylic acids, polar solvents, ethers, propylene glycol and esters thereof, halogenated hydrocarbons, aromatic hydrocarbons, fluorinated inert liquids, and the like. . As said alcohol, For example, ethanol, isopropyl alcohol, n-butanol, iso-butanol, tert-butanol, etc .; As said ketone, For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amino ketone, etc .; As said ester, For example, methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate etc .; Examples of the alkyl ester of the monocarboxylic acid include methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate and ethyl 2-methoxypropionate, 2-methoxy propionic acid propyl, 2-methoxypropionic acid butyl, etc .;

As said polar solvent, For example, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc .; As said ether, For example, methyl cellosolve, cellosolve, butyl cellosolve, butyl carbitol, ethyl cellosolve acetate, tetrahydrofuran, dioxane, etc .; As said propylene glycol and its ester, For example, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, a propylene glycol monoethyl ether acetate, a propylene glycol monobutyl ether acetate, etc .; Examples of the halogenated hydrocarbons include 1,1,1-trichloroethane, chloroform and the like; As said aromatic hydrocarbon, For example, benzene, toluene, xylene, etc .; As said fluorinated inert liquid, perfluorooctane, a perfluoro tri- n-butylamine, etc. are mentioned, respectively, Any of these can be used.

When manufacturing a copolymer (D), you may further use chain transfer agents, such as lauryl mercaptan, 2-mercaptoethanol, ethyl thioglycolic acid, and octyl thioglycolic acid, as needed.

The use ratio of the (D) copolymer in the radiation-sensitive resin composition of the present invention is preferably 0.01 to 3 parts by mass, more preferably 0.05 to 2 with respect to 100 parts by mass of the (A) alkali-soluble resin. It is a mass part. Here, when the use ratio of the (D) copolymer is 0.01 to 3 parts by mass, even when slit coating is employed as the coating method, the film thickness uniformity becomes good. Moreover, when this value exceeds 3 mass parts, the roughness of a coating film may arise easily, and the film thickness uniformity of the spacer formed may be impaired.

<Other components>

Although the radiation sensitive resin composition of this invention contains the above-mentioned (A) alkali-soluble resin, (B) polymerizable unsaturated compound, (C) radiation sensitive polymerization initiator, and a copolymer (D) as essential components, It may contain other components as needed within the range which does not impair an effect. As such other components, (E) radiation absorbing agent, (F) radical trapping agent, (G) adhesion | attachment adjuvant, etc. are mentioned, for example.

Said (E) radiation absorber can be used for the purpose of controlling the pattern size of the spacer formed more precisely. As the (E) radiation absorbent, a compound having a property of absorbing radiation having a wavelength of 300 to 400 nm can be suitably used, and examples thereof include compounds represented by the following formula (E-1).

(In formula (E-1), two or more R <^13> may be same or different, and a hydrogen atom, a C1-C8 alkyl group, and a C1-C8 alkyl group are substituted by the C1-C4 alkoxy group. Alkoxyalkyl group, alkoxyl group having 1 to 8 carbon atoms, hydroxyl group, carboxyl group or alkoxycarbonyl group having 2 to 6 carbon atoms.)

In formula (E-1), a C1-C8 alkyl group, a C1-C8 alkoxy group, the alkoxy group and alkyl group in an alkoxyalkyl group, and the alkoxy group in an alkoxycarbonyl group may be linear or branched chain, respectively. The alkoxy group in the alkoxyalkyl group may be substituted at any position of the alkyl group.

As a preferable specific example of (E) radiation absorber in this invention, 2,4,2 ', 4'- tetrahydroxy benzophenone, 3-methyl- 2,4,2', 4'-tetra Hydroxybenzophenone, 3,3'-dimethyl-2,4,2 ', 4'-tetrahydroxybenzophenone, 5-methyl-2,4,2', 4'-tetrahydroxybenzophenone, 6- Methyl-2,4,2 ', 4'-tetrahydroxybenzophenone, 5,5'-dimethyl-2,4,2', 4'-tetrahydroxybenzophenone, 6,6'-dimethyl-2, 4,2 ', 4'- tetrahydroxy benzophenone, 3-methoxy-2,4,2', 4'- tetrahydroxy benzophenone, 3,3'- dimethoxy-2,4,2 ', 4'-tetrahydroxybenzophenone, 3-ethoxy-2,4,2 ', 4'-tetrahydroxybenzophenone, 6-ethoxy-2,4,2', 4'-tetrahydroxybenzophenone , 5, 5'-diethoxy-2,4,2 ', 4'-tetrahydroxybenzophenone, 6,6'-diethoxy-2,4,2', 4'-tetrahydroxybenzophenone, 2 , 3,4,2 ', 4'-pentahydroxybenzo There may be mentioned paddy field, 2,3,4,2 ', 3', and 4'-hexa-hydroxy benzophenone. These can be used individually by 1 type or in combination of 2 or more types.

Said (E) radiation absorbing agent can be used in 20 mass parts or less with respect to 100 mass parts of (A) alkali-soluble resin, Preferably it is 0.01-20 mass parts, More preferably, it is 0.1-10 mass It can be used in a range of negative. By using the (E) radiation absorbent in the above range, it is possible to precisely control the pattern size of the spacer without greatly changing the exposure amount, which is preferable.

