TW201840612A - Photosensitive transfer materials, method for producing circuit wiring and method for producing touch panel - Google Patents

Abstract

A photosensitive transfer material, and a circuit wiring manufacturing method and a touch panel manufacturing method that use said photosensitive transfer material, said photosensitive transfer material having: a temporary support body; and a photosensitive resin layer that includes a polymer component and a photoacid generator, said polymer component including a polymer that includes a structural unit with an acid group and a structural unit with a group in which an acid group is protected by the shape of an acetal, the average I/O value of said polymer component being 0.55 to 0.65, said I/O value being based on an organic conceptual diagram of the polymer component and being the inorganic value I divided by the organic value O, the content of the structural unit with an acid group being 0.5mass% to 15mass% with regard to the total mass of the polymer component, and the average glass transition temperature of said polymer component being 90 DEG C or less.

Description

Method for manufacturing photosensitive transfer material, circuit wiring, and method for manufacturing touch panel

The present disclosure relates to a method for manufacturing a photosensitive transfer material, a circuit wiring, and a method for manufacturing a touch panel.

In a display device (such as an organic EL display device and a liquid crystal display device) having a touch panel such as an electrostatic capacitance type input device, an electrode pattern of a sensor corresponding to a visible portion, an edge wiring portion, and A conductive layer pattern such as a wiring in the wiring portion is drawn. Generally, in the formation of a patterned layer, the number of steps for obtaining a desired pattern shape is small. Therefore, a layer of a photosensitive resin composition provided on an arbitrary substrate using a photosensitive transfer material is widely used. A method in which a mask of a desired pattern is developed after exposure.

For example, Japanese Patent Application Laid-Open No. 2015-194715 discloses a chemically amplified positive photosensitive resin composition for a thick film. The chemically amplified positive photosensitive resin composition for a thick film contains: (A) by actinic Acid generators that generate acids by irradiation with radiation or radiation; (B) resins that increase the solubility of alkalis by the action of acids; and (S) organic solvents that (B) increase the alkalis by the action of acids The soluble resin includes an acrylic resin containing a structural unit derived from an acrylate containing a cyclic group containing (B-3) -SO ₂ -or a cyclic group containing a lactone. The total mass of the resin component contained in the amplification type positive photosensitive resin composition, the mass ratio of the above (B-3) acrylic resin is 70% by mass or more, and is used to form a thick film photoresist pattern having a film thickness of 10 μm or more.

An object to be solved by one embodiment of the present invention is to provide a photosensitive transfer material capable of obtaining a pattern having excellent lamination adaptability and excellent resolution, and having excellent peelability of the pattern. In addition, another aspect of the present invention is to provide a method for manufacturing a circuit wiring using the photosensitive transfer material or a method for manufacturing a touch panel.

The mechanism for solving the above problems includes the following aspects. <1> A photosensitive transfer material comprising: a temporary support; and a photosensitive resin layer containing a polymer component and a photoacid generator, and the polymer component contains an acetal having an acid group. The average value of the I / O value of the organic unit based on the organic concept diagram of the polymer component of the protected group and the polymer having the acid unit is 0.55 or more. In addition, the content of the structural unit having an acid group with respect to the total mass of the polymer component is 0.65 or less, and the content is 0.5% by mass or more and 15% by mass or less, and the average value of the glass transition temperature is 90 ° C or less. <2> The photosensitive transfer material according to <1>, wherein the constituent unit having an acid group protected in the form of an acetal is a constituent unit represented by the following formula A.

[Chemical Formula 1]

In Formula A, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R ³¹ and R ³² is an alkyl group or an aryl group, R ³³ represents an alkyl group or an aryl group, R ³¹ or R ³² may be bonded to R ³³ to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or a divalent linking group. <3> The photosensitive transfer material according to <1> or <2>, wherein the content of the structural unit having an acid group with respect to the total mass of the polymer component is 1 relative to the total mass of the polymer component Above 10% by mass. <4> The photosensitive transfer material according to any one of <1> to <3>, wherein the acid group-based carboxyl group contained in the structural unit having an acid group is described above. <5> The photosensitive transfer material according to any one of <1> to <4>, wherein the weight average molecular weight of the polymer component is 60,000 or less. <6> A method for manufacturing a circuit wiring, including the following steps: On a substrate, the photosensitive transfer material according to any one of <1> to <5>, on the opposite side to the temporary support. A step of laminating the outermost layer in contact with the substrate; a step of pattern exposing the photosensitive resin layer of the photosensitive transfer material after the step of laminating; a photosensitive resin layer of the pattern exposing step A step of developing to form a pattern; and a step of performing an etching process on the substrate in a region where the pattern is not arranged. <7> A method for manufacturing a touch panel, which includes the following steps: On a substrate, the side of the photosensitive transfer material according to any one of <1> to <5> opposite to the temporary support A step of laminating the outermost layer of the substrate in contact with the substrate; a step of pattern exposing the photosensitive resin layer of the photosensitive transfer material after the step of laminating; a photosensitive resin after the step of exposing the pattern A step of developing a layer to form a pattern; and a step of performing an etching process on the substrate in a region where the above pattern is not arranged. [Inventive effect]

According to an aspect of the present invention, it is possible to provide a photosensitive transfer material capable of obtaining a pattern having excellent build-up adaptability and excellent resolution, and having excellent pattern peelability. Moreover, according to another aspect of the present invention, it is possible to provide a method for manufacturing a circuit wiring using the photosensitive transfer material or a method for manufacturing a touch panel.

The contents of the present disclosure will be described below. In addition, description is made with reference to the attached drawings, but the symbols are sometimes omitted. In addition, the numerical range shown using "~" in this specification means the range which included the numerical value described before and after "~" as a lower limit and an upper limit. In addition, in this specification, "(meth) acrylic acid" means both or any one of acrylic acid and methacrylic acid, and "(meth) acrylate" means both or any one of acrylate and methacrylate. In addition, in the present specification, when a plurality of substances corresponding to each component are present in the composition, the amount of each component in the composition refers to the total amount of the plurality of substances present in the composition unless otherwise specified. . In this specification, the term "step" not only means an independent step, but even if it cannot be clearly distinguished from other steps, it is included in the term as long as the intended purpose of the step can be achieved. In the description of the group (atomic group) in the present specification, the unlabeled and unsubstituted labels include a group having no substituent and having a substituent. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups), but also alkyl groups with substituents (substituted alkyl groups). In addition, the chemical structural formula in this specification may be described as a simple structural formula in which a hydrogen atom is omitted. In the present disclosure, "mass%" has the same meaning as "weight%", and "mass parts" has the same meaning as "weight parts". Moreover, in the present disclosure, a combination of two or more preferable aspects is a more preferable aspect.

(Photosensitive transfer material) The photosensitive transfer material according to this embodiment includes: a temporary support; and a photosensitive resin layer containing a polymer component and a photoacid generator. The polymer component contains a polymer having an acid. For the structural unit of a group whose radical is protected in the form of an acetal and the structural unit having an acidic group, divide the inorganic value I of the polymer component based on the organic concept map by the I / O value of the organic value O The average value is 0.55 or more and 0.65 or less, the content of the structural unit having an acid group with respect to the total mass of the polymer component is 0.5% by mass or more and 15% by mass or less, and the average value of the glass transition temperature is 90 ° C or less.

In the circuit wiring for a touch panel or the like, the electrode pattern of the sensor corresponding to the recognition portion does not cross the wiring of the peripheral extraction portion (peripheral wiring portion and extraction wiring portion), and there is no need for a three-dimensional connection by a bridge or the like. Therefore, in the technical field of a circuit wiring manufacturing method, as in the conventional patterning method using a photosensitive resin composition, it is expected that the photoresist formation will not be performed for each desired pattern, and the photoresist formation will be performed in a single photoresist formation. Circuit wiring including a conductive layer of a plurality of types of patterns is omitted. From the viewpoint of improving productivity, for example, it is more convenient to attach a substrate for forming circuit wiring and a photosensitive transfer material while conveying it in a roll-to-roll manner, and perform exposure and development. good. As a photosensitive transfer material, from the viewpoint of producing finer patterns with high accuracy, it is preferable that the resolution of the circuit wiring formed by the pattern is high. Moreover, as a photosensitive transfer material, it is preferable to be able to perform bonding by low temperature from a viewpoint of energy saving and speeding up a process. In particular, when a base material such as a heat-resistant resin film is used as the base material, it is more preferable to be able to perform bonding at a low temperature.

Among them, in the case where a resist layer is formed using a photosensitive transfer material, a photoresist pattern obtained by developing the resist layer is finally peeled off after the completion of etching or the like. The peeling in the present invention includes both the concept of the phenomenon that the swelling in the peeling solution can be removed peelably and the phenomenon that the peeling solution is completely dissolved and can be removed. When peeling a resist layer formed using a photosensitive transfer material, for example, an alkaline aqueous peeling liquid is used. The present inventors have found that the chemically amplified positive-type photosensitive resin composition of Japanese Patent Laid-Open No. 2015-194715 has insufficient releasability (hereinafter, also simply referred to as "peelability") based on a photoresist pattern of a release liquid.

Therefore, as a result of intensive research by the present inventors, it has been found that the photosensitive transfer material according to this embodiment can provide a photosensitive transition that can obtain a pattern with excellent lamination adaptability and excellent resolution and has excellent peelability of the pattern. Printed materials. Although a detailed mechanism for obtaining the above effects is unknown, it can be inferred as follows. Japanese Patent Application Laid-Open No. 2015-194715 describes a hydrophobic positive-type photosensitive resin composition using a small amount of acid groups contained in the polymer component and a low average value of the I / O value of the polymer component. The resist layer formed is difficult to dissolve or swell in a peeling solution (especially an alkaline aqueous peeling solution), and is considered to have low peelability. In addition, in order to improve the solubility in the stripping solution, when a composition having a large amount of acid groups contained in the polymer component and a high average value of the I / O value of the polymer component is used, it is used to form a resist. When the developer layer is developed, the developer is also swollen, and the resolution is considered to decrease. In the photosensitive transfer material of this embodiment, the average value of the I / O value of the polymer component is 0.55 or more and 0.65 or less, and the content of the structural unit having an acid group relative to the total mass of the polymer component is 0.5 mass. % To 15% by mass. By setting the average value of the I / O value of the polymer component and the content of the constituent unit having an acid group to the above range, the dissolution or swelling with the developing solution when the resist layer is formed is suppressed, and the contact with the peeling solution is easily caused. Dissolving or swelling, it is inferred that a pattern having excellent resolution can be obtained, and the pattern has excellent peelability. In addition, in the photosensitive transfer material of this embodiment, by limiting the average value of the Tg of the polymer component, it is estimated that a photosensitive transfer material having excellent lamination adaptability can be obtained. In the photosensitive transfer material of this embodiment, it is considered that even when laminating is performed at a low temperature, a photosensitive transfer material having excellent lamination adaptability is easily obtained. The "low temperature" in the above-mentioned laminate is preferably 120 ° C or lower, more preferably 100 ° C or lower, and even more preferably 90 ° C or lower. The lower limit of the temperature during lamination is not particularly limited, but is preferably 40 ° C or higher, and more preferably 60 ° C or higher. Hereinafter, the photosensitive transfer material of this embodiment is demonstrated in detail.

