JP5720604B2 - Radiation-sensitive composition, cured film and method for forming the same - Google Patents

Description

  The present invention relates to a radiation-sensitive composition suitable as a material for forming a protective film or an interlayer insulating film of a display element, a cured film formed from the radiation-sensitive composition, and a method for forming the same.

  For display elements such as liquid crystal display elements, integrated circuit elements, solid-state imaging elements, and organic EL elements, protective films for preventing deterioration and damage of electronic components such as touch panels and insulation between wirings arranged in layers are provided. A cured film such as an interlayer insulating film is provided to maintain the properties. For the formation of such a cured film, a radiation-sensitive composition is used. For example, a coating film of the radiation-sensitive composition is formed on a substrate, and radiation is applied through a photomask having a predetermined pattern. A cured film can be formed by irradiation (hereinafter referred to as “exposure”), development with an organic alkali developer to dissolve and remove unnecessary portions, and then post-baking.

  The cured film used as the protective film of the touch panel has high adhesion to the wiring of the touch panel element, the film itself is smooth and high in hardness, excellent in scratch resistance, and discolored even under high temperature conditions. It maintains transparency (heat-resistant transparency), does not generate cracks even under high-temperature conditions (heat-resistant cracking), has excellent sensitivity to radiation, and has a good pattern with no residual film. Properties such as being formable (developability) are required.

  On the other hand, in the cured film used as an interlayer insulating film, it is necessary to form a pattern of contact holes for wiring, so in addition to the required characteristics of the protective film described above, pattern images can be formed with high resolution and high definition. What can be done (high resolution) is required.

  Conventionally, acrylic resins are mainly used as components of radiation-sensitive compositions, but in recent years, polysiloxane materials that are superior in heat resistance and transparency as compared to acrylic resins have attracted attention (Patent Documents 1 to 3). 3). However, since the polysiloxane-based material does not have sufficient adhesion to an ITO (indium tin oxide) substrate and cracks are likely to occur, there is a problem that it is not practical for use as a protective film. In addition, as a material for forming an interlayer insulating film of a liquid crystal display element, a negative radiation sensitive composition advantageous in terms of cost has been developed (Patent Document 4). Such a negative radiation sensitive composition has been developed. Therefore, it is difficult to form a contact hole having a hole diameter that can be used practically. For this reason, positive radiation-sensitive compositions are widely used to form interlayer insulating films for display elements because of the superiority of contact hole formation (Patent Document 5).

JP 2000-001648 A JP 2006-178436 A JP 2008-248239 A JP 2000-162769 A JP 2001-354822 A

As described above, the required characteristics for the protective film and the interlayer insulating film have many overlapping portions. Nevertheless, various radiation-sensitive compositions are used depending on the purpose and process. It is a fact. It would be extremely advantageous in terms of cost if a cured film such as a protective film or an interlayer insulating film can be formed from one type of radiation-sensitive composition and the pattern transfer system can be made negative using it. Therefore, development of the negative radiation sensitive composition which can form both a protective film and an interlayer insulation film is earnestly desired.
In developing, TMAH (tetramethylammonium hydroxide) is usually used as an alkali developer. From the viewpoint of cost reduction and productivity improvement, radiation sensitivity that can be developed with an inorganic alkali developer is also used. Development of compositions is desired.

  Accordingly, an object of the present invention is to provide a radiation-sensitive composition that can form a cured film that balances the above required characteristics for a protective film and an interlayer insulating film at a high level in a well-balanced manner and that can be developed even with an inorganic alkaline developer. It is to provide. Another object of the present invention is to provide a cured film and a method for forming the same, which can achieve the above required characteristics for the protective film and the interlayer insulating film in a balanced manner at a high level.

In order to solve the above problems, the present invention firstly includes the following components [A ¹ ], [B] and [C];
[A ¹ ] tetraethoxysilane or a partial hydrolyzate thereof, a hydrolyzable silane compound represented by the following formula (1) or a partial hydrolyzate thereof, and a hydrolyzable silane represented by the following formula (2) Polysiloxane [B] compound obtained by hydrolyzing and condensing a compound or a partial hydrolyzate thereof, a compound having two or more ethylenically unsaturated groups (excluding component [A ¹ ])
[C] A radiation-sensitive composition containing a radical photopolymerization initiator is provided.

[In the formula (1), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and R ² represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a (meth) acryloyloxy group. , M represents an integer of 1 to 3, and n represents an integer of 0 to 6. In Formula (2), R ³ represents an alkyl group having 1 to 6 carbon atoms, x represents an integer of 1 to 3, y represents an integer of 1 to 6, and z represents an integer of 0 to 3. ]

The present invention secondly includes the following components [A ² ], [B] and [C];
[A ² ] A compound having two or more polysiloxane [B] ethylenically unsaturated groups having a SiO ₂ unit, a structural unit represented by the following formula (1a), and a structural unit represented by the following formula (2a) (However, excluding component [A ² ])
[C] A radiation-sensitive composition containing a radical photopolymerization initiator is provided.

[In the formula (1a), R ² represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms or a (meth) acryloyloxy group, m represents an integer of 1 to 3, and n represents 0 Represents an integer of ~ 6. In formula (2a), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, x represents an integer of 1 to 3, y represents an integer of 1 to 6, and z represents an integer of 0 to 3 Indicates. ]

  Thirdly, this invention provides the cured film formed using the said radiation sensitive composition.

Fourthly, the present invention provides the following steps (1) to (4);
(1) The process of forming the coating film of the said radiation sensitive composition on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) A method for forming a cured film, comprising: a step of developing the coating film irradiated with radiation in step (2) with an alkali developer; and (4) a step of heating the coating film developed in step (3). It is to provide.

According to the present invention, radiation sensitivity effective for forming a cured film capable of achieving a high level of balance among various properties such as heat transparency, hardness, scratch resistance, heat crack resistance, adhesion, sensitivity, and developability. A composition can be provided. In addition, since the radiation-sensitive composition of the present invention has sufficient resolution, it can form fine contact holes and can be developed with an inorganic alkaline developer.
Therefore, the cured film formed using the radiation-sensitive composition of the present invention is extremely useful as a protective film for a touch panel of a display element and an interlayer insulating film for a display element.

Radiation-sensitive composition The radiation-sensitive composition of the present invention comprises component [A ¹ ] or [A ² ], component [B], and component [C]. Hereinafter, each component will be described in detail. In the following description, components [A ¹ ] and [A ² ] will be comprehensively described as component [A].

Ingredient [A]
Component [A ¹ ] includes tetraethoxysilane or a partial hydrolyzate thereof (hereinafter also simply referred to as “TEOS”), a hydrolyzable silane compound represented by the following formula (1) or a partial hydrolyzate thereof (hereinafter referred to as “TEOS”). , Also referred to as “compound (1)”) and a hydrolyzable silane compound represented by the following formula (2) or a partial hydrolyzate thereof (hereinafter also referred to as “compound (2)”). It is a polysiloxane obtained. By including this component [A], the solubility in an alkali developer used in the development step, particularly an inorganic alkali developer, can be improved, the developability can be improved, and the resulting cured film has heat-resistant transparency. It becomes possible to improve the scratch resistance. Here, the “partial hydrolyzate” refers to a siloxane compound (having a number of silicon atoms of 2 to 2) produced by hydrolysis condensation reaction of an alkoxy group and having at least one, preferably two or more alkoxy groups remaining in the molecule. 100, preferably about 2 to 30 siloxane oligomers).

