TW201910916A - Photosensitive resin composition, photosensitive transfer material, method for manufacturing circuit wiring, and method for manufacturing touch panel - Google Patents

Abstract

Provided is a photosensitive resin composition that comprises: a polymer containing a structural unit having a group obtained by protecting a carboxylic acid group by an acid-decomposable group; a photoacid generator; and a latent pigment which is a compound that has formed therein a conjugate acid having a pKa of less than 4.5 or no conjugate acid, the latent pigment having a local maximum absorption wavelength of 500 nm or higher in a wavelength range of 400-780 nm at color development. Also provided are a photosensitive transfer material, a circuit wiring production method, and a touch panel production method that use the abovementioned photosensitive resin composition.

Description

Manufacturing method of photosensitive resin composition, photosensitive transfer material, circuit wiring, and manufacturing method of touch panel

The invention relates to a method for manufacturing a photosensitive resin composition, a photosensitive transfer material, circuit wiring, and a touch panel.

In display devices (organic electroluminescence (EL) display devices, liquid crystal display devices, etc.) equipped with a touch panel such as an electrostatic capacitance type input device, the electrode pattern, edge wiring portion and extraction of the sensor corresponding to the visual recognition part Conductive layer patterns such as wiring in the wiring portion are provided inside the touch panel. Generally, when forming a patterned layer, since the number of steps for obtaining a desired pattern shape is small, a layer of a photosensitive resin composition provided on an arbitrary substrate using a photosensitive transfer material is widely used to have a desired The method of developing after the pattern mask is exposed.

In addition, as a conventional photosensitive resin composition, it is known to be described in JP 2008-64908, JP 2004-54106, JP 2009-3000, or JP 2002-341544. Of content.

A problem to be solved by an embodiment of the present invention is to provide a photosensitive resin composition that is particularly excellent in sensitivity and excellent in visibility of exposed and unexposed portions. In addition, a problem to be solved by another embodiment of the present invention is to provide a method for manufacturing a photosensitive transfer material, circuit wiring, or touch panel using the photosensitive resin composition.

The means for solving the above-mentioned problems include the following. <1> A photosensitive resin composition comprising: a polymer containing a structural unit having a group having a carboxylic acid group protected by an acid-decomposable group; a photo-acid generator; and a latent pigment, the pKa of the conjugate acid is less than 4.5 The maximum absorption wavelength of the compound with no conjugate acid formation and color development in the wavelength range of 400 nm to 780 nm is above 500 nm. <2> The photosensitive resin composition according to the above <1>, wherein the maximum absorption wavelength of the latent dye is 550 nm or more. <3> The photosensitive resin composition according to the above <1> or <2>, wherein the latent coloring matter is a latent coloring matter developed by the acid generated by the photoacid generator. <4> The photosensitive resin composition according to any one of the above <1> to <3>, wherein the acid generated by the photoacid generator is at least 1 selected from the group consisting of phosphoric acid and sulfonic acid Kind of acid. <5> The photosensitive resin composition according to the above <4>, wherein the acid generated by the photoacid generator is a sulfonic acid represented by the following formula S1 or formula S2.

[Chem 1]

S1 and S2 in formula formula, R ^S represents an alkyl group, L ^S represents 2 or more carbon atoms, alkylene group, 1 represents 0 or NS, wherein, R ^S system having a case where the halogen atom of the alkyl group, n is 1, X ^S independently represents an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and ms represents an integer of 0 to 5.

<6> The photosensitive resin composition according to any one of the above <1> to <5>, wherein the acid generated by the photoacid generator has a pKa of -4.0 or more. <7> The photosensitive resin composition according to any one of the above <1> to <6>, wherein the pKa of the acid generated by the photoacid generator is 4.0 or less. <8> The photosensitive resin composition according to any one of the above <1> to <7>, which further contains a basic compound. <9> The photosensitive resin composition as described in any one of <1> to <8> above, which further contains a solvent. <10> The photosensitive resin composition according to any one of the above <1> to <9>, wherein the latent dye is a compound represented by the following formula I.

[Chem 2]

In Formula I, Ar ^1C and Ar ^2C each independently represent an aromatic group, X ^C represents C, S, or S = O, and R ^1C to R ^4C each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group.

<11> The photosensitive resin composition according to the above <10>, wherein X ^C in the above formula I is C. <12> The photosensitive resin composition according to any one of the above <1> to <11>, wherein the structural unit having a group in which the carboxylic acid group is protected by an acid-decomposable group is represented by the following formula II 'S constituent unit.

[Chemical 3]

In Formula II, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ represents an alkyl group or an aryl group, R ¹ Or R ² may be linked to R ³ to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an aryl group.

<13> A photosensitive transfer material having a temporary support and a photosensitive resin layer, the photosensitive resin layer comprising the photosensitive resin composition according to any one of the above <1> to <12>. <14> A method of manufacturing a circuit wiring, which sequentially includes: a step of bringing the photosensitive resin layer of the photosensitive transfer material described in the above <13> into contact with the substrate with respect to the substrate; A step of pattern exposure of the photosensitive resin layer of the photosensitive transfer material after the combined step; a step of developing the photosensitive resin layer after the exposure step to form a pattern; and a pattern not provided with the pattern The step of etching the substrate in the area. <15> A method of manufacturing a touch panel, which sequentially includes: a step of bringing the photosensitive resin layer of the photosensitive transfer material described in the above <13> into contact with the substrate with respect to the substrate; A step of pattern exposing the photosensitive resin layer of the photosensitive transfer material after the step of laminating; a step of developing the photosensitive resin layer after the step of exposing to form a pattern; The step of etching the substrate in the area. [Effect of invention]

According to one embodiment of the present invention, it is possible to provide a photosensitive resin composition having excellent sensitivity and excellent visibility of exposed portions and unexposed portions. Furthermore, according to another embodiment of the present invention, it is possible to provide a method for manufacturing a photosensitive transfer material, circuit wiring, or a touch panel using the photosensitive resin composition.

Hereinafter, the content of the present invention will be described. In addition, the description will be made with reference to the drawings, but the symbols are sometimes omitted. In addition, the numerical range represented by "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. In addition, in this specification, "(meth) acrylic acid" means two or either acrylic acid and methacrylic acid, and "(meth) acrylate" means two or any one of acrylate and methacrylate. In addition, regarding the amount of each component in the composition in this specification, unless otherwise specified, when there are a plurality of substances corresponding to each component in the composition, it refers to the plurality of substances present in the composition Total measurement. In this specification, the term "step" not only includes independent steps, even if it cannot be clearly distinguished from other steps, as long as the intended purpose of the step is achieved, it is also included in this term. In the label of the group (atomic group) in the present specification, the unrepresented and unsubstituted labels include those having a substituent as well as those having no substituent. For example, "alkyl" means not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group). In addition, the chemical structural formulas in this specification are sometimes described as abbreviated structural formulas omitting hydrogen atoms. In the present invention, the meaning of "mass%" is the same as the meaning of "weight%", and the meaning of "parts by mass" is the same as the meaning of "parts by weight". In addition, in the present invention, a combination of two or more preferred aspects is a more preferred aspect. In addition, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present invention use tubes using TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all product names manufactured by TOSOH CORPORATION) unless otherwise specified. The column gel permeation chromatography (GPC) analyzer uses a solvent THF (tetrahydrofuran) and a differential refractometer to detect molecular weights converted using polystyrene as a standard substance.

(Photosensitive resin composition) The photosensitive resin composition of the present invention contains: a polymer, a constituent unit having a group having a carboxylic acid group protected by an acid-decomposable group; a photoacid generator; and a latent dye, conjugated The acid has a pKa of less than 4.5 or a compound that does not form a conjugate acid and has a maximum absorption wavelength of 500 nm or more in the wavelength range of 400 nm to 780 nm during color development.

In the photosensitive resin composition for the resist layer of the dry film photoresist, the visibility of the exposed portion is required from the viewpoint of confirming the exposed portion. As a general color developing agent, an acid colorless colorless dye such as CVL (crystal violet lactone) is known, but the CVL has three dimethylamino groups in the molecule and is highly basic. Therefore, the present inventors found that not only can the color be developed, but also in the positive type resist using the photoacid generator, since the acid that needs to decompose the acid-decomposable group is neutralized, it is difficult to pattern or Problems such as low sensitivity. In addition, in order to reduce the alkalinity of the leuco dye and increase the sensitivity, a method of excluding the amine group from the leuco dye may be considered. However, the inventors found that the maximum absorption wavelength of the color former shifts to the short-wave side to expose the exposed portion Insufficient problem.

As a result of intensive studies on these problems, the inventors found that a photosensitive resin composition having excellent sensitivity and excellent visibility of exposed and unexposed areas can be obtained by using the photosensitive resin composition having the above-mentioned configuration . Although the mechanism for expressing the above-mentioned effects in detail is not clear, the inventors speculate that by using a compound with a latent dye-based conjugated acid having a pKa of less than 4.5 or that does not form a conjugated acid, sufficient sensitivity is obtained. The maximum absorption wavelength in the wavelength range from 400 nm to 780 nm in the color development of sex dyes is 500 nm or more, and the visibility of the exposed and unexposed areas is also excellent. Also, by containing the acid-decomposable group having a carboxylic acid group The constituent unit polymer of the protected group can balance sensitivity and visibility.

Hereinafter, the photosensitive resin composition of the present invention will be described in detail.

<Potential dye having a pKa of a conjugate acid of less than 4.5 or a compound that does not form a conjugate acid and has a maximum absorption wavelength of 400 nm to 780 nm in the color development range of 500 nm or more> The photosensitive resin composition of the present invention contains Potential pigments with a pKa of conjugated acid less than 4.5 or a compound that does not form a conjugate acid and has a maximum absorption wavelength range of 400 nm to 780 nm at the time of color development (below, also referred to as "specific latent pigment ".). The specific latent pigment may be a compound developed by exposure or may be a compound decolorized by exposure, but from the viewpoint of sensitivity and visibility, a compound developed by exposure is preferred, by photoacid The latent pigment developed by the acid generated by the generator is better.

Certain potential pigments are compounds with a pKa of conjugate acid (also known as "pKaH") of less than 4.5 or that do not form a conjugate acid. The pKa of the conjugate acid of the compound in the present invention refers to the pKa (negative common logarithm of the acid dissociation fixed number) of the chemical species (conjugated acid) obtained by bonding H ⁺ to the compound. In addition, certain compounds not latent pigment-based conjugate acid of the comparison means is formed by the dissociation of the compound ⁺ H, H ⁺ to obtain the potential of a particular pigment bonded chemical species (conjugate acid) is more stable. The pKa (pKaH) of the compound and the like in the present invention refers to calculation using ACD / pka DB ver 8.07 of ACD / Labs software Ver 8.0 for Microsoft windows manufactured by Advanced Chemistry Development Corporation. Moreover, the pKaH system of a specific latent pigment is preferably -30 or more, and more preferably -10 or more.

The maximum absorption wavelength in the wavelength range from 400 nm to 780 nm when a specific latent pigment is developed is 500 nm or more. From the viewpoint of visibility, 550 nm or more is preferable, and 550 nm or more and 700 nm or less is more preferable. 550 nm or more and 650 nm or less are further preferable. Moreover, the specific latent pigment may have only one maximum absorption wavelength, or may have more than two. When the specific latent pigment has more than two maximum absorption wavelengths, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths may be 500 nm or more. Regarding the method for measuring the maximum absorption wavelength in the present invention, in an atmospheric atmosphere, a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) is used at 25 ° C., the transmission spectrum is measured in the range of 400 nm to 780 nm, and the light is measured The intensity becomes a very small wavelength (maximum absorption wavelength).

Examples of specific latent pigments that develop color by exposure include colorless compounds. In addition, examples of specific latent dyes decolorized by exposure include triphenylmethane dyes, diphenylmethane dyes, oxazine dyes, dibenzopiperan dyes, and iminonaphthoquinone dyes. Pigments, methylimine-based pigments, anthraquinone-based pigments, etc. Among them, as a specific latent colorant, a colorless compound is preferred from the viewpoint of sensitivity and visibility. Examples of the colorless compound include triphenylmethane-based, spiropiperan-based, fluorescent yellow mother-system, diphenylmethane-based, rhodamine-lactam-based, indolylphthalide-based, colorless gold-amine-based colorless Compound. Further, as the colorless compound, from the viewpoint of sensitivity and visibility, a lactone ring, a sultines ring, or a sultone ring is preferably ring-opened, and a colorless compound in which the lactone ring is opened to develop color is more preferable.

In addition, from the viewpoint of sensitivity and visibility, a compound represented by the following formula I in which the specific latent pigment is preferred is preferable.

[Chem 4]

In Formula I, Ar ^1C and Ar ^2C each independently represent an aromatic group, X ^C represents C, S, or S = O, and R ^1C to R ^4C each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group.