FIG. 1 schematically shows an example of a layer structure of a photosensitive transfer material according to this embodiment. In the photosensitive transfer material 100 shown in FIG. 1, a temporary support 12, a photosensitive resin layer 14, and a cover film 16 are laminated in this order. The photosensitive resin layer 14 includes a polymer component and a photoacid generator. The polymer component includes a polymer including a structural unit having an acid group protected in the form of an acetal and a polymer having a structural unit having an acid group. The average value of the I / O value of the organic component based on the organic concept map of the polymer component divided by the organic value O is 0.55 or more and 0.65 or less. The constituent unit having an acid group relative to the total mass of the polymer component. The content of Ni is 0.5 mass% or more and 15 mass% or less, and the average value of the glass transition temperature is 90 ° C or less. Hereinafter, constituent materials and the like of the photosensitive transfer material according to this embodiment will be described. The above-described configuration in this embodiment may be referred to as the following in this specification. A polymer containing a constituent unit having an acid group protected in the form of an acetal and a constituent unit having an acid group is sometimes referred to as a "specific polymer". The above-mentioned photosensitive resin layer is a positive-type photosensitive resin layer and is sometimes referred to as a "positive-type photosensitive resin layer".

<Temporary support> A temporary support system supports a photosensitive resin layer and is a support that can be peeled from the photosensitive resin layer. The temporary support used in this embodiment is preferable in terms of having light transmittance from the viewpoint that the photosensitive resin layer can be exposed through the temporary support when the photosensitive resin layer is pattern-exposed. Transmittance means that the transmittance of the main wavelength of light used in pattern exposure is 50% or more, and the transmittance of the main wavelength of light used in pattern exposure is more than 60%. Good, more than 70% is better. As a method for measuring the transmittance, a method using a MCPD Series manufactured by Otsuka Electronics Co., Ltd. is mentioned. Examples of the temporary support include a glass substrate, a resin film, and paper. A resin film is particularly preferable from the viewpoints of strength and flexibility. Examples of the resin film include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferred.

The thickness of the temporary support is not particularly limited, and a range of 5 μm to 200 μm is preferable. In terms of ease of handling and versatility, a range of 10 μm to 150 μm is more preferable, and a range of 15 μm to 50 μm is most preferable. The temporary support may be selected depending on the material from the viewpoints of strength as a support, flexibility required for bonding to a circuit wiring forming substrate, and light transmittance required in the first exposure step.

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

<Photosensitive resin layer> The photosensitive transfer material of this embodiment has a photosensitive resin layer arrange | positioned on a temporary support body. The photosensitive resin layer in this embodiment includes a polymer component and a photoacid generator. The polymer component includes a structural unit containing an acid group protected in the form of an acetal and a structure having an acid group. For a unit polymer, the average value of the I / O value of the polymer component based on the inorganic value I based on the organic concept map divided by the organic value O is 0.55 or more and 0.65 or less, relative to the total mass of the polymer component. The content of the constituent units of the acid group is 0.5% by mass or more and 15% by mass or less, and the average value of the glass transition temperature is 90 ° C or less. The photosensitive resin layer in this embodiment is a positive photosensitive resin layer, and a chemically amplified positive photosensitive resin layer is preferred. In photoacid generators such as onium salts or oxime sulfonate compounds described later, the acid generated by sensing active radiation (actinic rays) acts as a catalyst to deprotect the protected acid groups in the specific polymer, Therefore, an acid generated by the action of one photoquantum contributes to most deprotection reactions, and a quantum yield exceeding 1 becomes a value as large as the power of ten, for example. As a result of so-called chemical amplification, high sensitivity can be obtained. On the other hand, when a quinonediazide compound is used as a photoacid generator for sensing active radiation, a carboxyl group is generated by a sequential photochemical reaction. The quantum yield must be 1 or less, but it is not the same in a chemically amplified type. in this way.

[Polymer component] -Specific polymer- The polymer component according to this embodiment includes a structural unit (hereinafter, also referred to as a "structural unit a1") having a group having an acid group protected in the form of an acetal, and For a polymer (specific polymer) of an acid-based constituent unit (hereinafter, also referred to as a “constituent unit a2”), an inorganic value I based on an organic concept map of a polymer component is divided by an organic value O / I / O. The average value is 0.55 or more and 0.65 or less, the content of the structural unit having an acid group with respect to the total mass of the polymer component is 0.5% by mass or more and 15% by mass or less, and the average value of the glass transition temperature is 90 ° C or less. The specific polymer contained in the photosensitive resin layer may be only one type, or may be two or more types. In the above-mentioned specific polymer, the acid group in the above-mentioned specific polymer undergoes a deprotection reaction to become an acid group by the action of an acidic substance in a catalytic amount generated by exposure. It can be developed by this acid group.

The polymer component may contain a polymer other than the specific polymer. Moreover, it is preferable that all the polymers contained in the said polymer component are polymers which each contain the structural unit which has an acidic group at least. The polymer component may contain polymers other than these. Unless otherwise specified, the above-mentioned polymer component in this embodiment means that it contains other polymers added as needed. In addition, plasticizers, heterocyclic compounds, and compounds that conform to surfactants described later may not be included in the polymer component even if they are polymer compounds.

The above-mentioned specific polymer-based addition polymerization type resin is preferable, and a polymer having a structural unit derived from (meth) acrylic acid or an ester thereof is more preferable. Moreover, you may have the structural unit other than the structural unit derived from (meth) acrylic acid or its ester, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc. Hereinafter, the preferable aspect of the structural unit a1 and the structural unit a2 is demonstrated.

<<< constituent unit a1 >> The said polymer component contains the polymer which contains the structural unit a1 which has a group in which an acid group is protected as an acetal. When the polymer component contains a polymer including the constituent unit a1, it is possible to provide a highly sensitive photosensitive resin layer. A well-known group can be used as an acid group in the "group in which an acid group is protected as an acetal" in this aspect, It does not specifically limit. Specific examples of the acid group include a carboxyl group and a phenolic hydroxyl group. It can be used in the form of an acetal which is relatively easily decomposed by an acid (for example, an acetal function such as an ester group, a tetrahydropyranyl ester group, or a tetrahydrofuran ester group protected as an acetal as described in Formula A) Group) to protect the acid groups.

As the above-mentioned constituent unit a1, the constituent unit (a) represented by the following formula A is preferable from the viewpoints of sensitivity at the time of pattern formation and resolution of an available pattern.

[Chemical Formula 2]

In Formula A, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group, or an aryl group. At least one of R ³¹ and R ³² is an alkyl group or an aryl group, R ³³ represents an alkyl group or an aryl group, and R ³¹ or R ³² may be bonded to R ³³ to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or a divalent linking group.

In Formula A, when R ³¹ or R ³² is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred. When R ³¹ and R ³² are aryl, phenyl is preferred. R ³¹ and R ³² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In Formula A, R ³³ represents an alkyl group or an aryl group, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred. The alkyl group and aryl group in R ³³ may have a substituent. In formula A, R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, R ³¹ or R ³² and R ³³ link to form a cyclic ether is preferred. The number of ring members of the cyclic ether is not particularly limited, and 5 or 6 is preferable, and 5 is more preferable. In Formula A, X ⁰ represents a single bond or a difluorene linking group, a single bond or an arylene group is preferred, and a single bond is more preferred. The arylene group may have a substituent.

In Formula A, R ³⁴ represents a hydrogen atom or a methyl group, and a hydrogen atom is more preferred from the viewpoint of lowering the Tg of the specific polymer. More specifically, it is preferable that the constitutional unit in which R ³⁴ is a hydrogen atom in the formula A is 20% by mass or more with respect to the total content of the constitutional unit (a) contained in the polymer. In addition, the content (content ratio: mass ratio) of the constituent unit of the R ^34- based hydrogen atom in Formula A in the constituent unit (a) can be measured by ¹³ C-nuclear magnetic resonance spectroscopy (NMR) by a conventional method The calculated intensity ratio of the peak intensity is used for confirmation.

Among the constituent units (a) represented by the formula A, from the viewpoint of further improving the sensitivity at the time of pattern formation, the constituent units represented by the following formula A1 are also more preferable.

[Chemical Formula 3]

In Formula A1, 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 A1, R ³⁴ is preferably a hydrogen atom. In Formula A1, R ³⁵ to R ⁴¹ are preferably a hydrogen atom.

As a preferable specific example of the constituent unit (a) represented by Formula A, the following constituent units can be exemplified. R ³⁴ represents a hydrogen atom or a methyl group.

[Chemical Formula 4]

Moreover, as said structural unit a1, the structural unit (b) represented by following formula B is preferable from a viewpoint of the storage stability of a photosensitive resin composition.

[Chemical Formula 5]

In Formula B, R ^B1 and R ^B2 each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R ^B1 and R ^B2 is an alkyl group or an aryl group, and R ^B3 represents an alkyl group or an aryl group, R ^B1 or R ^B2 can be linked to R ^B3 to form a cyclic ether. R ^B4 represents a hydrogen atom or a methyl group, X ^B represents a single bond or a difluorene linker, R ^B12 represents a substituent, and n represents an integer of 0 to 4. .

In Formula B, when R ^B1 or R ^B2 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred. When R ^B1 and R ^B2 are aryl, phenyl is preferred. R ^B1 and R ^B2 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In Formula B, R ^B3 represents an alkyl group or an aryl group, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred. The alkyl group and the aryl group in R ^B3 may have a substituent. In Formula B, R ^B1 or R ^B2 and R ^B3 may be linked to form a cyclic ether, R ^B1 or R ^B2 and R ^B3 connected to form a cyclic ether is preferred. The number of ring members of the cyclic ether is not particularly limited, and 5 or 6 is preferable, and 5 is more preferable. In Formula B, X ^B represents a single bond or a divalent linking group, a single bond or an alkylene group, -C (= O) O-, -C (= O) NR ^N- , -O-, or the like A combination is preferred, and a single bond or -C (= O) O- is more preferred. The alkylene group may be linear, may have a branch, may have a cyclic structure, and may have a substituent. The carbon number of the alkylene group is preferably 1 to 10, and more preferably 1 to 4. When X ^B contains -C (= O) O-, it is preferable that the carbon atom contained in -C (= O) O- and the carbon atom bonded to R ^B4 are directly bonded. When X ^B contains -C (= O) NR ^N- , it is preferable that the carbon atom contained in -C (= O) NR ^N -and the carbon atom bonded to R ^B4 are directly bonded. R ^N represents an alkyl group or a hydrogen atom, an alkyl group or a hydrogen atom having 1 to 4 carbon atoms is more preferred, and a hydrogen atom is more preferred. In Formula B, a group containing R ^B1 to R ^B3 and X ^B are preferably bonded to each other in a para position. In Formula B, it is preferable that R ^B12 represents a substituent, an alkyl group, or a halogen atom. The carbon number of the alkyl group is preferably 1 to 10, and more preferably 1 to 4. In Formula B, n represents an integer of 0 to 4, 0 or 1 is preferable, and 0 is more preferable.

In Formula B, R ^B4 represents a hydrogen atom or a methyl group, and a hydrogen atom is preferred from the viewpoint of lowering the Tg of a specific polymer. More specifically, it is preferable that the structural unit in which R ^B4 is a hydrogen atom in the formula B is 20% by mass or more with respect to the total content of the structural unit (a) contained in the specific polymer. In addition, the content (content ratio: mass ratio) of the constituent unit of the R ^B4- based hydrogen atom in Formula B in the constituent unit (a) can be measured by ¹³ C-nuclear magnetic resonance spectroscopy (NMR) by a conventional method The calculated intensity ratio of the peak intensity is used for confirmation.

Among the constituent units (b) represented by the formula B, from the viewpoint of further improving the sensitivity at the time of pattern formation, the constituent units represented by the following formula B1 are also more preferable.