[In the formula (1), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and R ² represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a (meth) acryloyloxy group. , M represents an integer of 1 to 3, and n represents an integer of 0 to 6.
In Formula (2), R ³ represents an alkyl group having 1 to 6 carbon atoms, x represents an integer of 1 to 3, y represents an integer of 1 to 6, and z represents an integer of 0 to 3. ]

First, the definition of symbols in formulas (1) and (2) will be described.
The alkyl group for R ¹ and R ³ may be linear, branched or cyclic. Although R ¹ and the carbon number of the alkyl group in R ³ is 1 to 6, from the viewpoint of the reactivity hydrolytic condensation, the number of carbon atoms is 1 to 4 preferably 1 or 2 is more preferred. Specific examples include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, and a cyclohexyl group. A methyl group or an ethyl group is particularly preferable. In addition, when two or more R < ¹ > exists in the same molecule, they may be the same or different. The same applies to R ³ .

The alkyl group for R ² may be linear, branched or cyclic. The number of carbon atoms of the alkyl group in R ² is 1 to 20, preferably 1 to 10, and more preferably 1 to 6. Specifically, in addition to alkyl exemplified for R ¹ and R ³ , n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n -Dodecyl group, n-tridecyl group, n-tetradecyl group, n-hexadecyl group, cycloheptyl group, cyclooctyl group and the like.
The aryl group in R ² means a monocyclic to tricyclic aromatic hydrocarbon group having 6 to 14 carbon atoms, and specific examples include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. Among these, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
The alkyl group and aryl group in R ² may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, a nitro group, a cyano group, and an alkoxy group having 1 to 6 carbon atoms. it can. In addition, the position and number of substituents are arbitrary, and when having two or more substituents, the substituents may be the same or different. Examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom, and among them, a fluorine atom is preferable. The halogen atom can substitute for some or all of the hydrogen atoms of the alkyl group and aryl group, but those in which all are substituted are preferred. Specific examples of the halogen-substituted alkyl group include perfluoroalkyl groups such as a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, and a perfluorocyclopropyl group. Moreover, as a C1-C6 alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, iso-propoxy group, etc. are mentioned.
The (meth) acryloyloxy group in R ² is a concept including an acryloyloxy group and a methacryloyloxy group.
Among these, as R ^2, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a (meth) acryloyloxy group is preferable. In addition, when ^two or more R < ² > exists in the same molecule, they may be the same or different.

Although m is an integer of 1-3, 1 or 2 is preferable and 1 is more preferable.
Although n is an integer of 0-6, the integer of 0-3 is preferable and 0 or 3 is more preferable.

x is an integer of 1 to 3, preferably 1 or 2, and more preferably 1.
Although y is an integer of 1-6, the integer of 1-3 is preferable and 3 is more preferable.
Although z is an integer of 0-3, 0 or 1 is preferable and 0 is more preferable.

Next, the constituent component of the polysiloxane of component [A ¹ ] will be described.
The component [A ¹ ] contains TEOS as an essential component. TEOS is a polyfunctional silane compound having four hydrolyzable groups. When a structural unit derived from TEOS is contained in polysiloxane, the adhesion with the substrate is enhanced by the interaction with the hydroxyl group on the surface of the metal substrate such as ITO, and the crosslinking density of the polysiloxane is further increased and obtained. Although the cured film can have higher hardness, it becomes brittle, so that it is likely to generate cracks and is inferior in scratch resistance. Contrary to such a prediction, in the present invention, TEOS is composed of a compound (1) and a compound (2), which will be described later, in combination with a polysiloxane and further containing a component [B]. It has been surprisingly found that a cured film having not only high hardness and substrate adhesion but also excellent scratch resistance and crack resistance can be obtained even if contained in a high concentration. This was completely unpredictable from conventional knowledge.

  The TEOS charge ratio is preferably 5 to 75 mol%, more preferably 10 to 70 mol%, more preferably 10 to 70 mol%, based on the total of the raw material compounds, from the viewpoint of improving hardness, adhesion, scratch resistance and heat cracking resistance. Preferably it is 25-65 mol%.

Component [A ¹ ] further contains compound (1) as an essential component. The compound (1) is a component that contributes to improvement of crack resistance and scratch resistance while suppressing an excessive increase in crosslink density due to TEOS and maintaining an appropriate crosslink density.
Examples of the compound (1) include a silane compound in which m is 1, a silane compound in which m is 2, and a silane compound in which m is 3. Specifically, the following compounds can be mentioned. In addition, a compound (1) may be used individually by 1 type, or may be used in combination of 2 or more type.

  Examples of the silane compound in which m is 1 include methyltrimethoxysilane, methyltriethoxysilane, methyltri-iso-propoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and ethyltri-iso-propoxysilane. Hydrolyzable silane compounds having one alkyl group having 1 to 20 carbon atoms such as ethyltributoxysilane, butyltrimethoxysilane, and decyltrimethoxysilane; halogens having 1 to 20 carbon atoms such as trifluoropropyltrimethoxysilane Hydrolyzable silane compound having one substituted alkyl group; Hydrolyzable silane compound having one aryl group having 6 to 14 carbon atoms such as phenyltrimethoxysilane and phenyltriethoxysilane; 3-methacryloyloxypropyltrimeth Silane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltripropoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltripropoxysilane, etc. And a hydrolyzable silane compound having one acryloyloxy group.

  Examples of the silane compound in which m is 2 include hydrolyzable silane compounds having two alkyl groups having 1 to 20 carbon atoms such as dimethyldimethoxysilane and dibutyldimethoxysilane; 6 to 14 carbon atoms such as diphenyldimethoxysilane. Hydrolyzable silane compound having two aryl groups; (meth) acryloyloxy group such as 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, and alkoxy having an alkyl group having 1 to 20 carbon atoms Silane compounds; alkoxysilane compounds having a (meth) acryloyloxy group such as 3-methacryloyloxypropylphenyldimethoxysilane, 3-acryloyloxypropylphenyldimethoxysilane, and an aryl group having 6 to 14 carbon atoms; 3,3′- Mention may be made of hydrolyzable silane compounds having two (meth) acryloyloxy groups such as dimethacryloyloxypropyldimethoxysilane and 3,3′-diaacryloyloxypropyldimethoxysilane.

  Examples of the silane compound in which m is 3 include hydrolyzable silane compounds having three alkyl groups having 1 to 20 carbon atoms such as tributylmethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, and tributylethoxysilane; Hydrolyzable silane compound having three aryl groups having 6 to 14 carbon atoms such as silane; 3,3 ′, 3 ″ -trimethacryloyloxypropylmethoxysilane, 3,3 ′, 3 ″ -triacryloyloxypropylmethoxysilane And hydrolyzable silane compounds having three (meth) acryloyloxy groups such as

  Among these compounds (1), a hydrolyzable silane compound having an alkyl group having 1 to 6 carbon atoms, a hydrolyzable silane compound having an aryl group having 6 to 14 carbon atoms, and a hydrolysis having a (meth) acryloyloxy group. Silane compounds are preferable, and in these compounds, a silane compound in which m according to the above formula (1) is 1 is particularly preferable. Specific examples of suitable compound (1) include alkoxy having one alkyl group having 1 to 6 carbon atoms such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and butyltrimethoxysilane. Silane compound; alkoxysilane compound having one aryl group having 6 to 14 carbon atoms such as phenyltrimethoxysilane; 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxy An alkoxysilane compound having one (meth) acryloyloxy group such as silane and 3-methacryloyloxypropyltriethoxysilane can be given.