The said (F) radical scavenger can be used for the purpose of making the height (film thickness) of the spacer formed more high, while raising the storage stability of the radiation sensitive resin composition obtained. As such (F) radical scavenging agent, a hindered phenol compound, a hindered amine compound, an alkyl phosphate compound, the compound containing a sulfur atom (except an alkyl phosphate compound), etc. can be used, for example.

As these specific examples, as said hindered phenolic compound, for example, pentaerythritol tetrakis [3- (3,5-di-tert- butyl- 4-hydroxyphenyl) propionate], thiodiethylene bis [3] -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1 , 3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N'-hexane-1,6-diylbis [3- ( 3,5-di-tert-butyl-4-hydroxyphenylpropionamide), 3,3 ', 3 ", 5', 5" -hexa-tert-butyl- alpha, alpha ', alpha "-(mesitylene -2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylenebis ( Oxyethylene) bis [3- (5-tert- butyl- 4-hydroxy-m-tolyl) propionate, hexamethylene bis [3- (3,5-di) -Tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine- 2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris ((4-tert-butyl-3-hydroxy-2,6-xyllin) methyl] -1,3, 5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5- And triazine-2-ylamine) phenol and 1,3,5-tris (3 ', 5'-di-tert-butyl-4'-hydroxybenzyl) isocyanuric acid.

As these commercial items, for example, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-330 (above, manufactured by ADEKA); sumilizer GM, sumilizer GS, sumilizer MDP-S, sumilizer BBM-S, sumilizer WX-R, sumilizer GA-80 (above, manufactured by Sumitomo Chemical Co., Ltd.); IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1098, IRGANOX 1135, IRGANOX 1330, IRGANOX 1726, IRGANOX 1425WL, IRGANOX 1520L, IRGANOX 245, IRGANOX 259, IRGANOX 3114, IRGANOX 565, IRGAMOD 2 ; YOSHINOX BHT, YOSHINOX BB, YOSHINOX 2246G, YOSHINOX 425, YOSHINOX 250, YOSHINOX 930, YOSHINOX SS, YOSHINOX TT, YOSHINOX 917, YOSHINOX 314 (or more)

As said hindered amine compound, for example, tetrakis (2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate and bis (1-octyloxy-) 2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1 , 1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, and the like, and examples of commercially available products thereof include ADK STAB LA-52, ADK STAB LA57, ADK STAB LA-62, and ADK STAB. LA-67, ADK STAB LA-63P, ADK STAB LA-68LD, ADK STAB LA-77, ADK STAB LA-82, and ADK STAB LA-87 (above, manufactured by ADEKA);

sumilizer 9A (manufactured by Sumitomo Chemical Co., Ltd.);

CHIMASSORB 119FL, CHIMASSORB 2020FDL, CHIMASSORB 944FDL, TINUVIN 622LD, TINUVIN 123, TINUVIN 144, TINUVIN 765, and TINUVIN 770DF (above, manufactured by Chiba Specialty Chemicals Co., Ltd.).

As said alkyl phosphate compound, for example, butylidenebis {2-tert- butyl- 5-methyl- p-phenylene} -P, P, P, P, P- tetratridecylbis (phosphine), distea Ryl pentaerythritol diphosphite, 2,2'- methylenebis (4,6-di-tert- butyl- phenyloxy) (2-ethylhexyloxy) phosphorus, tris (2, 4-di-tert- Butylphenyl) phosphite, 3, 9-bis (2, 6- di-tert- butyl- 4-methylphenoxy)-2, 4, 8, 10- tetraoxa-3, 9- diphosphaspiro [5.5] Undecane etc. are mentioned, As these commercial items, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8W, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP- 10, ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 135A, ADK STAB 3010, ADK STAB TPP (above, manufactured by ADEKA); IRGAFOS 168 (made by Chiba Specialty Chemicals Co., Ltd.), etc. are mentioned.

Examples of the compound containing the sulfur atom include pentaerythritol tetrakis (3-laurylthiopropionate), di (propionic acid-n-tridecanyl) sulfide, thiodiethylenebis [3- (3,5) -Di-tert-butyl-4-hydroxyphenyl) propionate] and the like, and thioethers can be used. As a commercial item of a thioether, For example, ADK STAB AO-412S and ADK STAB AO-503 (above, ADEKA make); sumilizer TPL-R, sumilizer TPM, sumilizer TPS, sumilizer TP-D, sumilizer MB (above, Sumitomo Chemical Co., Ltd. make); IRGANOX PS800FD, IRGANOX PS802FD, and IRGANOX 1035 (above, Chiba Specialty Chemicals Co., Ltd. product); DLTP, DSTP, DMTP, DTTP (above, Apia Corporation) etc. are mentioned.

These (F) radical scavengers can be used individually or in combination of 2 or more types.

The radical scavenging agent (F) can be used in a proportion of 15 parts by mass or less with respect to 100 parts by mass of the (A) alkali-soluble resin, preferably in the range of 0.01 to 15 parts by mass, more preferably 1 to 10 parts by mass. By using in the range, the effect of the (F) radical trapping agent can be exhibited effectively, without impairing the radiation sensitivity of the radiation sensitive resin composition obtained, and it is preferable.

The said (G) adhesion | attachment adjuvant can be used in order to improve the adhesiveness of the spacer formed and a board | substrate further. As such (G) adhesion | attachment adjuvant, the functional silane coupling agent which has reactive functional groups, such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, an oxiranyl group, is preferable. As a specific example of (G) adhesion | attachment adjuvant, (gamma) -methacryloxypropyl trimethoxysilane, (gamma) -isocyanate propyl triethoxysilane, (gamma)-glycidoxy propyl trimethoxysilane, (beta)-(3, 4- epoxycyclohexyl) Ethyl trimethoxysilane etc. are mentioned.