[Chemical Formula 6]

In the formula B1, R ^B4 represents a hydrogen atom or a methyl group, R ^B5 to R ^B11 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^B12 represents a substituent, and X ^B represents a single bond or difluorene. For a linking group, n represents an integer of 0 to 4. In Formula B1, X ^B has the same meaning as X ^{B in} Formula B described above, and the preferred aspects are also the same. In Formula B1, R ^B4 is a hydrogen atom. In Formula B1, R ^B5 to R ^B11 are preferably hydrogen atoms. In the formula B1, R ^B12 represents a substituent, and an alkyl group or a halogen atom is preferred. The carbon number of the alkyl group is preferably 1 to 10, and more preferably 1 to 4. In Formula B1, n represents an integer of 0 to 4, 0 or 1 is preferable, and 0 is more preferable.

As a preferable specific example of the structural unit (b) represented by Formula B, the following structural unit can be illustrated. R ^B4 represents a hydrogen atom or a methyl group.

[Chemical Formula 7]

The structural unit a1 contained in the specific polymer may be one type, or two or more types. The content of the constituent unit a1 in the specific polymer is preferably 10% by mass or more and 30% by mass or less, and 12% by mass or more from 28 in terms of excellent pattern resolution. It is more preferable that the content is not more than 15% by mass, and it is more preferable that the content is not less than 15% by mass and not more than 25% by mass. The content (content ratio: mass ratio) of the constituent unit a1 in the specific polymer can be confirmed by measuring the intensity ratio of the peak intensity calculated by a conventional method from ¹³ C-NMR. In addition, the content of the structural unit represented by the formula A in the specific polymer is 10% by mass or more with respect to the total mass of the specific polymer from the viewpoint of the sensitivity at the time of pattern formation and the resolution of the pattern that can be obtained. It is more preferably 30% by mass or less, more preferably 12% by mass or more and 28% by mass or less, and more preferably 15% by mass or more and 25% by mass or less. In addition, after all polymer components are decomposed into constituent units (monomer units), the proportion of the constituent unit a1 is preferably 10% by mass or more and 30% by mass or less with respect to the total mass of the polymer component, and 12% by mass or more 28 mass% or less is more preferable, and 15 mass% or more and 25 mass% or less is more preferable.

<<< Constitutional unit a2 >> The specific polymer used in this embodiment also contains the constitutional unit a2 which has an acid group. The structural unit a2 is a structural unit containing an acid group which is not protected in the form of an acetal, that is, an acid group which does not have a group in the form of an acetal. When the specific polymer includes the constituent unit a2, the sensitivity of the specific polymer during pattern formation is good, and it is easy to dissolve in the alkaline developer in the development step after the pattern exposure, and it is possible to shorten the development time. The acid group in this specification means a proton dissociative group having a pKa system of 12 or less. The acid group is usually incorporated into a specific polymer using a monomer capable of forming an acid group as a structural unit [structural unit a2] having an acid group. From the viewpoint of improving sensitivity, the pKa of the acid group is preferably 10 or less, and more preferably 6 or less. An acid group having a pKa of -5 or more is preferred.

Examples of the acid group contained in the structural unit a2 include an acid group derived from a carboxyl group, an acid group derived from a sulfoamido group, an acid group derived from a sulfoimino group, an acid group derived from a phosphonic acid group, and an acid group derived from Acid groups derived from sulfonic acid groups, acid groups derived from phenolic hydroxyl groups, and the like. Among them, at least one selected from the group consisting of an acid group derived from a carboxyl group and an acid group derived from a phenolic hydroxyl group is more preferred, and the carboxyl group is more preferred. The introduction of a structural unit having an acid group into a specific polymer can be performed by copolymerizing a monomer having an acid group. The constituent unit having an acid group as the constituent unit a2 is preferably a constituent unit derived from styrene or a constituent unit derived from a vinyl compound in place of an acid group, a constituent unit derived from (meth) acrylic acid, and the like. . Specific examples of the monomer having an acid group include acrylic acid, methacrylic acid, hydroxystyrene, carboxystyrene, 2-propenyloxyethyl phthalic acid, and 2-propenyloxyethyl Hexahydrophthalic acid, 2-propenyloxyethyl-phthalic acid, 2-methacryloxyethyl-succinic acid, 2-methacryloxyethylhexahydrophthalate Formic acid, 2-methacryloxyethyl-phthalic acid, and the like.

As the structural unit a2 included in the specific polymer, a structural unit having a carboxyl group and a structural unit having a phenolic hydroxyl group are preferred from the viewpoint of better sensitivity during pattern formation. The monomer having an acid group capable of forming the structural unit a2 is not limited to the examples described above.

The constituent unit a2 contained in the specific polymer may be only one kind, or two or more kinds. From the viewpoint of pattern formability, the content of the structural unit (constituting unit a2) having an acid group is preferably 0.1% to 20% by mass, and 0.5% to 15% by mass relative to the total mass of the specific polymer. More preferably, 1% to 10% by mass is more preferable. The content (content ratio: mass ratio) of the structural unit a2 in the specific polymer can be confirmed by measuring the intensity ratio of the peak intensity calculated by a conventional method from ¹³ C-NMR.

<<< Constitutional unit a3 >> The above-mentioned specific polymer may further include a constitutional unit other than the constitutional unit having an acid group protected as an acetal and a constitutional unit having an acid group (sometimes also Called "constituting unit a3".). The monomers forming other constituent units are not particularly limited, and examples thereof include styrenes, alkyl (meth) acrylates, cyclic alkyl (meth) acrylates, and aryl (meth) acrylates. , Unsaturated dicarboxylic acid diesters, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated Saturated dicarboxylic anhydride, a group having an aliphatic cyclic skeleton, and other unsaturated compounds. By adjusting at least one of the type and the content using other constituent units, various characteristics of the specific polymer can be adjusted. In particular, by appropriately using other constituent units, the Tg of a specific polymer can be easily adjusted to 90 ° C or lower. The specific polymer may contain only one kind of other constituent units, or may contain two or more kinds.

Specific examples of the other constituent units include styrene, tertiary butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, ethoxylated styrene, and methoxy. Styrene, ethoxystyrene, chlorostyrene, vinyl methyl benzoate, ethyl vinyl benzoate, 4-hydroxybenzoic acid (3-methacryloxypropyl) ester, (meth) acrylic acid Methyl ester, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , Diphenylethylene diketone (meth) acrylate, dicyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isoamidine (meth) acrylate, acrylonitrile, or ethylene glycol monoethenylethyl A structural unit such as an acid ester mono (meth) acrylate. In addition, the compounds described in paragraphs 0021 to 0024 of Japanese Patent Application Laid-Open No. 2004-264623 can be cited.

In addition, as another constituent unit, a group having an aromatic ring or a group having an aliphatic cyclic skeleton is preferred from the viewpoint of improving the electrical characteristics of the available transfer material. Specific examples include styrene, third butoxystyrene, methylstyrene, α-methylstyrene, dicyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, Isoamidine (meth) acrylate and diphenylethylene diketone (meth) acrylate. Among these, as another structural unit, the structural unit derived from cyclohexyl (meth) acrylate is mentioned preferably.

In addition, as a monomer forming other constituent units, from the viewpoint of lamination adaptability and resolution, alkyl (meth) acrylate is more preferred, and alkyl acrylate is more preferred, having a carbon number of 4 to 12. Alkyl acrylates are particularly preferred. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. ester.

The specific polymer preferably has a structural unit represented by the following formula 2 as another structural unit.

[Chemical Formula 8]

In Formula 2, R ^b represents a hydrogen atom or a methyl group, and R ^c represents an alkyl group.

From the standpoint of lamination adaptability and resolution, the R ^b- based hydrogen atom in Formula 2 is preferred. From the viewpoint of lamination adaptability and resolution, the R ^c- based alkyl group having 1 to 20 carbon atoms in Formula 2 is more preferable, the alkyl group having 2 to 12 carbon atoms is more preferable, and the alkyl group having 4 to 12 carbon atoms is preferable. The group is more preferably, and the alkyl group having 5 to 9 carbon atoms is particularly preferable. The alkyl group in R ^c may be a straight chain, may have a branched chain, or may have a ring structure.

With respect to the total mass of the specific polymer, the content of the constituent unit a3 is preferably 85% by mass or less, more preferably 80% by mass or less, and still more preferably 75% by mass or less. The lower limit value may be 0% by mass, 1% by mass or more is preferred, 5% by mass or more is more preferable, and 10% by mass or more is more preferable. Also, from the standpoint of stacking adaptability and resolution, With respect to the total mass of the specific polymer, the content of the constituent unit represented by the above formula 2 is preferably 10% to 85% by mass, more preferably 15% to 80% by mass, and 20% to 75% by mass. Is even better.

Preferred examples of the specific polymer in this embodiment include A-1 to A-15 used in the examples, but needless to say, they are not limited to these.

＜ Production method of specific polymer ＞ There is no particular limitation on the production method (synthesis method) of the specific polymer, but as an example, it just contains a group which is used to form an acetal protected with an acid group. In the organic solvent of the polymerizable monomer of the constituent unit a1 and the polymer monomer for forming the constituent unit a2 having an acid group, and further, if necessary, the polymerizable monomer for forming the other constituent unit a3, Synthesis was performed by polymerization using a polymerization initiator. Moreover, it can synthesize | combine by what is called a polymer reaction.

-Other polymers- The above-mentioned photosensitive resin layer is added as a polymer component to the above-mentioned specific polymer, and may further include a polymer (sometimes also including a structural unit a1 which does not have an acid group protected in the form of an acetal) Called "other polymers".). When the photosensitive resin layer contains other polymers, the blending amount of the other polymers in the total polymer component is preferably 50% by mass or less, more preferably 30% by mass or less, and 20% by mass or less is more preferable. good. Other polymers may include only one kind, or may include two or more kinds.

As another polymer, the polymer component of this embodiment is preferably a polymer having an acid group. As an acid group, a carboxyl group is mentioned preferably. The polymer having an acid group is not particularly limited, and a known polymer can be used, but a polymer (linear organic polymer) having a linear acid group is preferably used. As such a linear organic polymer, a known polymer can be arbitrarily used. In order to enable water development or weak alkaline water development, it is preferable to select a linear organic polymer that is soluble or swellable in water or weak alkaline water. The linear organic polymer can be used not only as a film-forming agent, but also in accordance with the use of water, weak alkaline water, or an organic solvent as a developer. For example, if a water-soluble organic polymer is used, water development can be performed. Examples of such linear organic polymers include a radical polymer having a carboxylic acid group in a side chain, for example, Japanese Patent Laid-Open No. 59-44615, Japanese Patent Laid-Open No. 54-34327, and Japanese Patent Laid-Open No. 58-34327. Those disclosed in Japanese Patent Publication No. 12577, Japanese Patent Publication No. 54-25957, Japanese Patent Publication No. 54-92723, Japanese Patent Publication No. 59-53836, and Japanese Patent Publication No. 59-71048. A carboxyl monomer alone or copolymerized resin, a monomer having an acid anhydride alone or copolymerized to hydrolyze or decompose an acid anhydride unit, or half-esterified or half-aminated resin, made of unsaturated monocarboxylic acid and acid anhydride Epoxy acrylate modified by epoxy resin, etc. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxystyrene, and the like. As the monomer having an acid anhydride, Examples include maleic anhydride. Moreover, it has the same acidic cellulose derivative which has a carboxyl group in a side chain similarly. This polymer having other hydroacid groups is useful for addition of a cyclic acid anhydride derivative or the like.

The polymer having an acid group may contain one kind alone or two or more kinds. When the photosensitive resin layer according to this embodiment contains a polymer having an acid group, the content of the polymer having an acid group is not particularly limited, but it is 1% to 70% by mass based on the total solid content of the photosensitive resin layer. Mass% is more preferred, 2% to 50% by mass is more preferred, and 5% to 30% by mass is further preferred.