  The total charge ratio of the compound (1) is preferably 10 with respect to the total of the raw material compounds from the viewpoints of heat-resistant transparency, hardness, scratch resistance, heat-cracking resistance, adhesion, sensitivity, resolution, and developability. It is -80 mol%, More preferably, it is 10-75 mol%, More preferably, it is 15-70 mol%.

In the present invention, from the viewpoint of further improving scratch resistance and heat crack resistance, among the above-mentioned preferred compound (1), a hydrolyzable silane compound having an alkyl group having 1 to 6 carbon atoms, and carbon It is preferable to use at least one silane compound selected from hydrolyzable silane compounds having an aryl group of several 6 to 14 (hereinafter also referred to as “silane compound (1b ¹ )”). These silane compounds (1b ¹ In particular, a silane compound in which m according to the above formula (1) is 1 is particularly preferable.

From the viewpoint of further improving sensitivity and developability, it is preferable to use a hydrolyzable silane compound having a (meth) acryloyloxy group among the above-mentioned preferred compounds (1). A silane compound in which m according to the formula (1) is 1 is particularly preferable. Examples of the hydrolyzable silane compound having a (meth) acryloyloxy group include a hydrolyzable silane compound having a methacryloyloxy group (hereinafter also referred to as “silane compound (1c ¹ )”) and a hydrolyzable having an acryloyloxy group. It is preferable to use at least one selected from silane compounds having silane (hereinafter also referred to as “silane compound (1d ¹ )”), and it is more preferable to use silane compound (1c ¹ ) and silane compound (1d ¹ ) together. preferable. The hydrolyzable silane compound having a (meth) acryloyloxy group is preferably used together with the silane compound (1b ¹ ).

When the silane compound (1b ¹ ) is used as the compound ( ¹ ), the total charge ratio of the silane compound (1b ¹ ) is the sum of the raw material compounds from the viewpoint of further improving scratch resistance and heat crack resistance. On the other hand, it is preferably 10 to 80 mol%, more preferably 15 to 75 mol%, still more preferably 30 to 70 mol%.

  From the viewpoint of further improving sensitivity and resolution, the total charge ratio of the hydrolyzable silane compound having a (meth) acryloyloxy group is preferably 5 to 25 mol%, more preferably, relative to the total of the raw material compounds. 10 to 20 mol%.

Further, when used in combination silane compound (1c ¹⁾ and the silane compound (1d ^1), both charged ratio of (1c ¹ / 1d ^1), from the viewpoint of further improving scratch resistance and heat crack resistance, mol The ratio is preferably 0.05 to 3, more preferably 0.2 to 1.5, and still more preferably 0.3 to 1.

Component [A ¹ ] further contains compound (2) as an essential component. The compound (2) is a component that contributes to improvement of heat cracking resistance and scratch resistance by suppressing an excessive increase in crosslink density due to TEOS, and also contributes to improvement of developability.
Examples of the compound (2) include a silane compound in which x is 1, a silane compound in which x is 2, and a silane compound in which x is 3. Specifically, the following compounds can be mentioned. In addition, a compound (2) may be used individually by 1 type, or may be used in combination of 2 or more type.

  Examples of the silane compound in which x is 1 include 2-trimethoxysilylethyl succinic anhydride, 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylsilylpropyl succinic anhydride, and 3-triphenoxysilylpropyl anhydride. Examples thereof include succinic acid, 3-trimethoxysilylpropyl glutaric anhydride, 3-triethoxysilylsilylpropyl glutaric anhydride, and 3-triphenoxysilylpropyl glutaric anhydride.

  Examples of the silane compound in which x is 2 include di-1-butoxy-bis [3- (dihydro-2,5-furandionyl) propyl] silane, bis [3- (dihydro-2,5-furandionyl) propyl]. And dimethoxysilane, bis [3- (dihydro-2H-pyran-2,6 (5H) -dionyl) propyl] dimethoxysilane, and the like.

  Examples of the silane compound in which x is 3 include tris [3- (dihydro-2,5-furandionyl) propyl] methoxysilane.

  Of these compounds (2), a silane compound wherein x is 1 is preferable, and specific examples of suitable compounds (2) include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylsilylpropyl succinic anhydride, and the like. Can be mentioned.

  The total charge ratio of the compound (2) is preferably 15 with respect to the total of the raw material compounds from the viewpoints of heat-resistant transparency, hardness, scratch resistance, heat-cracking resistance, adhesion, sensitivity, resolution, and developability. It is at most 13 mol%, more preferably at most 10 mol%, still more preferably at most 7 mol%. The lower limit of the total charge ratio of compound (2) is preferably 0.5 mol%, more preferably 1 mol%, still more preferably 2 mol%, particularly preferably 3 mol%, relative to the total of the raw material compounds. is there. The range of the total charge ratio of the compound (2) is preferably 0.5 to 15 mol%, more preferably 1 to 13 mol%, still more preferably 2 to 10 mol%, further based on the total of the raw material compounds. Preferably it is 3-7 mol%.

  As a method for hydrolytic condensation of TEOS, compound (1) and compound (2), TEOS, compound (1) and compound (2) as raw material compounds are mixed in a solvent, and water is added to the mixed solution. A method of hydrolytic condensation is preferably employed. In this case, each raw material compound and water may be added to the reaction system at once, and the reaction may be performed in one step. Also, by adding each raw material compound and water into the reaction system in several times, The hydrolysis condensation reaction may be performed in multiple stages. The hydrolyzed condensate includes not only a product obtained by hydrolytic condensation of all hydrolyzable groups but also a product in which a part of the hydrolyzable group remains without being hydrolyzed or condensed.

In the hydrolysis-condensation reaction, the acid anhydride group of compound (2) is opened as shown in the following scheme to generate a carboxyl group. Incidentally, OR ⁴ group in formula represents an alkoxy group formed by alcoholysis of a hydroxyl group from the carboxyl group formed by hydrolysis of 1-6 carbon atoms produced in the reaction system or by hydrolysis, alcohol.

In the formula, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and z has the same meaning as described above. Examples of the alkyl group for R ⁴ include the same groups as those for R ^1, and the specific configuration thereof is as described for R ¹ .

  Although the solvent used for a hydrolysis condensation reaction is not specifically limited, Usually, the thing similar to the solvent used for preparation of a radiation sensitive composition is used. Examples of such solvents include ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and propionic acid esters. These solvents may be used alone or in combination of two or more. Among these, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, and methyl 3-methoxypropionate are preferable.

As water used for the hydrolysis condensation reaction, it is preferable to use water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment or distillation. By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved.
The amount of water used is preferably 0.1 to 3 mol, more preferably 0.3 to 2 mol, relative to 1 mol in total of the hydrolyzable groups of TEOS, compound (1) and compound (2). Preferably it is 0.5-1.5 mol. By using such an amount of water, the reaction rate of the hydrolysis condensation can be optimized.

