JP6902822B2 - A photosensitive resin composition for forming a touch panel insulating film / protective film, and a cured film and a touch panel using the same. - Google Patents

Description

The present invention contains a silica sol treated with a specific coupling agent as an essential component, and the obtained cured film is excellent in optical properties, hardness, adhesion, light resistance, chemical resistance, reliability, etc., and insulates a touch panel. The present invention relates to a photosensitive resin composition suitable for forming a film or a protective film.

Surface protective materials such as protective films for color filters, hard coating materials, and encapsulants for organic devices and interlayer insulating materials have transparency, light resistance, weather resistance, heat resistance, flatness, surface hardness, adhesion, and resistance. Chemical properties are required. In addition, as seen in the growing demand for touch panels, the demand for flat panel displays continues, and the required characteristics of surface protection materials and interlayer insulation materials are increasing in these fields as well.

FIG. 1 shows, as an example, a partial cross-sectional view of a touch panel in which an X electrode and a Y electrode extending in directions orthogonal to each other are formed on the same surface. In this type of touch panel, an X electrode 2 and a Y electrode made of a translucent material such as ITO or ZnO are placed on a transparent substrate 1 having a shield layer 8 on the back surface side and made of glass, acrylic resin or the like. 3 and 3 are arranged, these electrodes are covered with a flattening film 4, and a protective substrate 6 is provided via an adhesive layer 5. Here, each of the X electrode 2 and the Y electrode 3 has a plurality of island-shaped electrodes and a bridge electrode connecting the island-shaped electrodes having the same poles, and the bridge electrodes are three-dimensionally intersected with each other. By forming an insulating film 7 at this intersecting portion, the X pole and the Y pole are arranged without being in electrical contact (in FIG. 1, the island-shaped electrode 2a and the bridge electrode 2b on the X side, and the bridge electrode 2b, and The bridge electrode 3b on the Y side is shown). Further, after forming both the X-pole and Y-pole electrode layers, a flattening film 4 is formed in order to eliminate the step generated by the portion where the electrode layer is formed and the portion where the electrode layer is not formed, and the protective substrate 6 is attached. It becomes a touch panel. In addition, such a flattening film 4 flattens the space between the layer having the wiring (electrode) and the protective substrate 6 (via the adhesive layer 5), and is between the metal wiring layers as described above. Along with the insulating film 7 for the purpose of insulating the above, it is a transparent film that requires optical processing, and is an example of a protective film in a touch panel.

Including the above example, the structure of the touch panel tends to be thinner and lighter. Among them, the insulating film that fills the space between the electrodes has transparency, adhesion to the substrate, flatness, surface hardness, and light resistance. In addition to various characteristics such as weather resistance, heat resistance, and reliability, it is necessary to satisfy the required characteristics in the touch panel manufacturing process. That is, if an insulating film is to be formed by photolithography in order to arrange the electrodes accurately and without gaps, the material (composition) for forming the insulating film is required to have developability. Further, when the ITO is vapor-deposited on the insulating film and partially etched to form an electrode, it has chemical resistance (alkali resistance, acid resistance) to chemicals used in the etching process. There must be.

Here, a cured resin product containing an inorganic compound such as silica particles or an inorganic filler is widely used as a protective material for a flexible circuit board, an interlayer insulating film, a protective film for a color filter, and the like. For example, Japanese Patent Application Laid-Open No. 2009-217037 describes a photosensitive composition used as a protective material for a circuit board, and states that it can have a fine wire forming ability of about 30 μm and high thermal shock resistance. However, since the silica particles contained in this composition have a relatively large particle size of 0.5 μm, they are highly transparent and have high hardness, for example, when a protective film for a color filter has a strong demand for high hardness. When silica particles are contained in a high concentration assuming the use as a coating material, there is a concern that the resolution and transparency may be lowered.

Further, Japanese Patent Application Laid-Open No. 2010-32916 describes a photosensitive composition used as a scratch-resistant layer material for an optical film containing nanosilica particles, which has no whitening and is excellent in scratch resistance. It is said that an anti-glare film can be obtained. However, the curable resin used to obtain this film does not have alkali developability in particular, and cannot be applied to applications using an optical processing process utilizing alkali developability.

Further, Japanese Patent Application Laid-Open No. 2002-179993 exemplifies the application of a resin composition containing silica particles as a protective material for a thermosetting color filter, and can reduce the film thickness distribution due to foreign matter on the color filter. Is disclosed. However, in this technique, the effect of correcting the non-uniformity of the film thickness is aimed at depending on the resin type used in the resin composition, and the effect directly given by the silica particles is limited.

On the other hand, Japanese Patent Application Laid-Open No. 2010-27033 discloses a photosensitive resin composition for an insulating film of a touch panel that does not contain an inorganic compound. It is described that the photosensitive resin composition is excellent in transparency, adhesion to a glass substrate and a transparent conductive film, and scratch resistance. However, there is no mention of developability, chemical resistance, electrical reliability (migration resistance), and adhesion under high temperature and high humidity.

Japanese Unexamined Patent Publication No. 2009-217037 Japanese Unexamined Patent Publication No. 2010-32916 Japanese Patent Application Laid-Open No. 2002-179993 Japanese Unexamined Patent Publication No. 2010-27033

Therefore, as a result of diligent studies to solve the above-mentioned problems in the photosensitive resin composition containing an inorganic compound such as silica particles or an inorganic filler, the present inventors have applied a specific surface treatment agent. By using the treated silica sol, it is possible to achieve both developability and electrical reliability as an insulating film, which is a characteristic that is difficult to achieve depending on the type or amount of the surface treatment agent used in the silica sol, and an insulating film for a touch panel. A cured film capable of clearing the required levels of transparency, light resistance, weather resistance, heat resistance, surface hardness, adhesion, chemical resistance, and reliability can be obtained, and in addition, a predetermined cured film can be obtained. By using an alkali-soluble (meth) acrylate resin containing a polymerizable double bond, it was found that the light resistance can be further improved and it is suitable for forming a touch panel insulating film or a protective film, and the present invention has been completed. I let you.

Therefore, an object of the present invention is excellent in transparency, light resistance, weather resistance, heat resistance, surface hardness, adhesion, chemical resistance, reliability, etc. while maintaining alkali developability, and a touch panel insulating film / protective film. It is an object of the present invention to provide a photosensitive resin composition suitable for forming the above.

Another object of the present invention is to provide a cured film having excellent reliability such as deterioration due to light or heat, discoloration with time, and electrical reliability, and further, this cured film can be used as an insulating film and / or. The purpose is to provide a touch panel provided as a protective film.

（但し、Ｒ₁は水素原子又はメチル基を示す。Ｒ₂は炭素数１〜２０の炭化水素基を示し、内部にエーテル性酸素原子、又はウレタン結合を含んでいてもよい。）

（但し、Ｒ₃は水素原子又はメチル基を示す。）

（但し、Ｒ₄は水素原子又はメチル基を示す。Ｒ₅は炭素数２〜１０の２価の炭化水素基を示す。ｐは０または１の数を表す。）
（ii）少なくとも１個の重合性二重結合を有する重合性モノマー、
（iii）一般式（IV）で表される表面処理剤で表面処理され、且つ平均粒子径が１０〜３００ｎｍのシリカゾル、
（iv）光重合開始剤、及び
（ｖ）シランカップリング剤、
を必須の成分として含有するタッチパネル絶縁膜・保護膜形成用の感光性樹脂組成物であり、固形分中における（ｉ）〜（v）の必須成分の含有量が、(i)重合性二重結合含有アルカリ可溶性（メタ）アクリレート樹脂１０〜６０質量％、(iii)シリカゾル１０〜５０質量％、(v)シランカップリング剤０．１〜２０質量％であると共に、(ii)重合性モノマーは(ｉ)／(ii)（質量比）＝２０／８０〜８５／１５の範囲を満たし、(iv)光重合開始剤は［(iv)／〔(ｉ)＋(ii)〕］(質量比)＝０．００５〜０．２の範囲を満たすことを特徴とするタッチパネル絶縁膜・保護膜形成用感光性樹脂組成物である。

（但し、Ｒ₆は分子内にヘテロ原子を含んでもよい炭素数１〜１０の炭化水素基であり、かつ不飽和結合又はエポキシ基を有する反応性基を含む、Ｒ₇はそれぞれ独立に水素原子、炭素数１〜４のアルキル基を示し、Ｒ₈はそれぞれ独立に炭素数１〜４のアルキル基を示し、ｑは１〜３である） That is, the present invention relates to (i) at least the carboxyl group in the copolymer of the (meth) acrylate compound represented by the general formula (I) and the (meth) acrylic acid compound represented by the general formula (II). A polymerizable double bond-containing alkali-soluble (meth) acrylate resin obtained by partially reacting a (meth) acrylate compound having an epoxy group represented by the general formula (III).

(However, R ₁ represents a hydrogen atom or a methyl group. R ₂ represents a hydrocarbon group having 1 to 20 carbon atoms, and may contain an ether oxygen atom or a urethane bond inside.)

(However, R ₃ indicates a hydrogen atom or a methyl group.)