These (G) adhesion | attachment adjuvant can be used individually or in mixture of 2 or more types. The use ratio of the (G) adhesion aid is preferably 20 parts by mass or less, more preferably 0.1 to 20 parts by mass, and still more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin. It is wealth. (G) When the use ratio of an adhesive adjuvant is 0.1-20 mass parts, the adhesiveness with respect to the board | substrate of the spacer formed becomes the most favorable.

<Preparation of a radiation sensitive resin composition>

The radiation sensitive resin composition of this invention is added arbitrarily as mentioned above with said (A) alkali-soluble resin, (B) polymerizable unsaturated compound, (C) radiation sensitive polymerization initiator and copolymer (D) Other components are prepared by uniformly mixing the respective components in a predetermined ratio. This radiation sensitive resin composition is preferably dissolved in a suitable solvent and used in a solution state.

As a solvent used for preparation of the radiation sensitive resin composition of this invention, (A) alkali-soluble resin, (B) polymerizable unsaturated compound, (C) radiation sensitive polymerization initiator, and a copolymer (D) are added arbitrarily. It is used that dissolves other components uniformly and does not react with each component. As such a solvent, the same thing as what was illustrated as a solvent which can be used for manufacturing above-mentioned (A) alkali-soluble resin is mentioned.

Among these solvents, for example, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and di from the viewpoints of solubility of each component, reactivity with each component, ease of coating film formation, and the like. Ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, cyclohexanol acetate, benzyl alcohol, 3- Methoxybutanol can be used particularly preferably. These solvent can be used individually by 1 type, and can also be used in mixture of 2 or more type.

Moreover, in order to improve the in-plane uniformity of a film thickness with the said solvent, you may use a high boiling point solvent together. As a high boiling point solvent which can be used together, N-methylpyrrolidone, N, N- dimethylacetamide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, 1-octanol, 1-nonanol, acetic acid, for example Benzyl, ethyl benzoate, diethyl oxalate, diethyl maleate, gamma -butyrolactone, propylene carbonate and the like. Among them, N-methylpyrrolidone, γ-butyrolactone or N, N-dimethylacetamide is preferable.

When using a high boiling point solvent together as a solvent of the radiation sensitive resin composition of this invention, the use ratio is 1-40 mass% with respect to solvent whole quantity, More preferably, it is 3-30 mass%. can do. When the usage-amount of a high boiling point solvent is 1-40 mass%, the film thickness uniformity of a coating film becomes favorable and patterning property also becomes favorable.

When preparing the radiation sensitive resin composition of this invention as a solution state, solid content concentration (components other than the solvent which occupies in a composition solution, ie, said (A) alkali-soluble resin, (B) polymerizable unsaturated compound, (C) sense) The ratio of the total amount of the radiation polymerization initiator and the copolymer (D) and other components optionally added) can be set to an arbitrary concentration (for example, 5 to 50% by mass) according to the purpose of use or the value of the desired film thickness. have. The more preferable solid content concentration changes with the formation method of the coating film on a board | substrate. It is more preferable that solid content concentration at the time of employ | adopting a spin coating method as a coating method is 20-50 mass%, and it is especially preferable that it is 30-40 mass%. It is further more preferable that it is 10-35 mass%, and, as for solid content concentration at the time of employ | adopting the slit coating method, it is especially preferable that it is 15-30 mass%.

The composition solution thus prepared may be used for use after being filtered using a Millipore filter having a pore size of about 0.5 μm or the like.

<Formation method of spacer>

Next, the method of forming a spacer using the radiation sensitive resin composition of this invention is demonstrated.

The method for forming a spacer of the present invention is characterized by including at least the following steps (1) to (4) in the order described below.

(1) process of apply | coating the radiation sensitive resin composition of this invention on a board | substrate, and forming a coating film,

(2) exposing to at least part of the coating film;

(3) the process of developing the coating film after exposure, and

(4) The process of heating the coating film after image development.

Hereinafter, each of these steps will be described sequentially.

[(1) Process of Applying the Radiation-Resistant Composition of the Present Invention on a Substrate to Form a Coating Film]

First, the radiation sensitive resin composition of this invention is apply | coated on a board | substrate, and a coating film is formed.

When forming a spacer for use in a liquid crystal display element using an electric field generated in a direction perpendicular to the substrate surface, such as TN (Twisted Nematic) mode, STN (Super Twisted Nematic) mode, VA (Vertical Alignment) mode, A transparent conductive film is further formed on the board | substrate with which the element and the protective film of an element were formed, and the radiation sensitive resin composition of this invention is apply | coated on the said transparent conductive film. On the other hand, when forming the spacer used for the liquid crystal display element of the IPS (In-Plane Switching) mode which uses the electric field which generate | occur | produced in the horizontal direction with respect to the board | substrate surface, on the board | substrate with which the element of the element and the protective film were formed, The radiation sensitive resin composition of this invention is apply | coated.

In any of the above cases, the substrate is preferably a transparent substrate, and examples thereof include a glass substrate and a resin substrate. More specifically, Glass substrates, such as a soda lime glass and an alkali free glass; The resin substrate which consists of synthetic resins, such as a polyethylene terephthalate, a polybutylene terephthalate, a polyether sulfone, a polycarbonate, and a polyimide, is mentioned.