The hydrolysis-condensation reaction proceeds in a self-catalytic manner by the carboxylic acid produced by hydrolysis of the compound (2) without adding a catalyst, but an acid catalyst may be added separately.
Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and polyphosphoric acid, organic acids such as formic acid, oxalic acid, acetic acid, trifluoroacetic acid, and trifluoromethanesulfonic acid, and acidic ion exchange resins. be able to.
From the viewpoint of promoting the hydrolysis and condensation reaction, the amount of the catalyst used is preferably 0.2 mol or less, more preferably 0.8 mol or less with respect to 1 mol in total of TEOS, compound (1) and compound (2). 00001 to 0.1 mol.

  The reaction temperature and reaction time in the hydrolysis-condensation reaction can be appropriately set. For example, the following conditions can be employed. The reaction temperature is preferably 40 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 30 minutes to 24 hours, more preferably 1 to 12 hours. By setting such reaction temperature and reaction time, the hydrolysis condensation reaction can be performed most efficiently.

  After the hydrolysis condensation reaction, water and produced alcohol can be removed from the reaction system by adding a dehydrating agent and then subjecting it to evaporation. The dehydrating agent used in this stage is generally consumed or adsorbed with excess water, or the dehydrating ability is completely consumed or removed by evaporation.

Ingredient [A ² ]
Component [A ² ] includes a TEOS-derived SiO ₂ unit, a structural unit represented by the following formula (1a) derived from compound (1) (hereinafter also referred to as “structural unit (1a)”), and compound (2) And a structural unit represented by the following formula (2a) derived from (hereinafter, also referred to as “structural unit (2a)”). Each of the structural units of the SiO ₂ unit, the structural unit (1a), and the structural unit (2a) may be composed of one kind or two or more kinds.

[Wherein, R ² , R ⁴ , m, n, x, y and z are as defined above. ]

Among these, in formula (1a), m is preferably 1, and in formula (2a), x is preferably 1.
Structural units where m is 1 in formula (1a) and x is 1 in formula (2a) are shown in formulas (1-1a) and (2-1a) below, respectively.

[Wherein, R ² , R ⁴ , n, y and z are as defined above. ]

Such polysiloxane can be obtained by subjecting TEOS, the compound (1), and the compound (2) to the hydrolysis condensation reaction described above. However, TEOS, the compound (1), and the compound (2) It is also possible to obtain it by a hydrolysis condensation reaction of a hydrolyzed condensate of two compounds selected from That is, the SiO ₂ unit, the structural unit (1a), and the structural unit (2a) may be contained in any form of random copolymerization and block copolymerization, respectively.

The respective content ratios of the SiO ₂ unit, the structural unit (1a), and the structural unit (2a) in the component [A ² ] are as follows: heat-resistant transparency, hardness, scratch resistance, heat-cracking property, adhesion, sensitivity, From the viewpoint of improving the resolution and developability, it is as follows.
The SiO ₂ unit is preferably 5 to 75 mol%, more preferably 10 to 70 mol%, and still more preferably 25 to 65 mol% in the total structural unit of the component [A ² ].
The structural unit (1a) is preferably 10 to 80 mol%, more preferably 10 to 75 mol%, and still more preferably 15 to 70 mol%, in all the structural units of the component [A ² ].
The structural unit (2a) is preferably 15 mol% or less, more preferably 13 mol% or less, still more preferably 10 mol% or less, still more preferably 7 mol% or less, in all the structural units of the component [A ² ]. The lower limit thereof is preferably 0.5 mol%, more preferably 1 mol%, more preferably 2 mol%, particularly preferably 3 mol%. The range for the content of the structural unit (2a), in the total structural units of component [A ^2], preferably 0.5 to 15 mol%, more preferably 1 to 13 mol%, more preferably 2 to 10 It is mol%, More preferably, it is 3-7 mol%.

  Further, as the structural unit (1a), a structural unit represented by the following formula (1b) (hereinafter also referred to as “structural unit (1b)”) is 1 from the viewpoint of further improving heat cracking resistance and scratch resistance. It is preferable to contain above.

In Formula (1b), R ⁵ represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms, and m is as defined above.
Examples of the alkyl group for R ⁵ include the same groups as those described above for R ^1, and examples of the aryl group for R ⁵ include the same groups as those described above for R ² . The specific configuration is as described above.
Further, m is preferably 1. The structural unit in the case where m is 1 in the formula (1b) is shown in the following formula (1-1b).

[Wherein, R ⁵ has the same meaning as described above. ]

The content of the unit (1b) is present in the total structural units of the component [A ^2], and preferably 10 to 80 mol%, more preferably 15 to 75 mol%, more preferably 30 to 70 mol%.

  Furthermore, in the present invention, from the viewpoint of further improving sensitivity and developability, the structural unit (1a) is a structural unit represented by the following formula (1c) (hereinafter also referred to as “structural unit (1c)”). And at least one selected from structural units represented by the following formula (1d) (hereinafter also referred to as “structural unit (1d)”), and both the structural unit (1c) and the structural unit (1d) It is more preferable to contain. Furthermore, it is preferable to contain at least one selected from the structural unit (1c) and the structural unit (1d) together with the structural unit (1b).

In formulas (1c) and (1d), m and n have the same meanings as described above, but m is preferably 1, and n is preferably 3.
Structural units where m is 1 in formula (1c) and formula (1d) are shown in formulas (1-1c) and (1-1d) below, respectively.

[Wherein, n has the same meaning as described above. ]

The total content of the structural unit (1c) and the structural unit (1d) is preferably 5 to 25 mol% in all the structural units of the component [A ² ], from the viewpoint of further improving sensitivity and resolution. Preferably it is 10-20 mol%.
Further, when the structural unit (1c) and the structural unit (1d) are contained, the content ratio (1c / 1d) of the structural unit (1c) and the structural unit (1d) is further improved in scratch resistance and crack resistance. From the viewpoint of improvement, the molar ratio is preferably 0.05 to 3, more preferably 0.2 to 1.5, and still more preferably 0.3 to 1.

  Examples of the structural unit (2a) include structural units derived from the above compound (2). Among them, 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylsilylpropyl succinic anhydride, etc. It is preferable that it is a unit derived from.

Component [A] may be used alone or in combination of two or more.
The molecular weight of component [A] can be measured as a weight average molecular weight in terms of polystyrene using GPC (gel permeation chromatography) using tetrahydrofuran as the mobile phase. 500-10000 are preferable and, as for the weight average molecular weight (Mw) of component [A], 1000-7000 are still more preferable. By making the value of the weight average molecular weight of component [A] 500 or more, the film formability of the coating film of the radiation sensitive composition can be improved. On the other hand, the fall of the alkali developability of a radiation sensitive composition can be prevented by making a weight average molecular weight into 10,000 or less.
The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured under the same conditions, that is, the degree of dispersion (Mw / Mn) is preferably 1.0 to 15.0, more preferably 1 .1 to 10.0, more preferably 1.1 to 5.0. By setting it within such a range, it is possible to achieve both alkali developability, adhesion and heat cracking resistance.

Ingredient [B]
Component [B] is a compound having two or more ethylenically unsaturated groups, but is a polyfunctional monomer that polymerizes by irradiation with radiation in the presence of the photoradical polymerization initiator of component [C] described later. Is the body. However, component [A] is excluded from component [B].