The aromatic group in Ar ^1C and Ar ^2C may be an aryl group or a heteroaryl group, or a monocyclic aromatic group, or a condensed ring in which two or more rings are condensed. In addition, Ar ^1C and Ar ^2C may be bonded to form a ring, and from the viewpoint of sensitivity and visibility, Ar ^1C and Ar ^2C are preferably bonded to form a dibenzopiperan ring. The aromatic group in Ar ^1C and Ar ^2C may have a substituent. Examples of the substituents include halogen atoms, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, dialkylamine groups, alkylarylamine groups, and diarylamine groups. Dialkylamine groups , Alkylarylamino group, diarylamino group is preferred. The alkyl group in the dialkylamino group and the alkylarylamino group independently represents a C 2-20 alkyl group, and a C 2-10 alkyl group is more preferred. In addition, among the two alkyl groups in the dialkylamine group, at least one is preferably an alkyl group having 3 to 20 carbon atoms, and more preferably an alkyl group having 3 to 10 carbon atoms. These substituents can also be substituted by substituents. From the viewpoint of sensitivity and visibility, it is preferable that the total carbon number of Ar ^1C and Ar ^2C is independently 4 to 50, 6 to 40 is more preferable, and 10 to 30 is even more preferable.

From the viewpoint of sensitivity and visibility, X ^C is preferably C or S = O, and C is more preferable. The monovalent organic group of R ^1C to R ^4C is preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a dialkylamine group, an alkylarylamine group, or a diarylamine group. Moreover, it is preferable that the carbon numbers of R ^1C to R ^4C are independently 0-20, and 0-10 is more preferable. R ^1C to R ^4C are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group, preferably a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group or an aryl group, The hydrogen atom is particularly good.

As a preferable specific example of the specific latent coloring matter, the compounds C-1 to C-9 are described below. It goes without saying that the specific latent coloring matter in the present invention is not limited to these.

[Chemical 5]

[化 6]

[化 7]

[Chem 8]

[化 9]

Specific latent pigments can be used alone or in combination of two or more. From the viewpoint of sensitivity and visibility, the content of the specific latent pigment in the photosensitive resin composition of the present invention is preferably 0.01% by mass to 10% by mass relative to the total solid content of the photosensitive resin composition, and 0.1% by mass % To 8% by mass is more preferable, 0.5% by mass to 5% by mass is further preferable, and 1.0% by mass to 3.0% by mass is particularly preferable. In addition, in the present invention, the "solid content" in the photosensitive resin composition refers to a component from which the solvent-free volatile component is removed.

<Polymer having a structural unit having a group having a carboxylic acid group protected by an acid-decomposable group> The photosensitive resin composition of the present invention contains a polymer (also referred to as "specific polymer"), and the polymer contains Constituent unit of a carboxylic acid group protected by an acid-decomposable group (also called "constituent unit A"). In addition, the photosensitive resin composition of the present invention may contain other polymers in addition to the polymer constituting the unit A. In the present invention, the polymer having the structural unit A and other polymers are collectively referred to as "polymer component". The above-mentioned specific polymer generates a deprotection reaction by the destructive reaction of the constituent unit A having a carboxylic acid group which is protected by the acid decomposable in the specific polymer due to the acidic substance in the amount of catalyst generated by exposure, and becomes a carboxylic acid group. By this acid group, the hardening reaction can proceed. Hereinafter, a preferred aspect of the constituent unit A will be described.

The photosensitive resin composition may further include a polymer other than a polymer having a structural unit containing an acid group protected by acid decomposition. Moreover, it is preferable that all the polymers contained in the above-mentioned polymer component are polymers each having at least a structural unit containing a carboxylic acid group described later. In addition, the above-mentioned photosensitive resin composition may further contain polymers other than these. Unless otherwise specified, the above-mentioned polymer component in the present invention means that it contains other polymers added as necessary. In addition, even if the compound described later, a plasticizer, a heterocyclic compound, and a compound corresponding to a surfactant are polymer compounds, they are also compounds not included in the polymer component.

A specific polymer is preferably an addition polymerization type resin, and a polymer having a structural unit derived from (meth) acrylic acid or its ester is more preferable. Further, in addition to the structural units derived from (meth) acrylic acid or its ester, for example, it may also have structural units derived from styrene or vinyl compounds.

From the viewpoints of the formability of the pattern shape, the solubility in the developing solution, and the transferability, the photosensitive resin composition contains, as the polymer, the polymer having the structural unit A1 represented by the following formula II as the structural unit A as a polymer The component is preferable, and it is preferable that the photosensitive resin composition contains a specific polymer having the structural unit A1 represented by the following formula II as the structural unit A and having a glass transition temperature of 90 ° C. or less as a polymer component, and The photosensitive resin composition contains as the polymer component a specific polymer having the structural unit A1 represented by the following formula II and the structural unit B having a carboxylic acid group described below and having a glass transition temperature of 90 ° C. or lower as the polymer component Is further preferred. The specific polymer included in the photosensitive resin composition may be one kind, or two or more kinds.

<< Constitutional unit A >> The above-mentioned polymer component includes a polymer having at least a constitutional unit A containing a group in which a carboxylic acid group is protected by an acid-decomposable group. The polymer component contains a polymer having a structural unit A, and thus can be used as a chemically amplified positive photosensitive resin layer having extremely high sensitivity. The "group in which the carboxylic acid group is protected by an acid-decomposable group" in the present invention can use a known group as an acid-decomposable group, and is not particularly limited. As the acid-decomposable group, an acetal-based function such as an ester group, a tetrahydropyranyl group, or a tetrahydrofuranyl ester group that is relatively easily decomposed by an acid (for example, an ester group protected by a group represented by Formula II to be described later) can be used Groups) or groups that are relatively difficult to decompose by acid (for example, tertiary alkyl groups such as tertiary butyl ester groups, tertiary alkyl carbonate groups such as tertiary butyl carbonate groups). Among these, as the acid-decomposable group, a group having a structure protected in an acetal form is preferred.

From the viewpoint of sensitivity and resolution, the structural unit A having a group in which the carboxylic acid group is protected by an acid-decomposable group is preferably a structural unit A1 represented by the following formula II.

[化 10]

In Formula II, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ represents an alkyl group or an aryl group, R ¹ Or R ² may be linked to R ³ to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an aryl group.

In Formula II, when R ¹ or R ² is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred. In the case where R ¹ or R ² is an aryl group, phenyl is preferred. R ¹ and R ² are each preferably a hydrogen atom or a C 1-4 alkyl group. In Formula II, R ³ represents an alkyl group or an aryl group, preferably a C 1-10 alkyl group, and more preferably a C 1-6 alkyl group. In addition, the alkyl group and aryl group in R ¹ to R ³ may have a substituent. In Formula II, R ¹ or R ² may be linked to R ³ to form a cyclic ether, and R ¹ or R ² to R ^{3 may be} linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but 5 or 6 is preferred, and 5 is more preferred. In formula II, X represents a single bond or an aryl group, and a single bond is preferred. The arylene group may have a substituent. The specific polymer includes the structural unit A1 represented by Formula II, whereby the sensitivity during pattern formation is excellent and the resolution is even more excellent.

In Formula II, R ⁴ represents a hydrogen atom or a methyl group, and a hydrogen atom is preferred from the viewpoint that the Tg of the specific polymer can be further reduced. More specifically, it is preferable that the structural unit of the R ⁴ series hydrogen atom in Formula II is 20% by mass or more with respect to the total amount of the structural unit A1 contained in the specific polymer. In addition, in the structural unit A1, the content (content ratio: mass ratio) of the structural unit of the R ⁴ -based hydrogen atom in Formula II can be measured by ¹³ C-nuclear magnetic resonance spectroscopy (NMR) and calculated according to the usual peak value The strength ratio is confirmed.

In the structural unit A1 represented by Formula II, the structural unit represented by the following Formula A2 is more preferable from the viewpoint of further improving the sensitivity during pattern formation.

[化 11]

In Formula A2, R ³⁴ represents a hydrogen atom or a methyl group, and R ³⁵ to R ⁴¹ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In formula A2, R ³⁴ is preferably a hydrogen atom. In formula A2, R ³⁵ to R ⁴¹ are preferably hydrogen atoms.

As a preferable specific example of the structural unit A1 represented by Formula II having a group in which the carboxylic acid group is protected by an acid-decomposable group, the following structural units can be exemplified. In addition, R ³⁴ represents a hydrogen atom or a methyl group.

[Chem 12]

The structural unit A included in the specific polymer may be one kind, or two or more kinds. The content of the structural unit A in the specific polymer is preferably 20% by mass or more with respect to the total mass of the specific polymer, more preferably 20% by mass to 90% by mass, and further preferably 30% by mass to 70% by mass. The content (content ratio: mass ratio) of the structural unit A in the specific polymer can be confirmed by the intensity ratio of the peak intensity measured from ¹³ C-NMR and calculated by the usual method. Moreover, after decomposing all polymer components into structural units (monomer units), the ratio of the structural unit A is preferably 5% to 80% by mass relative to the total mass of the polymer components, and 10% to 80% by mass To be more preferable, 10% by mass to 40% by mass is even more preferable, and 10% by mass to 30% by mass is particularly preferable.

<< Constitutional unit B >> It is preferable that the specific polymer contains a constitutional unit B having a carboxylic acid group. The constituent unit B is a protective group, for example, a carboxylic acid group that is not protected by an acid-decomposable group, that is, a constituent unit that includes a carboxylic acid group that does not have a protective group. Since the specific polymer contains the structural unit B, the sensitivity during pattern formation is good, and it is easily dissolved in an alkaline developer in the development step after pattern exposure, and the development time can be shortened.

When a structural unit having a carboxylic acid group is introduced into a specific polymer, it can be carried out by copolymerizing a monomer having a carboxylic acid group. The structural unit containing the carboxylic acid group as the structural unit B is a structural unit in which a structural unit derived from styrene or a structural unit derived from a vinyl compound is replaced by a carboxylic acid group or a structural unit derived from (meth) acrylic acid For better.

The structural unit B included in the specific polymer may be one kind, or two or more kinds. With respect to the total mass of the specific polymer, the specific polymer preferably contains 0.1% to 20% by mass of a structural unit having a carboxylic acid group (constituent unit B), and more preferably contains 0.5% to 15% by mass. 1% by mass to 10% by mass is further preferable. Within the above range, the pattern formability is better. The content (content ratio: mass ratio) of the structural unit B in the specific polymer can be confirmed by the intensity ratio of the peak intensity measured from ¹³ C-NMR and calculated by the usual method.

<< Other structural units >> The specific polymer may include other structural units (hereinafter, below) in addition to the structural unit A and the structural unit B already described, as long as the effect of the photosensitive transfer material of the present invention is not impaired. Sometimes referred to as constituent unit C.). The monomer forming the structural unit C is not particularly limited, and examples thereof include styrenes, alkyl (meth) acrylates, cyclic alkyl (meth) acrylates, and aryl (meth) acrylates. , Unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated Dicarboxylic anhydride, group with aliphatic cyclic skeleton, other unsaturated compounds. Using structural unit C, by adjusting at least any one of the kind and content, various characteristics of a specific polymer can be adjusted. In particular, by appropriately using the structural unit C, the Tg of the specific polymer can be easily adjusted to 90 ° C or lower. The specific polymer may contain only one kind of structural unit C, or may contain two or more kinds.

Specifically, the structural unit C includes styrene, third butoxystyrene, methylstyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, and ethoxybenzene Ethylene, chlorostyrene, methyl vinyl benzoate, ethyl vinyl benzoate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylic acid Isopropyl ester, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobutyl (meth) acrylate, acrylonitrile or polymerized ethylene glycol A structural unit formed from acetoacetate mono (meth) acrylate and the like. In addition, the compounds described in paragraphs 0021 to 0024 of Japanese Patent Laid-Open No. 2004-264623 can be mentioned.

In addition, as the structural unit C, from the viewpoint of improving the electrical characteristics of the obtained transfer material, a structural unit having an aromatic ring or a structural unit having an aliphatic ring skeleton is preferable. Specific examples of the monomers forming these structural units include styrene, third butoxystyrene, methylstyrene, α-methylstyrene, dicyclopentyl (meth) acrylate, Cyclohexyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, etc. Among them, the structural unit C preferably includes a structural unit derived from cyclohexyl (meth) acrylate.

In addition, as the monomer forming the constituent unit C, from the viewpoint of adhesion, for example, alkyl (meth) acrylate is preferred. Among them, from the viewpoint of adhesion, alkyl (meth) acrylate having an alkyl group having 4 to 12 carbon atoms is more preferable. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. ester.

The content of the structural unit C is preferably 70% by mass or less relative to the total mass of the specific polymer, more preferably 60% by mass or less, and further preferably 50% by mass or less. The lower limit may be 0% by mass, but 1% by mass or more is preferable, and 5% by mass or more is more preferable. Within the above range, the resolution and the adhesiveness of the photosensitive resin layer formed by the photosensitive resin composition are further improved.

From the viewpoint of optimizing the solubility with respect to the developer and the physical properties of the photosensitive resin layer to be described later, it is preferable that the specific unit contains a structural unit of an ester having an acid group in the structural unit B as the structural unit C. Among them, it is preferable that the specific polymer includes a structural unit having a carboxylic acid group as the structural unit B, and further includes a structural unit C having a carboxylic acid ester group as a copolymerization component, for example, a structural unit B derived from (meth) acrylic acid And the polymer derived from the structural unit (c) derived from cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or n-butyl (meth) acrylate is more preferable. Hereinafter, preferred examples of the specific polymer in the present invention are given, but the present invention is not limited to the following examples. In addition, the ratio of the structural unit and the weight average molecular weight in the following exemplified compounds can be appropriately selected in order to obtain preferable physical properties.