As another polymer, for example, polyhydroxystyrene can be used, and commercially available ones such as SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (above, manufactured by Sartomer Company, Inc.) can also be used. ), 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).

-The average value of the I / O value of the polymer component- In the polymer component used in this embodiment, from the standpoint of peelability, the inorganic value I based on the organic concept map is divided by the organic value O The average value of the I / O value is 0.55 or more and 0.65 or less, and preferably 0.57 or more and 0.63 or less. In addition, the I / O value of the specific polymer used in this embodiment may be appropriately set such that the average value of the I / O values is included in the above range, and is preferably 0.55 or more and 0.65 or less, and 0.57 or more. In addition, 0.63 or less is more preferable. The above I / O values are shown in the organic concept map (by Koda Shansheng, published by Sankyo (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, pp. 1-16 (1954); Chemistry, Vol. 11, Vol. 10 No., 719-725 (1957); FRAGRANCE JOURNAL, No. 34, Nos. 97-111 (1979); FRAGRANCE JOURNAL, No. 50, Nos. 79-82 (1981); and other literatures have details instruction of. The concept of I / O value is to divide the properties of compounds into organic groups showing covalent bonding and inorganic groups showing ionic bonding, and locate all organic compounds on the right-angled coordinates named organic and inorganic axes While showing every 1 point.

The I / O value when the polymer component contains two or more polymers can be considered as described below. For example, when the polymer component contains three polymers (Polymer 1 to Polymer 3), set the I / O value of Polymer 1 to A1, the mass fraction to M1, and the I of polymer 2 When the / O value is A2, the mass fraction is M2, the I / O value of the polymer 3 is A3, and the mass fraction is M3, the I / O value Am of the mixed component can be estimated as follows Described. Am = A1 × M1 + A2 × M2 + A3 × M3 In addition, when the polymer component contains only one polymer, the I / O value of only one polymer contained becomes the I / O in the polymer component The average of the values.

-The average value of the glass transition temperature of the polymer component- From the viewpoint of lamination adaptability, the average value of the glass transition temperature (Tg) of the polymer component used in this embodiment is 90 ° C or lower and -20 ° C ～ 90 ° C is preferred, 20 ° C to 90 ° C is more preferred, 20 ° C to 60 ° C is even more preferred, and 25 ° C to 45 ° C is particularly preferred. In addition, the Tg of the specific polymer used in this embodiment may be appropriately set so that the average value of the Tg is included in the above range, preferably 0 ° C or higher and 90 ° C or lower, and preferably 20 ° C or higher and 70 ° C or lower. The following is more preferable, and more preferably 20 ° C to 50 ° C. The glass transition temperature of a resin such as a polymer in this embodiment is measured using a differential scanning calorimeter (DSC). A specific measurement method is performed according to the method described in JIS K 7121 (1987) or JIS K 6240 (2011). As the glass transition temperature in this specification, an extrapolated glass transition start temperature (hereinafter, sometimes referred to as Tig) can be used. A method for measuring the glass transition temperature will be described more specifically. In the case where the glass transition temperature is obtained, the device is kept stable at a temperature about 50 ° C lower than the expected Tg of the polymer, and then heated at a heating rate of 20 ° C / minute to a temperature higher than the temperature at which the glass transition ends. At a temperature of 30 ° C, draw a DTA curve or a DSC curve. Extrapolate the glass transition initiation temperature (Tig), that is, the glass transition temperature Tg in this specification, as the straight line extending from the low-temperature side baseline in the DTA curve or DSC curve to the high-temperature side and the stepwise change in the glass transition. The gradient of the curve is obtained by taking the temperature at the intersection of the tangent line drawn at the maximum point.

As a method of adjusting the Tg of the polymer to the above-mentioned preferable range, for example, the mass ratio of the Tg of each polymer of each constituent unit of the target polymer and the mass of each constituent unit can be guided by the FOX formula. The Tg of the target polymer is controlled. Regarding the FOX formula, for example, in the case of a binary copolymer, the Tg of the individual polymer of the first constituent unit included in the polymer is Tg1, and the mass fraction of the copolymer of the first constituent unit is set It is W1. When the Tg of the individual polymer of the second constituent unit is Tg2, and when the mass fraction of the copolymer of the second constituent unit is W2, Tg0 (K) can be estimated by the following formula. FOX formula: 1 / Tg0 = (W1 / Tg1) + (W2 / Tg2) In the case of an n-copolymer of 3 or more members, the Tg of the individual polymer of the nth constituent unit contained in the polymer is Tg When Tgn is set, and when the mass fraction in the copolymer of the n-th constitutional unit is Wn, it can be estimated by the following formula in the same manner as described above. FOX formula: 1 / Tg0 = (W1 / Tg1) + (W2 / Tg2) + (W3 / Tg3) ... + (Wn / Tgn) Use the FOX formula described above to adjust the composition of each constituent unit contained in the copolymer The kind and mass fraction can obtain a copolymer having a desired Tg. In addition, by adjusting the weight average molecular weight of the polymer, the Tg of the polymer can also be adjusted.

In addition, as a method of separating the specific polymer and the like from the photosensitive resin layer for measuring Tg and the like, it is preferable that the photosensitive resin layer is dissolved in an organic solvent and then separated by a reprecipitation method. Method.

The glass transition temperature when the polymer component contains two or more polymers can be considered as follows. For example, when the polymer component contains three polymers (Polymer 1 to Polymer 3), the glass transition temperature of Polymer 1 is Tg1 (K), the mass fraction is M1, and Polymer 2 is When the glass transition temperature of Tg2 (K) is set, the mass fraction is set to M2, the glass transition temperature of polymer 3 is set to Tg3 (K), and the glass transition temperature of the mixed component is set to Tgm (K) can be estimated as follows. 1 / Tgm = 1 / Tg1 × M1 + 1 / Tg2 × M2 + 1 / Tg3 × M3 When the polymer component contains only one polymer, the Tg of only one polymer is included in the polymer component The average of Tg.

-Weight average molecular weight of polymer component-The molecular weight of the polymer component is preferably 60,000 or less in terms of polystyrene equivalent weight average molecular weight (Mw). When the weight average molecular weight of the polymer is 60,000 or less, the melt viscosity of the photosensitive resin layer is suppressed to be low, and bonding at a low temperature (for example, 130 ° C or lower) can be achieved when bonding to the substrate. The weight average molecular weight of the polymer component is preferably 2,000 to 60,000, and more preferably 3,000 to 50,000. The weight-average molecular weight of the specific polymer used in this embodiment may be appropriately set such that the weight-average molecular weight of the polymer component is included in the above range, and is preferably 6,000 or more and 40,000 or less, and 10,000 or more and 30,000 or less. Is even better. The weight-average molecular weight of a resin such as a polymer in this embodiment is measured by GPC (gel permeation chromatography). In the measurement of the weight-average molecular weight by gel permeation chromatography (GPC), HLC (registered trademark) -8220GPC (manufactured by TOSOH CORPORATION) can be used as a measurement device, and TSKgel (registered trademark) Super HZM can be used as a column. -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) Each of) is connected in series, and THF (tetrahydrofuran) can be used as the eluent. In addition, as the measurement conditions, the sample concentration can be set to 0.2% by mass, the flow rate can be set to 0.35ml / min, the sample injection volume can be set to 10 μl, the measurement temperature can be set to 40 ° C, and the differential refractive index (RI ) Detector. For the calibration curve, "standard sample TSK standard, polystyrene" manufactured by TOSOH CORPORATION: "F-40", "F-20", "F-4", "F-1", "A-5000", "A -2500 "and" A-1000 "are produced from any of the seven samples. The ratio (degree of dispersion) of the number average molecular weight and the weight average molecular weight of the specific polymer component is preferably 1.0 to 5.0, and more preferably 1.05 to 3.5.

—Amount of Acid Group of Polymer Component— From the standpoint of releasability, the content of the structural unit having an acid group with respect to the total mass of the polymer component is 0.5% by mass or more with respect to the total mass of the polymer component and 15 mass% or less, 0.5 mass% or more and 12 mass% or less is more preferable, and 1 mass% or more and 10 mass% or less is more preferable. The content of the structural unit having an acid group is the content of the structural unit having an acid group when all the polymers included in the polymer component with respect to the total mass of the polymer component are decomposed into structural units (monomer units). Quality ratio.

From the viewpoint of lamination adaptability, it is preferred that the above-mentioned photosensitive resin layer with respect to the total mass of the photosensitive resin layer in the present embodiment contain the above-mentioned polymer component in a proportion of 50% to 99.9% by mass. A content of 70% to 98% by mass is more preferable. Moreover, it is preferable that the said photosensitive resin layer contains the said specific polymer in the ratio of 50 mass%-99.9 mass% with respect to the total mass of the photosensitive resin layer from a viewpoint which shows favorable adhesiveness with respect to the said substrate, It is more preferable to contain it in the ratio of 70 mass%-98 mass%.

[Photoacid generator] The photosensitive resin layer contains a photoacid generator. The photoacid generator used in this embodiment is a compound capable of generating an acid by irradiating active radiation such as ultraviolet rays, extreme ultraviolet rays, X-rays, and charged particle beams. As the photo-acid generator used in this embodiment, actinic rays with a wavelength of 300 nm or more, preferably 300-450 nm, are induced, and compounds that generate acids are preferred, but are not limited to this chemical structure. Moreover, even if it is a photoacid generator that does not directly sense actinic rays with a wavelength of 300 nm or more, it can be combined with a sensitizer as long as it is a compound that uses a sensitizer to sense actinic rays with a wavelength of 300 nm or more and generate acid. To better use. As the photoacid generator used in this embodiment, a photoacid generator that generates an acid with a pKa of 4 or less is preferred, a photoacid generator that generates an acid with a pKa of 3 or less is more preferred, and a pKa that is 2 The following acid photoacid generators are particularly preferred. The lower limit of pKa is not particularly limited, but is preferably -10.0 or more, for example.

Examples of the photoacid generator include an ionic photoacid generator and a nonionic photoacid generator. 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 consisting of an onium salt compound described later and an oxime sulfonate compound described later, and to include an oxime sulfonic acid Salt compounds are more preferred.

Examples of the non-ionic photoacid generator include trichloromethyl meso-three wells, diazomethane compounds, amidine sulfonate compounds, and oxime sulfonate compounds. Among these, from the viewpoints of sensitivity, resolution, and adhesiveness, the photoacid generator is preferably an oxime sulfonate compound. These photoacid generators can be used alone or in combination of two or more. As specific examples of the trichloromethyl mesothree wells and diazomethane derivatives, the compounds described in paragraphs 0083 to 0088 of Japanese Patent Application Laid-Open No. 2011-221494 can be exemplified.

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

[Chemical Formula 9]

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

Any group of the compound containing an oxime sulfonate structure represented by the formula (B1) may be substituted, and the alkyl group in R ²¹ may be linear, may have a branched structure, or may have a ring structure. Permitted substituents are described below. As the alkyl group of R ²¹ , a linear or branched alkyl group having 1 to 10 carbon atoms is preferred. The alkyl group of R ²¹ can be bridged with an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (including 7,7-dimethyl-2-oxonorbornyl group). A cyclic group, a bicycloalkyl group or the like is preferred) or a halogen atom is substituted. As the aryl group of R ^21, an aryl group having 6 to 18 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ²¹ may be substituted with one or more types of groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group, and a halogen atom.

The compound containing the oxime sulfonate structure represented by the above formula (B1) is also preferably the oxime sulfonate compound described in paragraphs 0078 to 0111 of Japanese Patent Application Laid-Open No. 2014-85643.