  As such a compound, a bifunctional or trifunctional (meth) acrylic acid ester is preferably used from the viewpoints of good polymerizability and improved strength of the resulting cured film.

  As the bifunctional (meth) acrylic acid ester, a polyfunctional (meth) acrylate obtained by reacting a divalent aliphatic polyhydroxy compound such as ethylene glycol, propylene glycol, polyethylene glycol or polypropylene glycol with (meth) acrylic acid. Is mentioned. Specifically, ethylene glycol diacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexane Examples include diol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, and 1,9-nonanediol dimethacrylate. Examples of commercially available products include Aronix M-210, M-240, and M-6200 (above, Toagosei Co., Ltd.); KAYARAD HDDA, HX-220, R-604 (above, Nippon Kayaku Co., Ltd.); Viscoat 260, 312 and 335HP (Osaka Organic Chemical Co., Ltd.); Light acrylate 1,9-NDA (Kyoeisha Chemical Co., Ltd.) and the like.

  The trifunctional or higher functional (meth) acrylic acid ester is obtained by reacting a trivalent or higher aliphatic polyhydroxy compound such as glycerin, trimethylolpropane, pentaerythritol and dipentaerythritol with (meth) acrylic acid. (Meth) acrylate is mentioned. Specifically, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentahydrate Examples thereof include pentaerythritol hexaacrylate, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene oxide-modified dipentaerythritol hexaacrylate, and the like. Examples of commercially available products include Aronix M-309, M-315, M-400, M-405, M-450, M-7100, M-8030, M-8060, and TO- 1450 (above, Toagosei Co., Ltd.); KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-60, DPCA-12, DPEA-12 (above, Nippon Kayaku Co., Ltd.); , 300, 360, GPT, 3PA, 400 (above, Osaka Organic Chemical Industry Co., Ltd.).

  Further, tri (2-acryloyloxyethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate, succinic acid modified pentaerythritol triacrylate, succinic acid modified dipentaerythritol pentaacrylate, tris (acryloxyethyl) isocyanurate In addition, a compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups, and having one or more hydroxyl groups in the molecule, and 3, 4, or 5 A polyfunctional urethane acrylate compound obtained by reacting with a compound having a (meth) acryloyloxy group can also be used. As a commercial item containing a polyfunctional urethane acrylate type compound, new frontier R-1150 (Daiichi Kogyo Seiyaku Co., Ltd.), KAYARAD DPHA-40H (Nippon Kayaku Co., Ltd.), etc. are mentioned.

  Among these, 1,9-nonanediol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate and dipenta Contains a mixture with erythritol pentaacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid modified pentaerythritol triacrylate, succinic acid modified dipentaerythritol pentaacrylate, tris (acryloxyethyl) isocyanurate, polyfunctional urethane acrylate compound A commercially available product is preferred. Among them, trifunctional or more, especially 3-6 functional (meth) acrylic acid esters are preferable, and a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate is particularly preferable.

  Component [B] may be used alone or in combination of two or more. The content of the component [B] is preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass, still more preferably 15 to 100 parts by mass, and still more preferably 20 to 100 parts by mass of the component [A]. ~ 80 parts by mass. By setting the content of the component [B] within the above range, the hardness, heat resistance and sensitivity are further improved.

Ingredient [C]
Component [C] is a radical photopolymerization initiator. The radical photopolymerization initiator is a compound capable of generating an active species capable of initiating the curing reaction of the component [B] by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. .
Examples of the photo radical polymerization initiator used in the present invention include O-acyl oxime compounds, acetophenone compounds, acyl phosphine oxide compounds, and the like.

  Specific examples of the O-acyloxime compound include ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxy Benzoyl} -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] and the like. . These O-acyloxime compounds can be used alone or in admixture of two or more.

  Among these, preferable O-acyloxime compounds include etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxy Benzoyl} -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)].

  Examples of acetophenone compounds include α-aminoketone compounds and α-hydroxyketone compounds. An acetophenone compound can be used alone or in admixture of two or more.

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

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

  Of these acetophenone compounds, α-aminoketone compounds are preferred, and 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2- Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one is particularly preferred.

  Specific examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. These acylphosphine oxide compounds can be used alone or in admixture of two or more.

  Of these acylphosphine oxide compounds, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide is preferred.

  In this invention, it is preferable to contain an O-acyl oxime compound as component [C].

Ingredient [C] may be used individually by 1 type, and 2 or more types may be mixed and used for it.
The content of the component [C] is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 15 parts by mass, and still more preferably, with respect to 100 parts by mass in total of the components [A] and [B]. 1 to 15 parts by mass. By setting the content of the component [C] within the above range, a cured film having high radiation sensitivity and sufficient hardness can be formed even in the case of a low exposure amount.

Ingredient [D]
Component [D] is a solvent. The radiation-sensitive composition is usually prepared as a liquid composition by blending a solvent. As a solvent, as long as each component which comprises a radiation sensitive composition is disperse | distributed or melt | dissolved, and it does not react with these components and has moderate volatility, it can select suitably and can be used.
As such a solvent, it is preferable to contain an alcohol solvent which is a protic solvent. By using an alcohol-based solvent, it is possible to improve the coating properties of a radiation-sensitive composition on a large substrate, and further suppress the occurrence of coating unevenness (such as streaky unevenness, pin mark unevenness, and moyen unevenness), and the film thickness is uniform. The property can be further improved.

As an alcohol solvent, for example,
Long-chain alkyl alcohols such as 1-hexanol, 1-octanol, 1-nonanol, 1-dodecanol, 1,6-hexanediol, 1,8-octanediol;
Aromatic alcohols such as benzyl alcohol;
Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;
Examples include dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether. These alcohol solvents can be used alone or in combination of two or more.

  Of these alcohol solvents, propylene glycol monoalkyl ether is particularly preferable from the viewpoint of improving coating properties, and propylene glycol monomethyl ether and propylene glycol monoethyl ether are particularly preferable.

  Ingredient [D] may be used individually by 1 type, and 2 or more types may be mixed and used for it. The content of component [D] is preferably 1 to 1,200 parts by mass, and more preferably 10 to 900 parts by mass with respect to 100 parts by mass of component [A]. By setting the content of the component [D] within the above range, it is possible to improve the coating property on a glass substrate and the like, and further suppress the occurrence of coating unevenness (such as streaky unevenness, pin mark unevenness, and unevenness), and the film Thickness uniformity can be further improved.

  In the present invention, together with alcohol solvents, other solvents such as ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ether propionates, aromatic hydrocarbons, ketones, esters Etc. can be contained.

Additives The radiation-sensitive composition of the present invention can contain various additives as required.
Examples of additives include fillers such as silica, alumina, and acrylic fine particles; radiation sensitive acid generators such as triphenylsulfonium salts and tetrahydrothiophenium salts; 2-nitrobenzylcyclohexyl carbamate, O-carbamoylhydroxyamide Radiation sensitive base generators such as: Nonionic surfactants, fluorosurfactants and silicone surfactants; 2,2-thiobis (4-methyl-6-t-butylphenol), 2 Antioxidants such as 1,6-di-t-butylphenol; and UV absorbers such as 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones Can do.
The content of these additives can be appropriately selected within a range that does not impair the object of the present invention.