(However, R ₄ represents a hydrogen atom or a methyl group. R ₅ represents a divalent hydrocarbon group having 2 to 10 carbon atoms. P represents a number of 0 or 1.)
(Ii) A polymerizable monomer having at least one polymerizable double bond,
(Iii) A silica sol that has been surface-treated with a surface treatment agent represented by the general formula (IV) and has an average particle size of 10 to 300 nm.
(Iv) Photopolymerization initiator and (v) Silane coupling agent,
Is a photosensitive resin composition for forming a touch panel insulating film / protective film containing the above as an essential component, and the content of the essential components (i) to (v) in the solid content is (i) polymerizable double. The bond-containing alkali-soluble (meth) acrylate resin is 10 to 60% by mass, (iii) the silica sol is 10 to 50% by mass, (v) the silane coupling agent is 0.1 to 20% by mass, and (ii) the polymerizable monomer is (i) / (ii) (mass ratio) = 20/80 to 85/15, and (iv) the photopolymerization initiator is [(iv) / [(i) + (ii)]] (mass ratio). ) = A photosensitive resin composition for forming an insulating film / protective film for a touch panel, which satisfies the range of 0.005 to 0.2.

(However, R ₆ is a hydrocarbon group having 1 to 10 carbon atoms which may contain a hetero atom in the molecule, and also contains a reactive group having an unsaturated bond or an epoxy group. R ₇ is an independent hydrogen atom. , Representing an alkyl group having 1 to 4 carbon atoms, R ₈ independently indicating an alkyl group having 1 to 4 carbon atoms, and q being 1 to 3).

Further, the present invention is a cured film obtained by curing the photosensitive resin composition, and is a touch panel having the cured film as an insulating film and / or a protective film.

Since the photosensitive resin composition of the present invention contains a silica sol whose surface has been treated with a specific surface treatment agent, it is more transparent than the resin compositions conventionally used in the field of electronic materials and the like while maintaining developability. It is possible to obtain a cured product having excellent light resistance, weather resistance, heat resistance, surface hardness, adhesion, electrical reliability, chemical resistance and the like. Further, in the present invention, the developability is not impaired even if the content of the silica sol whose surface is treated with a specific surface treatment agent in the photosensitive resin composition is increased. Therefore, the photosensitive resin composition of the present invention is extremely useful for forming a touch panel insulating film or a protective film.

FIG. 1 is a partial cross-sectional view showing an example of a touch panel.

（但し、Ｒ₁は水素原子又はメチル基を示す。Ｒ₂は炭素数１〜２０の炭化水素基を示し、内部にエーテル性酸素原子、又はウレタン結合を含んでいてもよい。）

（但し、Ｒ_３は水素原子又はメチル基を示す。）

（但し、Ｒ_４は水素原子又はメチル基を示す。Ｒ_５は炭素数２〜１０の２価の炭化水素基を示す。ｐは０または１の数を表す。） Hereinafter, the photosensitive resin composition of the present invention will be described in detail.
The photosensitive resin composition of the present invention is a carboxyl during copolymerization of a (meth) acrylate compound represented by the following general formula (I) and a (meth) acrylic acid compound represented by the following general formula (II). The main component is a polymerizable double bond-containing alkali-soluble (meth) acrylate resin (i) obtained by reacting a part of the groups with a (meth) acrylate compound having an epoxy group represented by the following general formula (III). It is a resin composition contained as. The polymerizable double bond-containing alkali-soluble (meth) acrylate resin (i) contained as the main component in the photosensitive resin composition of the present invention has a carboxyl group derived from the (meth) acrylic acid compound, as will be described later. Therefore, it is alkali-soluble and has a polymerizable double bond derived from a (meth) acrylate compound having an epoxy group, so that it is radically polymerizable.

(However, R ₁ represents a hydrogen atom or a methyl group. R ₂ represents a hydrocarbon group having 1 to 20 carbon atoms, and may contain an ether oxygen atom or a urethane bond inside.)

(However, R ₃ indicates a hydrogen atom or a methyl group.)

(However, R ₄ represents a hydrogen atom or a methyl group. R ₅ represents a divalent hydrocarbon group having 2 to 10 carbon atoms. P represents a number of 0 or 1.)

（式中、Ｒ₁は、それぞれ独立に水素原子又はメチル基を示す。Ｒ₂は、それぞれ独立に炭素数１〜２０の炭化水素基を示し、内部にエーテル性酸素原子、又はウレタン結合を含んでいてもよい。Ｒ₃は、それぞれ独立に水素原子又はメチル基を示す。ｋ、ｎは任意の整数を示す。） First, the polymerizable double bond-containing alkali-soluble (meth) acrylate resin (i) of the present invention is represented by a (meth) acrylate compound represented by the general formula (I) and a (meth) acrylate compound represented by the general formula (II). ) It is derived from a polyvalent carboxylic acid compound represented by the following general formula (VIII), which is obtained by copolymerizing with an acrylic acid compound. This polyvalent carboxylic acid contains a constituent component derived from a (meth) acrylate compound represented by the general formula (I) and a constituent component derived from a (meth) acrylic acid compound represented by the general formula (II). , Is basically a randomly bonded copolymer. As a method for copolymerizing, a known copolymerization method can be adopted. In the polyvalent carboxylic acid compound represented by the general formula (VIII), the structural unit k of the (meth) acrylate compound represented by the general formula (I) and the (meth) acrylic acid compound represented by the general formula (II). Considering that the structural unit n (k and n represent arbitrary integers) reacts with a (meth) acrylate compound having an epoxy group represented by the general formula (III) described later, k and n When the total is 100, the ratio of k is preferably 20 to 70.

(In the formula, R ₁ independently represents a hydrogen atom or a methyl group, and R ₂ independently represents a hydrocarbon group having 1 to 20 carbon atoms, and contains an ether oxygen atom or a urethane bond inside. R ₃ independently represents a hydrogen atom or a methyl group. K and n represent arbitrary integers.)

（但し、Ｒ_９は水素原子又はメチル基を示す。） _{R 1} in the (meth) acrylate compound represented by the general formula (I) independently represents a hydrogen atom or a methyl group. Further, R ₂ represents a hydrocarbon group having 1 to 20 carbon atoms, and may contain an ethereal oxygen atom or a urethane bond inside. Examples of these hydrocarbon groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, octyl group, isooctyl group, decyl group, dodecyl group, tetradecyl group, eicosyl group and the like. Cyclic aliphatic hydrocarbon groups such as linear hydrocarbon groups, cyclohexyl groups, norbornyl groups, isobornyl groups, tricyclodecylmethyl groups, decahydronaphthyl groups, substituents represented by the following general formula (IX), methoxyethyl. Examples include, but are not limited to, aliphatic ethers such as a group, 2- (methoxyethoxy) ethyl group, and aliphatic urethanes such as 2- (ethoxycarbonylamino) ethyl group. However, in the present invention, since it is preferable not to contain an unsaturated bond or an aromatic structure, R ₂ in the general formula (I) preferably contains a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and the like. It is preferably an isobutyl group, a cyclohexyl group, a norbornyl group, an isobornyl group, or a tricyclodecylmethyl group. Two or more kinds of (meth) acrylate compounds represented by the general formula (I) can also be used. _{Further, R 3} in the (meth) acrylic acid compound represented by the general formula (II) independently represents a hydrogen atom or a methyl group, and one or two types can be used.

(However, R ₉ indicates a hydrogen atom or a methyl group.)

Next, the polyvalent carboxylic acid represented by the general formula (VIII) obtained by copolymerizing the (meth) acrylate compound represented by the general formula (I) and the (meth) acrylic acid compound represented by the general formula (II). A method for producing a polymerizable double bond-containing alkali-soluble (meth) acrylate resin (i) by reacting an acid compound with a (meth) acrylate compound having an epoxy group represented by the general formula (III) will be described.

（但し、Ｒ₁は水素原子又はメチル基を示す。Ｒ₂は炭素数１〜２０の炭化水素基を示し、内部にエーテル性酸素原子、又はウレタン結合を含んでいてもよい。Ｒ₃、Ｒ₄は水素原子又はメチル基を示す。Ｒ_５は炭素数２〜１０の２価の炭化水素基を示す。ｐは０または１の数を表す。ｋ、ｌ、ｍは任意の整数を示す。） A (meth) acrylate compound having an epoxy group represented by the general formula (III) is reacted with a part of the carboxyl groups in the polyvalent carboxylic acid compound represented by the general formula (VIII), and the following general formula ( An alkali-soluble (meth) acrylate resin (i) containing a polymerizable double bond represented by X) is obtained. In the following general formula (X), the constituent components derived from the (meth) acrylate compound represented by the general formula (I), the constituent components derived from the (meth) acrylic acid compound represented by the general formula (II), and , There is no particular regularity in the bonding order of the three constituents of the constituents obtained by adding the (meth) acrylate compound having an epoxy group represented by the general formula (III) to the carboxyl group of the general formula (II). It is a copolymer in which the constituents of the species are basically randomly bonded.

(However, R ₁ represents a hydrogen atom or a methyl group. R ₂ represents a hydrocarbon group having 1 to 20 carbon atoms, and may contain an ether oxygen atom or a urethane bond inside. R ₃ , R. ₄ represents a hydrogen atom or a methyl group. R ₅ represents a divalent hydrocarbon group having 2 to 10 carbon atoms. P represents a number of 0 or 1. K, l and m represent arbitrary integers. )

In the (meth) acrylate compound having an epoxy group represented by the general formula (III), R ₅ represents a divalent hydrocarbon group having 2 to 10 carbon atoms. Examples of these hydrocarbon groups include an ethylene group, a 1,2-propylene group, a 1,4-butylene group, a 1,6-hexamethylene group and the like, but an ethylene group and a 1,2-propylene group are preferable. It is preferably a group or a 1,4-butylene group. p represents a number of 0s or 1s.