From the viewpoint of sensitivity, a compound containing an oxime sulfonate structure represented by the formula (B1) is also a compound represented by the following formula (B2).

[Chemical Formula 10]

In the formula B2 represents perhaloalkyl or perhalogenated aryl group, R ² represents an alkoxy group, R ³ represents an alkyl group, an aryl group or perhaloalkyl. In this specification, "perhaloalkyl" means an alkyl group in which one or more hydrogen atoms are replaced by a halogen atom, and "perhaloaryl" means that one or more hydrogen atoms are in a halogen group unless otherwise specified. Atomically substituted aryl. Examples of the halogen atom include fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). A fluorine atom is preferred.

In Formula B2, R ¹ is a perhaloalkyl group having 1 to 12 carbon atoms, and a perhaloaryl group having 6 to 10 carbon atoms is more preferred. A perhaloalkyl group having 1 to 12 carbon atoms is more preferred, and the carbon number is 1 to perhaloalkyl 4 is more excellent, -CF ₃ group is further preferred. In Formula B2, R ² is an alkoxy group, an alkoxy group having 1 to 4 carbon atoms is more preferable, and a methoxy group is more preferable. In Formula B2, R ³ is a perhaloalkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

As a preferable specific example of the compound represented by Formula B2, the following structure can be illustrated. However, the compound represented by Formula B2 is not limited to these.

[Chemical Formula 11]

Examples of the ionic photoacid generator include onium salt compounds such as diarylphosphonium salts and triarylphosphonium salt compounds, and quaternary ammonium salts. Among these, onium salt compounds are preferred, and triarylphosphonium salts and diarylphosphonium salts are particularly preferred.

As the ionic photoacid generator, the ionic photoacid generator described in paragraphs 0114 to 0133 of Japanese Patent Application Laid-Open No. 2014-85643 can also be preferably used.

The photoacid generator may be used alone or in combination of two or more. From the viewpoint of sensitivity and resolution, the content of the photoacid generator in the photosensitive resin layer is preferably 0.5% to 20% by mass, and 1% to 15% by mass of the total mass of the photosensitive resin layer. The mass% is more preferable, and 1 to 10 mass% is more preferable.

[Solvent] In the case of forming the above-mentioned photosensitive resin layer, it is preferable to form a photosensitive resin composition containing a polymer component, a photoacid generator, and a solvent by coating and drying. More specifically, in order to easily form the photosensitive resin layer, the viscosity of the photosensitive resin composition is adjusted by containing a solvent, and the photosensitive resin composition containing a solvent is coated and dried to appropriately form the photosensitive property. Resin layer. Examples of the solvent include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, and propylene glycol monoalkyl ethers. 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, amidines, and lactones. Specific examples of the solvent include the solvents described in paragraphs 0174 to 0178 of Japanese Patent Application Laid-Open No. 2011-221494, and the contents are incorporated into this specification.

Furthermore, benzyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, Caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate or Solvents such as propylene carbonate. Only one kind of solvent may be used, or two or more kinds may be used. The solvent may be used singly or in combination. When two or more solvents are used, for example, a combination of propylene glycol monoalkyl ether acetates and dialkyl ethers, a combination of diacetate and diethylene glycol dialkyl ethers, or an ester and succinic acid Combinations of alcohol alkyl ether acetates are preferred.

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 thereof is 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 ° C). ) And propylene glycol methyl-n-propyl ether (boiling point 131 ° C). Examples of the solvent 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 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether ( Boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), and 1,3-butanediol diacetate Acetate (boiling point: 232 ° C).

The content of the solvent when the photosensitive resin composition is applied is preferably 50 to 1,900 parts by mass per 100 parts by mass of the total solid content in the photosensitive resin composition, and 100 to 900 parts by mass is Better. The content of the solvent in the photosensitive resin layer is preferably 2% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less with respect to the total mass of the photosensitive resin layer.

[Other Additives] The above-mentioned specific polymer and photoacid generator are added to the photosensitive resin layer in this embodiment, and known additives can be included as necessary.

-Plasticizer- The photosensitive resin layer may contain a plasticizer for the purpose of improving plasticity. The weight average molecular weight of the plasticizer is preferably smaller 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, more 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 a compound that is compatible with the specific polymer described above and exhibits plasticity. From the viewpoint of imparting plasticity, the plasticizer preferably has an alkoxy group in the molecule. It is preferable that the alkoxy group contained in the plasticizer has the following structure.

[Chemical Formula 12]

In the above formula, R is an alkylene 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 a compound having the above-mentioned alkoxy group (referred to as "compound X"), the photosensitive resin layer obtained by mixing the compound X, the specific polymer, and the photoacid generator, and the compound X is not contained If the formed photosensitive resin layer does not have improved plasticity, it does not conform to the plasticizer in this aspect. For example, an arbitrarily added surfactant is generally not used in an amount that imparts plasticity to the photosensitive resin layer, and therefore does not conform to the plasticizer in this specification.

As a plasticizer, the compound which has a following structure is mentioned, for example, It is not limited to these.

[Chemical Formula 13]

When a plasticizer is used, the content of the plasticizer is preferably 1% to 50% by mass, and 2% to 20% by weight based on the total mass of the photosensitive resin layer. Quality% is better. The said photosensitive resin layer may contain only one type of plasticizer, and may contain two or more types.

-Sensitizer- The photosensitive resin layer may further include a sensitizer. The sensitizer absorbs active radiation (actinic rays) and becomes an electronically excited state. The sensitizer that is in an electronically excited state comes into contact with the photoacid generator to generate electron movement, energy movement, and heat generation. This causes the photoacid generator to undergo a chemical change to decompose and generate an acid. By containing a sensitizer, exposure sensitivity can be improved.

As a sensitizer, a compound selected from the group consisting of anthracene derivatives, acridone derivatives, oxanthine derivatives, coumarin derivatives, basic styrene derivatives, and distyrylbenzene derivatives More preferably, 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 are 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 more preferably 0% by mass to 10% by mass with respect to the total mass of the photosensitive resin layer, and more preferably 0.1% by mass to 10% by mass.

—Basic Compound— The photosensitive resin layer preferably further contains a basic compound. The basic compound can be arbitrarily selected from the basic compounds used in the resist. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxide, and quaternary ammonium salts of carboxylic acids. Specific examples of these include the compounds described in paragraphs 0204 to 0207 of Japanese Patent Application Laid-Open No. 2011-221494, and the contents are incorporated herein.

Specific examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, and tri-n-pentyl Amine, diethanolamine, triethanolamine, dicyclohexylamino and dicyclohexylmethylamine. Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, and diphenylamine. Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-hexylpyridine, 2-phenylpyridine, 4-phenylpyridine, and N-formyl 4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, Nicotinic acid, nicotinamide, quinoline, 8-oxoquinoline, pyrazine, pyrazol, pyridazine, purine, pyrrolidine, piperidine, pipelothole, morpholine, 4-methylmorpholine, 1,5 -Diazabicyclo [4.3.0] -5-nonene and 1,8-diazabicyclo [5.3.0] -7-undecene and the like. Examples of the tertiary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide. Examples of the quaternary ammonium salt of a carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium acetate.

The basic compound may be used singly or in combination of two or more kinds. The content of the basic compound is preferably 0.001% to 5% by mass, and more preferably 0.005% to 3% by mass based on the total mass of the photosensitive resin layer.

-Heterocyclic compound- The photosensitive resin layer in this embodiment can contain a compound containing a heterocyclic compound. The heterocyclic compound in this aspect is not particularly limited. For example, compounds containing epoxy groups or oxetanyl groups, alkoxymethyl-containing heterocyclic compounds, various other cyclic ethers, cyclic esters (lactones), etc. can be added to the molecules described below. Nitrogen-containing monomers such as acid monomers, cyclic amines, and oxazoline groups can be further added with heteroatom-containing ring monomers such as silicon, sulfur, and phosphine having an atom with a d electron.

When a heterocyclic compound is added, the addition amount of the heterocyclic compound in the photosensitive resin layer is preferably 0.01% by mass to 50% by mass, and 0.1% by mass to 10% by mass. For better quality, 1 to 5 mass% is more preferable. If it is the said range, it is preferable from a viewpoint of adhesiveness and etching resistance. The heterocyclic compound may be used singly or in combination of two or more kinds. When two or more kinds are used in combination, the above-mentioned preferable content means the total content of two or more kinds of heterocyclic compounds.

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

A compound having an epoxy group in the molecule can be purchased as a commercially available product. Examples include JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Corporation), JER157S65 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), etc., and commercially available products described in paragraph 0189 of Japanese Patent Application Laid-Open No. 2011-221494. . Other commercially available products include 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, NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD. Manufactured), CELLOXIDE 2021P, 2081, 2000, 3000, EHPE3150, Epolead GT400, CELVENUS B0134, B0177 (made by Daicel Corporation), and the like. The compound having an epoxy group in the molecule may be used singly or in combination of two or more kinds.

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 are more preferable, and particularly, Preferably, an aliphatic epoxy resin is mentioned.

As specific examples of the compound having an oxetanyl group 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.).

Further, the compound containing an oxetanyl group is preferably used alone or in combination with a compound containing an epoxy group.

It is preferable that the photosensitive resin layer in this embodiment contains a compound which has an epoxy group as a heterocyclic compound from a viewpoint of etching resistance and line width stability.

—Alkoxysilane compound— The photosensitive resin layer may contain an alkoxysilane compound. The alkoxysilane compound is preferably a trialkoxysilane compound. Examples of the alkoxysilane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropylalkoxysilane, and γ-epoxy Propoxypropylalkyldialkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloro Propyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, ethylenetrialkoxysilane. Among these, γ-glycidoxypropylalkoxysilane or γ-methacryloxypropyltrialkoxysilane is more preferable, and γ-glycidoxypropylalkoxy Silyl is further preferred, and 3-glycidoxypropyltrimethoxysilane is particularly preferred. These can be used individually by 1 type or in combination of 2 or more types.

-Surfactant- From the viewpoint of film thickness uniformity, it is preferable that the photosensitive resin layer contains a surfactant. As the surfactant, any of anionic, cationic, nonionic, or amphoteric can be used, but a preferred surfactant is a nonionic surfactant. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, polyoxyethylene higher fatty acid diesters, polysiloxanes, Fluorine surfactant. Examples include the following KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Japan Electronic Monetary Claim Organization), and Megaface (registered trademark, manufactured by DIC Corporation) ), Fluorad (made by Sumitomo 3M Limited), AsahiGuard, Surflon (registered trademark, made by Asahi Glass Co., Ltd.), PolyFox (made by OMNOVA SOLUTIONS INC.), And SH-8400 (made by Dow Corning Toray Co., Ltd.) Series such as trade names. In addition, as the surfactant, a polystyrene-equivalent weight measured by a gel permeation chromatography method including a constitutional unit A and a constitutional unit B represented by the following formula I-1 and using tetrahydrofuran (THF) as a solvent can be used. Copolymers having an average molecular weight (Mw) of 1,000 or more and 10,000 or less are given as preferred examples.

[Chemical Formula 14]

In 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 carbon atom Alkyl group of 4 or more, L is an alkylene group having 3 or more and 6 or less carbon, p and q are mass percentages of the polymerization ratio, p is a value of 10% by mass to 80% by mass, and q is 20 Numerical values of not less than mass% and not more than 90% by mass, r represents an integer of 1 to 18, s represents an integer of 1 to 10, and * represents a bonding position with another structure.

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

[Chemical Formula 15]

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

In addition, the surfactants 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.