  The radiation-sensitive composition of the present invention can be prepared by an appropriate method. For example, in the [D] solvent, the components [A], [B] and [C], and optionally additives are added. By mixing at a predetermined ratio, a radiation-sensitive composition in a solution or dispersion state can be prepared.

Cured film and a method of forming Next, using a radiation-sensitive composition of the present invention, a method for forming a cured film on the substrate. The method includes the following steps (1) to (4).
(1) A step of coating the radiation-sensitive composition of the present invention on a substrate to form a coating film,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) A step of developing the coating film irradiated with radiation in step (2) with an alkaline developer, and (4) a step of heating the coating film developed in step (3).

Process (1)
In step (1), after applying the solution or dispersion of the radiation-sensitive composition of the present invention on the substrate, the coating surface is preferably removed by heating (pre-baking) the coating surface to form a coating film. To do. Examples of the substrate material that can be used include glass, quartz, silicon, and resin. Specific examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, a ring-opening polymer of a cyclic olefin, and a hydrogenated product thereof.

  The application method of the solution or dispersion of the radiation-sensitive composition is not particularly limited. For example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, etc. The method can be adopted. Among these coating methods, a spin coating method or a slit die coating method is particularly preferable. The pre-baking conditions vary depending on the type of each component, the blending ratio, and the like, but can preferably be about 70 to 120 ° C. for about 1 to 10 minutes.

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

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

Process (3)
In step (3), the exposed coating film is developed with an alkali developer to remove unexposed portions and form a predetermined pattern. Thus, the radiation-sensitive composition of the present invention is a negative type since the non-irradiated portion of the radiation is removed.
Examples of the alkali developer include inorganic alkali developers such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia, and organic alkali developers such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. A liquid can be mentioned. Among these, from the viewpoint of cost and productivity, an inorganic alkali developer is preferable, and an alkali metal hydroxide developer such as sodium hydroxide or potassium hydroxide is particularly preferable. The radiation-sensitive composition of the present invention can form a pattern image with high resolution and high definition even when an inorganic alkaline developer is used.

  In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to such an alkaline developer. As a developing method, for example, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time varies depending on the composition of the radiation-sensitive composition, but is preferably about 10 to 180 seconds. Following such development processing, for example, after washing with running water for 30 to 90 seconds, a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.

Process (4)
In the step (4), a cured film having a desired pattern can be obtained by heating the developed and patterned coating film using a heating device such as a hot plate or an oven. The heating temperature is, for example, 120 to 250 ° C. Although heating time changes with kinds of heating apparatus, for example, when performing a heating process on a hotplate, it can be set to 30 to 90 minutes when performing a heating process in an oven. It is also possible to use a step baking method or the like in which the heating process is performed twice or more.
The film thickness of the cured film thus formed is preferably 0.1 to 10 μm, more preferably 0.1 to 6 μm, and still more preferably 0.1 to 4 μm.

  By passing through the steps as described above, a cured film having good adhesion to the substrate and excellent properties such as heat-resistant transparency, hardness, scratch resistance, heat crack resistance, sensitivity and developability can be formed. It is possible to form an image with high resolution and high definition. Moreover, such a pattern can be developed with an inorganic alkaline developer. And since the obtained cured film has such characteristics, it can be suitably used as, for example, a protective film for a touch panel of a display element and an interlayer insulating film for a display element.

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

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polysiloxane obtained from each of the following synthesis examples were measured by gel permeation chromatography (GPC) according to the following specifications.
Apparatus: GPC-101 (made by Showa Denko KK)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804 (manufactured by Showa Denko KK) mobile phase: tetrahydrofuran

Synthesis Example of Component [A] Polysiloxane [Synthesis Example 1]
In a container equipped with a stirrer, 20 parts by mass of propylene glycol monomethyl ether was charged, followed by 41 parts by mass of methyltrimethoxysilane (hereinafter referred to as “MTMS”), 12 parts by mass of tetraethoxysilane (TEOS), and 3- 5 parts by mass (MTMS / TEOS / TMSPS (molar ratio) = 80/15/5) of (trimethoxysilyl) propyl succinic anhydride (hereinafter referred to as “TMSPS”) was charged and heated until the solution temperature reached 60 ° C. . After the solution temperature reached 60 ° C., 0.1 part by mass of phosphoric acid and 19 parts by mass of ion-exchanged water were charged, heated to 75 ° C. and held for 3 hours. After cooling to 45 ° C., 28 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis condensation. Thus, polysiloxane (A-1) was obtained. Polysiloxane (A-1) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 2,500, and a dispersity (Mw / Mn) of 2.2. In the present specification, the “solid content” means a residue obtained by drying a sample on a hot plate at 175 ° C. for 1 hour to remove volatile substances.

[Synthesis Example 2]
In addition to MTMS, TEOS and TMSPS, 3-methacryloxypropyltrimethoxysilane (hereinafter referred to as “MPTMS”) is further added at a ratio of MTMS / TEOS / MPTMS / TMSPS (molar ratio) = 68/15/15/2. A polysiloxane (A-2) was obtained in the same manner as in Synthesis Example 1 except that it was used. Polysiloxane (A-2) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 2,300, and a dispersity (Mw / Mn) of 2.1.

[Synthesis Example 3]
Polysiloxane (A-3) was obtained in the same manner as in Synthesis Example 2, except that the ratio (molar ratio) of MTMS / TEOS / MPTMS / TMSPS was changed to 62/15/15/8. Polysiloxane (A-3) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 2,200, and a dispersity (Mw / Mn) of 2.1.

[Synthesis Example 4]
Polysiloxane (A-4) was obtained in the same manner as in Synthesis Example 2, except that the ratio (molar ratio) of MTMS / TEOS / MPTMS / TMSPS was changed to 55/15/15/15. Polysiloxane (A-4) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 2,200, and a dispersity (Mw / Mn) of 2.3.

[Synthesis Example 5]
In addition to MTMS, TEOS, and TMSPS, MPTMS and phenyltrimethoxysilane (hereinafter referred to as “PTMS”) are further changed to MTMS / TEOS / PTMS / MPTMS / TMSPS (molar ratio) = 50/15/15/15/5. A polysiloxane (A-5) was obtained in the same manner as in Synthesis Example 1 except that it was used in a proportion. Polysiloxane (A-6) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 1,900, and a dispersity (Mw / Mn) of 1.9.
[Synthesis Example 6]
In addition to MTMS, TEOS and TMSPS, 3-acryloxypropyltrimethoxysilane (hereinafter referred to as “APTMS”) is added at a ratio of MTMS / TEOS / APTMS / TMSPS (molar ratio) = 65/15/15/5. A polysiloxane (A-6) was obtained in the same manner as in Synthesis Example 1 except that it was used. Polysiloxane (A-6) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 2,400, and a dispersity (Mw / Mn) of 2.3.

[Synthesis Example 7]
Polysiloxane (A-7) was obtained in the same manner as in Synthesis Example 6 except that the ratio (molar ratio) of MTMS / TEOS / APTMS / TMSPS was changed to 50/30/15/5. Polysiloxane (A-7) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 3,500, and a dispersity (Mw / Mn) of 2.4.