A solvent used for reacting a (meth) acrylate compound having an epoxy group represented by the general formula (III) with a part of the carboxyl groups in the polyvalent carboxylic acid compound represented by the general formula (VIII). The reaction conditions of the catalyst and the like are not particularly limited, but a solvent having a boiling point higher than the reaction temperature is preferably used as the reaction solvent, and examples of such a solvent include cellosolve-based solvents such as ethyl cellosolve acetate and butyl cellosolve acetate. , Diglime, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, ethyl lactate, butyl acetate and other high boiling ether or ester solvents, and ketone solvents such as cyclohexanone and diisobutyl ketone. Is good. As the catalyst to be used, for example, known catalysts such as ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine can be used. it can. These are described in detail in Japanese Patent Application Laid-Open No. 9-325494.

A polyvalent carboxylic acid compound represented by the general formula (VIII) is reacted with a (meth) acrylate compound having an epoxy group represented by the general formula (III), and the polymerizable double represented by the general formula (X) is reacted. The reaction temperature for producing the double bond-containing alkali-soluble (meth) acrylate resin (i) is preferably in the range of 20 to 140 ° C, more preferably 40 to 130 ° C. A (meth) acrylate compound having an epoxy group represented by the general formula (III) when producing a polymerizable double bond-containing alkali-soluble (meth) acrylate resin (i) represented by the general formula (X) and general. The charging ratio of the polyvalent carboxylic acid compound represented by the formula (VIII) is the acid value and curability of the polymerizable double bond-containing alkali-soluble (meth) acrylate resin (i) represented by the general formula (X). Can be changed arbitrarily for the purpose of adjusting. At this time, the charging ratio of the epoxy group in the (meth) acrylate compound having the epoxy group represented by the general formula (III) to the carboxyl group in the polyvalent carboxylic acid compound is preferably 10 to 50 mol%.

Further, when the total of all the constituent units in the polymerizable double bond-containing alkali-soluble (meth) acrylate resin (i) represented by the general formula (X) is 100, the ratio of each constituent unit is the acid value and the ratio of each constituent unit. Although it can be arbitrarily changed for the purpose of adjusting the curability, the structural unit k of the (meth) acrylate compound represented by the general formula (I) is preferably 10 to 80 and represented by the general formula (II), respectively. The structural unit l of the (meth) acrylic acid compound is 10 to 50, and the structural unit m to which the (meth) acrylate compound having an epoxy group represented by the general formula (III) is added to the carboxyl group of the general formula (II) is 10. ~ 40. If the ratio of k is larger than the above range, there is a possibility that the content of the polymerizable double bond is lowered, and the adhesion and hardness of the cured product are lowered. Further, when the ratio of l is larger than the above range, the water absorption rate of the cured product becomes high, and further, the solubility in the organic solvent is lowered. Further, when the ratio of m is larger than the above range, the volume shrinkage at the time of curing becomes large, and there arises a problem that the adhesion to the substrate is lowered and the flatness of the surface is deteriorated. Furthermore, the weight average molecular weight (Mw) of the polymerizable double bond-containing alkali-soluble (meth) acrylate resin (i) represented by the general formula (X) is preferably 5,000 to 200,000, more preferably 10,000 to. It is preferably 200,000, more preferably 10,000 to 100,000, and even more preferably 10,000 to 50,000. If the weight average molecular weight (Mw) is smaller than the above range, the adhesion may decrease. Further, when the weight average molecular weight (Mw) is larger than the above range, there is a concern that the curability may be lowered. The acid value of the component (i) is preferably 10 to 120 mgKOH / g.

The content of the polymerizable double bond-containing alkali-soluble (meth) acrylate resin (i) of the above general formula (X) in the solid content of the photosensitive resin composition of the present invention is preferably 10 to 60% by mass. 20 to 50% by mass is preferable. If the content of the component (i) in the solid content is small, the strength of the cured product decreases. On the contrary, if the amount is too large, the proportion of the silica sol of the component (iii) in the photosensitive resin composition of the present invention decreases, and the effects such as the improvement of the surface hardness by the silica sol and the improvement of the adhesion by suppressing the coefficient of linear expansion are not exhibited.

（但し、Ｒ_６は分子内にヘテロ原子を含んでもよい炭素数１〜１０の炭化水素基であり、かつ不飽和二重結合又はエポキシ基を有する反応性基を含む、Ｒ_７はそれぞれ独立に水素原子、炭素数１〜４のアルキル基を示し、Ｒ_８はそれぞれ独立に炭素数１〜４のアルキル基を示し、ｑは１〜３である） In the present invention, the following (i), (ii), (iii), (iv) and (v) are contained as essential components in order to utilize the characteristics of the photosensitive resin composition. That is, (i) an alkali-soluble (meth) acrylate resin having a polymerizable double bond represented by the general formula (X), (ii) a polymerizable monomer having at least one polymerizable double bond, (iii). A silica sol having an average particle size of 10 to 300 nm surface-treated with a surface treatment agent represented by the following general formula (IV), (iv) a photopolymerization initiator, and (v) a silane coupling agent are included as essential components. ..

(However, R ₆ is a hydrocarbon group having 1 to 10 carbon atoms which may contain a hetero atom in the molecule, and contains a reactive group having an unsaturated double bond or an epoxy group, and R ₇ is independent of each other. A hydrogen atom indicates an alkyl group having 1 to 4 carbon atoms, R ₈ independently indicates an alkyl group having 1 to 4 carbon atoms, and q is 1 to 3).

Among these, as the polymerizable monomer having at least one polymerizable double bond which is the component (ii), a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate and the like. , Urethane (meth) acrylates such as additions of pentaerythritol triacrylate and hexamethylene diisocyanate, additions of dipentaerythritol pentaacrylate and hexamethylene diisocyanate, ethylene glycol di (meth) acrylates, diethylene glycol di (meth) acrylates. , Triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethyl propantri (meth) acrylate, trimethylol ethanetri (meth) acrylate, pentaerythritol di ( Meta) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, polyethylene glycol-modified bisphenol A di (Meta) acrylic acid esters of polyhydric alcohols such as acrylate can be exemplified, and one or more of them can be used.

Further, as the component (ii), a polymerizable monomer having at least one polymerizable double bond having a carboxyl group in the molecule can also be used. However, since there is a concern that the development margin during alkaline development may be narrowed, it is necessary to pay sufficient attention to the combination with the alkali-soluble resin. Examples of the polymerizable monomer having at least one polymerizable double bond having a carboxyl group in the molecule include a monoester of dipentaerythritol penta (meth) acrylate and succinic acid, and dipentaerythritol penta (meth) acrylate and phthal. Monoester with acid, monoester with dipentaerythritol penta (meth) acrylate and hexahydrophthalic acid, monoester with pentaerythritol tri (meth) acrylate and succinic acid, pentaerythritol tri (meth) acrylate and phthalic acid Monoester, pentaerythritol tri (meth) acrylate and hexahydrophthalic acid monoester, and examples of commercially available products include M-510 and M-520 manufactured by ARONIX [manufactured by Toa Synthetic Co., Ltd.]. Be done. These can be used alone or in combination of two or more, and can be used in combination with other polymerizable monomers having at least one polymerizable double bond.

The compounding mass ratio [(i) / (ii)] of the component (i) and these components (ii) is preferably 20/80 to 85/15, preferably 40/60 to 80/15. 20 is good. If the blending ratio of the alkali-soluble (meth) acrylate resin having the polymerizable double bond of (i) is less than the above range, there arises a problem that the cured product after curing becomes brittle. On the contrary, when the compounding ratio of the alkali-soluble (meth) acrylate resin having the polymerizable double bond of (i) is larger than the above range, the ratio of the curable functional group in the resin component is small and the formation of the crosslinked structure is insufficient. There is a risk of problems such as

The average particle size of the silica sol of the component (iii) is the average particle size of the cumulant obtained by the dynamic light scattering method, and retains the transparency of the cured product obtained by curing the photosensitive resin composition of the present invention. 10 to 300 nm is preferable for the purpose of More preferably, it is 30 to 200 nm.

The content of the silica sol in the solid content of the photosensitive resin composition of the present invention is 10 to 50% by mass, more preferably 20 to 40% by mass. If the content of the silica sol in the solid content is small, the effect of improving the surface hardness by the silica sol is not exhibited. On the contrary, if it is too large, the ratio of the component (i) and the component (ii) in the photosensitive resin composition of the present invention decreases, the strength of the cured product decreases, the migration resistance deteriorates, and the electrical component becomes poor. Reliability may be reduced.

Here, in the surface treatment agent represented by the general formula (IV) used for the surface treatment of the silica sol of the component (iii), R ₆ is a hydrocarbon group having 1 to 10 carbon atoms which may contain a hetero atom in the molecule. , And contains reactive groups with unsaturated bonds or epoxy groups. Examples of these hydrocarbon groups include 3-glycidoxypropyl group, vinyl group, allyl group, styryl group, 3-methacryloyloxypropyl group, 3-acryloyloxypropyl, 2- (3,4-epoxycyclohexyl). Examples thereof include a group containing an ethyl group and the like. Of these, R ₆ is preferably a vinyl group, 3-methacryloyloxypropyl group is preferable, and a vinyl group is particularly preferable. Further, when R ₆ is a hydrocarbon group having more than 10 carbon atoms, a residue tends to remain during development. In the general formula (IV), R ₇ independently represents a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, and R ₈ independently represents an alkyl group having 1 to 4 carbon atoms. Examples of these alkyl groups having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group and a butyl group, and a methyl group or an ethyl group is preferable. Q in the general formula (IV) is 1-3.