The surfactant may be used singly or in combination of two or more kinds. The content of the surfactant is preferably 10% by mass or less with respect to the total mass of the photosensitive resin layer, more preferably 0.001% by mass to 10% by mass, and still more preferably 0.01% by mass to 3% by mass.

-Other ingredients- The photosensitive resin layer in this embodiment can also be added with metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, colorants, and thermal radical polymerization initiators. Well-known additives such as thermal acid generators, ultraviolet absorbers, tackifiers, cross-linking agents, and organic or inorganic precipitation inhibitors. Preferred aspects of other ingredients are described in paragraphs 0165 to 0184 of Japanese Patent Application Laid-Open No. 2014-85643, the contents of which are incorporated herein.

[Thickness of Photosensitive Resin Layer] The thickness of the photosensitive resin layer is preferably 0.5 μm to 20 μm. When the thickness of the photosensitive resin layer is 20 μm or less, the resolution of the pattern is good, and when it is 0.5 μm or more, it is preferable from the viewpoint of pattern linearity. The thickness of the photosensitive resin layer is more preferably 0.8 μm to 15 μm, and particularly preferably 1.0 μm to 10 μm.

[Method for Forming Photosensitive Resin Layer] A photosensitive resin composition for forming a photosensitive resin layer can be prepared by mixing the components and the solvent at a specific ratio and by any method, and stirring and dissolving. For example, each component can be dissolved in a solvent to prepare a solution, and the obtained solution can be mixed at a specific ratio to prepare a composition. The composition prepared as described above can also be used after being filtered by a filter having a pore size of 0.2 μm or the like.

By applying the photosensitive resin composition to a temporary support and drying it, a photosensitive transfer material according to this embodiment having a photosensitive resin layer on the temporary support can be obtained. The coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, or inkjet coating. In addition, a photosensitive resin layer can also be applied to a laminated body between a temporary support having another layer described later and another layer on the temporary support.

<Other Layers> The photosensitive transfer material according to this embodiment may have layers other than the above-mentioned photosensitive resin layer (hereinafter, also referred to as “other layers”). Examples of the 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 according to this embodiment may include a contrast enhancement layer in addition to the above-mentioned photosensitive resin layer. Contrast Enhancement Layer (CEL) has a large absorption of the exposure wavelength before exposure, but the absorption gradually decreases as it is exposed, that is, a material containing light with a higher transmittance (called "light decolorization" Sex pigment ingredient ".). As a photochromic pigment component, a diazonium salt, a stilbazolium salt, an arylnitroso salt, etc. are known. As the film-forming component, a phenol resin or the like is 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, photopolymer manuals, and photopolymerization seminars can be used. , Industrial survey meeting (1989), photopolymerization and technology, edited by Yamaoka and Wingsong, THE NIKKAN KOGYO SHIMBUN, LTD. (1988).

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

<Thermoplastic resin layer, cover film, etc.> The photosensitive transfer material of this embodiment can also have a temporary support body, a thermoplastic resin layer, and a positive photosensitive resin layer in this order, for example. For the purpose of protecting the photosensitive resin layer, a cover film may be provided. The preferred aspect of the thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Application Laid-Open No. 2014-85643, and the preferred aspect of the other layers is described in paragraph 0194 of Japanese Patent Application Laid-Open No. 2014-85643. It is described in paragraph 0196, and the content of this bulletin is incorporated into this specification.

When the photosensitive transfer material of this embodiment has another layer such as a thermoplastic resin layer, it can be produced in accordance with the method for preparing a photosensitive transfer material described in paragraphs 0094 to 0098 of Japanese Patent Application Laid-Open No. 2006-259138. . For example, when producing the photosensitive transfer material of this embodiment having a thermoplastic resin layer and an intermediate layer, a solution (a coating solution for a thermoplastic resin layer) in which a thermoplastic organic polymer and an additive are dissolved is applied to After the thermoplastic resin layer is provided on the temporary support and dried, a preparation liquid (coating liquid for an intermediate layer) prepared by adding a resin and an additive to a solvent that does not dissolve the thermoplastic resin layer is applied to the obtained thermoplastic resin. Layer, and allowed to dry to laminate the intermediate layer. A photosensitive resin composition prepared using a solvent that does not dissolve the intermediate layer is also coated on the formed intermediate layer and dried to laminate the photosensitive resin layer, so that the photosensitive resin composition of this embodiment can be appropriately prepared. Printed materials.

(Method of Manufacturing Circuit Wiring) A first embodiment of a method of manufacturing a circuit wiring using the photosensitive transfer material of this embodiment will be described. The first embodiment of the method for manufacturing a circuit wiring includes, in order: a substrate on which the outermost layer of the photosensitive transfer material on the side opposite to the temporary support body of the embodiment is brought into contact with the substrate and bonded together. Step (adhesion step); pattern exposure step (exposure step) of the photosensitive resin layer of the photosensitive transfer material after the step of lamination; development of the photosensitive resin layer after the step of exposure A step of forming a pattern (developing step); and a step of performing an etching process (etching step) on a substrate in a region where the above pattern is not arranged. The substrate in the first embodiment of the circuit wiring manufacturing method may be a substrate such as glass, silicon dioxide, or a thin film itself, or a conductive layer may be provided on the substrate such as glass, silicon dioxide, or a thin film as required. And other arbitrary substrates. According to the first embodiment of the method for manufacturing a circuit wiring, a fine pattern can be formed on the substrate surface.

A second embodiment of a circuit wiring manufacturing method includes, in order, a base material and a plurality of conductive layers including a first conductive layer and a second conductive layer whose constituent materials are different from each other. The top surface layer of the substrate is sequentially laminated with the first surface layer, that is, the first conductive layer and the second conductive layer on the substrate, so that the photosensitive transfer material of this embodiment on the opposite side to the temporary support A laminating step of laminating an outer layer in contact with the first conductive layer; a first exposing step of pattern exposing the temporary support of the photosensitive transfer material after the laminating step via the photosensitive resin layer; After the photosensitive resin layer after the first exposure step is peeled off the temporary support, the photosensitive resin layer after the first exposure step is developed to form a first development step of a first pattern; a region where the first pattern is not arranged A first etching step of performing an etching treatment on at least the first conductive layer and the second conductive layer among the plurality of conductive layers in the first conductive layer; and the first pattern after the first etching step A second exposure step of pattern exposure in a pattern different from the first pattern; a second development step in which the first pattern after the second exposure step is developed to form a second pattern; and the second pattern is not arranged A second etching step of performing an etching process on at least the first conductive layer among the plurality of conductive layers in the region. As the second embodiment, reference may be made to International Publication No. 2006/190405, which is incorporated into this specification.

The manufacturing method of the circuit wiring of this aspect can be used as the manufacturing method of the circuit wiring for a touch panel or a touch panel display device. Hereinafter, details of each step will be described based on the second embodiment.

<Lamination Step> An example of the lamination step is schematically shown in (a) of FIG. 2. First, in the bonding step, the substrate 22 and the plurality of conductive layers including the first conductive layer 24 and the second conductive layer 26 which are different from each other in the constituent materials are arranged on the surface of the substrate 22 away from the surface of the substrate 22. In this order, on the substrate (circuit wiring formation substrate) 20 of the laminated outermost layer, that is, the first conductive layer 24 and the second conductive layer 26, the positive type of the photosensitive transfer material 100 of the embodiment described above is photosensitive. The flexible resin layer 14 is in contact with and bonded to the first conductive layer 24. In addition, the bonding of such a circuit wiring forming substrate and a photosensitive transfer material may be referred to as "transfer" or "lamination". The outermost layer on the side opposite to the temporary support may be a photosensitive resin layer or an adhesion layer or an ultraviolet absorbing layer.

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 is removed from the photosensitive transfer material 100 (the positive photosensitive resin layer 14). Thereafter, the positive-type photosensitive resin layer 14 of the photosensitive transfer material 100 is brought into contact with the first conductive layer 24 and bonded. Regarding the bonding (transfer) to the first conductive layer of the photosensitive transfer material, the positive photosensitive resin layer side of the photosensitive transfer material is overlapped with the first conductive layer, and pressure is applied by a roller or the like. And heating is preferred. For lamination, a known laminator such as a laminator, a vacuum laminator, and an auto-cut laminator that can further improve productivity can be used. In the case of the base-material-based resin film of the circuit wiring forming substrate, it is possible to attach the film on a roll-to-roll basis.

[Substrate] In 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 a film substrate is more preferable. In the manufacturing method of the circuit wiring of this embodiment, when the circuit wiring for a touch panel is used, it is particularly preferable that the base material is a sheet-like resin composition. It is preferable that the substrate is transparent. The refractive index of the substrate is preferably 1.50 to 1.52. The substrate may be made of a light-transmitting substrate such as a glass substrate, and tempered glass typified by Gorilla Glass, such as Corning Incorporated Co., Ltd., may be used. In addition, as the transparent substrate, materials used in Japanese Patent Application Laid-Open No. 2010-86684, Japanese Patent Application Laid-Open No. 2010-152809, and Japanese Patent Application Laid-Open No. 2010-257492 can be preferably used. When a film substrate is used as the substrate, it is more preferable to use a substrate without optical strain and a substrate with high transparency. Specific materials include polyethylene terephthalate (PET) and polyethylene naphthalate. Ethylene glycol formate, polycarbonate, triethyl cellulose, cycloolefin polymer.

[Conductive Layer] Examples of the plurality of conductive layers formed on the substrate include any conductive layer used in general circuit wiring or touch panel wiring. Examples of the material of the conductive layer include metals and metal oxides. Examples of the metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO ₂ . Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Mo, and the like.

Regarding the method for manufacturing circuit wiring in this embodiment, it is preferable that at least one of the plurality of conductive layers includes a metal oxide. As the conductive layer, the electrode pattern of the sensor corresponding to the visible portion used in the capacitive touch panel or the wiring of the edge lead-out portion is preferable.

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

<Exposure step (first exposure step)> The exposure step is performed in the first embodiment, and the first exposure step is performed in the second embodiment. 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-type photosensitive resin layer 14 is pattern-exposed through the temporary support 12 of the photosensitive transfer material after the bonding step.

As examples of the exposure step, the development step, and other steps in this embodiment, the methods of paragraphs 0035 to 0051 of Japanese Patent Application Laid-Open No. 2006-23696 can be appropriately used in this embodiment.

For example, a mask 30 having a specific pattern may be disposed above the photosensitive transfer material 100 disposed on the first conductive layer 24 (the side opposite to the side where the first conductive layer 24 contacts), and thereafter , A method of exposing with ultraviolet rays through the mask 30 from above the mask. The detailed arrangement and specific size of the patterns in this embodiment are not particularly limited. The display quality of a display device (for example, a touch panel) having an input device with circuit wiring manufactured by this embodiment is improved, and at least a part of the pattern is from the aspect of minimizing the area occupied by the wiring. (Especially the electrode pattern of the touch panel and the portion where the wiring is taken out) are preferably thin wires of 100 μm or less, and more preferably 70 μm or less. Among them, as a light source for exposure, as long as it can irradiate light (for example, 365 nm, 405 nm, etc.) in a wavelength region where the exposed portion of the photosensitive transfer material can be dissolved in a developing solution, it can be appropriately selected and used. Specifically, ultrahigh-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and the like. The exposure amount is usually about ⁵ mJ / cm ² to 200 mJ / cm ² , and preferably about 10 mJ / cm ² to 100 mJ / cm ² . It is also preferable to perform heat treatment before development for the purpose of improving the rectangularity and linearity of the pattern after exposure. The so-called PEB (Post Exposure Bake, post-exposure bake) step can reduce the roughness of the pattern edges caused by standing waves generated in the photosensitive resin layer during exposure.