Examples of the transparent conductive film include an NESA film made of tin oxide (SnO ₂ ) (registered trademark of US PPG), an ITO film made of indium tin oxide (In ₂ O ₃ —SnO ₂ ), and the like.

The method of applying the radiation-sensitive resin composition is not particularly limited, and for example, an appropriate method such as spraying, roll coating, rotary coating (spin coating), slit coating, bar coating or inkjet may be employed. A spin coating method and a slit coating method are preferable.

In particular, when the slit coating method is adopted, the advantageous effect of the present invention can be exhibited to the maximum, which is preferable.

After application, preferably, prebaking and postbaking are performed on the formed coating film. The conditions of prebaking and postbaking should be set suitably according to the kind, usage ratio, etc. of the component contained in the radiation sensitive resin composition of this invention, respectively. Prebaking can be performed, for example at 70-90 degreeC on conditions for about 1 to 15 minutes. Post-baking can be performed by appropriate heating apparatuses, such as a hotplate and a clean oven. As temperature of postbaking, it is preferable that it is 180-240 degreeC, and it is more preferable that it is 200-230 degreeC. Post-baking time changes with kinds of heating apparatus to be used. The postbaking time in the case of using a hot plate as the heating device for postbaking is preferably 10 to 60 minutes, and more preferably 15 to 40 minutes. Post-baking time in the case of using a clean oven becomes like this. Preferably it is 20 to 120 minutes, More preferably, it is 30 to 90 minutes.

The film thickness of the coating film formed in this way becomes like this. Preferably it is 0.1-8 micrometers, More preferably, it is 0.1-6 micrometers, More preferably, it is 0.1-4 micrometers.

[(2) Process of Exposing to At least Part of This Coating Film]

Subsequently, at least part of the formed coating film is irradiated with radiation. At this time, when irradiating only a part of coating film, it can be based on the method etc. which irradiate through the photomask which has a predetermined pattern, for example.

As radiation used for irradiation, visible light, an ultraviolet-ray, an ultraviolet ray, etc. are mentioned. Among these, radiation in which the wavelength is in the range of 250 to 550 nm is preferable, and radiation which includes ultraviolet rays of 365 nm is particularly preferable.

The radiation dose (exposure dose) is a value measured by an illuminometer (OAI model 356, manufactured by Optical Associates Inc.) at a wavelength of 365 nm of radiation to be irradiated, preferably 100 to 5,000 J / m 2, more preferably Is 200 to 3,000 J / m 2.

The radiation sensitive resin composition of this invention has a high radiation sensitivity compared with the composition known conventionally, and can obtain the spacer of desired film thickness, favorable shape, excellent adhesiveness, and high hardness even if the said radiation dose is 800 J / m <2> or less.

[(3) Process of Developing Coating Film After Exposure]

Next, by developing the coating film after irradiation, an unnecessary part (non-exposed part) is removed and a predetermined pattern is formed.

As a developing solution used for image development, For example, inorganic alkaline compounds, such as sodium hydroxide, potassium hydroxide, sodium carbonate;

Aqueous solutions of organic alkaline compounds such as quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide can be used. An appropriate amount of at least one selected from the group consisting of water-soluble organic solvents such as methanol and ethanol and a surfactant may be added to the aqueous solution of the alkaline compound.

As the image development method, any of a puddle method, a dipping method, a shower method, etc. may be sufficient, and it is preferable to make image development time into about 10 to 180 second. The developing temperature is good at room temperature.

Subsequently to the development treatment, a desired pattern can be obtained by, for example, washing with running water for 30 to 90 seconds and then air drying with compressed air or compressed nitrogen.

[(4) Process of Heating Coating Film After Development]

Subsequently, the obtained patterned coating film is heated at a predetermined temperature, for example, 100 to 250 ° C. for a predetermined time, for example, on a hot plate for 5 to 30 minutes by an appropriate heating device such as a hot plate or an oven. By heating for -180 minutes, the spacer which has a desired pattern can be obtained.

By passing through the above processes, there can be formed the spacer for liquid crystal display elements which is excellent in performance, such as film thickness uniformity, without the irregularity which consists of minute unevenness | corrugation in a coating film.

(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 these synthesis examples and an Example.

In addition, below, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were measured by the gel permeation chromatography (GPC) by the following conditions.

Measuring device: Toso Corporation, "HLC8220 system"

Separation column: Tosoh Co., Ltd. make and use four TSK gel GMH _HR- N connected in series

Column temperature: 40 degrees Celsius

Elution solvent: Tetrahydrofuran (made by Wako Pure Chemical Industries, Ltd.)

Flow rate: 1.0mL / minute

Sample concentration: 1.0 mass%

Sample injection volume: 100 μm

Detector: parallax refractometer

Standard material: Monodisperse polystyrene

In addition, the solution viscosity of the radiation sensitive resin composition was measured at 30 degreeC using the E-type viscosity meter by Tokyo Keiki Co., Ltd. make.