[Synthesis Example 8]
Synthesis Example 1 except that in addition to MTMS, TEOS and TMSPS, MPTMS and APTMS were further used in a ratio of MTMS / TEOS / MPTMS / APTMS / TMSPS (molar ratio) = 77/7/1/10/5. In the same manner as in Example 1, polysiloxane (A-8) was obtained. Polysiloxane (A-8) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 2,000, and a dispersity (Mw / Mn) of 2.0.

[Synthesis Example 9]
Polysiloxane (A-9) is obtained in the same manner as in Synthesis Example 8 except that the ratio (molar ratio) of MTMS / TEOS / MPTMS / APTMS / TMSPS is changed to 50/30/5/10/5. It was. Polysiloxane (A-9) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 3,400, and a dispersity (Mw / Mn) of 2.3.

[Synthesis Example 10]
Polysiloxane (A-10) is obtained in the same manner as in Synthesis Example 8 except that the ratio (molar ratio) of MTMS / TEOS / MPTMS / APTMS / TMSPS is changed to 15/62/8/10/5. It was. Polysiloxane (A-10) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 5,400, and a dispersity (Mw / Mn) of 2.6.

[Synthesis Example 11]
Polysiloxane (A-11) is obtained in the same manner as in Synthesis Example 8 except that the ratio (molar ratio) of MTMS / TEOS / MPTMS / APTMS / TMSPS is changed to 50/30/10/5/5. It was. Polysiloxane (A-11) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 3,100, and a dispersity (Mw / Mn) of 2.3.

[Comparative Synthesis Example 1]
Polysiloxane (a-1) is obtained in the same manner as in Synthesis Example 1 except that APTMS is used instead of TEOS and the ratio of MTMS / APTMS / TMSPS (molar ratio) = 80/15/5. It was. Polysiloxane (a-1) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 2,000, and a dispersity (Mw / Mn) of 1.9.

[Comparative Synthesis Example 2]
By using the same procedure as in Synthesis Example 1 except that MPTMS and APTMS were used instead of TEOS, and the ratio was MTMS / MPTMS / APTMS / TMSPS (molar ratio) = 80/5/10/5, polysiloxane ( a-2) was obtained. Polysiloxane (a-2) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 2,000, and a dispersity (Mw / Mn) of 1.9.

[Comparative Synthesis Example 3]
Polysiloxane (a-3) is obtained in the same manner as in Synthesis Example 1 except that APTMS is used instead of TMSPS and the ratio of MTMS / TEOS / APTMS (molar ratio) = 70/15/15. It was. Polysiloxane (a-3) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 2,400, and a dispersity (Mw / Mn) of 2.1.

Preparation of radiation-sensitive composition and formation of protective film and interlayer insulating film [Example 1]
To the solution containing polysiloxane (A-1) obtained in Synthesis Example 1 (100 parts by mass in terms of solid content), (B-1) dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate as component [B] 20 parts by mass of a mixture (molar ratio 50/50), (C-1) ethanone as component [C], 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, Add 3 parts by mass of 1- (O-acetyloxime) and add a mixed solvent of propylene glycol monomethyl ether and ethylene glycol monobutyl ether (mixing ratio 80/20 w / w%) so that the solid content concentration is 25% by mass. Thus, a radiation sensitive composition was prepared.

Next, this radiation-sensitive composition was applied to a SiO ₂ dip glass substrate using a spinner, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film (in ITO adhesion evaluation described later) Used a substrate with ITO. Subsequently, the obtained coating film was exposed to ultraviolet rays at an exposure amount of 300 mJ / cm ² . Subsequently, the film was developed with an aqueous 2.38 mass% tetramethylammonium hydroxide solution at 25 ° C. for 60 seconds, washed with pure water for 1 minute, and further heated in an oven at 230 ° C. for 60 minutes to obtain a film thickness of 2 A protective film of 0.0 μm was formed.
In addition, the spinner rotation speed during film formation is adjusted so that the film thickness after heating is 3.0 μm, and exposure is performed through a photomask having contact hole patterns of sizes of 20 μm, 30 μm, 40 μm, and 50 μm. An interlayer insulating film was formed in the same manner as in the above protective film formation except that the gap (interval between the substrate and the photomask) was exposed at 150 μm.
The following physical property evaluation was performed about the obtained protective film and interlayer insulation film. The results are also shown in Table 1.

Physical property evaluation 1) Heat-resistant transparency of protective film About the substrate having the protective film formed as described above, it was heated in a clean oven at 250 ° C. for 1 hour, and the light transmittance (%) at a wavelength of 400 nm before and after heating was After measurement using a spectrophotometer (150-20 type double beam manufactured by Hitachi, Ltd.), heat-resistant transparency (%) was calculated according to the following formula. When this value was 4% or less, it was judged that the heat-resistant transparency of the protective film was good.

  Heat-resistant transparency (%) = light transmittance before heating (%) − light transmittance after heating (%)

2) Pencil Hardness of Protective Film For the substrate having the protective film formed as described above, the pencil hardness (surface hardness) of the protective film was measured by “JIS K-5400-1990 8.4.1 Pencil Scratch Test”. . When this value was 4H or larger, it was judged that the surface hardness of the protective film was good.

3) Scratch resistance of protective film The substrate having the protective film formed as described above was reciprocated 10 times on steel wool # 0000 using a Gakushin type abrasion tester under a load of 200 g. The condition of abrasion was evaluated with the naked eye according to the following criteria. When the score was ◎ or ○, it was judged to have good scratch resistance. When the score was A or B, it was judged that the scratch resistance was good.

Judgment criteria ◎: Not scratched at all,
○: 1 to 3 scratches
Δ: 4-10 scratches
×: 10 or more scratches

4) Heat-resistant cracks in the protective film The substrate having the protective film formed as described above is additionally baked at 300 ° C. for 30 minutes and then left at 23 ° C. for 24 hours. It was confirmed using a laser microscope (Keyence VK-8500) according to the following criteria. When the score was ◎ or ○, the heat-resistant crack was judged to be good.
Judgment criteria A: No crack at all,
○: There are 1 to 3 cracks,
Δ: There are 4 to 10 cracks,
X: There are 10 or more cracks

5) ITO adhesion of protective film A protective film was formed by the same operation as above except that a substrate with ITO was used instead of the SiO ₂ dip glass substrate, and a pressure cooker test (120 ° C., humidity 100%, 4 hours) ) Thereafter, “8.5.3 Adhesive cross-cut tape method of JIS K-5400-1990” was performed to determine the number of cross-cuts remaining in 100 cross-cuts, and the ITO adhesion of the protective film was evaluated. When the number of grids remaining in 100 grids was 80 or less, the ITO adhesion was judged to be poor.

6) Sensitivity of protective film A mask having a 10 μm / 30 μm line and space pattern is applied to the coating film formed by the same operation as described above using an exposure machine (TME-400PRJ, manufactured by Topcon Corporation). Then, exposure was performed while changing the exposure amount, and then development was performed by a dipping method at 25 ° C. for 60 seconds in a 0.04 mass% KOH aqueous solution. Next, running water was washed with ultrapure water for 1 minute and dried to form a pattern on the glass substrate. At this time, the minimum exposure amount required for the 10 μm / 30 μm line and space pattern to remain without peeling was measured. This minimum exposure amount was evaluated as radiation sensitivity. When the minimum exposure amount was 100 mJ / cm ² or less, it was judged that the sensitivity was good. In addition, the case where a pattern could not be formed was set as x.