The pattern exposure may be performed after the temporary support is peeled from the positive-type photosensitive resin layer, or the temporary support may be exposed through the temporary support before the temporary support is peeled, and then the temporary support may be peeled off. In order to prevent contamination of the mask due to the contact between the photosensitive resin layer and the mask, and to avoid the effect of foreign matter adhering to the mask on exposure, it is preferable to perform exposure without peeling off the temporary support. In addition, the pattern exposure may be an exposure through a mask, or a digital exposure using a laser or the like.

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

The developing step (first developing step) is a step of forming a pattern (first pattern) by developing a pattern-exposed positive-type photosensitive resin layer. The development of the pattern-exposed positive-type photosensitive resin layer can be performed using a developing solution. The developer is not particularly limited as long as it can remove the exposed portion of the positive-type 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. Moreover, it is preferable that the developing solution is a developing solution which makes the exposed part of the photosensitive resin layer perform a dissolution-type developing behavior. For example, an alkaline aqueous solution-based developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol / L (liter) to 5 mol / L is preferable. The developer may further contain an organic solvent, a surfactant, and the like, which are miscible with water. Examples of the developer to be preferably used in this embodiment 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-on immersion development, shower development, shower and rotary development, and immersion development. Here, shower development is described. The developer is sprayed onto the positive-type photosensitive resin layer after exposure by shower, and the exposed portion can be removed. After the development, it is preferable to spray a cleaning agent or the like by spraying and remove the development residue while wiping with a brush or the like. The liquid temperature of the developer is preferably 20 ° C to 40 ° C.

Moreover, you may have the drying process after heat-processing the pattern containing the positive photosensitive resin layer obtained by image development. The post-baking heating is preferably performed in an environment of 8.1 kPa to 121.6 kPa, and more preferably performed in an environment of 506.6 kPa or more. On the other hand, it is more preferable to perform in an environment of 1114.6 kPa or less, and it is particularly preferable to perform 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-drying time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and even more preferably 2 minutes to 4 minutes. Post-drying can be performed in an air environment or in a nitrogen-replaced environment.

There may be other steps such as a post-exposure step.

<Etching Step (First Etching Step)> The etching step is performed in the first embodiment, and the first etching step is performed in the second embodiment. An example of the etching step (first etching step) is schematically shown in (d) of FIG. 2. In the etching step (first etching step), at least the first conductive layer 24 and the second conductive layer 26 are etched in the plurality of conductive layers in the region where the first pattern 14A is not arranged. The first conductive layer 24A and the second conductive layer 26A having a pattern are formed in the same manner by etching.

The conductive layer can be etched by a known method such as a method described in paragraphs 0048 to 0054 of Japanese Patent Application Laid-Open No. 2010-152155 and a method based on a known dry etching method such as plasma etching.

For example, as the etching method, a wet etching method which is usually performed by immersion in an etching solution is mentioned. The etching solution used in the wet etching may appropriately select an acidic type or an alkaline type etching solution depending on the etching target. Examples of the acidic etchant include aqueous solutions of acidic components alone such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid, and mixed aqueous solutions of acidic components and salts such as ferric chloride, ammonium fluoride, and potassium permanganate. As the acidic component, a combination of a plurality of types of acidic components can be used. Examples of the alkaline type etching solution include aqueous solutions of alkali components such as sodium hydroxide, potassium hydroxide, ammonia, organic amines, salts of organic amines such as tetramethylammonium hydroxide, alkali components, and permanganese. A mixed aqueous solution of salts such as potassium acid and the like. As the alkali component, a combination of a plurality of types of alkali components can be used.

The temperature of the etching solution is not particularly limited, but is preferably 45 ° C or lower. In this embodiment, it is preferable that the first pattern used as an etching mask (etching pattern) exhibits excellent resistance to acidic and alkaline etching solutions in a temperature range of 45 ° C. or lower. This prevents the positive photosensitive resin layer from being peeled off during the etching step, and the portion where the positive photosensitive resin layer does not exist can be selectively etched.

After the etching step, in order to prevent contamination of the production line, a washing step and a drying step may be performed as needed. The washing step is performed, for example, by washing the substrate with pure water for 10 seconds to 300 seconds at normal temperature, and the drying step is performed using, for example, a blower and appropriately adjusting the pressure of the blower (about 0.1 kg / cm ² to 5 kg / cm ² ). Just dry.

<Second exposure step> In the second embodiment, the second exposure step is performed. An example of the second exposure step is schematically shown in FIG. 2 (e). 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, the portion corresponding to at least the portion of the first conductive layer to be removed in the second development step described later is exposed relative to the first pattern remaining on the first conductive layer. In the pattern exposure in the second exposure step, the same method as the pattern exposure in the first exposure step can be applied except that a mask 40 having a pattern different from the mask 30 used in the first exposure step is used.

<Second Development Step> In the second embodiment, the second development step is performed. An example of the second development step is schematically shown in (f) of FIG. 2. In the second development step, the first pattern 14A after the second exposure step is developed to form a second pattern 14B. By the development, a part of the first pattern that is exposed in the second exposure step can be removed. In the second development step, the same method as that in the first development step can be applied.

<Second Etching Step> In the second embodiment, the second exposure step is performed. An example of the second etching step is schematically shown in (g) of FIG. 2. In the second etching step, at least the first conductive layer 24A is etched out of the plurality of conductive layers in the region where the second pattern 14B is not arranged.

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

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

The method of removing the remaining positive-type photosensitive resin layer is not particularly limited, and a method of removing it by chemical treatment can be mentioned. Examples of the method for removing the positive-type photosensitive resin layer include, for example, a base having a positive-type photosensitive resin layer in a peeling solution under stirring at 30 ° C to 80 ° C (50 ° C to 80 ° C is preferred). Method of immersing the material for 1 minute to 30 minutes.

Examples of the stripping solution include dissolving inorganic alkali components such as sodium hydroxide and potassium hydroxide or organic alkali components such as primary amine, secondary amine, tertiary amine, and quaternary ammonium salt in water, dimethylsulfine, N-methylpyrrolidone or stripping solution in these mixed solutions. The peeling liquid can be peeled by a spray method, a shower method, a spin-on immersion method, or the like.

The manufacturing method of the circuit wiring of this embodiment may include other arbitrary steps. For example, the following steps may be mentioned, but they are not limited to these steps.

<Procedure for attaching a protective film> In the above-mentioned second embodiment, it is also possible to attach a protective film (not shown) having a light-transmitting property to the first pattern before the second exposure step after the first etching step. step. At this time, in the second exposure step, the protective film is pattern-exposed via the first pattern. After the second exposure step, the protective film is peeled from the first pattern and then the second development step is performed.

<Step of Reducing Visible Light Reflectance> The method for manufacturing circuit wiring of this embodiment can include a step of reducing a part or all of the visible light reflectance of the plurality of conductive layers on the substrate. Examples of the treatment for reducing the visible light reflectance include an oxidation treatment and the like. For example, the copper can be oxidized to produce copper oxide to blacken it, thereby reducing visible light reflectance. Regarding the preferred aspect of the treatment for reducing the visible light reflectance, paragraphs 0017 to 0025 of Japanese Patent Application Laid-Open No. 2014-150118 and paragraphs 0041, 0041, 0048, and 0058 of Japanese Patent Laid-Open No. 2013-206315 It is described in this publication, and the content of this bulletin is incorporated in this specification.

<Steps of forming a new conductive layer on the insulating film> The method of manufacturing circuit wiring in this embodiment also includes a step of forming an insulating film on the formed circuit wiring and a step of forming a new conductive layer on the insulating film. good. With this configuration, the second electrode pattern and the first electrode pattern can be formed by being insulated. The step of forming the insulating film is not particularly limited, and a known method of forming a permanent film can be exemplified. Alternatively, an insulating film having a desired pattern may be formed by a photolithography method using a photosensitive material having an insulating property. The step of forming a new conductive layer on the insulating film is not particularly limited. A new conductive layer having a desired pattern can be formed by a photolithography method using a photosensitive material having conductivity.

In the description referring to (a) to (h) of FIG. 2, a case where a circuit wiring having two different patterns is formed on a circuit wiring forming substrate having two conductive layers will be described, but it is applicable to this embodiment. The number of conductive layers of the substrate of the circuit wiring manufacturing method is not limited to two, and the conductive wiring forming substrate is used to form three or more circuit wiring forming substrates, and the aforementioned exposure step, development step, and etching step are performed three or more times. In this way, it is also possible to form three or more conductive layers on different circuit wiring patterns.

Also, although not shown in (a) to (h) of FIG. 2, in the method for manufacturing a circuit wiring according to this embodiment, the substrate has a plurality of conductive layers on the surfaces of both sides. It is also preferable that the conductive layers on the surfaces of both sides are formed sequentially or simultaneously. With this configuration, circuit wiring for a touch panel in which a first conductive pattern is formed on one surface of the base material and a second conductive pattern is formed on the other surface can be formed. Moreover, it is preferable to form the circuit wiring for a touch panel of such a structure from the both sides of a base material in a roll-to-roll method.

(Circuit Wiring and Circuit Board) The circuit wiring of this embodiment is a circuit wiring manufactured by the method of manufacturing a circuit wiring of this embodiment. The circuit board according to this embodiment is a substrate having circuit wiring manufactured by the method for manufacturing a circuit wiring according to this embodiment. The use of the circuit substrate of this embodiment is not particularly limited, and for example, a circuit substrate for a touch panel is preferred.

(Input Device and Display Device) As the device provided with the circuit wiring manufactured by the method for manufacturing a circuit wiring according to this embodiment, an input device is mentioned. It is preferable that the input device in this embodiment is a capacitive touch panel. It is preferable that the display device in this aspect includes the input device in this aspect. The display device in this aspect is preferably an image display device such as an organic EL display device and a liquid crystal display device.

(Touch panel, touch panel display device, and manufacturing method thereof) The touch panel of this embodiment is a touch panel having at least circuit wiring manufactured by the method of manufacturing a circuit wiring of this embodiment. In addition, it is preferable that the touch panel of this embodiment has at least a transparent substrate, electrodes, and an insulating layer or a protective layer. The touch panel display device of this embodiment is a touch panel display device having at least circuit wiring manufactured by the method of manufacturing a circuit wiring of this embodiment, and a touch panel display device having a touch panel of this embodiment Is better. It is preferable that the manufacturing method of the touch panel or the touch panel display device of this embodiment includes the manufacturing method of the circuit wiring of this embodiment. The method for manufacturing a touch panel or a touch panel display device according to this embodiment sequentially includes: contacting the above-mentioned photosensitive layer of the photosensitive transfer material obtained by the manufacturing method of the photosensitive transfer material with the substrate and pasting the same A combination step; a step of pattern exposure of the photosensitive layer of the photosensitive transfer material after the step of laminating; a step of developing a pattern of the photosensitive layer after the step of exposing to form a pattern; and The step of arranging the substrate in the region of the above pattern to perform the etching process is preferable. The details of each step have the same meaning as the details of each step in the above-mentioned manufacturing method of circuit wiring, and the preferred aspect is also the same. As the detection method of the touch panel of the embodiment and the touch panel display device of the embodiment, known methods such as a resistance film method, an electrostatic capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method can be used. Either. Among them, the electrostatic capacitance method is preferable. Examples of the touch panel type include a so-called in-cell type (for example, those described in FIGS. 5, 6, 7, and 8 of Japanese Patent Application Publication No. 2012-517051), and an so-called in-cell type (for example, in Japanese Published in Figure 19 of 2013-168125, disclosed in Figures 1 and 5 of Japanese Unexamined Patent Publication No. 2012-89102), OGS (One Glass Solution) type, TOL (Touch -on-Lens (lens touch) type (for example, described in FIG. 2 of JP 2013-54727), other structures (for example, described in FIG. 6 of JP 2013-164871), Various plug-in types (so-called GG, G1, G2, GFF, GF2, GF1, G1F, etc.). As the touch panel of this embodiment and the touch panel display device of this embodiment, it can be applied to "the latest touch panel technology" (July 6, 2009, issued by Techno Times Co., Ltd.), Mitani Yuji Supervisor, "Technology and Development of Touch Panel", CMC Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, etc. [Example]

Examples are given below to more specifically describe the embodiments of the present invention. The materials, usage amounts, proportions, processing contents, processing steps, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present disclosure. Therefore, the scope of the present disclosure is not limited to the specific examples shown below. In addition, as long as there is no particular limitation, "parts" and "%" are mass standards.