<Synthesis of (A) alkali-soluble resin>

Synthesis of Polymer [A]

Synthesis Example 1 (Production of Polymer (A-1))

In a flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2'-azobisisobutyronitrile, 125 parts by mass of 3-methoxybutyl acetate and 125 parts by mass of propylene glycol monomethyl ether acetate were added, followed by methacryl. 18 parts by mass of acid, methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8- 25 parts by mass, styrene 5 parts by mass, 1,3-butadiene 5 parts by mass, methacrylic acid 2- (6-hydro) Roxyhexanoyloxy) ethyl ester (trade name PLACCEL FM1D, manufactured by Daicel Kagaku Kogyo Co., Ltd.) 25 parts by mass and 22 parts by mass of methacrylic acid tetrahydrofuran-2-yl are added, and after nitrogen substitution, the solution is slowly stirred. The polymer solution containing a copolymer [α-1] was obtained by raising the temperature of to 80 degreeC and holding this temperature for 5 hours. Solid content concentration (the ratio which the mass of the polymer contained in a polymer solution occupies in the total mass of a polymer solution. The same below) is 29.1 mass%, and the weight average molecular weight of a copolymer [(alpha-1)] of the obtained polymer solution. (Mw) was 18,000.

Subsequently, the obtained copolymer [α-1] solution was taken in an amount equivalent to 100 parts by mass (solid content) in terms of the polymer contained therein, and 2-methacryloyloxyethyl isocyanate (trade name Karenz MOI, Show After adding 14 parts by mass of Wadenko Co., Ltd.) and 0.1 parts by mass of 4-methoxyphenol, the mixture was stirred at 40 ° C for 1 hour, and further stirred at 60 ° C for 2 hours for reaction.

The progress of reaction with the isocyanate group derived from 2-methacryloyloxyethyl isocyanate and the hydroxyl group derived from copolymer [α-1] was confirmed by IR (infrared absorption) spectrum. According to the IR spectra of the solution after reacting at 40 ° C for 1 hour and the solution after further reacting at 60 ° C for 2 hours, 2,270 cm ^{−1 in the} vicinity of 2,270 cm ⁻¹ derived from an isocyanate group of 2-methacryloyloxyethyl isocyanate The state which the peak is decreasing was confirmed. By the said reaction, the solution containing the polymer (A-1) of 34.0% of solid content concentration was obtained.

[Synthesis of Copolymer [β]]

Synthesis Example 2 (Manufacture of Copolymer (β-1))

5 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol methylethyl ether were placed in a flask equipped with a cooling tube and a stirrer, followed by 18 parts by mass of methacrylic acid. , 40 parts by mass of glycidyl methacrylate, 5 parts by mass of styrene, and 32 parts by mass of methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl were substituted with nitrogen, and then 1,3- 5 mass parts of butadienes were added, and the solution temperature was raised to 70 degreeC, stirring slowly, and this solution was hold | maintained for 5 hours, and superposition | polymerization was obtained, and the solution containing copolymer [beta-1] was obtained. Solid content concentration of this polymer solution was 33.0 mass%, and Mw of copolymer [beta-1] was 11,000.

Synthesis Example 3 (Preparation of Copolymer (β-2))

In a flask equipped with a cooling tube and a stirrer, 4 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 250 parts by mass of diethylene glycol methylethyl ether were placed. Subsequently, 5 parts by mass of styrene, 20 parts by mass of methacrylic acid, 20 parts by mass of tetrahydrofurfuryl methacrylate, 30 parts by mass of glycidyl methacrylate, and 3- (methacryloyloxymethyl) -3-ethyl jade After 25 mass parts of cetane was substituted for nitrogen, 5 mass parts of 1, 3- butadienes were further added, and while stirring slowly, the temperature of a solution was raised to 70 degreeC, this temperature was maintained for 5 hours, and a superposition | polymerization [ A solution containing β-2] was obtained. Solid content concentration of this solution was 28.3 mass%, and Mw of the copolymer [β-2] was 11,000.

[Synthesis of Copolymer [γ]]

Synthesis Example 4 (Manufacture of Copolymer (γ-1))

In a flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2'-azobis (isobutyronitrile) and 250 parts by mass of diethylene glycol methylethyl ether were added, followed by 2-methacryloyloxyethyl succinic acid 35 After adding a mass part, 25 mass parts of n-butyl methacrylates, and 35 mass parts of benzyl methacrylates, and nitrogen-substituted, 5 mass parts of 1, 3- butadienes were further added, and the temperature of a solution was made into 90 degreeC, stirring slowly. The copolymer [γ-1] was obtained by raising and maintaining this temperature for 5 hours and superposing | polymerizing. Solid content concentration of this solution was 28.0 mass%, and Mw of copolymer [γ-1] was 12,000.

<Synthesis of Copolymer (D)>

Synthesis Example 5 (Preparation of Copolymer (D-1))

28.4 parts by mass of the compound represented by the formula (d1-1) as the compound (d1), and NK-ester M-90G (brand name, Shinnakamuraka) in a glass flask equipped with a stirring device, a condenser and a thermometer. 20.7 parts by mass of Kaku Co., Ltd., 18.1 parts by mass of the compound represented by the following formula (d3-1-1-1) as the compound (d3) and 5.9 parts by mass of methyl methacrylate as the compound (d4) and 2-ethyl 23.5 mass parts of hexyl acrylate, 3.4 mass parts of compounds which methacrylated both ends of tetramethylene glycol as a (d5) compound, and 414 mass parts of isopropyl alcohol as a solvent are put, and it is a polymerization initiator in reflux in nitrogen gas stream. After adding 0.7 mass part of 2,2'- azobisisobutyronitrile as a 4 mass part of lauryl mercaptans as a chain transfer agent, and copolymerizing by refluxing at 75 degreeC for 8 hours, copolymer (D-1) was made into The solution containing was obtained. Then, the solvent was removed on 70 degreeC or less heating conditions using the evaporator, and the copolymer (D-1) was isolated.