[Chem 13]

<< Glass transition temperature of polymer: Tg >> The glass transition temperature (Tg) of the specific polymer in the present invention is preferably 90 ° C. or lower. With a Tg of 90 ° C. or lower, the photosensitive resin layer formed of the photosensitive resin composition has high adhesion and is more excellent in transferability. The above Tg system is more preferably 60 ° C or lower, and further preferably 40 ° C or lower. In addition, the lower limit of the above-mentioned Tg is not particularly limited, but it is preferably -20 ° C or higher, and more preferably -10 ° C or higher. The Tg of the specific polymer is -20 ° C. or higher to maintain good pattern formability. For example, when a cover film is used, the decrease in peelability when the cover film is peeled off is suppressed. From the viewpoint of transferability, the glass transition temperature (Tg) of the entire polymer component in the present invention is preferably 90 ° C. or lower, more preferably 60 ° C. or lower, and further preferably 40 ° C. or lower.

The glass transition temperature of the polymer can be measured using a differential scanning calorimeter (DSC). The specific measurement method is performed in the order of the method described in JIS K 7121 (1987) or JIS K 6240 (2011). The glass transition temperature in this specification uses the extrapolated glass transition start temperature (hereinafter, sometimes referred to as Tig). The method for measuring the glass transition temperature will be described more specifically. When the glass transition temperature is determined, after maintaining the device at a temperature about 50 ° C lower than the expected Tg of the polymer until it is stable, it is heated to a temperature higher than the temperature at which the glass transition is completed at a heating rate of 20 ° C / min. A temperature of 30 ° C and draw a DTA curve or DSC curve. The extrapolated glass transition starting temperature (Tig), which is the glass transition temperature Tg in this specification, serves as a straight line extending the reference line on the low temperature side of the DTA curve or DSC curve along the high temperature side and the stepwise change in the glass transition The gradient of the curve becomes the temperature at the intersection of the tangents drawn at the point where the maximum is drawn.

As a method for adjusting the Tg of the polymer to the above-described preferred range, for example, it is possible to control the Tg of the homopolymer of each constituent unit of the target polymer and the FOX formula as a criterion based on the mass ratio of each constituent unit. The Tg of the specific polymer as the target. Regarding the FOX formula, the Tg of the homopolymer of the first structural unit included in the polymer is Tg1, the mass fraction of the copolymer of the first structural unit is W1, and the homopolymerization of the second structural unit When the Tg of the substance is Tg2 and the mass fraction in the copolymer of the second constitutional unit is W2, the Tg0 (K) of the copolymer including the first constitutional unit and the second constitutional unit can be estimated from the following formula . FOX formula: 1 / Tg0 = (W1 / Tg1) + (W2 / Tg2) Using the FOX formula already described, adjusting the type and mass fraction of each constituent unit included in the copolymer can obtain the desired Tg Copolymer. Also, by adjusting the weight average molecular weight of the polymer, the Tg of the polymer can also be adjusted.

<< Molecular weight of polymer: Mw >> The molecular weight of the specific polymer is preferably 60,000 or less in terms of polystyrene-equivalent weight average molecular weight. The weight-average molecular weight of the specific polymer is 60,000 or less, which can lower the melt viscosity of the photosensitive resin layer in the photosensitive transfer material described later, and can achieve a low temperature (for example, 130 ° C or less) when bonding to the substrate ) Under the fit. In addition, the weight average molecular weight of the specific polymer is preferably 2,000 to 60,000, more preferably 3,000 to 50,000, and even more preferably 10,000 to 30,000. In addition, the weight-average molecular weight of the polymer can be measured by GPC (gel permeation chromatography). As a measuring device, various commercially available devices can be used. Those skilled in the art will know the contents of the device and the measuring technique. . For the measurement of the weight average molecular weight by gel permeation chromatography (GPC), HLC (registered trademark) -8220GPC (manufactured by TOSOH CORPORATION) is used as the measuring device, and each TSKgel (registered trademark) Super is connected in series as the column HZM-M (4.6mmID × 15cm, manufactured by TOSOH CORPORATION), Super HZ4000 (4.6mmID × 15cm, manufactured by TOSOH CORPORATION), Super HZ3000 (4.6mmID × 15cm, manufactured by TOSOH CORPORATION), Super HZ2000 (4.6mmID × 15cm, manufactured by TOSOH CORPORATION) System), as the eluent, THF (tetrahydrofuran) can be used. In addition, as the measurement conditions, the sample concentration is set to 0.2% by mass, the flow rate is set to 0.35 ml / min, the sample injection amount is set to 10 μl, and the measurement temperature is set to 40 ° C. Differential refractive index (RI ) The detector. The calibration curve can use "standard sample TSK standard, polystyrene" manufactured by TOSOH CORPORATION: "F-40", "F-20", "F-4", "F-1", "A-5000", "A -2500 "and" A-1000 "any one of 7 samples to make.

The ratio (dispersion degree) of the number average molecular weight to the weight average molecular weight of the specific polymer is preferably 1.0 to 5.0, and more preferably 1.05 to 3.5.

＜< Specific polymer manufacturing method >＞ The specific polymer manufacturing method (synthesis method) is not particularly limited, but as an example, it is as follows: The polymerizable property used to form the structural unit A1 represented by formula II The monomer, the polymerizable monomer used to form the structural unit B having a carboxylic acid group, and the solvent containing the polymerizable monomer used to form the other structural unit C as needed can be synthesized by polymerization using a polymerization initiator . It can also be synthesized by a so-called polymer reaction.

From the viewpoint of sensitivity and resolution, it is preferable that the photosensitive resin composition of the present invention contains a specific polymer at a ratio of 50% by mass to 99.9% by mass relative to the total solid content of the photosensitive resin composition at 70% by mass The ratio of% to 98% by mass is more preferably included. In addition, from the viewpoint of sensitivity and analysis, it is preferable that the photosensitive resin composition of the present invention contains the polymer component in a ratio of 50% by mass to 99.9% by mass relative to the total solid content of the photosensitive resin composition. It is more preferable to include at a ratio of 70% by mass to 98% by mass.

<< Other polymer >> In the above-mentioned photosensitive resin composition, as the polymer component, in addition to the specific polymer, the composition may be included in a range that does not impair the effect of the photosensitive resin composition of the present invention. Unit A polymer (sometimes called "other polymer".). When the above-mentioned photosensitive resin composition contains other polymers, the blending amount of other polymers is preferably 50% by mass or less in the total polymer component, more preferably 30% by mass or less, and further more than 20% by mass. good.

In addition to the specific polymer, the photosensitive resin composition may contain only one kind of other polymer, or may contain two or more kinds. As other polymers, for example, polyhydroxystyrene can be used, and commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (above, manufactured by Sartomer Company, Inc), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920 and ARUFON UC-3080 (above, manufactured by TOAGOSEI CO., LTD.) And Joncryl 690, Joncryl 678, Joncryl 67 and Joncryl 586 (above, manufactured by BASF), etc.

<Photoacid generator> The photosensitive resin composition of this invention contains a photoacid generator. The photoacid generator used in the present invention is a compound capable of generating an acid by irradiating radiation such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams. As the photo-acid generator used in the present invention, a compound that induces an actinic ray with a wavelength of 300 nm to 450 nm or more and preferably generates an acid at a wavelength of 300 nm or more is preferable, and its chemical structure is not limited. In addition, for photoacid generators that are not directly induced by actinic rays with a wavelength of 300 nm or more, if they are used in combination with sensitizers to induce actinic rays with a wavelength of 300 nm or more and generate an acid, it can increase Sensitive agents are preferably used in combination. From the viewpoint of sensitivity and visibility, the pKa of the acid generated by the photoacid generator used in the present invention is preferably 4.0 or less, more preferably 3.0 or less, further preferably 2.0 or less, and particularly preferably -1.0 or less. . The lower limit value of the pKa of the acid generated by the photoacid generator is not particularly limited, but for example, -10.0 or more is preferable, and from the viewpoint of sensitivity and visibility, -4.0 or more is more preferable, and -3.5 or more is more Good, above -3.0 is especially good.

In addition, from the viewpoint of sensitivity and visibility, the acid generated by the above photoacid generator is preferably at least one acid selected from the group consisting of phosphoric acid and sulfonic acid, and sulfonic acid is more preferred. The sulfonic acid represented by Formula S1 or Formula S2 is further preferred.

[化 14]

S1 and S2 in formula formula, R ^S represents an alkyl group, L ^S represents 2 or more carbon atoms, alkylene group, 1 represents 0 or NS, wherein, R ^S system having a case where the halogen atom of the alkyl group, n is 1, X ^S independently represents an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and ms represents an integer of 0 to 5.

The alkyl group in R ^S may have a substituent. Examples of the substituents include halogen atoms, aryl groups, alkoxy groups, and aryloxy groups. The carbon number of the alkyl group in R ^S is preferably 1-20, and more preferably 2-16. L ^S is preferably a C 2-20 alkylene group, a C 2-8 alkyl group is more preferred, and an ethyl group is particularly preferred. X ^{S is} independently preferably an alkyl group, a C 1-20 alkyl group is more preferred, a C 1-8 alkyl group is further preferred, and a methyl group is particularly preferred. The integer of ms is 0 to 3 is better, 0 or 1 is better, and 1 is particularly good.

Examples of the photoacid generator include ionic photoacid generators and nonionic photoacid generators. In addition, as the photoacid generator, from the viewpoint of sensitivity and resolution, it is preferable to include at least one compound selected from the group including an onium salt compound described later and an oxime sulfonate compound described later, and include an oxime sulfonate. The acid salt compound is more preferable.

Examples of nonionic photoacid generators include trichloromethyl s-triazines, diazomethane compounds, amide imine sulfonate compounds, and oxime sulfonate compounds. Among these, a photoacid generator-based oxime sulfonate compound is preferred from the viewpoint of sensitivity, resolution, and adhesion. These photoacid generators can be used alone or in combination of two or more. As specific examples of trichloromethyl s-triazines and diazomethane derivatives, the compounds described in paragraphs 0083 to 0088 of JP-A-2011-221494 can be exemplified.

As the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure, a compound having an oxime sulfonate structure represented by the following formula (B1) is preferred.

[化 15]

In formula (B1), R ²¹ represents an alkyl group or an aryl group, and * represents a bonding site with other atoms or other groups.

The compound having the oxime sulfonate structure represented by the formula (B1) may replace all groups, and the alkyl group in R ²¹ may be linear or branched, or may have a ring structure. Hereinafter, the permissible substituents will be described. The alkyl group of R ²¹ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R ²¹ may also be bridged by an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group (including 7,7-dimethyl-2-oxonorcinol, etc.) The alicyclic group of the formula is preferably substituted with a bicycloalkyl group or a halogen atom. The aryl group of R ²¹ is preferably an aryl group having 6 to 18 carbon atoms, and more preferably a phenyl group or a naphthyl group. The aryl group of R ²¹ may be substituted with one or more groups selected from the group consisting of C 1-4 alkyl groups, alkoxy groups, and halogen atoms.

In addition, as the compound having an oxime sulfonate structure represented by formula (B1), the oxime sulfonate compound described in paragraphs 0078 to 0111 of Japanese Patent Laid-Open No. 2014-85643 or Japanese Patent Laid-Open No. 2015- The compounds described in paragraphs 0080 to 0081 of 151347.

Examples of the ionic photoacid generators include onium salt compounds such as diarylionium salts and triarylammonium salts, and quaternary ammonium salts. Among these, onium salt compounds are preferred, and triaryl alkoxide salts and diaryl phosphonium salts are particularly preferred.

As the ionic photoacid generator, the ionic photoacid generator described in paragraphs 0114 to 0133 of JP-A-2014-85643 can also be preferably used.

One type of photoacid generator may be used alone, or two or more types may be used in combination. From the viewpoint of sensitivity and resolution, the content of the photoacid generator in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass relative to the total solid content of the photosensitive resin composition, and 0.5% by mass ~ 5 mass% is better.

<Basic compound> It is preferable that the photosensitive resin composition of this invention further contains a basic compound. As the basic compound, it can be arbitrarily selected from the basic compounds used in the chemical amplifier. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Examples of these specific examples include the compounds described in paragraphs 0204 to 0207 of Japanese Patent Application Laid-Open No. 2011-221494, and these contents are incorporated in this specification.

Specifically, examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tris -N-pentylamine, diethanolamine, triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, etc. Examples of aromatic amines include aniline, benzylamine, N, N-dimethylaniline, and diphenylamine. Examples of heterocyclic amines include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, and N- Methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, smoke Alkali, nicotinic acid, nicotinamide, quinoline, 8-hydroxyquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholin, 4-methylmorpholine, Cyclohexylmorpholinoethylthiourea (CMTU), 1,5-diazepine [4.3.0] -5-nonene and 1,8-diazepine [5.3.0] -7-undecene, etc. . Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide. Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

These basic compounds may be used alone or in combination of two or more. The content of the basic compound is preferably 0.001% by mass to 5% by mass relative to the total solid content of the photosensitive resin composition, and more preferably 0.005% by mass to 3% by mass.