7) Resolution of interlayer insulating film The contact hole pattern size that could be resolved in the formation of the interlayer insulating film was measured. If a contact hole pattern of 30 μm or less could be resolved, it was judged that the resolution was good. In addition, the case where a pattern could not be formed was set as x.

8) KOH developability of protective film About the board | substrate which has a protective film formed as mentioned above, a 3.0 micrometer coating film is formed, 25 degreeC and 60 second are immersed in 0.04 mass% KOH aqueous solution by the immersion method. Developed. Thereafter, the substrate was washed with water, and the presence or absence of a film residue remaining on the substrate was observed with an optical microscope and evaluated according to the following criteria. If no film residue is confirmed, it is determined that the KOH developability is good. On the other hand, if the film residue is confirmed on the entire surface of the substrate, it can be determined that there is no KOH developability and is defective.

Judgment criteria ○: No film residue is confirmed Δ: Some film residue is confirmed ×: Film residue is confirmed on the entire surface of the substrate

[Examples 2 to 15 and Comparative Examples 1 to 4]
A radiation-sensitive composition was prepared in the same manner as in Example 1 except that the types and amounts (parts by mass) of the respective components were as shown in Table 1. Subsequently, the protective film and interlayer insulation film were formed like Example 1 using the obtained radiation sensitive composition. About the obtained protective film and interlayer insulation film, the physical-property evaluation similar to Example 1 was performed. The results are also shown in Table 1.

  In Table 1, each symbol in components [A], [B], and [C] represents the following.

Ingredient [A]
A-1: MTMS / TEOS / TMSPS = 80/15/5 (mol%)
A-2: MTMS / TEOS / MPTMS / TMSPS = 68/15/15/2 (mol%)
A-3: MTMS / TEOS / MPTMS / TMSPS = 62/15/15/8 (mol%)
A-4: MTMS / TEOS / MPTMS / TMSPS = 55/15/15/15 (mol%)
A-5: MTMS / TEOS / PTMS / MPTMS / TMSPS = 50/15/15/15/5 (mol%)
A-6: MTMS / TEOS / APTMS / TMSPS = 65/15/15/5 (mol%)
A-7: MTMS / TEOS / APTMS / TMSPS = 50/30/15/5 (mol%)
A-8: MTMS / TEOS / MPTMS / APTMS / TMSPS = 77/7/1/10/5 (mol%), 1c ¹ / 1d ¹ = 0.1
A-9: MTMS / TEOS / MPTMS / APTMS / TMSPS = 50/30/5/10/5 (mol%), 1c ¹ / 1d ¹ = 0.5
A-10: MTMS / TEOS / MPTMS / APTMS / TMSPS = 15/62/8/10/5 (mol%), 1c ¹ / 1d ¹ = 0.8
A-11: MTMS / TEOS / MPTMS / APTMS / TMSPS = 50/30/10/5/5 (mol%), 1c ¹ / 1d ¹ = 2.0
a-1: MTMS / APTMS / TMSPS = 80/15/5 (mol%)
a-2: MTMS / MPTMS / APTMS / TMSPS = 80/5/10/5 (mol%)
a-3: MTMS / TEOS / APTMS = 70/15/15 (mol%)

Ingredient [B]
B-1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (molar ratio 50/50) (trade name: DPHA, manufactured by Nippon Kayaku Co., Ltd.)
B-2: Pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
B-3: Succinic acid-modified dipentaerythritol pentaacrylate (trade name: Aronix M-520, manufactured by Toa Gosei Co., Ltd.)
B-4: Tris (acryloxyethyl) isocyanurate (trade name: Aronix M-315, manufactured by Toa Gosei Co., Ltd.)

Ingredient [C]
C-1: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (trade name: IRGACURE OX02, manufactured by BASF )
C-2: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: IRGACURE 819, manufactured by BASF)
C-3: 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (trade name: IRGACURE OXE01, manufactured by BASF)
C-4: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one

Claims (12)

The following components [A ¹ ], [B] and [C];
[A ¹ ] tetraethoxysilane or a partial hydrolyzate thereof, a hydrolyzable silane compound represented by the following formula (1) or a partial hydrolyzate thereof, and a hydrolyzable silane represented by the following formula (2) Polysiloxane [B] compound obtained by hydrolyzing and condensing a compound or a partial hydrolyzate thereof, a compound having two or more ethylenically unsaturated groups (excluding component [A ¹ ])
[C] A radiation-sensitive composition containing a radical photopolymerization initiator.

[In Formula (1),
R ¹ represents an alkyl group having 1 to 6 carbon atoms,
R ² represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a (meth) acryloyloxy group,
m represents an integer of 1 to 3,
n shows the integer of 0-6.
In formula (2),
R ³ represents an alkyl group having 1 to 6 carbon atoms,
x represents an integer of 1 to 3,
y represents an integer of 1 to 6,
z shows the integer of 0-3. ]   The radiation sensitive composition of Claim 1 whose preparation ratio of the hydrolysable silane compound or its partial hydrolyzate represented by said Formula (2) is 15 mol% or less with respect to the sum total of a raw material compound.   The hydrolyzable silane compound having an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms is contained as the hydrolyzable silane compound represented by the formula (1). Radiation sensitive composition.   The hydrolyzable silane compound represented by the formula (1) contains at least one selected from a hydrolyzable silane compound having a methacryloyloxy group and a hydrolyzable silane compound having an acryloyloxy group. The radiation sensitive composition of any one of 1-3. The following components [A ² ], [B] and [C];
[A ² ] Polysiloxane [B] having two or more ethylenically unsaturated groups having as structural units a SiO ₂ unit, a unit represented by the following formula (1a), and a unit represented by the following formula (2a) Compound (excluding component [A ² ])
[C] A radiation-sensitive composition containing a radical photopolymerization initiator.

[In Formula (1a),
R ² represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a (meth) acryloyloxy group,
m represents an integer of 1 to 3,
n shows the integer of 0-6.
In formula (2b),
R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
x represents an integer of 1 to 3,
y represents an integer of 1 to 6,
z shows the integer of 0-3. ]   The radiation sensitive composition of Claim 5 whose content rate of the unit represented by the said following formula (2a) is 15 mol% or less in all the structural units. The radiation sensitive composition of Claim 5 or 6 containing the unit represented by a following formula (1b) as a unit represented by the said Formula (1a).

[In the formula (1b), R ⁵ represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms, and m is as defined above. ] The unit represented by the formula (1a) contains at least one selected from a unit represented by the following formula (1c) and a unit represented by the following formula (1d). The radiation-sensitive composition according to item.

[In formulas (1c) and (1d), m and n are as defined above. ]   The radiation sensitive composition of any one of Claims 1-8 used for formation of the protective film of a touchscreen, or the interlayer insulation film of a display element.   The cured film formed using the radiation sensitive composition of any one of Claims 1-9. Next steps (1) to (4);
(1) The process of apply | coating the radiation sensitive composition of any one of Claims 1-9 on a board | substrate, and forming a coating film,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) A method for forming a cured film, comprising: a step of developing the coating film irradiated with radiation in step (2) with an alkali developer; and (4) a step of heating the coating film developed in step (3). .   The forming method according to claim 11, wherein an inorganic alkali developer is used as the alkali developer.