Further, as a method for treating the silanol group on the silica sol surface with the surface treatment agent represented by the general formula (IV), a known method can be used, for example, as described in Japanese Patent Publication No. 3-29823. , A surface treatment agent, an acid catalyst, and water are added to the silica sol, and the mixture is heated and stirred. The ratio of silanol groups on the surface of the silica sol with the surface treatment agent represented by the general formula (IV) varies depending on the charging ratio of the silica sol and the surface treatment agent to be used, the solvent type used for the silica sol, and the photosensitive resin of the present invention. It can be arbitrarily changed according to each component in the composition.

Examples of the photopolymerization initiator of the component (iv) include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butyl. Acetphenones such as acetophenone, benzophenone, 2-chlorobenzophenone, benzophenones such as p, p'-bisdimethylaminobenzophenone, benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2- (o-Chlorophenyl) -4,5-Phenyl biimidazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4,5-diphenyl Biimidazole compounds such as biimidazole, 2- (o-methoxyphenyl) -4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole, 2-trichloromethyl-5-styryl-1,3 , 4-Oxaziazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4 -Halomethyldiazole compounds such as oxadiazole, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3 , 5-Phenyl, 2-Phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-Phenylphenyl) -4,6-bis (trichloromethyl) -1,3,5 -Triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -1 , 3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4, Halomethyl-s-triazines such as 6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine Compounds, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), 1- (4-fe Nylsulfanylphenyl) Butane-1,2-dione-2-oxime-O-benzoate, 1- (4-methylsulfanylphenyl) butane-1,2-dione-2-oxime-O-acetate, 1- (4) -Methylsulfanylphenyl) Butane-1-one oxime-O-acetate, etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) ), Metanon, (9-ethyl-6-nitro-9H-carbazole-3-yl) [4- (2-methoxy-1-methylethoxy) -2-methylphenyl]-, O-acetyloxime, methanone, ( 2-Methylphenyl) (7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-, acetyloxime, etanone, 1-[7- (2-methylbenzoyl) -9,9-dipropyl-9H) -Fluoren-2-yl]-,1- (O-acetyloxime), Etanone, 1- (-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-, 1-O-acetyloxime O-acyloxime compounds such as, benzyl dimethyl ketal, thioxanson, 2-chlorothioxenson, 2,4-diethylthioxanson, 2-methylthioximeson, sulfur compounds such as 2-isopropylthioxanson, 2 -Anthraquinones such as ethyl anthraquinone, octamethyl anthraquinone, 1,2-benz anthraquinone, 2,3-diphenyl anthraquinone, organic peroxides such as azobisisobutylnitrile, benzoyl peroxide, and cumeper oxide, 2-mercaptobenzoimidazole. , 2-Mercaptobenzoxazole, 2-mercaptobenzothiazole and other thiol compounds, triethanolamine, triethylamine and other tertiary amines and the like. As these photopolymerization initiators, one kind or two or more kinds thereof can be used.

Further, in the present invention, in addition to the photopolymerization initiator of the component (iv), the thermal polymerization initiator (vii) can be further used in combination. Examples of the thermal polymerization initiator of the component (vii) include benzoyl peroxide, lauroyl peroxide, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-2-ethylhexanoate, 1,1-. Organic peroxides such as t-butylperoxy-3,3,5-trimethylcyclohexane, azobisisobutyronitrile, azobis-4-methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile , Azodibenzoyl, 1,1'-azobis (1-acetoxy-1-phenylethane), 2,2'-azobisisobutyrate and other azo compounds, potassium persulfate, ammonium persulfate and other water-soluble catalysts and excesses. Any material that can be used for ordinary radical polymerization, such as a redox catalyst using a combination of an oxide or a persulfate and a reducing agent, can be used. The thermal polymerization initiator of the component (vii) can be selected in consideration of the storage stability of the photosensitive resin composition of the present invention, the formation conditions of the cured product, and the transparency of the cured product.

The amount of the photopolymerization initiator used as the component (iv) is as follows: a polymerizable double bond-containing alkali-soluble (meth) acrylate resin [(i) component] and a polymerizable monomer having at least one polymerizable double bond [ The mass ratio [(iv) / [(i) + (ii)]] of the component (iv) to the total of (ii) component] is preferably 0.005 to 0.2, preferably 0.01. It should be ~ 0.1. If the blending ratio of the photopolymerization initiator is small, the polymerization rate becomes slow and the curability deteriorates. On the other hand, if it is too large, the sensitivity will be too strong and the pattern line width will be thicker than the pattern mask, and the line width faithful to the mask cannot be reproduced, or the pattern edges will not be rattled and sharpened. May occur.

Examples of the silane coupling agent of the component (v) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Etc., (meth) acrylates such as 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p. -Vinyls such as styryltrimethoxysilane, aminos such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane , Ureids such as 3-ureidopropyltrialkoxysilane, isocyanates such as 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and silane coupling agents such as alkoxy oligomers.

The amount of the silane coupling agent used as the component (v) is preferably 0.1 to 20% by mass, preferably 0.5 to 10% by mass in the solid content of the photosensitive resin composition of the present invention. It is good to have it.

（但し、Ｒ_1０は水素原子またはメチル基を示す。Ｘは単結合又は内部にヘテロ元素を含んでいてもよい炭素数１〜２０の２価の有機基を示し、Ｙは４価のカルボン酸残基を示し、Ｚは水素原子又は下記一般式（VI）で表される置換基を示し、Ｇは水素原子または下記一般式（VII）で表される置換基を示す。ｒは１〜２０の平均値を示す。）

（但し、Ｒ_1１は水素原子又はメチル基を示し、Ｒ₁₂は炭素数２〜１０の２価の炭化水素基を示し、Ｌは２価又は３価のカルボン酸残基を示す。uは０又は１を表す。ｓ及びｔは、それぞれ０、１又は２であり、ｓ＋ｔは１又は２である。）

（但し、Ｒ₁₃は水素原子又はメチル基を示し、Ｒ₁₄は炭素数２〜１０の２価の炭化水素基を示す。ｖは０又は１を表す。） Here, as another embodiment of the photocurable resin composition of the present invention, as a part of the polymerizable double bond-containing alkali-soluble (meth) acrylate resin of (i), in (vi) general formula (V). The represented polymerizable double bond-containing alkali-soluble resin can be used. By using this resin in combination with (i), it is possible to control the developability when the photosensitive resin composition is used in photolithography, and to control the physical properties such as heat resistance and light resistance when the composition is used as a cured product. It is possible to increase the degree of freedom in designing. For example, in order to uniformly disperse the silica sol, it may be effective to use an unsaturated group-containing alkali-soluble resin having one or more different structures, molecular weights, acid values, etc. in combination, thereby ensuring transparency. , It is possible to prevent an unfavorable haze (cloudiness) from occurring. When the component (vi) is used as a part of the component (i) in this way, the content and mass ratio of the components (i) to (v) described above are all described in "((i)". "i)" shall be read as "(i) + (vi)".

(However, R ₁₀ represents a hydrogen atom or a methyl group. X represents a divalent organic group having 1 to 20 carbon atoms which may contain a hetero element in a single bond or inside, and Y represents a tetravalent carboxylic acid. Indicates a residue, Z indicates a hydrogen atom or a substituent represented by the following general formula (VI), G indicates a hydrogen atom or a substituent represented by the following general formula (VII), and r indicates 1 to 20. Shows the average value of.)

(However, R ₁₁ indicates a hydrogen atom or a methyl group, R ₁₂ indicates a divalent hydrocarbon group having 2 to 10 carbon atoms, L indicates a divalent or trivalent carboxylic acid residue, and u indicates 0. Or 1; s and t are 0, 1 or 2, respectively, and s + t is 1 or 2.)

(However, R ₁₃ represents a hydrogen atom or a methyl group, R ₁₄ represents a divalent hydrocarbon group having 2 to 10 carbon atoms, and v represents 0 or 1.)

〔但し、Ｘは一般式（V）に示したものと同義である。〕 The method for producing the alkali-soluble resin of the general formula (V) is shown in detail below.
First, an unsaturated group-containing monocarboxylic acid is reacted with an epoxy compound having two epoxycycloalkyl groups in one molecule represented by the general formula (XI), and preferably (meth) acrylic acid is reacted. Obtain an epoxy (meth) acrylate compound. Examples of the unsaturated group-containing monocarboxylic acid compound include compounds obtained by reacting acrylic acid or methacrylic acid with an acid monoanhydride such as succinic anhydride, maleic anhydride, or phthalic anhydride, in addition to acrylic acid and methacrylic acid. Be done.

[However, X is synonymous with the one shown in the general formula (V). ]

〔但し、Ｒ₁₀、Ｘは一般式（V）に示したものと同義である。〕 For the reaction of such an epoxy compound with (meth) acrylic acid, a known method can be used. For example, about 2 mol of (meth) acrylic acid is added to 1 mol of the epoxy compound having two epoxy groups. Do using. The reactants obtained by this reaction are described in, for example, Japanese Patent Application Laid-Open No. 4-355450. The reactant obtained by this reaction is a diol compound containing a polymerizable unsaturated group, and is an epoxy (meth) acrylate compound represented by the following general formula (XII).

[However, R ₁₀ and X are synonymous with those shown in the general formula (V). ]

The X of the epoxy compound having two epoxycycloalkyl groups in the molecule represented by the general formula (XI) is a divalent organic having 1 to 20 carbon atoms which may contain a hetero element in a single bond or inside. It is a group. As a divalent organic group having 1 to 20 carbon atoms which may contain a hetero element inside, it is a divalent hydrocarbon group or a divalent group having a carboxyl group at one or two ends of the hydrocarbon group. Examples thereof include a group, and the hydrocarbon group referred to here may have an ether-bonding oxygen atom or an ester bond inside. Examples of such a divalent hydrocarbon group include a linear hydrocarbon group such as a methylene group, an ethylene group, a propylene group, an isopropylidene group, a sec-butylene group, a methylisobutylene group, a hexylene group, a decylene group and a dodecylene group. Can be mentioned.