<Solvent> The photosensitive resin composition of the present invention preferably contains a solvent. In addition, in order to easily form the photosensitive resin layer to be described later, the photosensitive resin composition temporarily contains a solvent to adjust the viscosity of the photosensitive resin composition, and the photosensitive resin composition containing the solvent is coated and dried, so that The photosensitive resin layer is preferably formed. As the solvent used in the present invention, a known solvent can be used. As the solvent, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol mono Alkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl Ether acetates, esters, ketones, amides and lactones, etc. In addition, as specific examples of the solvent, the solvents described in paragraphs 0174 to 0178 of Japanese Patent Laid-Open No. 2011-221494 can also be cited, and such contents are incorporated in this specification.

Further, according to need, benzyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone can be added to the solvent described above , Hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate or Propylene carbonate and other solvents. Only one type of solvent may be used, or two or more types may be used. The solvent that can be used in the present invention can be used alone, and it is more preferable to use two kinds. When two or more solvents are used, for example, a combination of propylene glycol monoalkyl ether acetates and dialkyl ethers, a combination of diacetates and diethylene glycol dialkyl ethers, or esters and butyl The combined use of glycol alkyl ether acetates is preferred.

In addition, as the solvent, a solvent having a boiling point of 130 ° C. or higher and less than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture of these are preferred. Examples of solvents having a boiling point of 130 ° C or higher and less than 160 ° C include propylene glycol monomethyl ether acetate (boiling point 146 ° C), propylene glycol monoethyl ether acetate (boiling point 158 ° C), and propylene glycol methyl-n-butyl ether (boiling point 155) ℃) and propylene glycol methyl-n-propyl ether (boiling point 131 ℃). Examples of solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ether (boiling point 176 ° C), and propylene glycol monomethyl ether propionate (boiling point 160 ° C) , Dipropylene glycol methyl ether acetate (boiling point 213 ℃), 3-methoxybutyl ether acetate (boiling point 171 ℃), diethylene glycol diethyl ether (boiling point 189 ℃), diethylene glycol dimethyl ether ( Boiling point 162 ℃), propylene glycol diacetate (boiling point 190 ℃), diethylene glycol monoethyl ether acetate (boiling point 220 ℃), dipropylene glycol dimethyl ether (boiling point 175 ℃) and 1,3-butanediol di Acetate (boiling point 232 ° C).

The content of the solvent when coating the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass, and more preferably 100 parts by mass to 900 parts by mass relative to 100 parts by mass of the total solid content in the photosensitive resin composition. . In addition, the content of the solvent in the photosensitive resin layer described later is preferably 2% by mass or less, more preferably 1% by mass or less, and further preferably 0.5% by mass or less relative to the total mass of the photosensitive resin layer.

<Other Additives> The photosensitive resin composition of the present invention may contain known additives in addition to the above-mentioned respective components such as a specific latent dye, a specific polymer, and a photoacid generator.

-Plasticizer- The photosensitive resin composition of the present invention may contain a plasticizer for the purpose of improving plasticity. The weight average molecular weight of the plasticizer is preferably less than the weight average molecular weight of the specific polymer. From the viewpoint of imparting plasticity, the weight average molecular weight of the plasticizer is preferably 500 or more and less than 10,000, preferably 700 or more and less than 5,000, and more preferably 800 or more and less than 4,000. The plasticizer is not particularly limited as long as it is compatible with a specific polymer and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkoxyl group in the molecule. The alkyleneoxy group contained in the plasticizer preferably has the following structure.

[Chem 16]

In the above formula, R is an alkyl group having 2 to 8 carbon atoms, n represents an integer of 1 to 50, and * represents a bonding site with another atom.

In addition, for example, even if it is an alkoxylated compound having the above structure (referred to as “compound X”), compared with the chemically amplified positive photosensitive resin composition formed without compound X, compound X and specific If the plasticity of the chemically amplified positive photosensitive resin composition obtained by the latent pigment, the specific polymer, and the photoacid generator is not improved, it is not suitable as a plasticizer in the present invention. For example, an arbitrarily added surfactant is usually not used in an amount that imparts plasticity to the photosensitive resin composition, so it is not suitable as a plasticizer in this specification.

Examples of the plasticizer include compounds having the following structures, but they are not limited thereto.

[化 17]

From the viewpoint of the adhesiveness of the photosensitive resin layer formed by the photosensitive resin composition, the content of the plasticizer is preferably 1% by mass to 50% by mass relative to the total solid content of the photosensitive resin composition. 2% by mass to 20% by mass is better. The photosensitive resin composition may contain only one kind of plasticizer, or may contain two or more kinds.

-Sensitizer- The photosensitive resin composition of this invention can also contain a sensitizer. The sensitizer absorbs actinic rays and becomes an electronically excited state. The sensitizer in the electronically excited state comes into contact with the photoacid generator to produce electron transfer, energy transfer and heat generation. By this, the photoacid generator causes chemical changes to decompose, thereby generating acids. By containing a sensitizer, exposure sensitivity can be improved.

As a sensitizer, it is selected from the group consisting of anthracene derivatives, acridone derivatives, 9-oxathioxanthene derivatives, coumarin derivatives, basic styrene derivatives and stilbene benzene derivatives The compounds in are preferred, and anthracene derivatives are more preferred. As anthracene derivatives, anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromo Anthracene, 9-chloroanthracene, 9,10-dibromoanthracene, 2-ethylanthracene or 9,10-dimethoxyanthracene is preferred.

Examples of the sensitizer include compounds described in paragraphs 0139 to 0141 of International Publication No. 2015/093271.

The content of the sensitizer is preferably 0% by mass to 10% by mass relative to the total solid content of the photosensitive resin composition, and more preferably 0.1% by mass to 10% by mass.

-Heterocyclic Compound- The photosensitive resin composition of the present invention can contain a heterocyclic compound. The heterocyclic compound in the present invention is not particularly limited. For example, a compound having an epoxy group or oxetanyl group in the molecule described below, a heterocyclic compound containing an alkoxymethyl group, various other cyclic ethers, cyclic esters (lactones), etc. can be added Nitrogen-containing monomers such as oxygen monomers, cyclic amines, oxazolines, and heterocyclic monomers having d electrons such as silicon, sulfur, and phosphorus.

When a heterocyclic compound is added, the content of the heterocyclic compound in the photosensitive resin composition is preferably 0.01% by mass to 50% by mass relative to the total solid content of the photosensitive resin composition, and 0.1% by mass to 10% by mass is more preferable, and 1% to 5% by mass is even more preferable. Within the above range, it is preferable from the viewpoint of adhesion and etching resistance. Only one kind of heterocyclic compound can be used, or two or more kinds can be used in combination.

Specific examples of the compound having an epoxy group in the molecule include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, Aliphatic epoxy resin, etc.

The compound having an epoxy group in the molecule can be obtained as a commercially available product. For example, JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Corporation.), JER157S65 (manufactured by Mitsubishi Chemical Holdings Corporation), etc., and the commercially available products described in paragraph 0189 of Japanese Patent Laid-Open No. 2011-221494, etc. may be mentioned. As other commercially available products, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (above, manufactured by ADEKA CORPORATION), NC-2000, NC-3000, NC-7300, XD -1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA CORPORATION), DENACOL EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411 , EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX -832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203 , DLC-204, DLC-205, DLC-206, DLC-301, DLC-402, EX-111, EX-121, EX-141, EX-145, EX-146, EX-147, EX-171, EX -192 (above manufactured by Nagase Chemtex Corporation), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (above, manufactured by NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD.) CELLOXIDE 2021P , 2081, 2000, 3000, EHPE3150, EPOLEAD GT400, SERUBINASU B0134, B0177 (made by Daicel Corporation), etc. The compound having an epoxy group in the molecule may be used alone or in combination of two or more.

Among the compounds having an epoxy group in the molecule, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin can be more preferably mentioned. Good examples include aliphatic epoxy resins.

As specific examples of compounds having oxetanyl groups in the molecule, Aron Oxetane OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ, PNOX ( Above, manufactured by TOAGOSEI CO., LTD.).

In addition, the compound containing oxetanyl group is preferably used alone or in combination with an epoxy group-containing compound.

In the photosensitive resin composition of the present invention, a compound having an epoxy group in the heterocyclic compound is preferred from the viewpoint of etching resistance and line width stability of the obtained pattern.

-Alkoxysilane compound- The photosensitive resin composition of the present invention may contain an alkoxysilane compound. As the alkoxysilane compound, a trialkoxysilane compound is preferably mentioned. Examples of alkoxysilane compounds include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, and γ- Glycidoxypropylalkyldialkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ- Chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane. Among these, γ-glycidoxypropyltrialkoxysilane or γ-methacryloxypropyltrialkoxysilane is better, and γ-glycidoxypropyltrialkoxysilane For further preference, 3-glycidoxypropyltrimethoxysilane is particularly preferred. These can be used alone or in combination of two or more. The content of the alkoxysilane compound is preferably 0.1% by mass to 30% by mass relative to the total solid content of the photosensitive resin composition, and more preferably 0.5% by mass to 20% by mass.

-Surfactant- From the viewpoint of film thickness uniformity, the photosensitive resin composition of the present invention preferably contains a surfactant. As the surfactant, any of anionic, cationic, nonionic (Nonionic), or amphoteric can be used, but a preferred surfactant-based nonionic surfactant. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, polysilicone, Fluorine surfactant. In addition, the following product names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by JEMCO CORPORATION), MEGAFACE (DIC Corporation Co., Ltd.), FLUORAD (manufactured by Sumitomo 3M Limited), ASAHI GUARD, SURFLON (manufactured by ASAHI GLASS CO., LTD.), POLYFOX (manufactured by OMNOVA Solutions Inc.) and SH-8400 (manufactured by Dow Corning Toray Co., Ltd.) ) And other series. In addition, as the surfactant, the structural unit A and the structural unit B represented by the following formula I-1 are included. As a preferable example, gel permeation chromatography can be given when tetrahydrofuran (THF) is used as a solvent. The polystyrene-equivalent weight average molecular weight (Mw) measured by the method is a copolymer of 1,000 or more and 10,000 or less.

[Chemical 18]

In the formula (I-1), R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or 1 or more carbon atoms And the alkyl group of 4 or less, L represents an alkylene group having a carbon number of 3 or more and 6 or less, p and q represent the mass percentage of the polymerization ratio, p represents a value of 10% by mass and more than 80% by mass, q represents 20 Values of more than 90% by mass to 90% by mass, r represents an integer of 1 or more and 18 or less, s represents an integer of 1 or more and 10 or less, and * represents a bonding site with another structure.

L is preferably a branched alkylene group represented by the following formula (I-2). R ⁴⁰⁵ in formula (I-2) represents an alkyl group having a carbon number of 1 or more and 4 or less, and from the viewpoint of compatibility and wettability with respect to the coated surface, an alkyl group having a carbon number of 1 or more and 3 or less Preferably, an alkyl group having 2 or 3 carbon atoms is more preferable. The sum of p and q (p + q) is preferably p + q = 100, that is, 100% by mass.

[Chem 19]

The weight average molecular weight (Mw) of the copolymer is preferably 1,500 or more and 5,000 or less.

Moreover, the surfactant described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Patent Laid-Open No. 2009-237362 can also be used.

One type of surfactant may be used alone, or two or more types may be used in combination. The added amount of the surfactant is preferably 10% by mass or less relative to the total solid content of the photosensitive resin composition, 0.001% by mass to 10% by mass is more preferable, and 0.01% by mass to 3% by mass is even more preferable.

-Other components- The photosensitive resin composition of the present invention can also include metal oxide particles, antioxidants, dispersants, acid multiplication agents, development accelerators, conductive fibers, colorants, thermal radical polymerization initiators, Well-known additives such as thermal acid generators, ultraviolet absorbers, tackifiers and organic or inorganic Shendian preventives. The preferred aspects of other components are described in paragraphs 0165 to 0184 of Japanese Patent Laid-Open No. 2014-85643, and the contents of this bulletin are incorporated in this specification.

(Photosensitive transfer material) The photosensitive transfer material of the present invention has a temporary support and a photosensitive resin layer. The photosensitive resin layer contains: a polymer containing a group having a carboxylic acid group protected by an acid-decomposable group Constituent unit; photoacid generator; and latent pigment, the pKa of the conjugated acid is less than 4.5 or the compound that does not form the conjugate acid and the color absorption wavelength range is 400 nm to 780 nm. The maximum absorption wavelength is 500 nm or more and has The temporary support and the photosensitive resin layer, the photosensitive resin layer preferably containing the photosensitive resin composition of the present invention.