The number average molecular weight (Mn) of the obtained copolymer (D-1) was 2,800, the weight average molecular weight (Mw) was 5,300, and molecular weight distribution (Mw / Mn) was 1.9.

(In the formula, Me is a methyl group.)

Synthesis Example 6 (Preparation of Copolymer (D-2))

In the said Synthesis example 5, it carried out similarly to the synthesis example 5 except having made the addition amount of the lauryl mercaptan as a chain transfer agent into 1 mass part, and obtained the copolymer (D-2).

The number average molecular weight (Mn) of the obtained copolymer (D-2) was 4,700, the weight average molecular weight (Mw) was 11,000, and molecular weight distribution (Mw / Mn) was 2.3.

Synthesis Example 7 (Preparation of Copolymer (D-3))

In the said Synthesis example 5, copolymer (D-3) was carried out similarly to the synthesis example 5 except not using lauryl mercaptan as a chain transfer agent, and making copolymerization temperature and time into 73 degreeC and 10 hours, respectively. Got.

The number average molecular weight (Mn) of the obtained copolymer (D-3) was 5.600, the weight average molecular weight (Mw) was 21,000, and molecular weight distribution (Mw / Mn) was 3.8.

Synthesis Example 8 (Preparation of Copolymer (D-4))

In a glass flask equipped with a stirring device, a condenser, and a thermometer, 39.4 parts by mass of the compound represented by the formula (d1-1) as the compound (d1), and NK-ester M-90G (Shinnakamura Kagaku Co., Ltd.) as the (d2) compound. Shikisha) 31.6 parts by mass and 29.0 parts by mass of the compound represented by the above formula (3) as a compound (d3), and 414 parts by mass of isopropyl alcohol as a solvent, and 2,2 'as a polymerization initiator in a nitrogen gas stream under reflux. After adding 0.7 mass part of azobisisobutyronitrile and 4 mass parts of lauryl mercaptans as a chain transfer agent, it refluxed at 75 degreeC for 8 hours and copolymerized, and the solution containing copolymer (D-4) was obtained. . Then, the solvent was removed on 70 degreeC or less heating conditions using the evaporator, and the copolymer (D-4) was isolated.

The number average molecular weight (Mn) was 3,000, and the weight average molecular weight (Mw) of the molecular weight of the obtained copolymer (D-4) was 6,000. In addition, the molecular weight distribution (Mw / Mn) was 2.0.

Synthesis Example 9 (Preparation of Copolymer (D-5))

In a glass flask equipped with a stirring device, a condenser, and a thermometer, 28.4 parts by mass of the compound represented by the formula (d1-1) as the compound (d1), and NK-ester M-90G (Shinnakamura Kagaku Kabu) as the (d2) compound. 20.7 parts by mass of Shikisha) and 21.5 parts by mass of the compound represented by the formula (d3-1-1-1) as the compound (d3), 5.9 parts by mass of methyl methacrylate and 2-ethylhexyl acryl as the (d4) compound. 23.5 mass parts of rates and 414 mass parts of isopropyl alcohols as a solvent, and 0.7 mass parts of 2,2'- azobisisobutyronitriles and a lauryl mercaptan 4 as a chain transfer agent in a nitrogen gas stream under reflux under a reflux. After adding a mass part, it copolymerized by refluxing at 75 degreeC for 8 hours, and obtained the solution containing a copolymer (D-5). Then, the solvent was removed on 70 degreeC or less heating conditions using the evaporator, and the copolymer (D-5) was isolated.

The number average molecular weight (Mn) of the obtained copolymer (D-5) was 2,600, the weight average molecular weight (Mw) was 5,000, and molecular weight distribution (Mw / Mn) was 1.9.

Example 1

<Preparation of a radiation sensitive resin composition>

(A) An amount equivalent to 100 parts by mass (solid content) of the solution of copolymer (β-1) obtained in Synthesis Example 2 as copolymer (β-1) as alkali-soluble resin, (B) polymerizable unsaturated 130 mass parts of mixtures (B-1) of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate as a compound, and (C) ethanone-1- [9-ethyl-6- (2-) as a radiation sensitive polymerization initiator Methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyl oxime) ("Irgacure OXE02" by Chiba Specialty Chemicals) (C-1) 5 Mass part and 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (brand name Irgacure 379, Chiba specialty chemical) (C-2) (20 parts by mass), 0.3 parts by mass of the copolymer (D-1) obtained in Synthesis Example 5 as the copolymer (D) and γ-glycidoxy Radiation radiation was obtained by adding diethylene glycol ethyl methyl ether (DEG) as a solvent to 5 parts by mass of lofiltrimethoxysilane (GPT) and dissolving it to a solid content concentration of 23% by mass, followed by filtration with a Millipore filter having a pore size of 0.5 µm. Sex resin composition (S-1) was prepared. The viscosity of the radiation sensitive resin composition (S-1) after preparation was 5.0 cP.

The radiation sensitive resin composition (S-1) prepared above was evaluated in accordance with the following procedure. The evaluation results are shown in Table 1.

<Evaluation>

(1) Appearance Evaluation of Coating Film

The above-mentioned radiation sensitive resin composition (S-1) was apply | coated on 550x650 mm chromium film-forming glass using the slit die coater (TR632105-CL, the Tokyo Okako Corp. make), and a solvent was applied at 65Pa. After removing, heating was conducted at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.5 μm.