（但し、ｇは１〜２０の整数を表し、ｈは２〜２０の整数を表し、ｉは１〜１０の整数を表し、ｊは１〜２０の整数を表し、ｄは１〜１８の整数を表す。） Specific examples of the epoxy compound having two epoxycycloalkyl groups in the molecule represented by the general formula (XI) include epoxy compounds represented by the following general formulas (XIII) to (XIX), and at the same time. Two or more types may be used together. It is preferably an epoxy compound represented by the general formula (XVI) or (XVII) from the viewpoint of easy availability and physical characteristics of the cured product, and it is preferable that g is 1, h is 5 and i is 1.

(However, g represents an integer of 1 to 20, h represents an integer of 2 to 20, i represents an integer of 1 to 10, j represents an integer of 1 to 20, and d represents an integer of 1 to 18. Represents.)

Synthesis of epoxy (meth) acrylate compound as represented by the above general formula (XII), subsequent addition reaction of polyvalent carboxylic acid or its anhydride, and polymerizable unsaturated group having reactivity with carboxyl group. In the production of the alkali-soluble resin of the general formula (V), the reaction is usually carried out in a solvent using a catalyst, if necessary, by reacting a monofunctional epoxy compound or the like having the above. Here, the reaction conditions such as the solvent and the catalyst to be used are not particularly limited, but for example, a solvent having no hydroxyl group and having a boiling point higher than the reaction temperature is preferably used as the main component of the reaction solvent, and such a solvent is used. Examples include cellosolve-based solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high-boiling ether-based or ester-based solvents such as jiglime, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate, and cyclohexanone. , A ketone solvent such as diisobutylketone is preferable. Further, it is preferable to use a catalyst in the reaction between the carboxyl group and the epoxy group, and the catalyst to be used includes, for example, ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, triphenylphosphine, and tris (2,6-). Known substances such as phosphines such as dimethoxyphenyl) phosphine can be used. These are described in detail in Japanese Patent Application Laid-Open No. 9-325494.

〔但し、Ｒ_1０は水素原子またはメチル基を示す。Ｘは単結合又は内部にヘテロ元素を含んでいてもよい炭素数１〜２０の２価の有機基を示し、Ｙは４価のカルボン酸残基を表し、Ｗはそれぞれ独立して水素原子又は−ＯＣ−Ｌ−（ＣＯＯＨ）_ｆ（但し、Ｌは２価又は３価のカルボン酸残基を表し、ｆは１又は２を表す）を表し、ｒは１つ１つの分子において各々１〜２０の整数であり、一般式（XX）のアルカリ可溶性樹脂は、これらの混合物である。つまり、一般式（XX）におけるｒは１〜２０の平均値を示す。〕 As the second reaction, the epoxy (meth) acrylate compound (XII) obtained by the reaction of the epoxy compound with (meth) acrylic acid [hereinafter, this may be referred to as “(c)”. ] And the acid components (a) and (b) described later are reacted to form a polymerizable unsaturated group-containing alkali-soluble resin represented by the general formula (XX) (hereinafter, "alkali-soluble resin of the general formula (XX)). ”) Can be obtained.

[However, R ₁₀ indicates a hydrogen atom or a methyl group. X represents a divalent organic group having 1 to 20 carbon atoms which may contain a hetero element in a single bond or inside, Y represents a tetravalent carboxylic acid residue, and W represents a hydrogen atom or a hydrogen atom independently of each other. -OC-L- (COOH) _f (where L represents a divalent or trivalent carboxylic acid residue and f represents 1 or 2), where r represents 1 to 20 in each molecule. The alkali-soluble resin of the general formula (XX) is a mixture of these. That is, r in the general formula (XX) indicates an average value of 1 to 20. ]

The acid component used for synthesizing the alkali-soluble resin of the general formula (XX) is a polyvalent acid component capable of reacting with the hydroxyl group in the molecule of the epoxy (meth) acrylate compound (c), and (a). It is necessary to use (b) a tetracarboxylic acid or an acid dianhydride thereof in combination with a dicarboxylic acid or a tricarboxylic acid or an acid monoanhydride thereof.

Examples of (a) dicarboxylic acid or tricarboxylic acid or acid monoanhydride thereof used for these include the following compounds and acid monoanhydrides thereof. Examples of the chain hydrocarbon dicarboxylic acid or tricarboxylic acid include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citralinic acid, malonic acid, glutaric acid, citric acid, tartaric acid, and oxoglutaric acid. There are compounds such as pimeric acid, succinic acid, succinic acid, and diglycolic acid, and further, a dicarboxylic acid or a tricarboxylic acid into which an arbitrary substituent is introduced may be used. Further, examples of the alicyclic dicarboxylic acid or tricarboxylic acid include compounds such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and norbornandicarboxylic acid, and further introduction of an arbitrary substituent. It may be a dicarboxylic acid or a tricarboxylic acid. Further, examples of the aromatic dicarboxylic acid or tricarboxylic acid include compounds such as phthalic acid, isophthalic acid and trimellitic acid, and further, a dicarboxylic acid or tricarboxylic acid into which an arbitrary substituent is introduced may be used.

Examples of (b) tetracarboxylic acid or acid dianhydride thereof include the compounds shown below and acid dianhydrides thereof. Examples of the chain hydrocarbon tetracarboxylic dian include compounds such as butanetetracarboxylic dian, pentanetetracarboxylic dian, and hexanetetracarboxylic dian, and tetracarboxylic dians having a substituent introduced therein may be used. Further, examples of the alicyclic tetracarboxylic dian include compounds such as cyclobutanetetracarboxylic dian, cyclopentanetetracarboxylic dian, cyclohexanetetracarboxylic dian, cycloheptantetracarboxylic dian, norbornanetetracarboxylic dian, and further, a substituent. It may be the tetracarboxylic dian in which the above is introduced. Further, examples of the aromatic tetracarboxylic dian include compounds such as pyromellitic dian, benzophenone tetracarboxylic dian, biphenyl tetracarboxylic dian, and biphenyl ether tetracarboxylic dian, and further, tetracarboxylic dians having a substituent introduced therein. Good.

The method of reacting the epoxy (meth) acrylate compound (c) with the acid components (a) and (b) is not particularly limited, and is described in, for example, JP-A-9-325494. A known method for reacting an epoxy (meth) acrylate compound with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140 ° C. can be adopted. Preferably, the epoxy (meth) acrylate compound (c), the dicarboxylic acid or tricarboxylic acid or its acid monoanhydride (a), and the tetracarboxylic acid or its acid dianhydride are preferable so that the end of the compound becomes a carboxyl group. It is desirable to react so that the molar ratio with (b) is (c) :( a) :( b) = 1: 0.01 to 1.0: 0.2 to 1.0. Here, a quantitative explanation will be given by taking the case of using (a) acid monoanhydride and (b) acid dianhydride as an example. A diol compound containing a polymerizable unsaturated group [epoxy (meth) acrylate compound] Reaction so that the molar ratio [(c) / [(a) / 2+ (b)]] of the amount of the acid component to (c) [(a) / 2+ (b)] is 0.5 to 1.0. It is desirable to let it. When the molar ratio exceeds 1.0, the content of the diol compound containing an unreacted polymerizable unsaturated group increases, and there is a concern that the stability of the alkali-soluble resin composition over time may decrease. On the other hand, when the molar ratio is less than 0.5, the terminal of the alkali-soluble resin represented by the general formula (V) becomes an acid anhydride, and the content of the unreacted acid dianhydride increases to be alkali-soluble. There is concern that the stability of the resin composition may decrease over time. The molar ratio of each component (c), (a) and (b) can be arbitrarily changed within the above range for the purpose of adjusting the acid value and molecular weight of the alkali-soluble resin represented by the above general formula (V). ..

As the third reaction, a monofunctional epoxy compound having a polymerizable unsaturated group of the general formula (III) is reacted with the carboxyl group of the alkali-soluble resin of the general formula (XX) to be alkaline-soluble of the general formula (V). Get the resin.

The molar ratio of the epoxy group of the unsaturated group-containing epoxy compound represented by the general formula (III) to the carboxyl group of the general formula (XX) is the photoreaction of the alkali-soluble resin represented by the general formula (V). It can be arbitrarily changed for the purpose of adjusting the sensitivity (depending on the amount of polymerizable double bond) and the acid value. If the number of moles of the general formula (III) is 90% or less of the total number of moles of the number of moles of the component (a) and twice the number of moles of the component (b), alkali developability can be imparted. Therefore, it can be used for a photosensitive resin composition having photopatterning properties. Further, when it is desired to impart the effect of improving the sensitivity of the photoreaction, it is necessary to set it to 10% or more, so it is preferably 10 to 90%. Further, it is more preferably 30 to 70%. The weight average molecular weight of the alkali-soluble resin of the general formula (V) used is preferably 1,000 to 100,000, and the acid value is preferably 30 to 120 mgKOH / g.

When the polymerizable double bond-containing alkali-soluble resin represented by the general formula (V) of (vi) is used as a part of the polymerizable double bond-containing alkali-soluble (meth) acrylate resin of (i). The mass composition ratio of (i) and (vi) may be (vi) / [(i) + (vi)] = 0 to 0.8, and more preferably 0.1 to 0.7. preferable.