FIG. 1 schematically shows an example of the layer structure of the photosensitive transfer material of the present invention. In the photosensitive transfer material 100 shown in FIG. 1, a temporary support 10, an intermediate layer 12, a photosensitive resin layer 14, and a cover film 16 are sequentially stacked. The photosensitive resin layer 14 contains: a polymer, a constituent unit having a group having a carboxylic acid group protected by an acid-decomposable group; a photoacid generator; and a latent pigment, the pKa of the conjugate acid is less than 4.5 or no conjugation is formed The acid compound has a maximum absorption wavelength of 500 nm or more in the wavelength range of 400 nm to 780 nm at the time of color development. Hereinafter, constituent materials and the like of the photosensitive transfer material of the present invention will be described. In addition, the above-mentioned configuration in the present invention may be abbreviated as the following in this specification. Sometimes a polymer containing a structural unit having an acid group protected by an acid-decomposable group is called a "specific polymer". The above-mentioned photosensitive resin layer is a positive photosensitive resin layer, and is sometimes referred to as a "positive photosensitive resin layer".

<Temporary Support> The photosensitive transfer material of the present invention has a temporary support. The temporary support supports the photosensitive resin layer and can be peeled off. From the viewpoint that the photosensitive resin layer can be exposed via the temporary support when the photosensitive resin layer is exposed by the pattern, it is preferable that the temporary support used in the present invention has translucency. Transmittance means that the transmittance of the main wavelength of light used for pattern exposure is 50% or more. From the viewpoint of improving the exposure sensitivity, the transmittance of the main wavelength of light used for pattern exposure is preferably 60% or more , More than 70% is better. As a method for measuring the transmittance, a method using MCPD Series manufactured by Otsuka Electronics Co., Ltd. can be mentioned. Examples of the temporary support include glass substrates, resin films, and paper. From the viewpoint of strength and flexibility, resin films are particularly preferred. Examples of the resin film include polyethylene terephthalate film, cellulose triacetate film, polystyrene film, and polycarbonate film. Among them, biaxially stretched polyethylene terephthalate film is particularly preferred.

The thickness of the temporary support is not particularly limited, and the range of 5 μm to 200 μm is preferable, and the range of 10 μm to 150 μm is more preferable from the viewpoint of ease of handling and versatility. The thickness of the temporary support may be selected according to the material from the viewpoint of strength as a support, flexibility required for bonding to a circuit wiring forming substrate, and light transmittance required in the initial exposure step, etc. .

A preferred form of the temporary support is described in paragraphs 0017 to 0018 of Japanese Patent Application Laid-Open No. 2014-85643, and the contents of this publication are incorporated in this specification.

<Photosensitive resin layer> The photosensitive transfer material of the present invention has a photosensitive resin layer, and the above-mentioned photosensitive resin layer contains: a polymer, a structural unit polymer having a group having a carboxylic acid group protected by an acid-decomposable group; Photo-acid generator; and potential pigments, the pKa of the conjugate acid is less than 4.5 or the compound that does not form the conjugate acid and the color absorption wavelength range is 400 nm to 780 nm. The maximum absorption wavelength is more than 500 nm. The photosensitive resin layer is preferably a layer formed of the photosensitive resin composition of the present invention. Moreover, it is preferable that the said photosensitive resin layer contains the photosensitive resin composition of this invention. In addition, the photosensitive resin layer in the present invention is a positive photosensitive resin layer, and a chemically amplified positive photosensitive resin layer is preferred. In a photoacid generator such as an onium salt or an oxime sulfonate compound described later, the deprotection of the acid generated by induction of active radiation (actinic rays) from the protected acid group in the above-mentioned specific polymer functions as a catalyst As a result, the acid generated by the action of a light quantum contributes to most deprotection reactions. The quantum yield is greater than 1 and becomes a large value such as a power of 10. As a result of the so-called chemical amplification, high sensitivity is obtained. On the other hand, when a quinone dimer compound is used as a photoacid generator induced by active radiation, a carboxyl group is generated by a chain-type photochemical reaction, but the quantum yield must be 1 or less, and does not meet the chemical amplification type .

In the above-mentioned photosensitive resin layer, a polymer including a structural unit having a group having a carboxylic acid group protected by an acid-decomposable group, a photoacid generator, and a conjugate acid have a pKa of less than 4.5 or a compound that does not form a conjugate acid The maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development is 500 nm or more. The meaning of the latent pigment is the same as that of the above-mentioned photosensitive resin composition, including the group having a carboxylic acid group protected by an acid-decomposable group. The polymer with the constituent unit of the group, photoacid generator and conjugate acid have a pKa of less than 4.5 or a compound that does not form a conjugate acid and the color range is 400 nm to 780 nm. The maximum absorption wavelength is above 500 nm. The meanings of the pigments are the same, and the preferred forms are also the same. In addition, the photosensitive resin layer may preferably contain each component in the photosensitive resin composition other than the solvent. In addition, in the photosensitive resin layer, the preferable content of each component with respect to the total mass of the photosensitive resin layer is also the same as the total solid content of the photosensitive resin composition in the photosensitive resin composition. The preferable content of each component is the same.

-Thickness of photosensitive resin layer- The thickness of the photosensitive resin layer is preferably 0.5 μm to 20 μm. If the thickness of the photosensitive resin layer is 20 μm or less, the resolution of the obtained pattern is good, and if it is 0.5 μm or more, it is preferable from the viewpoint of pattern linearity. As the thickness of the photosensitive resin layer, 0.8 μm to 15 μm is more preferable, and 1.0 μm to 10 μm is particularly preferable.

-Method of forming photosensitive resin layer- The components and the solvent are mixed in a specific ratio and by any method, and are stirred and dissolved to prepare a photosensitive resin composition for forming a photosensitive resin layer. For example, it is also possible to prepare each composition by separately dissolving each component as a solution previously dissolved in a solvent, and then mixing the obtained solution at a specific ratio. After filtering the composition prepared as above using a filter with a pore size of 0.2 μm, etc., it can also be used.

By applying the photosensitive resin composition to the temporary support and drying it, the photosensitive transfer material of the present invention having the photosensitive resin layer on the temporary support can be obtained. The coating method is not particularly limited, and can be applied by a well-known method such as slit coating, spin coating, curtain coating, and inkjet coating. In addition, a photosensitive resin layer can also be coated on the temporary support having the other layer described later on the temporary support and the laminate of the other layer.

<Other Layers> The photosensitive transfer material of the present invention may have a layer other than the above-mentioned photosensitive resin layer (hereinafter, sometimes referred to as "other layer"). Examples of other layers include a contrast enhancement layer, an intermediate layer, a cover film, and a thermoplastic resin layer.

<Contrast Enhancement Layer> The photosensitive transfer material of the present invention can have a contrast enhancement layer in addition to the above-mentioned photosensitive resin layer. Contrast Enhancement Layer (CEL) contains a material that absorbs a large amount of light relative to the exposure wavelength before exposure but gradually decreases with exposure, that is, a material with high light transmittance (called a photobleaching pigment component) Layer. As the photobleaching pigment component, diazonium salts, stilbene salts, arylnitroso salts and the like are known. As the film-forming component, a phenol resin or the like can be used. In addition, as the contrast enhancement layer, paragraphs 0004 to 0051 of Japanese Patent Laid-Open No. 6-97065, paragraphs 0012 to 0055 of Japanese Patent Laid-Open No. 6-332167, manual of photosensitive resin, and photosensitive resin conference (Conference) Editor, Industrial Investigation Association (1989), Photosensitive Resin and Technology, Shan Gang, Yongsong Editor, NIKKAN KOGYO SHIMBUN, LTD. (1988).

<Intermediate layer> The intermediate layer can be provided for the purpose of coating a plurality of layers on the above-mentioned photosensitive resin layer and for the purpose of preventing mixing of components during storage after coating. As the intermediate layer, the intermediate layers described in Japanese Patent Laid-Open No. 2005-259138 0084-0087 can be used. The intermediate layer is preferably dispersed or dissolved in water or an alkaline aqueous solution. Examples of materials used for the intermediate layer include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, and vinyl ether-based resins. , Polyamide resin and copolymers of such resins. Among them, particularly preferred is a combination of polyvinyl alcohol and polyvinylpyrrolidone.

<Thermoplastic resin layer, cover film, etc.> The photosensitive transfer material of this invention can also have a temporary support, a thermoplastic resin layer, and a photosensitive resin layer in this order, for example. In addition, a cover film may be provided for the purpose of protecting the photosensitive resin layer. The preferred aspect of the thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Laid-Open No. 2014-85643, and the preferred aspect of the other layer is 0194 of Japanese Patent Laid-Open No. 2014-85643 From paragraphs to 0196, the contents of this bulletin are incorporated in this specification.

When the photosensitive transfer material of the present invention has other layers such as a thermoplastic resin layer, it can be produced according to the method for producing a photosensitive transfer material described in paragraphs 094 to 0098 of JP-A 2006-259138. For example, when producing the photosensitive transfer material of the present invention having a thermoplastic resin layer and an intermediate layer, a solution of thermoplastic organic polymer and additives dissolved in the temporary support is applied (coating solution for thermoplastic resin layer) ), And after drying to provide a thermoplastic resin layer, apply a preparation liquid (coating liquid for intermediate layer) prepared by heating the resin and additives to a solvent that does not dissolve the thermoplastic resin layer on the obtained thermoplastic resin layer, and dry And build up the middle layer. The photosensitive resin composition of the present invention prepared by using a solvent that does not dissolve the intermediate layer is further coated on the formed intermediate layer, and dried to laminate the photosensitive resin layer, thereby making it possible to produce the photosensitive resin layer of the present invention better Photosensitive transfer material.

(Method of Manufacturing Circuit Wiring) The first embodiment of the method of manufacturing circuit wiring using the photosensitive transfer material of the present invention will be described. The first embodiment of the method for manufacturing a circuit wiring includes, in order: a step of attaching the above-mentioned photosensitive resin layer of the photosensitive transfer material of the present invention to the above-mentioned substrate with respect to the substrate (lamination step); The step of performing pattern exposure on the photosensitive resin layer of the photosensitive transfer material after the step of laminating (exposure step); the step of developing the photosensitive resin layer after the exposure step to form a pattern (development step ); And the step of etching the substrate in the area where the pattern is not configured (etching step). The substrate in the first embodiment of the method for manufacturing circuit wiring may be a substrate provided with a desired conductive layer or the like on a substrate such as glass, silicon, or thin film. According to the first embodiment of the manufacturing method of circuit wiring, a fine pattern can be formed on the surface of the substrate.

The second embodiment of the method for manufacturing a circuit wiring includes, in order: a plurality of conductive layers including a base material and a first conductive layer and a second conductive layer having different constituent materials from each other, on the surface of the base material The order in which the surfaces are away from each other is to make the photosensitive resin layer of the photosensitive transfer material of the present invention and the first conductive layer to the outermost layer, that is, the substrate on which the first conductive layer and the second conductive layer are stacked The bonding step of contacting and bonding; the first exposure step of pattern exposing the temporary support of the photosensitive transfer material after the bonding step through the photosensitive resin layer; after the first exposure step After the temporary support is peeled off, the photosensitive resin layer after the first exposure step is developed to form a first pattern of the first development step; in the area where the first pattern is not arranged, the above A first etching step of etching the first conductive layer and the second conductive layer at least among the plurality of conductive layers; the first pattern after the first etching step is combined with A second exposure step of pattern exposure for patterns having different first patterns; a second development step of developing the first pattern after the second exposure step to form a second pattern; and when the second pattern is not arranged In the plurality of conductive layers in the region, at least a second etching step is performed to etch the first conductive layer. As the second embodiment described above, it is possible to refer to International Publication No. 2006/190405, which is incorporated in this specification.

The method for manufacturing circuit wiring of the present invention can be used as a method for manufacturing circuit wiring for touch panels or touch panel display devices. Hereinafter, according to the second embodiment, the details of each step will be described.

<Lamination Step> FIG. 2 (a) schematically shows an example of the bonding step. First, in the bonding step, a plurality of conductive layers including the base material 22 and the first conductive layer 24 and the second conductive layer 26 having different constituent materials are separated from the surface of the base material 22 on the surface of the base material 22 Of the photosensitive transfer material 100 of the present invention described above with respect to the substrate (circuit wiring forming substrate) 20 on which the first conductive layer 24 and the second conductive layer 26 are stacked as the outermost layer The sexual resin layer 14 is in contact with and bonded to the first conductive layer 24. In addition, the bonding of the circuit wiring forming substrate and the photosensitive transfer material is sometimes referred to as "transfer" or "lamination".

As shown in FIG. 1, when the cover film 16 is provided on the positive photosensitive resin layer 14 of the photosensitive transfer material 100, the cover film 16 is removed from the photosensitive transfer material 100 (positive photosensitive resin layer 14) After that, the positive photosensitive resin layer 14 of the photosensitive transfer material 100 is brought into contact with the first conductive layer 24 to be bonded. When laminating (transferring) the photosensitive transfer material to the first conductive layer, the positive photosensitive resin layer side of the photosensitive transfer material is superimposed on the first conductive layer, and is pressed and heated by a roller or the like It is better to carry out lamination. At the time of bonding, a known laminator such as a laminator, a vacuum laminator, and an automatic cutting laminator that can further improve productivity can be used. In the case where the substrate of the circuit wiring forming substrate is a resin film, roll-to-roll bonding can also be performed.