About the appearance of this coating film surface, after formation, the coating film was visually observed under the sodium lamp and observed. The nonuniformity which generate | occur | produced was classified as follows, and the presence or absence and intensity | strength of the nonuniformity were evaluated about each.

(Classification of nonuniformity)

Misty shape: Non-uniformity of the misty shape that occurs all over the surface of the coating

Vertical Stripe Smears: Unevenness of the stripe shape that occurs in the sweep direction of the application nozzle

Stage vacuum adsorption marks: non-uniformity resulting from holes for vacuum adsorption of the substrate at the application stage

Support Pin Marks: Marks Derived from the Support Pins for Transferring Substrate

(Evaluation of the presence and absence of nonuniformity)

None: If nonuniformity is not confirmed

About: When a little unevenness is confirmed

Strong: When unevenness is clearly identified

(2) Evaluation of film thickness uniformity

In the said "(1) external appearance evaluation of coating film", it replaces with 550x650 mm chromium film-forming glass, and is made similarly to said "(1) external appearance evaluation of the coating film" except having used the alkali free glass of 550x650 mm. The coating film was formed on the board | substrate.

About this coating film, the film thickness was measured in 20 measuring points, and the film thickness uniformity was computed by the following formula.

Uniformity (%) of film thickness = (maximum value-minimum value of coating film thickness) * 100 / ((average of 20 coating film thicknesses) * 2)

When the uniformity of the coating film thickness calculated in this way is 1% or less, it can be said that film thickness uniformity is favorable.

In addition, the said 20 measurement point was determined as follows. That is, the inner region (450x550mm) excluding the 50 mm range from each of the long sides and short sides of the substrate (550x650mm) is used as the measurement region, and in a straight line in the longside direction and the shortside direction in the region. Each 10 points (total 20 points) were determined at 40-mm intervals, respectively, and these were made into measuring points.

(3) evaluation of sensitivity

3.5 micrometers of film thicknesses are apply | coated to a radiation-sensitive resin composition (S-1) on a alkali free glass substrate of 95 mm x 95 mm, and then prebaked for 3 minutes on a 90 degreeC hotplate. Formed a coating film.

Subsequently, the obtained coating film was exposed through a photomask in which a circular pattern having a diameter of 12 μm was formed as an opening, and the exposure time was varied as ultraviolet rays with an intensity of 250 W / m 2 at 365 nm. Then, after developing at 25 degreeC for 60 second by 0.05 mass% potassium hydroxide aqueous solution, it wash | cleaned for 1 minute with pure water, and also post-baked for 30 minutes in 230 degreeC oven, and formed the spacer which consists of a patterned coating film. At this time, the minimum exposure amount which the residual film ratio (film thickness of the coating film after postbaking x 100 / after exposure (before postbaking) film thickness) after postbaking becomes 90% or more was investigated, and this value was made into the sensitivity. When this value is 800 J / m <2> or less, it can be said that a sensitivity is favorable.

(4) evaluation of rubbing resistance

The spacer was formed on the board | substrate similarly to "(3) sensitivity evaluation" except having made exposure amount into the exposure amount corresponded to the sensitivity determined by "(3) sensitivity evaluation." After apply | coating liquid crystal aligning agent AL3046 (brand name, the JSR Corporation make) on the obtained board | substrate with the printer for liquid crystal aligning film application, it heats at 180 degreeC for 1 hour, and removes a solvent, The liquid crystal aligning agent of film thickness 0.05micrometer. Formed a coating film.

Next, the rubbing process was performed with respect to this coating film on the conditions of 500 rpm of rolls, and the movement speed of 1 cm / sec of a roll by the rubbing machine which has the roll which wound the cloth made from polyamide. At this time, the pattern was scraped and peeled off.

(5) evaluation of compression performance

The spacer which consists of a cylindrical pattern was formed on the board | substrate similarly to "(3) sensitivity evaluation" except having made exposure amount into the exposure amount corresponded to the sensitivity determined by "(3) sensitivity evaluation." In this spacer, a compression test was conducted under a load of 40 mN using a 50 micrometer square planar indenter using a microscopic compression tester (Fischer Scope H100C (manufactured by Fisher Instruments Co., Ltd.)). The change in compression displacement with respect to was measured, and the recovery rate (%) was calculated from the displacement amount at the time of 40 mN load, and the displacement amount at the time of removing 40 mN load. At this time, when the recovery rate is 90% or more, and the displacement at the load of 40 mN is 0.15 µm or more, it can be said to be a spacer having compression performance with both high recovery rate and flexibility.

Examples 2-20 and Comparative Examples 1-4

In the said Example 1, the used (A) alkali-soluble resin, (B) polymerizable unsaturated compound, (C) radiation sensitive polymerization initiator and copolymer (D), the kind and quantity of other components, and the kind of solvent used Except having made each as described in Tables 1-3, the radiation sensitive resin composition was prepared and evaluated similarly to Example 1, and evaluated.

In Comparative Examples 1 to 3, commercially available surfactants were used instead of the copolymer (D). In Comparative Example 4, neither the copolymer (D) nor the surfactant was used. Evaluation results were shown in Tables 1-3.

The abbreviation of each component in Table 1-Table 3 has the following meanings, respectively. (C) When using a radiation sensitive polymerization initiator, an amino sensitizer, and a thiol compound together, the kind and quantity of the used amino sensitizer and a thiol compound are (C) radiation sensitive polymerization initiators in Tables 1-3. It was written in the column. "-" In a component column shows that the component corresponded to the column was not used.