Further, as a resin component (viii), an epoxy resin or an epoxy compound having two or more epoxy groups can be used in combination. Specific examples of the epoxy resin or epoxy compound include 3,3', 5,5'-tetramethyl-4,4'-biphenol type epoxy resin, bisphenol A type epoxy resin, bisphenol fluorene type epoxy resin, and phenol novolac. Type Epoxy Resin, 3,4-Epoxy Cyclohexenyl Methyl-3', 4'-Epoxy Cyclohexene Carboxylate, 2,2-Bis (Hydroxymethyl) -1-Butanol 1,2-Epoxy-4- (2-oxylanyl) ) Cyclohexane adduct, epoxy silicone resin and the like can be mentioned.

(Viii) Sufficient adhesion required for the touch panel insulating film / protective film while ensuring the surface hardness of the cured product by adding an epoxy resin or epoxy compound having two or more epoxy groups as a component. At the same time, it is possible to provide chemical resistance such as excellent acid resistance, alkali resistance, and solvent resistance, as well as excellent weather resistance and heat resistance.

The amount of the epoxy resin or epoxy compound having two or more epoxy groups as the component (viii) is preferably an amount that is uniformly compatible with the obtained cured product (coating film) so as not to cause turbidity, and is polymerizable. The mass ratio of the component (viii) to the total of the epoxy-soluble (meth) acrylate resin [(i) component] containing a heavy bond and the polymerizable monomer [(ii) component] having at least one polymerizable double bond [ (viii) / [(i) + (ii)]] should be 0 to 0.35. When the component (vi) is included as a part of the component (i), the mass ratio of the component (viii) to the total of the components (i), (ii) and (vi) [(viii) / [(i). ) + (Ii) + (vi)]] should be 0 to 0.35. (Viii) An epoxy resin or epoxy compound having two or more epoxy groups as a component is effective when it is necessary to impart adhesiveness and chemical resistance, but if the amount added is too large, the alkali developability deteriorates. However, there is a risk that the line width faithful to the mask cannot be reproduced, or the pattern edges do not rattle and become sharp.

The photosensitive resin composition of the present invention can be dissolved in a solvent or mixed with various additives, if necessary. Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and propylene glycol, terpenes such as α- or β-terpineol, acetone, methyl ethyl ketone, cyclohexanone and N-methyl-2-. Ketones such as pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene. Glycol ethers such as glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, ethyl lactate, Examples thereof include esters such as cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate, which are used for dissolution. , A uniform solution-like composition can be obtained by mixing. Two or more kinds of these solvents may be used in order to obtain necessary properties such as coatability.

In addition, the photosensitive resin composition of the present invention may contain additives such as a curing accelerator, an antioxidant, a plasticizer, a leveling agent, and an antifoaming agent, if necessary. Among these, examples of the antioxidant include a hindered phenolic antioxidant and the like, and examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate and the like. Further, examples of the defoaming agent and the leveling agent include silicon-based or fluorine-based surfactants.

In the photosensitive resin composition of the present invention, the polymerizable double bond-containing alkali-soluble component (i) is contained in the solid content (the solid content includes a polymerizable monomer that becomes a solid content after curing) from which the solvent has been removed. Meta) Acrylate resin, (ii) Polymerizable monomer having at least one polymerizable double bond of the component, (iii) Average particle size surface-treated with the surface treatment agent represented by the general formula (IV) of the component When the silica sol having a temperature of 10 to 300 nm and the photopolymerization initiator of the component (iv) contain the component (vi) as a part of the total [(i) component, the relevant (i) to (iv) and (vi) It is desirable that the total content is 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more. The amount of the solvent varies depending on the target solution viscosity suitable for film formation, but is preferably in the range of 60 to 90% by mass with respect to the total amount of the photosensitive resin composition.

Further, the coating film (cured product) of the present invention is, for example, coated with a solution of the above-mentioned photosensitive resin composition on a substrate or the like, dried, irradiated with light (including ultraviolet rays, radiation, etc.) and cured. Obtained by A coating film having a desired pattern can be obtained by providing a portion exposed to light and a portion not exposed to light, curing only the portion exposed to light, and dissolving the other portion with an alkaline developer.

Next, an example of a method for forming a coating film (cured product) using the photosensitive resin composition will be described below. First, a photosensitive resin composition is applied onto the surface of a substrate or the like, and then the first-stage baking is performed to evaporate the solvent to form a coating film. Next, when forming a pattern, the coating film is exposed to a photomask and then developed with an alkaline developer to dissolve and remove the unexposed portion of the coating film. Then, in the second stage baking, the thermal polymerization reaction is promoted to form a cured product.

When applying the photosensitive resin composition to the substrate, in addition to the known solution dipping method and spray method, any method such as a roller coater machine, a land coater machine, a slit coater machine or a spinner machine is adopted. can do. By these methods, after coating to a desired thickness, the solvent is removed by baking in the first stage, and after exposure and development, the thermal polymerization reaction is promoted by baking in the second stage to form a cured product. To. The first stage baking is performed by heating in an oven, a hot plate, etc., vacuum drying, or a combination thereof. The heating temperature and heating time in the first stage baking are appropriately selected according to the solvent used, and are carried out at a temperature of, for example, 80 to 120 ° C. for 1 to 20 minutes. The second stage baking is carried out at a temperature of, for example, 150 to 300 ° C. for 10 to 120 minutes.

The following is based on synthetic examples of a polymerizable double bond-containing alkali-soluble (meth) acrylate resin represented by the general formula (X) and a polymerizable double bond-containing alkali-soluble resin represented by the general formula (V). The present invention will be described in more detail. The scope of the present invention is not limited by these synthetic examples and the like. Moreover, the evaluation of the resin in the following synthetic examples was carried out as follows unless otherwise specified.

[Solid content concentration]
1 g of the resin solution obtained in the synthesis example _{was impregnated into a glass filter [mass: W 0} (g)], weighed [W ₁ (g)], and heated at 160 ° C. for 2 hr, and then mass [W ₂ (mass: W 0 (g)]. g)] was obtained from the following equation.
Solid content concentration (mass%) = 100 x (W _2- W ₀ ) / (W _1- W ₀ )

[Epoxy equivalent]
After dissolving the resin solution in dioxane, add an acetic acid solution of tetraethylammonium bromide, and titrate with a 1 / 10N-perchloric acid solution using a potentiometric titrator [trade name COM-1600 manufactured by Hiranuma Sangyo Co., Ltd.]. I asked.

[Acid value]
The resin solution was dissolved in dioxane and titrated with a 1 / 10N-KOH aqueous solution using a potentiometric titrator [trade name COM-1600 manufactured by Hiranuma Sangyo Co., Ltd.].

[Molecular weight]
Gel Permeation Chromatography (GPC) [HLC-8220GPC manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgelSuper-H5000 ( 1) [manufactured by Tosoh Corporation], temperature: 40 ° C, speed: 0.6 ml / min], measured with standard polystyrene [PS-oligoform kit manufactured by Tosoh Corporation], weight average molecular weight (Mw) Is the value obtained.

[Synthesis Example 1]
51.65 g (0.60 mol) of methacrylic acid, 38.44 g (0.38 mol) of methyl methacrylate, 36.33 g (0.22 mol) of cyclohexyl methacrylate, 5.91 azobisisobutyronitrile in a 1000 ml four-necked flask with a nitrogen introduction tube and a perfusion tube. g and 368 g of diethylene glycol dimethyl ether were charged and polymerized by stirring at 80 to 85 ° C. under a nitrogen stream for 8 hours. Further, 39.23 g (0.28 mol) of glycidyl methacrylate, 1.44 g of triphenylphosphine, and 0.055 g of 2,6-di-tert-butyl-p-cresol were placed in the flask, and the mixture was stirred at 80 to 85 ° C. for 16 hours to polymerize. A double bond-containing (meth) acrylate resin (i) -1 was obtained. The solid content concentration of the obtained polymerizable double bond-containing (meth) acrylate resin was 35% by mass, the acid value (in terms of solid content) was 110 mgKOH / g, and the Mw by GPC analysis was 18080. Moreover, from the IR measurement of the obtained polymerizable double bond-containing (meth) acrylate resin, peaks were observed at ^{1409 cm -1} (vinyl group) and 1186 cm ^{-1 (carboxyl group).} From this, it was confirmed that the resin was a polymerizable double bond-containing (meth) acrylate resin having a polymerizable double bond and a carboxyl group.

[Synthesis Example 2]
51.65 g (0.60 mol) of methacrylic acid, 36.04 g (0.36 mol) of methyl methacrylate, 40.38 g (0.24 mol) of cyclohexyl methacrylate, 5.91 of azobisisobutyronitrile in a 1000 ml four-necked flask with a nitrogen introduction tube and a perfusion tube. g and 420 g of diethylene glycol dimethyl ether were charged and polymerized by stirring at 80 to 85 ° C. under a nitrogen stream for 8 hours. Further, 61.41 g (0.43 mol) of glycidyl methacrylate, 2.27 g of triphenylphosphine, and 0.086 g of 2,6-di-tert-butyl-p-cresol were placed in the flask, and the mixture was stirred at 80 to 85 ° C. for 16 hours for polymerization. A sex double bond-containing (meth) acrylate resin (i) -2 was obtained. The solid content concentration of the obtained polymerizable double bond-containing (meth) acrylate resin was 33% by mass, the acid value (in terms of solid content) was 50 mgKOH / g, and the Mw by GPC analysis was 20600. Moreover, from the IR measurement of the obtained polymerizable double bond-containing (meth) acrylate resin, peaks were observed at ^{1411 cm -1} (vinyl group) and 1186 cm ^{-1 (carboxyl group).} From this, it was confirmed that the resin was a polymerizable double bond-containing (meth) acrylate resin having a polymerizable double bond and a carboxyl group.