[Substrate] For a substrate in which a plurality of conductive layers are laminated on a substrate, the substrate is preferably a glass substrate or a film substrate, and the film substrate is more preferable. When the circuit wiring manufacturing method of the present invention is a circuit wiring for a touch panel, the base sheet resin composition is particularly preferred. In addition, the base material is preferably transparent. The refractive index of the substrate is preferably 1.50 to 1.52. The base material may be composed of a light-transmitting base material such as a glass base material, and tempered glass typified by Corning Incorporated GORILLA glass can also be used. In addition, as the transparent substrate, materials used in Japanese Patent Laid-Open No. 2010-86684, Japanese Patent Laid-Open No. 2010-152809, and Japanese Patent Laid-Open No. 2010-257492 can be preferably used. When a film substrate is used as the substrate, it is better to use a substrate without optical strain and a substrate with high transparency. Specific materials include polyethylene terephthalate (PET) and poly Ethylene naphthalate, polycarbonate, triacetyl cellulose, cycloolefin polymer.

[Conductive layer] As the plurality of conductive layers formed on the base material, any conductive layer used for ordinary circuit wiring or touch panel wiring can be mentioned. Examples of the material of the conductive layer include metals and metal oxides. Examples of metal oxides include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO ₂ . Examples of metals include Al, Zn, Cu, Fe, Ni, Cr, and Mo.

In the manufacturing method of the circuit wiring of the present invention, it is preferable that at least one of the conductive layers contains a metal oxide. As the conductive layer, the electrode pattern corresponding to the sensor used in the visual recognition part of the electrostatic capacitance type touch panel or the wiring of the edge extraction part is preferable.

[Circuit wiring formation substrate] This is a substrate having a conductive layer on the surface of the base material. The circuit wiring is formed by patterning the conductive layer. In this example, it is preferable to provide a plurality of conductive layers such as metal oxide or metal on a film substrate such as PET.

<Exposure Step (First Exposure Step)> The exposure step is performed in the first embodiment described above, and the first exposure step is performed in the second embodiment described above. An example of the exposure step (first exposure step) is schematically shown in FIG. 2 (b). In the exposure step (first exposure step), the positive photosensitive resin layer 14 is pattern-exposed via the temporary support 12 of the photosensitive transfer material after the bonding step.

As examples of the exposure step, development step, and other steps in the present invention, the method described in paragraphs 0035 to 0051 of Japanese Patent Laid-Open No. 2006-23696 can also be preferably used in the present invention.

For example, a mask 30 having a specific pattern is disposed above the photosensitive transfer material 100 (the side opposite to the side in contact with the first conductive layer 24) disposed on the first conductive layer 24, and then passes The mask 30 is exposed by ultraviolet rays from above the mask. The detailed arrangement and specific dimensions of the pattern in the present invention are not particularly limited. From the viewpoint of improving the display quality of a display device equipped with an input device (such as a touch panel) and minimizing the area occupied by the extracted wiring, at least a part of the pattern (especially the electrode pattern of the touch panel and the part where the wiring is extracted) is 100 μm The following thin wires are preferred, and 70 μm or less is further preferred. The input device has circuit wiring manufactured by the method for manufacturing circuit wiring of the present invention. Among them, as a light source for exposure, if light that can irradiate the exposed photosensitive transfer material can be dissolved in the wavelength region of the developer (for example, 365 nm, 405 nm, etc.), it can be appropriately selected and used . Specifically, an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, etc. are mentioned. The exposure amount is preferably about 5 mJ / cm ² to 200 mJ / cm ² , and more preferably about 10 mJ / cm ² to 100 mJ / cm ² . In addition, for the purpose of improving the rectangularity and linearity of the pattern after exposure, heat treatment before development is also preferable. The step called so-called PEB (Post Exposure Bake) can reduce the roughness of the pattern edge based on the standing wave generated in the photosensitive resin layer during exposure.

In addition, the pattern exposure may be performed after the temporary support is peeled off from the photosensitive resin layer, or it may be exposed through the temporary support before the temporary support is peeled off, and then the temporary support is peeled off. In order to prevent contamination of the mask based on the contact between the photosensitive resin layer and the mask or to avoid the influence of foreign objects attached to the mask on exposure, it is preferable to perform exposure without peeling off the temporary support. In addition, the pattern exposure may be exposure through a mask, or digital exposure using a laser or the like.

<Development Step (First Development Step)> The development step is performed in the first embodiment described above, and the first development step is performed in the second embodiment described above. An example of the development step (first development step) is schematically shown in FIG. 2 (c). In the development step (first development step), after the temporary support 12 is peeled off from the positive photosensitive resin layer 14 after the exposure step (first exposure step), the positive sensitivity after the exposure step (first exposure step) The resin layer 14 is developed to form the first pattern 14A.

The developing step (first developing step) is a step of forming a pattern (first pattern) by developing the positive photosensitive resin layer exposed to the pattern. The development of the positive photosensitive resin layer for pattern exposure can be performed using a developer. The developer is not particularly limited as long as it can remove the exposed portion of the positive photosensitive resin layer. For example, a known developer such as the developer described in Japanese Patent Application Laid-Open No. 5-72724 can be used. In addition, the developer is preferably a developer that can perform a dissolution-type development operation on the exposed portion of the positive photosensitive resin layer. For example, an alkaline aqueous developer containing a compound having a pKa = 7 to 13 at a concentration of 0.05 mol / L (liter) to 5 mol / L is preferred. The developer may also contain an organic solvent having a miscibility with water, a surfactant, and the like. Examples of the developer that can be preferably used in the present invention include the developer described in paragraph 0194 of International Publication No. 2015/093271.

The development method is not particularly limited, and may be any of spin immersion development, shower development, shower and rotary development, and immersion development. Among them, if spray development is described, the exposed portion of the positive photosensitive resin layer after exposure is sprayed into the developer by spraying, thereby removing the exposed portion. Furthermore, it is preferable to remove the developing residue while wiping with a brush or the like by spraying a cleaning agent or the like after development. The liquid temperature of the developer is preferably 20 ° C to 40 ° C.

Moreover, you may have the baking process after heat-processing the pattern containing the positive photosensitive resin layer obtained by development. Post-baking heating is preferably performed in an environment of 8.1 kPa to 121.6 kPa, and more preferably in an environment of 506.6 kPa or more. On the other hand, it is better to perform in an environment of 1114.6 kPa or less, and particularly preferably in an environment of 101.3 kPa or less. The post-baking temperature is preferably 80 ° C to 250 ° C, more preferably 110 ° C to 170 ° C, and particularly preferably 130 ° C to 150 ° C. The post-baking time is preferably from 1 minute to 30 minutes, more preferably from 2 minutes to 10 minutes, and particularly preferably from 2 minutes to 4 minutes. The post-baking can also be carried out in an air environment or a nitrogen replacement environment.

The manufacturing method of the circuit wiring of the present invention may also have other steps such as a post-exposure step.

<Etching Step (First Etching Step)> In the above-mentioned first embodiment, the etching step is performed, and in the above-described second embodiment, the first etching step is performed. An example of the etching step (first etching step) is schematically shown in FIG. 2 (d). In the etching step (first etching step), at least the first conductive layer 24 and the second conductive layer 26 among the plurality of conductive layers in the region where the first pattern 14A is not disposed are subjected to an etching process. By etching, the first conductive layer 24A and the second conductive layer 26A having the same pattern are formed.

Regarding the etching of the conductive layer, it is possible to apply etching by a known method such as a method described in paragraphs 0048 to 0054 of JP-A-2010-152155, etc., and a known plasma etching method based on dry etching.

For example, as a method of etching, a wet etching method that is generally performed and immersed in an etchant is mentioned. The etching solution used for wet etching may be an acid solution or an alkaline solution appropriately selected according to the object to be etched. Examples of the acid type etching solution include aqueous solutions of individual acid components such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid, and mixed aqueous solutions of acid components and salts such as ferric chloride, ammonium fluoride, and potassium permanganate. As the acid component, a combination of a plurality of acid components can be used. Examples of alkaline type etching solutions include aqueous solutions of alkaline components such as sodium hydroxide, potassium hydroxide, ammonia, organic amines, and tetramethylammonium hydroxide, alkaline components, and high manganese. Mixed aqueous solutions of salts such as potassium acid. As the alkaline component, a combination of plural alkaline components can be used.

The temperature of the etching solution is not particularly limited, but it is preferably 45 ° C or lower. It is preferable that the first pattern used as an etching mask (etching pattern) in the present invention exhibit particularly excellent resistance to acidic and alkaline etching solutions in a temperature range of 45 ° C. or lower. Therefore, peeling of the positive photosensitive resin layer in the etching step is prevented, and the portion where the positive photosensitive resin layer does not exist is selectively etched.

After the etching step, in order to prevent contamination of the production line, a cleaning step and a drying step can also be performed as needed. For the cleaning step, for example, the substrate is washed with pure water at normal temperature for 10 seconds to 300 seconds. For the drying step, for example, using a blast, the blast pressure is appropriately adjusted (about 0.1 kg / cm ² to 5 kg / cm ² ) To dry.

<Second exposure step> The second exposure step is performed in the second embodiment described above. FIG. 2 (e) schematically shows an example of the second exposure step. After the first etching step, the first pattern 14A after the first etching step is pattern exposed in a pattern different from the first pattern.

In the second exposure step, for the first pattern remaining on the first conductive layer, a portion corresponding to at least a portion of the first conductive layer to be removed in the second development step described later is exposed. Regarding the pattern exposure in the second exposure step, a mask 40 having a pattern different from the mask 30 used in the first exposure step is used, and other than that, the same method as the pattern exposure in the first exposure step can be applied.

<Second development step> The second development step is performed in the second embodiment described above. FIG. 2 (f) schematically shows an example of the second development step. In the second development step, the first pattern 14A after the second exposure step is developed to form the second pattern 14B. By developing, the exposed portion of the first pattern in the second exposure step is removed. In the second development step, the same method as the development in the first development step can be applied.

<Second etching step> In the second embodiment described above, the second exposure step is performed. FIG. 2 (g) schematically shows an example of the second etching step. In the second etching step, at least the first conductive layer 24A among the plurality of conductive layers in the area where the second pattern 14B is not disposed is subjected to an etching process.

For the etching in the second etching step, the same method as the etching in the first etching step can be used except that the etching solution corresponding to the conductive layer to be removed by etching is selected. In the second etching step, it is preferable to selectively etch fewer conductive layers than in the first etching step according to the desired pattern. For example, as shown in FIG. 2, an etching solution that selectively etches the first conductive layer 24B in an area where the positive photosensitive resin layer is not disposed is used to etch the first conductive layer and the second conductive layer The patterns of the layers are different. After the second etching step is completed, circuit wiring including at least two patterns of the conductive layer 24B and the conductive layer 26A is formed.

<Positive Photosensitive Resin Layer Removal Step> An example of the positive photosensitive resin layer removal step is schematically shown in FIG. 2 (h). After the second etching step is completed, the second pattern 14B remains on a part of the first conductive layer 24B. If the positive photosensitive resin layer is not required, all remaining positive photosensitive resin layers 14B may be removed.

The method for removing the remaining positive photosensitive resin layer is not particularly limited, but a method of removing by means of falsification can be mentioned. Examples of a method for removing the positive photosensitive resin layer include, for example, immersing the positive photosensitive resin layer in a stripping solution that is stirred at preferably 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. The method of 1 minute to 30 minutes for the substrate.

Examples of the stripping solution include inorganic alkaline components such as sodium hydroxide and potassium hydroxide, or organic alkaline components such as first-level amine, second-level amine, third-level amine, and fourth-level ammonium salt dissolved in water. , Dimethyl sulfoxide, N-methylpyrrolidone or the stripping solution of these mixed solutions. It is also possible to use a peeling liquid and peeling by spraying method, spraying method, spin immersion method and the like.

The method for manufacturing circuit wiring of the present invention may also include any other steps. For example, the following steps may be mentioned, but they are not limited to these steps.

<Procedure for bonding protective film> In the second embodiment described above, after the first etching step and before the second exposure step, a protective film (not shown) may be bonded to the first pattern with translucency Steps. In this case, in the second exposure step, the first pattern is subjected to pattern exposure via the protective film, and after the second exposure step, after the protective film is peeled off from the first pattern, the second development step is preferably performed.

<Step of reducing visible light reflectance> The method of manufacturing a circuit wiring of the present invention can include a step of performing a process of reducing a part of a plurality of conductive layers or all visible light reflectance on a substrate. As the treatment for reducing the reflectance of visible rays, oxidation treatment and the like can be mentioned. For example, copper is oxidized to copper oxide and blackened, thereby reducing visible light reflectance. Regarding a preferable aspect of the treatment for reducing the reflectance of visible light, paragraphs 0017 to 0025 of JP-A-2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of JP-A 2013-206315 It is stated in the paragraph that the contents of this bulletin are incorporated in this specification.

<Step of forming a new conductive layer on the insulating film> The manufacturing method of the circuit wiring of the present invention includes the step of forming an insulating film on the formed circuit wiring and the step of forming a new conductive layer on the insulating film Better. With this structure, the second electrode pattern can be formed while being insulated from the first electrode pattern. There is no particular limitation on the step of forming an absolute film, and a known method of forming a permanent film can be mentioned. In addition, it is also possible to use a photosensitive material having an insulative property and to form an insulative film in a desired pattern by photolithography. There is no particular limitation on the step of forming a new conductive layer on the insulating film. It is also possible to use a photosensitive material having conductivity, and to form a new conductive layer in a desired pattern by photolithography.