<(B) polymerizable unsaturated compound>

B-1: dipentaerythritol hexaacrylate (trade name KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)

B-2: Polymerizable unsaturated monomer containing a polyfunctional urethane acrylate compound (brand name KAYARAD DPHA-40H, the Nippon Kayaku Co., Ltd. make)

B-3: Ethylene oxide modified dipentaerythritol hexaacrylate (trade name KAYARAD DPEA-12, manufactured by Nippon Kayaku Co., Ltd.)

<(C) radiation sensitive polymerization initiator>

C-1: ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyl oxime) (Chiba specialty chemicals) "Irgacure OXE02" of the Kaisha Corporation)

C-2: 2- (4-methylbenzoyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one (brand name Irgacure 379, Chiba specialty chemicals) Shikiisha Co., Ltd.)

C-3: 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl- 1,2'- biimidazole

C-4: 4,4'-bis (diethylamino) benzophenone

C-5: 2-mercaptobenzothiazole

<Other components>

(E) radiation absorbers

THBP: 2,4,2 ', 4'-tetrahydroxybenzophenone

(F) radical scavengers

AO-20: 1,3,5-tris (3 ', 5'-di-tert-butyl-4'-hydroxybenzyl) isocyanuric acid (brand name "ADK STAB AO-20", the product made by ADEKA) )

AO-330: 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (brand name "ADK STAB AO-330", KK) ADEKA manufacture)

PEP-8: distearyl pentaerythritol diphosphite (brand name "ADK STAB PEP-8", the product made by ADEKA Corporation)

(G) Adhesion Aids

GPT: γ-glycidoxypropyltrimethoxysilane

<Surfactant>

δ-1 (Comparative Example 1): Silicone-based surfactant (manufactured by Toray Dow Corning Silicon Co., Ltd., trade name: SH-193)

δ-2 (Comparative Example 2): Fluorine-based surfactant (manufactured by Neos Co., Ltd., product

Person: FTERGENT 222F)

<Solvent>

DEG: diethylene glycol ethyl methyl ether

PGM: Propylene Glycol Monomethyl Ether Acetate

Claims (6)

(A) alkali-soluble resin,
(B) a polymerizable unsaturated compound,
(C) a radiation sensitive polymerization initiator, and
(D) (d1) a compound represented by the following formula (1 ⁰ ),
(d2) a compound represented by the following General Formula (2 ⁰ ), and
(d3) Polymerizable unsaturated compound which has group represented by following General formula (3)
Copolymer of polymerizable unsaturated compounds
A radiation sensitive resin composition characterized by containing.
CH ₂ = CR ¹ COO-C _α H _{2 α} -C _β F _{2β + 1} (1 ⁰ )
(In formula (1 ⁰ ), R ¹ is a hydrogen atom or a methyl group, α is an integer of 0 to 6, and β is an integer of 1 to 20.)
CH ₂ = CR ² COO- (C _γ H _{2 γ} -O) _a -R ³ (2 ⁰ )
(In formula (2 ⁰ ), R ² is a hydrogen atom or a methyl group, R ³ is an alkyl group having 1 to 12 carbon atoms, γ is 2 or 3, a is the number of repeating units, and the number average thereof is 1 to 30). .)
<Formula 1>

(In formula (3), R <^4> , R <^5> , R <^6> , R <^7> and R <^8> are respectively independently group represented by a C1-C20 alkyl group, a phenyl group, or the following general formula (4), b is an integer of 0 to 3)
<Formula 2>

(In formula (4), R <^9> , R <^10> and R <^11> is respectively independently a C1-C20 alkyl group or a phenyl group, and c is an integer of 0-3.) The method of claim 1,
The polymerizable (D) copolymer which contains the polymerizable unsaturated compound which has an alkyl group of (d4) C1-C8 further in addition to the said compound (d1), a compound (d2), and a compound (d3). A radiation sensitive resin composition which is a copolymer of an unsaturated compound. The method of claim 2,
The (D) copolymer is a polymerizable unsaturated compound having at least two unsaturated bonds in (d5) 1 molecule in addition to the compound (d1), the compound (d2), the compound (d3) and the compound (d4). A radiation sensitive resin composition which is a copolymer of the polymerizable unsaturated compound containing. The method of claim 3,
The compound (d1) is a compound represented by the following formula (1),
The compound (d2) is a compound represented by the following formula (2), further
(D) the copolymer,
25-35 mass% of compound (d1),
20-30 mass% of compound (d2),
15-20 mass% of compound (d3),
25-35 mass% of compound (d4), and
1-5 mass% of compound (d5)
A radiation sensitive resin composition which is a copolymer of the polymerizable unsaturated compound which consists of.
CH ₂ = CR ¹ COOCH ₂ CH ₂ C ₈ F ₁₇ (1)
(In formula (1), R ¹ is as defined in the formula (1 ⁰ ).)
CH ₂ = CR ² COO (C ₂ H ₄ O) _a R ³ (2)
(Formula (2) of, R ² and R ³ are, respectively, the same meanings as defined in the formula ^(20), the number average value of a number of repeating units is 4 to 12). The formation method of the liquid crystal display element spacer characterized by including at least the following processes in the order described below.
(1) Process of apply | coating the radiation sensitive resin composition of any one of Claims 1-4 on a board | substrate, and forming a coating film,
(2) exposing to at least part of the coating film;
(3) the process of developing the coating film after exposure, and
(4) The process of heating the coating film after image development. The spacer for liquid crystal display elements formed by the method of Claim 5.