[Synthesis Example 3]
3,4-Epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate 85.78 g (0.34 mol), acrylic acid 49.00 g (0.68 mol), propylene glycol monomethyl ether acetate in a 500 ml four-necked flask with a return condenser. 139.0 g and 2.15 g of tetraethylammonium bromide (TEAB) were charged and reacted by stirring at 100 to 105 ° C. under heating for 20 hours. Next, 35.31 g (0.12 mol) of 3,3', 4,4'-biphenyltetracarboxylic dianhydride and 41.08 g (0.27 mol) of 1,2,3,6-tetrahydrophthalic anhydride were charged in the flask. The reaction was carried out by stirring at 120 to 125 ° C. under heating for 8 hours. Further, 39.80 g (0.28 mol) of glycidyl methacrylate was charged and stirred at 100 to 105 ° C. under heating for 8 hr to obtain a polymerizable double bond-containing alkali-soluble resin solution (vi) -1. The solid content concentration of the obtained resin solution was 57.0 wt%, the acid value (in terms of solid content) was 82 mgKOH / g, and the Mw by GPC analysis was 3500.

(Examples 1 to 5, Comparative Example 1)
Next, the present invention will be specifically described based on Examples and Comparative Examples relating to the production of the photosensitive resin composition and the cured product thereof, but the present invention is not limited thereto. Here, the raw materials and abbreviations used in the production of the photosensitive resin compositions of the following Examples and Comparative Examples and the cured products thereof are as follows.

(i) -1 component: Alkali-soluble resin solution obtained in Synthesis Example 1 above
(i) -2 component: The alkali-soluble resin solution obtained in Synthesis Example 2 above.
(ii) Ingredients: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name DPHA manufactured by Nippon Kayaku Co., Ltd.)
(iii) -1 Component: Solvent-dispersed silica sol [YA010C-SV1 manufactured by Admatex, dispersion medium: propylene glycol monomethyl ether acetate (PGMEA), solid content concentration = 20%, dynamic light scattering measuring device (manufactured by Otsuka Electronics) Cumulant average particle size 65 nm (dynamic light scattering method) determined by particle size analyzer FPAR-1000), surface treatment agent: R ₆ in formula (IV) is vinyl group, R ₇ and R ₈ are methyl groups, q = 3 ]
(iii) -2 component: Solvent-dispersed silica sol [PMA-ST manufactured by Nissan Chemical Industries, Ltd., dispersion medium: PGMEA, solid content concentration = 30%, cumulant average particle size 47 nm (dynamic light scattering method), surface treatment agent: formula ( In IV) q = 1, R ₆ , R ₇ , R ₈ = CH ₃ ]
(iv) Ingredients: Oxime ester-based photopolymerization initiator (BASF, Irgacure OXE01)
(v) Ingredients: 3-glycidoxypropyltrimethoxysilane
Component (vi): Polymerizable double bond-containing alkali-soluble resin solution (vi) -1 obtained in Synthesis Example 3 above.
Additive 1: Hindered phenolic antioxidant (BASF, Ilganox 1010)
Additive 2: Surfactant (manufactured by Toray Dow Corning, trade name FZ-2122)
Solvent-1: Propylene glycol monomethyl ether acetate Solvent-2: Diethylene glycol dimethyl ether

The above-mentioned compounding components were blended in the proportions shown in Table 1 to prepare photosensitive resin compositions of Examples 1 to 5 and Comparative Example 1. All the numerical values in Table 1 represent parts by mass.

[Creation of cured product]
The surface of the photosensitive resin composition shown in Table 1 was ^{washed by irradiating the surface with ultraviolet rays having a wavelength of 254 nm and an illuminance of 1000 mJ / cm 2} in advance with a low-pressure mercury lamp (EAGLE XG manufactured by Corning Co., Ltd.) (EAGLE XG manufactured by Corning Co., Ltd.). The film thickness after baking in the second stage is on the indium-tin oxide vapor-deposited glass substrate (UV-cleaned ITO substrate) and molybdenum-aluminum alloy-deposited substrate (UV-cleaned MAM substrate). The coating was applied using a spin coater so as to have a wavelength of 1.5 μm, and the first-stage baking was carried out at 90 ° C. for 1 minute using a hot plate to prepare a coated plate. Next, a photocuring reaction was carried out by irradiating ultraviolet rays of ^{60 mJ / cm 2} with a high-pressure mercury lamp having an illuminance of 50 mW / cm ^{2 at a wavelength of 365 nm.} Then, the second stage baking was carried out at 230 ° C. for 30 minutes using a hot air dryer to obtain a cured product (coating film) according to Examples 1 to 5 and Comparative Example 1.

Table 2 shows the results of evaluation of the following items with respect to the cured product (coating film) composed of the photosensitive resin compositions of Examples 1 to 5 and Comparative Example 1 obtained above. These evaluation methods were performed as follows. The high-temperature and high-moisture adhesion resistance and chemical adhesion resistance (acid resistance and basic resistance) were prepared not only on the cured product on the UV-cleaned glass substrate but also on the UV-cleaned ITO substrate and the UV-cleaned MAM substrate. The cured product was also evaluated.

Film thickness:
The measurement was performed using a stylus type step shape measuring device [trade name P-10 manufactured by KLA Tencor Co., Ltd.].

High temperature and high humidity adhesion:
The cured product prepared on the UV-cleaned glass substrate, the UV-cleaned ITO substrate, and the UV-cleaned MAM substrate was left to stand for 5 hours under the conditions of a temperature of 121 ° C., a humidity of 100%, and an atmospheric pressure of 2 atm. In addition, use the Super Cutter Guide manufactured by Taiyu Kikai Co., Ltd. to make cuts in the left-standing cured product so that 100 1 mm x 1 mm square squares are formed, and use cellophane tape (made by Nichiban) on the squares. ) Was attached and then peeled off. A tape peeling test was conducted. ○ if the cured product in the square is not peeled off at all, △ if less than 1/3 of the cured product in the square is peeled off, × if 1/3 or more is peeled off And said.

Acid resistance: Adhesion resistance:
The cured product prepared on the UV-cleaned glass substrate, the UV-cleaned ITO substrate, and the UV-cleaned MAM substrate is immersed in a petri dish containing royal water for 2 minutes at room temperature, and then washed with pure water to wipe off moisture. In addition, use the Super Cutter Guide manufactured by Taiyu Kikai Co., Ltd. to make cuts so that 100 1 mm x 1 mm square squares are formed, attach cellophane tape (made by Nichiban) on the squares, and then peel off. A tape peeling test was performed. ○ if the cured product in the square is not peeled off at all, △ if less than 1/3 of the cured product in the square is peeled off, × if 1/3 or more is peeled off And said.

Base adhesion resistance:
The cured product prepared on the UV-cleaned glass substrate, UV-cleaned ITO substrate, and UV-cleaned MAM substrate is immersed in a chalet containing a 4 wt% potassium hydroxide aqueous solution at 40 ° C. for 3 minutes, then washed with pure water and moisturized. Wipe off. In addition, use the Super Cutter Guide manufactured by Taiyu Kikai Co., Ltd. to make a notch so that 100 squares of 1 mm x 1 mm are formed, attach cellophane tape (made by Nichiban) on the squares, and then peel it off. A tape peeling test was performed. ○ if the cured product in the squares is not peeled off at all, △ if less than 1/3 of the cured product in the squares is peeled off, and × if 1/3 or more is peeled off. did.

Coating film hardness 1:
The cured product prepared on the glass substrate was displayed with the highest pencil hardness without scratching the coating film when a load of 1 kg was applied using a pencil hardness tester according to the JIS-K5400 test method. The pencil used is "Mitsubishi Hi-Uni". Here, this evaluation was carried out as an index of resistance to lateral force (scratch) on the surface of the coating film. 3H or more was marked with ◯, 2H was marked with Δ, and 1H was marked with x when the hardness was lower than this.

Coating hardness 2:
The cured product prepared on the glass substrate was measured using a microfilm hardness tester (HM2000 manufactured by Fisher Instruments). The indenter was a Vickers indenter, and ^{a load of 5 mN / μm 2} was applied at a load rate of 0.25 mN / sec. After holding for 1 second, the load was removed and the Martens hardness (according to ISO 14577) was measured. Here, the Martens hardness say, load - that hardness calculated from the penetration depth curve, when Martens hardness of 65N / mm ² or more ○, less than 65N / mm ² ~60N / mm ² or more In some cases, it was evaluated as Δ, and in the case of less than ^{60 N / mm 2, it was evaluated as ×.} Here, this evaluation was carried out as an index of resistance to a vertical force (pushing) of the coating film surface.

Transmittance:
The cured product prepared on a glass substrate (EAGLE XG manufactured by Corning Inc.) was measured for transmittance using a transmittance meter (trade name SPECTRO PHOTOMETER SD5000 manufactured by Nippon Denshoku Industries Co., Ltd.), and the transmittance at a wavelength of 400 nm was 95% or more. In the case of, it was evaluated as ◯, in the case of less than 95% to 90% or more, it was evaluated as Δ, and in the case of less than 90%, it was evaluated as ×.