Also, referring to the description of FIG. 2, the case where a circuit wiring having two different patterns is formed on a circuit wiring forming substrate provided with two conductive layers has been described, but a substrate to which the circuit wiring manufacturing method of the present invention is applied The number of conductive layers is not limited to two, and a circuit wiring forming substrate using three or more conductive layers is stacked, and the combination of the exposure step, the development step, and the etching step described above is performed three or more times, which can also be different from each other. The circuit wiring pattern forms three or more conductive layers.

Also, not shown in FIG. 2, but in the method of manufacturing a circuit wiring of the present invention, the two surfaces of the substrate have a plurality of conductive layers, and the conductive layers formed on the two surfaces of the substrate are sequentially or simultaneously It is also preferable to form a circuit. With this structure, it is possible to form a circuit wiring for a touch panel in which the first conductive pattern is formed on one surface of the substrate and the second conductive pattern is formed on the other surface. In addition, it is also preferable to form the circuit wiring for a touch panel having such a structure from both sides of the base material in a roll-to-roll manner.

(Circuit wiring and circuit board) The circuit wiring of this invention is the circuit wiring manufactured by the manufacturing method of the circuit wiring of this invention. The circuit board of the present invention is a board having circuit wiring manufactured by the method of manufacturing a circuit wiring of the present invention. The use of the circuit board of the present invention is not limited, but for example, a circuit board for a touch panel is preferable.

(Input device and display device) As a device provided with the circuit wiring manufactured by the manufacturing method of the circuit wiring of this invention, an input device is mentioned. The input device in the present invention is preferably an electrostatic capacitance type touch panel. It is preferable that the display device in the present invention includes the input device in the present invention. Furthermore, the display device in the present invention is preferably an image display device such as an organic EL display device and a liquid crystal display device.

(Touch panel and touch panel display device and method of manufacturing the same) The touch panel of the present invention is a touch panel having at least circuit wiring manufactured by the method of manufacturing a circuit wiring of the present invention. Furthermore, it is preferred that the touch panel of the present invention has at least a transparent substrate, electrodes, and an insulating layer or protective layer. The touch panel display device of the present invention is a touch panel display device having at least circuit wiring manufactured by the circuit wiring manufacturing method of the present invention, and the touch panel display device having the touch panel of the present invention is preferred. The manufacturing method of the touch panel or the touch panel display device of the present invention including the manufacturing method of the circuit wiring of the present invention is preferred. The method for manufacturing a touch panel or a touch panel display device of the present invention sequentially includes the steps of bringing the photosensitive resin layer of the photosensitive transfer material obtained by the method of manufacturing a photosensitive transfer material into contact with the substrate and bonding , A step of pattern exposing the photosensitive resin layer of the photosensitive transfer material after the step of laminating, a step of developing a pattern of the photosensitive resin layer after the step of exposing to form a pattern, and The step of etching the substrate in the area of the above pattern is preferred. The meaning of the detailed content of each step is the same as the detailed content of each step in the above-mentioned method of manufacturing a circuit wiring, and the preferred aspect is also the same. As the detection method of the touch panel of the present invention and the touch panel display device of the present invention, any one of known methods such as a resistive film method, an electrostatic capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method may be used. Among them, the electrostatic capacitance method is preferred. As the touch panel type, a so-called in-cell type (for example, those described in FIG. 5, FIG. 6, FIG. 7, and FIG. 8 of Japanese Patent Publication No. 2012-517051), and a so-called out-cell type (for example, Japanese Patent Laid-Open No. 2013-168125, Figure 19, Japanese Patent Laid-Open No. 2012-89102, Figures 1 and 5), OGS (One Glass Solution) type, TOL (Touch-on-Lens) Type (for example, those described in FIG. 2 of Japanese Patent Application Publication No. 2013-54727), other structures (for example, those described in the graph of Japanese Patent Application Publication No. 2013-164871), and various plug-in types (so-called GG, G1. G2, GFF, GF2, GF1, G1F, etc.). As the touch panel of the present invention and the touch panel display device of the present invention, "the latest touch panel technology" (July 6, 2009, issued by Techno Times Co., Ltd.), Mitani Yuji supervision, "touch Control panel technology and development ", CMC Publishing (2004, 12), FPD International 2009 Forum T-11 lecture textbook, Cypress Semiconductor Corporation application note AN2292 and other structures disclosed. [Example]

Hereinafter, the embodiments of the present invention will be described in more detail with examples. The materials, usage amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed as long as they do not depart from the gist of the embodiments of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. In addition, unless otherwise specified, "parts" and "%" are quality standards. In addition, the “maximum absorption wavelength” in this embodiment refers to the maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development.

<Calculation method of pKa and pKaH> The ACD / pka DB ver 8.07 of ACD / Labs software Ver 8.0 for Microsoft windows manufactured by Advanced Chemistry Development Co. was used to calculate the pKa of the compound and the pKa of the conjugate acid of the compound (pKaH).

[Polymer] In the following examples, the following abbreviations represent the following compounds, respectively. ATHF: 2-tetrahydrofuran acrylate (synthetic product) MATHF: 2-tetrahydrofuran methacrylate (synthetic product) ATHP: tetrahydro-2H-pyran-2-yl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) ) MATHP: Tetrahydro-2H-pyran-2-yl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) MAEVE: 1-ethoxyethyl methacrylate (Wako Pure Chemical Industries, Ltd .) TBMA: tertiary butyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) AA: acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) MAA: methacrylic acid (Tokyo Chemical Industry Co., Ltd. System) EA: ethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) MMA: methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) CHA: cyclohexyl acrylate (Tokyo Chemical Industry Co., Ltd.) .) CHMA: cyclohexyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) EHMA: 2-ethylhexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) BMA: n-butyl acrylate (Tokyo Chemical Industry Co., Ltd.) PGMEA (Propylene Glycol Monomethyl Ether B Ester): (manufactured by Showa Denko K.K.) V-601: dimethyl-2,2’-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)

<Synthesis of ATHF> Acrylic acid (72.1 parts, 1.0 molar equivalent) and hexane (72.1 parts) were added to the three-necked flask and cooled to 20 ° C. After adding camphorsulfonic acid (0.00070 parts by mass, 0.003 millimolar equivalent) and 2-dihydrofuran (70.1 parts by mass, 1.0 molar equivalent)), after stirring at 20 ° C ± 2 ° C for 1.5 hours, the temperature was increased to Stirred at 35 ° C for 2 hours. After sequentially covering the suction filter with KYOWARD 200 (aluminum hydroxide adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.) and KYOWARD 1000 (hydrotalcite-based adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.), the reaction liquid was filtered and The filtrate was obtained. After adding hydroquinone monomethyl ether (MEHQ, 0.0012 parts) to the obtained filtrate, it was concentrated under reduced pressure at 40 ° C, thereby obtaining 140.8 parts of tetrahydrofuran-2-yl acrylate (ATHF) as a colorless oil (Yield 99.0%).

<Synthesis of MATHF> To a three-necked flask, methacrylic acid (86.1 parts, 1.0 molar equivalent) and hexane (86.1 parts) were added and cooled to 20 ° C. After adding camphorsulfonic acid (0.00070 parts by mass, 0.003 millimolar equivalent) and 2-dihydrofuran (70.1 parts by mass, 1.0 molar equivalent)), after stirring at 20 ° C ± 2 ° C for 1.5 hours, the temperature was raised Stirred at 35 ° C for 2 hours. After sequentially covering the suction filter with KYOWARD 200 and KYOWARD 1000, the reaction solution was filtered to obtain a filtration solution. After adding MEHQ (0.0012 parts) to the obtained filtrate, it was concentrated under reduced pressure at 40 ° C, thereby obtaining 156.2 parts of tetrahydrofuran-2-yl methacrylate (MATHF) as a colorless oily substance (yield 98.0%) ).

<Synthesis Example of Polymer A1> n-propyl acetate (150.0 parts by mass) was added to a three-necked flask, and the temperature was raised to 90 ° C under a nitrogen atmosphere. ATHF (25.0 parts by mass), AA (3.7 parts by mass), EA (15.0 parts by mass), and MMA (32.4 parts by mass) were added dropwise to a three-necked flask solution maintained at a temperature range of 90 ° C ± 2 ° C over 2 hours. ), CHMA (23.9 parts by mass), V-601 (3.1 parts by mass) solution. After the completion of the dropping, the mixture was stirred for 2 hours in a temperature range of 90 ° C ± 2 ° C, thereby obtaining a polymer A1 (solid content concentration 40.0% by mass).

<Synthesis Examples of Polymers A-2 to A-9> The types of monomers were changed as shown in Table 1 below, and other conditions were synthesized in the same manner as the polymer A-1. The solid content concentration of the polymer was 40% by mass.

[Table 1]

<Synthesis Example of Polymer A-10> A polymer synthesized by the same method as the acid-decomposable polymer compound PS-2 described in Japanese Patent Laid-Open No. 2008-64908 is referred to as polymer A-10 (excluding (A polymer of constituent units of a carboxylic acid group protected by an acid-decomposable group).

[Photoacid generator] B-1: Compound of the structure shown below (Synthesized according to the method described in paragraph 2227 of JP-A-2013-47765.)

[化 20]

B-2: Irgacure PAG-103 manufactured by BASF, the following compounds

[化 21]

B-3: Compounds of the structure shown below (Synthesized according to the method described in paragraph 0210 of JP-A-2014-197155.)

[化 22]

B-4: WPAG-281 (product name, manufactured by Wako Pure Chemical Industries, Ltd.)

[化 23]

B-5: Compounds of the structure shown below (Synthesized according to the method described in paragraph 0138 of Japanese Patent Laid-Open No. 2015-151347.)

[化 24]

[Latent pigment] C-1: The same compound as the above C-1, manufactured by Fukui Yamada Chemical Co., Ltd., Maximum absorption wavelength: 576 nm, pKaH: -3.53 C-2: Same as the above C-2 The same compound, manufactured by Chameleon, maximum absorption wavelength: 533 nm, pKaH: does not form conjugate acid C-3: the same compound as the above C-3, manufactured by Yamamoto Chamicals Inc., maximum absorption wavelength: 531 nm, pKaH : Conjugate acid C-4 is not formed: the same compound as C-4 above, manufactured by Fukui Yamada Chemical Co., Ltd., maximum absorption wavelength: 460 nm and 595 nm, pKaH: 0.53 C-5: same as above C-5 same compound, manufactured by Fukui Yamada Chemical Co., Ltd., maximum absorption wavelength: 470 nm and 672 nm, pKaH: 0.23 C-6: same compound as the above C-6, Fukui Yamada Chemical Co., Ltd., maximum absorption wavelength: 525 nm, pKaH: 0.27 C'-1: the following compound, manufactured by Fukui Yamada Chemical Co., Ltd., maximum absorption wavelength: 598 nm, pKaH: 4.73 C'-2: the following Compound, manufactured by Hodogaya Chemical Co., Ltd., maximum absorption wavelength: 444 nm, pKaH: 1.86

[化 25]

[Basic compound] D-1: Compound of the structure shown below (CMTU)

[化 26]

D-2: 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) D-3: 1,5-diazepine [4.3.0] -5-nonene (Tokyo Chemical Industry Co., Ltd.)

[Surfactant] E-1: MEGAFACE F-554 (fluorine-based nonionic surfactant, manufactured by DIC Corporation Co., Ltd.) E-2: MEGAFACE F-552 (fluorine-based nonionic surfactant, DIC Corporation Co., Ltd.) E-3: MEGAFACE F-253 (fluorine-based nonionic surfactant, manufactured by DIC Corporation Co., Ltd.)

(Examples 1 to 22 and Comparative Examples 1 to 4) <Preparation of photosensitive transfer material> In Examples 1 to 22 and Comparative Examples 1 to 4, the solid content ratios shown in Table 2 below were used , Dissolve the polymer component, photoacid generator, basic compound, surfactant and other components in such a way that n-propyl acetate / methyl ethyl ketone = 70/30 (vol%) becomes a solid content concentration of 14% by mass The mixture was mixed and filtered through a filter made of polytetrafluoroethylene with a pore size of 0.2 μm to obtain a photosensitive resin composition. A 16 μm-thick polyethylene terephthalate film (hereinafter also referred to as “PET (A)”) that becomes a temporary support is coated with a slit-shaped nozzle so that the dry film thickness becomes 3.0 μm The photosensitive resin composition is distributed. After that, it was dried in a convection oven at 100 ° C for 2 minutes, and finally a polypropylene film (manufactured by Oji F-Tex Co., Ltd., ALPHAN PK-002) was pressure-bonded as a cover film to make a photosensitive transfer material.

[Performance evaluation] A PET layer with a copper layer and a copper layer was prepared by sputtering on a 100 μm thick polyethylene terephthalate (PET) film with a thickness of 200 nm.