Light resistance:
The cured product prepared on a glass substrate (EAGLE XG manufactured by Corning Inc. ^{) was irradiated with an Xe lamp (irradiation surface illuminance 250 W / m 2} ) from the glass surface side and left for 200 hours under the conditions of temperature 60 ° C. and humidity 50%. .. This is measured with a transmittance meter (trade name SPECTRO PHOTOMETER SD5000 manufactured by Nippon Denshoku Industries Co., Ltd.), and when the transmittance at a wavelength of 400 nm is 95% or more, ◎, when it is less than 95% to 90% or more. ○, less than 90% to 85% or more was evaluated as Δ, and less than 85% was evaluated as ×.

Gasogenicity:
The cured product prepared on a glass substrate (EAGLE XG manufactured by Corning Inc.) is scraped with a scraper or the like, and the obtained powdered cured product shows a thermogravimetric loss of 4 to 6 mg. Differential thermal analysis device (TG / DTA) [SII EXSTER6000 manufactured by Co., Ltd.] was used for measurement. The measurement conditions were pretreatment at 120 ° C. for 30 minutes in the air and then holding at 230 ° C. for 2 hours. The gasogenicity was evaluated from the weight loss rate, and the smaller the weight loss rate, the better the low gastricity. The weight loss rate was calculated from the weight loss before and after heating at 230 ° C. When the weight loss rate was less than 5%, it was marked as ○, when it was 5% or more and less than 15%, it was marked as △, and when it was 15% or more, it was marked as ×. ..

Alkaline developability (pattern formation and residue):
The photosensitive resin composition shown in Table 1 was applied to a 125 mm × 125 mm UV-cleaned glass substrate using a spin coater so that the film thickness after baking in the second stage was 1.5 μm, and a hot plate was used. The first stage was baked at 80 ° C. for 1 minute to prepare a coated plate. Next, an exposure mask for pattern formation with a line and space of quartz glass = 20 μm / 100 μm was installed on the coating film so that the GAP was 150 μm, and a high-pressure mercury lamp ^{with a wavelength of 365 nm and an illuminance of 50 mW / cm 2 was used at 100 mJ /} A photocuring reaction of the photosensitive part was carried out by irradiating with ultraviolet rays of ^{cm 2.} Next, this exposed coated plate is developed in a 0.04 wt% potassium hydroxide aqueous solution or a 0.2 wt% sodium carbonate aqueous solution at 23 ° C. for 80 seconds by dip development, and further washed with water to remove the unexposed portion of the coating film. did. Then, the second stage baking was carried out at 230 ° C. for 30 minutes using a hot air dryer to obtain patterns according to Examples 1 to 5 and Comparative Example 1. The alkali developability (pattern formation) was rated as ◯ when a 20 μm line pattern was formed, and as x when the 20 μm line pattern was peeled off and did not remain on the glass substrate. The alkali developability (residue) is ○ when all the coating film in the unexposed area is removed, Δ when the coating film residue remains in the range of less than 2 μm from the end face of the pattern, and 2 μm or more from the end face of the pattern. When the coating film residue remained in the range of, it was marked with x.

Migration resistance test:
On a comb-shaped electrode substrate (IPC-B-24 type specified in ISO9455-17) in which a Cu electrode with a thickness of 12 μm and a line / space of 50 μm / 50 μm is formed on a glass substrate (EAGLE XG manufactured by Corning Inc.). A migration resistance test substrate was prepared by forming an insulating film layer having a thickness of 15 μm using the photosensitive resin composition shown in Table 1. This test board was installed in a comb-shaped board rack, connected to an ion migration evaluation system (made by ESPEC, AMI-U), and the comb-shaped board rack was installed in a HAST Chamber (manufactured by ESPEC, EHS-211M). Then, in an environment of a temperature of 110 ° C. and a humidity of 85%, a voltage of 6.0 V was applied and the resistance value was measured. Continuing to measure the 300 hours resistance, if the resistance value is maintained a 1 × 10 ⁶ or more ○, and as × when the resistance off the 1 × 10 ⁶ is greatly reduced in the middle.

As is clear from the results in Table 2 above, the cured products according to Examples 1 to 5 are excellent in each performance and also have good electrical reliability. Comparative Example 1 has both adhesion and coating film hardness, can form a cured product having high transmittance, and also exhibits high adhesion and chemical resistance on the surfaces of metals and metal oxide films. , It can be seen from the migration resistance test results that electrical reliability has not been ensured. That is, in the photosensitive resin composition of the present invention, a touch panel insulating film or protective film having electrical reliability in addition to transparency, light resistance, weather resistance, heat resistance, surface hardness, adhesion, and low gas generation property. It was found that a cured film satisfying the required characteristics of the above can be provided.

The photosensitive resin composition of the present invention does not impair alkali developability even if it contains silica sol, and is excellent in transparency, light resistance, weather resistance, heat resistance, surface hardness, adhesion, chemical resistance, reliability and the like. A cured product can be formed. Therefore, it is suitable as a touch panel insulating film or a protective film. In addition, for example, various display elements such as color liquid crystal displays, color facsimiles, and image sensors, protective film materials for color filters, protective layers for organic devices such as organic semiconductors, encapsulants, and adhesives. , Can be suitably used as an insulating film.

1: Substrate 2: X electrode
2a: Island-shaped electrode (X side)
2b: Bridge electrode (X side)
3: Y electrode
3b: Bridge electrode (Y side)
4: Flattening film 5: Adhesive layer 6: Protective substrate 7: Insulating film 8: Shield layer (conductive film)

Claims (7)

(I) At least a part of the carboxyl groups in the copolymer of the (meth) acrylate compound represented by the general formula (I) and the (meth) acrylic acid compound represented by the general formula (II) has a general formula. A polymerizable double bond-containing alkali-soluble (meth) acrylate resin obtained by reacting a (meth) acrylate compound having an epoxy group represented by (III).

(However, R ₁ represents a hydrogen atom or a methyl group. R ₂ represents a hydrocarbon group having 1 to 20 carbon atoms, and may contain an ether oxygen atom or a urethane bond inside.)

(However, R ₃ indicates a hydrogen atom or a methyl group.)

(However, R ₄ represents a hydrogen atom or a methyl group. R ₅ represents a divalent hydrocarbon group having 2 to 10 carbon atoms. P represents a number of 0 or 1.)
(Ii) A polymerizable monomer having at least one polymerizable double bond,
(Iii) A silica sol that has been surface-treated with a surface treatment agent represented by the general formula (IV) and has an average particle size of 10 to 300 nm.
(Iv) Photopolymerization initiator and (v) Silane coupling agent,
Is a photosensitive resin composition for forming a touch panel insulating film / protective film containing the above as an essential component, and the content of the essential components (i) to (v) in the solid content is (i) polymerizable double. The bond-containing alkali-soluble (meth) acrylate resin is 10 to 60% by mass, (iii) the silica sol is 10 to 50% by mass, (v) the silane coupling agent is 0.1 to 20% by mass, and (ii) the polymerizable monomer is (i) / (ii) (mass ratio) = 20/80 to 85/15, and (iv) the photopolymerization initiator is [(iv) / [(i) + (ii)]] (mass ratio). ) = A photosensitive resin composition for forming an insulating film / protective film for a touch panel, which satisfies the range of 0.005 to 0.2.

(However, R ₆ is a vinyl group , R ₇ is an independent hydrogen atom and an alkyl group having 1 to 4 carbon atoms, R ₈ is an independent alkyl group having 1 to 4 carbon atoms, and q is 1 to 1. 3) The photosensitive material for forming a touch panel insulating film / protective film according to claim 1, wherein the component (i) and the component (i) contain (vi) a polymerizable double bond-containing alkali-soluble resin represented by the general formula (V). Sex resin composition.

(However, R ₁₀ represents a hydrogen atom or a methyl group. X represents a divalent organic group having 1 to 20 carbon atoms which may contain a hetero element in a single bond or inside, and Y represents a tetravalent carboxylic acid. Indicates a residue, Z indicates a hydrogen atom or a substituent represented by the following general formula (VI), G indicates a hydrogen atom or a substituent represented by the following general formula (VII), and r indicates 1 to 20. Shows the average value of.)

(However, R ₁₁ indicates a hydrogen atom or a methyl group, R ₁₂ indicates a divalent hydrocarbon group having 2 to 10 carbon atoms, L indicates a divalent or trivalent carboxylic acid residue, and u indicates 0. Or 1; s and t are 0, 1 or 2, respectively, and s + t is 1 or 2.)

(However, R ₁₃ represents a hydrogen atom or a methyl group, R ₁₄ represents a divalent hydrocarbon group having 2 to 10 carbon atoms, and v represents 0 or 1.) The touch panel insulating film / protective film according to claim 1 or 2, wherein the alkali-soluble (meth) acrylate resin containing a polymerizable double bond of (i) has a weight average molecular weight of 5,000 to 200,000. Photosensitive resin composition for formation. The touch panel according to claim 2 or 3, wherein the polymerizable double bond-containing alkali-soluble resin represented by the general formula (V) of (vi) has a weight average molecular weight of 1,000 to 100,000. A photosensitive resin composition for forming an insulating film / protective film. (I) A structural unit derived from a (meth) acrylate compound represented by the general formula (I), where the total of all the structural units in the polymerizable double bond-containing alkali-soluble (meth) acrylate resin is 100 mol%. Is 10 to 80 mol%, and the constituent unit containing a carboxyl group derived from the (meth) acrylic acid compound represented by the general formula (II) is 10 to 50 mol%, and the carboxyl of the general formula (II) is The invention according to any one of claims 1 to 4, wherein the structural unit containing the polymerizable double bond obtained by reacting the group with the epoxy group of the general formula (III) is 10 to 40 mol%. A photosensitive resin composition for forming a touch panel insulating film / protective film. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 5. A touch panel having the cured film according to claim 6 as an insulating film and / or a protective film.

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