<Sensitivity evaluation> Under the stacking conditions of a linear pressure of 0.8 MPa and a linear speed of 3.0 m / min., The produced photosensitive transfer material was laminated on a PET substrate with a copper layer. In addition, at a roll temperature of 90 ° C, visually confirm the area where the photosensitive resin layer is in close contact with the copper layer without bubbles or ridges. If the area is less than 95%, increase the roll temperature until the area becomes 95 The sample was made above%. Without peeling the temporary support, the line and the space pattern mask (Duty ratio 1: 1) with a line width of 3 μm to 20 μm are exposed to the photosensitive resin layer with an ultra-high pressure mercury lamp, and the temporary support is peeled off after standing for 1 hour development. Regarding the development, a 28% 1.0% sodium carbonate aqueous solution was used, and spray development was performed for 30 seconds. When a line and space pattern of 10 μm was formed by the above-mentioned method, the residue in the space portion was observed by a scanning electron microscope (SEM) for evaluation, and the amount of exposure in which the residue could not be confirmed was obtained by observation based on SEM. Exposure levels of 200 mJ / cm ² or less are practical levels. The smaller the exposure amount, the better the exposure sensitivity. -Evaluation criteria- A: 80 mJ / cm ² or less B: more than 80 mJ / cm ² and 100 mJ / cm ² or less C: more than 100 mJ / cm ² and 200 mJ / cm ² or less D: more than 200 mJ / cm ² And below 300 mJ / cm ² E: greater than 300 mJ / cm ²

<Visibility evaluation> Under the lamination conditions of linear pressure of 0.8 MPa and linear velocity of 3.0 m / min., The produced photosensitive transfer material was laminated on a PET substrate with a copper layer. In addition, at a roll temperature of 90 ° C, visually confirm the area where the photosensitive resin layer is in close contact with the copper layer without bubbles or ridges. If the area is less than 95%, increase the roll temperature until the area becomes 95 The sample was made above%. After the temporary support was not peeled off, part of the light was shielded, and after the photosensitive resin layer was exposed with an ultra-high pressure mercury lamp, it was left for 4 hours. As the exposure amount, the exposure amount obtained from the sensitivity evaluation described above was used. An optical lens with a magnification of 4 times is attached to the front end of the black and white CCD (Charge Coupled Device) camera, and the reflected light intensity of the exposed portion and the reflected light intensity of the unexposed portion are measured respectively. Reflected light intensity ratio = (reflected light intensity of exposed part) / (reflected light intensity of unexposed part) The smaller the value of the above-mentioned reflected light intensity ratio, the better the performance. The practical evaluation system is A to C in the following evaluation criteria.

-Measurement conditions- Reading camera pixels: 5 million pixels (2,432 × 2,050) Reading camera spectral sensitivity: 400 nm = x0.6, 500 nm = x1.0, 600 nm = x0.84, 700 nm = x0. 55 Light source: The D65 light source (CIE standard light source D65) is passed through the sharp wave filter SC-42 manufactured by FUJIFILM Co., Ltd.

-Evaluation criteria- A: The reflected light intensity ratio is less than 0.45 B: The reflected light intensity ratio is 0.45 or more and less than 0.65 C: The reflected light intensity ratio is 0.65 or more and less than 0.78 D: The reflected light intensity ratio is 0.78 or more and less than 0.90 E: The reflected light intensity ratio is above 0.90

<Straightness evaluation> Under the lamination conditions of linear pressure of 0.8 MPa and linear velocity of 3.0 m / min., The produced photosensitive transfer material was laminated on a PET substrate with a copper layer. In addition, at a roll temperature of 90 ° C, the area where the photosensitive resin layer is in close contact with the copper layer in a state of no bubbles or bumps is confirmed by visual evaluation. When the above area is less than 95%, the roll temperature is increased until the above area becomes More than 95% of the samples. Without peeling off the temporary support, the line and the space pattern (Duty ratio 1: 1) with a line width of 3 μm to 20 μm are covered, and the photosensitive resin layer is exposed with the exposure amount determined in the sensitivity evaluation with an ultra-high pressure mercury lamp. After standing for 4 hours, the temporary support was peeled off and developed. Regarding the development, a 1.0% aqueous solution of sodium carbonate at 28 ° C. was used for 30 seconds by spray development. With the line and space pattern thus obtained, the line width was within the range of 40 μm in the long-side edge of the pattern of 7 ± 0.5 μm, and the line width was measured at 50 points, and the standard deviation of the measurement change was calculated to calculate 3σ. The average value (LWR, line width roughness, line width roughness) was determined by measuring n = 5. The smaller the value, the better the performance, and the practical grade is A to C. -Evaluation criteria- A: LWR less than 200 nm B: LWR series 200 nm or more and less than 240 nm C: LWR system 240 nm or more and less than 290 nm D: LWR system 290 nm or more and less than 340 nm E: LWR system 340 nm or more

Table 2 summarizes the evaluation results.

[Table 2]

In addition, the unit of the amount of each component in Table 2 is a mass part. Furthermore, in Comparative Example 4, since there is no sensitivity, a clear pattern cannot be formed, and the linearity becomes "E". As shown in Table 2, the photosensitive resin composition of the present invention can achieve both sensitivity and visibility at a high level. In addition, as shown in Table 2, the photosensitive transfer material of the present invention can transfer to the copper layer.

(Example 101) On a 100-μm-thick PET substrate, indium tin oxide (ITO) was formed as a second conductive layer at a thickness of 150 nm by sputtering as a second conductive layer, and vacuum deposition was applied at 200 A copper film was formed with a thickness of nm to serve as the first conductive layer, thereby producing a circuit-forming substrate. The photosensitive transfer material 1 obtained in Example 1 (linear pressure 0.8 MPa, linear speed 3.0 m / min, roller temperature 90 ° C.) was laminated on the copper layer. The contact pattern was performed using the light mask provided with the pattern shown in FIG. 3 (hereinafter, also referred to as “pattern A”) having a structure in which the conductive layer sheet is connected in one direction without peeling off the temporary support exposure. In addition, in the pattern A shown in FIG. 3, the solid line portion SL and the gray portion G are light-shielding portions, and the dotted line portion DL is assumed to indicate an aligned frame. After that, the temporary support was peeled off, developed, and washed with water to obtain pattern A. Next, after etching the copper layer using a copper etching solution (Cu-02 manufactured by KANTO CHEMICAL CO., INC.), The ITO layer was etched using an ITO etching solution (ITO-02 manufactured by KANTO CHEMICAL CO., INC.), Thereby obtaining A substrate in which copper (solid line SL) and ITO (grey part G) are drawn by pattern A together.

Next, using a light mask in which the pattern shown in FIG. 4 (hereinafter, also referred to as “pattern B”) was placed in an aligned state, pattern exposure was performed, followed by development and water washing. In addition, in the pattern B shown in FIG. 4, the gray portion G is a light-shielding portion, and the dotted line portion DL is assumed to indicate an aligned frame. After that, the copper layer was etched using Cu-02, and the remaining photosensitive resin layer was stripped using a stripping solution (10% by mass sodium hydroxide aqueous solution) to obtain a circuit wiring board. By this, a circuit wiring board was obtained. Observed with a microscope, there are no peeling defects, and the pattern is clear.

(Example 102) On a 100 μm thick PET substrate, ITO was deposited by sputtering at a thickness of 150 nm as a second conductive layer, and copper was deposited by vacuum evaporation at a thickness of 200 nm. As the first conductive layer, a circuit-forming substrate was produced. The photosensitive transfer material 1 obtained in Example 1 (linear pressure 0.8 MPa, linear speed 3.0 m / min, roller temperature 90 ° C.) was laminated on the copper layer. The contact pattern exposure was performed using a photomask provided with a pattern A shown in FIG. 3 having a structure in which the conductive layer sheet was connected in one direction without peeling off the temporary support. After that, the temporary support was peeled off, developed, and washed with water to obtain pattern A. Next, after etching the copper layer using a copper etching solution (Cu-02 manufactured by KANTO CHEMICAL CO., INC.), The ITO layer was etched using an ITO etching solution (ITO-02 manufactured by KANTO CHEMICAL CO., INC.), Thereby obtaining A substrate in which copper (solid line SL) and ITO (grey part G) are drawn by pattern A together. Next, PET (A) is deposited on the remaining resist as a protective layer. In this state, in the aligned state, a light mask provided with an opening of the pattern B shown in FIG. 4 was used for pattern exposure, and after PET (A) was peeled off, development and water washing were performed. Thereafter, copper wiring was etched using Cu-02, and the remaining photosensitive resin layer was peeled off using a stripping solution (KP-301 manufactured by KANTO CHEMICAL CO., INC.) To obtain a circuit wiring board. Observation with a microscope shows clear patterns without peeling defects.

12‧‧‧Temporary support

14‧‧‧Photosensitive resin layer

14A‧‧‧The first pattern

14B‧‧‧The second pattern

16‧‧‧covering film

20‧‧‧ Circuit forming substrate

22‧‧‧ Base material

24‧‧‧The first conductive layer

24A‧‧‧The first conductive layer (after the first etching step)

24B‧‧‧The first conductive layer (after the second etching step)

26‧‧‧The second conductive layer

26A‧‧‧Second conductive layer (after the first etching step and the second etching step)

30‧‧‧Mask

40‧‧‧Mask

100‧‧‧Photosensitive transfer material

SL‧‧‧Solid line department

G‧‧‧Gray

DL‧‧‧dot line department

FIG. 1 is a schematic diagram showing an example of the layer structure of the photosensitive transfer material of the present invention. 2 is a schematic diagram showing an example of a method for manufacturing a circuit wiring for a touch panel using the photosensitive transfer material of the present invention. FIG. 3 is a schematic diagram showing the pattern A. FIG. FIG. 4 is a schematic diagram showing pattern B. FIG.

Claims (15)

A photosensitive resin composition comprising: a polymer, a constituent unit having a group having a carboxylic acid group protected by an acid-decomposable group; a photo-acid generator; and a latent pigment, which is a conjugate acid with a pKa of less than 4.5 Or a compound that does not form a conjugated acid, and the maximum absorption wavelength in the color range of 400 nm to 780 nm is above 500 nm. The photosensitive resin composition as described in item 1 of the patent application range, wherein the maximum absorption wavelength in the latent pigment is 550 nm or more. The photosensitive resin composition as described in item 1 or item 2 of the patent application scope, wherein the latent pigment is a latent pigment developed by the acid generated by the photoacid generator. The photosensitive resin composition according to item 1 or 2 of the patent application scope, wherein the acid generated by the photoacid generator is at least one acid selected from the group consisting of phosphoric acid and sulfonic acid. The photosensitive resin composition as described in item 4 of the patent application scope, wherein the acid generated by the photoacid generator is a sulfonic acid represented by the following formula S1 or formula S2, S1 and S2 in formula formula, R ^S represents an alkyl group, L ^S represents 2 or more carbon atoms, alkylene group, 1 represents 0 or NS, wherein, R ^S system having a case where the halogen atom of the alkyl group, n is 1, X ^S independently represents an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and ms represents an integer of 0 to 5. The photosensitive resin composition as described in the first or second patent application, wherein the acid generated by the photoacid generator has a pKa of -4.0 or more. The photosensitive resin composition as described in item 1 or 2 of the patent application, wherein the pKa of the acid generated by the photoacid generator is 4.0 or less. The photosensitive resin composition as described in item 1 or 2 of the scope of patent application further contains a basic compound. The photosensitive resin composition as described in item 1 or item 2 of the scope of patent application further contains a solvent. The photosensitive resin composition as described in item 1 or item 2 of the patent application scope, wherein the latent pigment is a compound represented by the following formula I, In Formula I, Ar ^1C and Ar ^2C each independently represent an aromatic group, X ^C represents C, S, or S = O, and R ^1C to R ^4C each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group. The photosensitive resin composition as described in item 10 of the patent application, wherein X ^C in the formula I is C. The photosensitive resin composition as described in item 1 or 2 of the patent application scope, wherein the structural unit having a group having a carboxylic acid group protected by an acid-decomposable group is a structural unit represented by the following formula II, In Formula II, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ represents an alkyl group or an aryl group, R ¹ Or R ² may be linked to R ³ to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an aryl group. A photosensitive transfer material having a temporary support and a photosensitive resin layer, the photosensitive resin layer comprising the photosensitive resin composition as described in the first or second patent application. A method for manufacturing circuit wiring, which in turn includes: a step of bonding the photosensitive resin layer of the photosensitive transfer material as described in item 13 of the patent application to the substrate with respect to the substrate to perform bonding; A step of pattern exposure of the photosensitive resin layer of the photosensitive transfer material after the step of combining; a step of developing a pattern of the photosensitive resin layer after the step of exposure to form a pattern; and The step of etching the substrate in the area. A method for manufacturing a touch panel, which in turn includes: the step of bringing the photosensitive resin layer of the photosensitive transfer material as described in item 13 of the patent application in contact with the substrate with respect to the substrate to perform bonding; A step of pattern exposing the photosensitive resin layer of the photosensitive transfer material after the step of laminating; a step of developing a pattern to form the photosensitive resin layer after the step of exposing; and to disposing the pattern The step of etching the substrate in the area.