(Synthesis of polymer component) In the following synthesis examples, the following abbreviations indicate the following compounds, respectively. ATHF: 2-tetrahydrofuryl acrylate (synthetic product) MATHF: 2-tetrahydrofuryl methacrylate (synthetic product) ATHP: tetrahydro-2H-pyran-2-yl acrylate (Shin-Nakamura Chemical Co., Ltd (Manufactured) MATHP: tetrahydro-2H-pyran-2-yl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) MAEVE: ethoxyethyl 1-methacrylate (Wako Pure Chemical Industries, Ltd.) ATB: tertiary butyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) HS: 4-hydroxystyrene (synthetic product) CS: 4-carboxystyrene (Tokyo Chemical Industry Co., Ltd.) (Manufactured) THFHS: 4- (2-tetrahydrofuryloxy) styrene (synthetic product) THFCS: 4- (2-tetrahydrofuryloxyhydroxy) styrene (synthetic product) THFMS: succinic acid 1- [2- (formaldehyde) Protective body (synthetic product) of 2-tetrahydrofuran based on propylene alkoxy) ethyl] AA: acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) MAA: methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) EA : Acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) MMA: methyl methacrylate (tokyo chemical Industry Co., Ltd.) CHA: cyclohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) CHMA: cyclohexyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) EHMA: 2-ethyl acrylate Hexyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.) BMA: n-butyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) PGMEA: propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO KK) V-601: Dimethyl 2,2'-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)

<Synthesis of MATHF> A 3-necked flask was charged with methacrylic acid (86.1 parts by mass, 1.0 mol equivalent) and hexane (86.1 parts by mass), and cooled to 20 ° C. After adding camphorsulfonic acid (0.00070 parts by mass, 0.03 millimolar equivalent) and 2-dihydrofuran (70.1 parts by mass, 1.0 mole equivalent) dropwise and stirring at 20 ° C ± 2 ° C for 1.5 hours, the temperature was raised to 35 ° C and Stirring was performed for 2 hours. KYOWARD 200 and KYOWARD 1000 (aluminum hydroxide adsorbent, both manufactured by Kyowa Chemical Industry Co., Ltd.) were sequentially spread on a suction filter, and then the reaction solution was filtered to obtain a filtrate. MEHQ (0.0012 parts by mass) was added to the obtained filtrate, and then concentrated under reduced pressure at 40 ° C to obtain 156.2 parts by mass of tetrahydro-2H-furan-2-yl methacrylate (MATHF) as a colorless oily substance ( Yield: 98.0%).

<Synthesis of ATHF> A 3-necked flask was charged with acrylic acid (72.1 parts by mass, 1.0 mol equivalent) and hexane (72.1 parts by mass), and cooled to 20 ° C. Camphor sulfonic acid (0.00070 parts, 0.03 millimolar equivalent) and 2-dihydrofuran (77.9 parts by mass, 1.0 mole equivalent) were added dropwise, and the mixture was stirred at 20 ° C ± 2 ° C for 1.5 hours, and then heated to 35 ° C and carried out. Stir for 2 hours. KYOWARD 200 and KYOWARD 1000 (both manufactured by Kyowa Chemical Industry Co., Ltd.) were sequentially spread on a suction filter, and then the reaction solution was filtered to obtain a filtrate. MEHQ (0.0012 parts by mass) was added to the obtained filtrate, and then concentrated under reduced pressure at 40 ° C to obtain 140.8 parts by mass of tetrahydro-2H-furan-2-yl (ATHF) as a colorless oil (yield) 99.0%).

<Synthesis of HS> In a 3-necked flask, 4-vinylbenzene acetate (25.0 parts by mass, 0.154 mole equivalents) and ethyl acetate (34.2 parts by mass) were added and cooled to 5 ° C. A 28% sodium methoxide methanol solution (59.5 parts by mass) was added dropwise, followed by stirring for 2 hours. Ethyl acetate (100 parts by mass), water (200 parts by mass), and ammonium chloride (33.0 parts by mass) were added, and a liquid separation operation was performed to extract an organic layer. The obtained organic layer was sequentially washed with a saturated aqueous solution of ammonium chloride and saturated brine, and concentrated under reduced pressure at 40 ° C to obtain 17.0 parts by mass of 4-hydroxystyrene (HS) as a yellow oil (product). (91.9%).

<Synthesis of THFHS> A 3-necked flask was charged with 4-hydroxystyrene (120.2 parts by mass, 1.0 mole equivalent) and hexane (120.2 parts by mass), and cooled to 20 ° C. After adding camphorsulfonic acid (0.00070 parts, 0.03 millimolar equivalent) and 2-dihydrofuran (70.1 parts by mass, 1.0 mole equivalent) dropwise, the temperature was raised to 80 ° C and stirring was performed for 5 hours. KYOWARD 200 and KYOWARD 1000 (both manufactured by Kyowa Chemical Industry Co., Ltd.) were sequentially spread on a suction filter, and then the reaction solution was filtered to obtain a filtrate. MEHQ (0.0019 parts by mass) was added to the obtained filtrate, and then concentrated under reduced pressure at 40 ° C. to obtain 185.0 parts by mass of 4- (2-tetrahydrofuranoxy) styrene (THFHS) as a colorless oil (yield) 97.3%).

<Synthesis of THFCS> A 3-necked flask was charged with 4-carboxystyrene (148.2 parts by mass, 1.0 mole equivalent) and hexane (148.2 parts by mass), and cooled to 20 ° C. After adding camphorsulfonic acid (0.00070 parts by mass, 0.03 millimolar equivalent) and 2-dihydrofuran (70.1 parts by mass, 1.0 mole equivalent) dropwise and stirring at 20 ° C ± 2 ° C for 1.5 hours, the temperature was raised to 35 ° C and Stirring was performed for 2 hours. KYOWARD 200 and KYOWARD 1000 (both manufactured by Kyowa Chemical Industry Co., Ltd.) were sequentially spread on a suction filter, and then the reaction solution was filtered to obtain a filtrate. MEHQ (0.0021 parts by mass) was added to the obtained filtrate, and then concentrated under reduced pressure at 40 ° C, thereby obtaining 212.3 parts by mass of 4- (2-tetrahydrofuryloxycarbonyl) styrene (THFCS) as a colorless oily substance (product Rate 97.3%).

<Synthesis of THFMS> A 3-necked flask was charged with mono-2- (methacryloyloxy) ethyl succinate (230.2 parts by mass, 1.0 mole equivalent) and hexane (230.2 parts by mass). ) And cooled to 20 ° C. Camphor sulfonic acid (0.00070 parts, 0.03 millimolar equivalent) and 2-dihydrofuran (70.1 parts by mass, 1.0 mole equivalent) were added dropwise, and the mixture was stirred at 20 ° C ± 2 ° C for 1.5 hours, and then heated to 35 ° C and carried out. Stir for 2 hours. KYOWARD 200 and KYOWARD 1000 (both manufactured by Kyowa Chemical Industry Co., Ltd.) were sequentially spread on a suction filter, and then the reaction solution was filtered to obtain a filtrate. MEHQ (0.0030 parts by mass) was added to the obtained filtrate, and then concentrated under reduced pressure at 40 ° C to obtain 1- [2- (methacryloxy) ethyl] succinate 2 as a colorless oil. -299.0 parts by mass of tetrahydrofuran protector (THFMS, compound of the following structure) (yield 99.6%).

[Chemical Formula 16]

<Synthesis of polymer A-1> PGMEA (75.0 parts by mass) was put in a 3-necked flask, and the temperature was raised to 90 ° C in a nitrogen environment. Added ATHF (40.0 parts by mass), AA (0.5 parts by mass), EA (15.0 parts by mass), MMA (22.5 parts by mass), CHMA (22.0 parts by mass), V-601 (3.7 parts by mass), PGMEA (75.0 The solution in parts by mass) was added dropwise to the 3-necked flask solution maintained at a temperature range of 90 ° C ± 2 ° C for 2 hours. After completion of the dropwise addition, polymer A-1 (solid content concentration: 40.0%) was obtained by stirring in a temperature range of 90 ° C. ± 2 ° C. for 2 hours.

<Synthesis Examples of Polymers A-2 to A-28> As shown in Table 1 below, the types and amounts of monomers were changed, and other conditions were used to synthesize them in the same manner as in A-1. The solid content concentration of the polymer was 40% by mass. In Table 1, the usage-amount of a monomer is shown by mass%.

[Table 1]

In Table 1, the description of "-" indicates that this monomer is not used. In Table 1, I / O values, Tg, and Mw were measured by the methods described above.

Hereinafter, it is used for the preparation of the photosensitive resin composition mentioned later, and the detail of each component shown in Table 2 mentioned later is shown.

<Photoacid generator> B-1: The structure shown below (is a compound described in paragraph 0227 of Japanese Patent Application Laid-Open No. 2013-47765 and synthesized by the method described in paragraph 0204)

[Chemical Formula 17]

B-2: PAG-103 (trade name, the following compound, manufactured by BASF)

[Chemical Formula 18]

B-3: Structure shown below (Synthesized according to the method described in paragraph 0160 of International Publication No. 2014/020984. In addition, Ts represents p-toluenesulfonyl.)

[Chemical Formula 19]

B-4: GSID-26-1, triarylsulfonium salt (manufactured by BASF)

[Chemical Formula 20]

B-5: It was synthesized according to the structure shown below (the method described in International Publication No. 2016/124493, page 103).

[Chemical Formula 21]

<Surfactant> C-1: Compound having the structure shown below

[Chemical Formula 22]

<Basic compound> D-1: Compound having the structure shown below (CMTU) D-2: 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) D-3: 1 , 5-diazabicyclo [4.3.0] -5-nonene (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Chemical Formula 23]

<Sensitizer> DBA: 9,10-dibutoxyanthracene (manufactured by Kawasaki Kasei Chemicals Ltd.)

(Examples 1 to 20 and Comparative Examples 1 to 10) <Preparation of Photosensitive Transfer Material> In Examples 1 to 20 and Comparative Examples 1 to 10, the solid content ratios shown in Table 2 below were changed. The polymer component, photoacid generator, basic compound, surfactant, and other components are dissolved and mixed in PGMEA (propylene glycol monomethyl ether acetate) so as to have a solid content concentration of 10% by mass. A tetrafluoroethylene filter was used for filtration to obtain a photosensitive resin composition. Regarding the photosensitive compositions of Examples 1 to 18, 20 and Comparative Examples 1 to 10, the photosensitive resin composition was applied to a polyethylene terephthalate having a thickness of 50 μm as a temporary support using a slit nozzle. (Polyethylene terephthalate) film (hereinafter referred to as "PET (A)") so that the dry film thickness becomes 3.0 μm. Then, it was dried in a convection oven at 100 ° C for 2 minutes, and finally a polyethylene film (OSM-N manufactured by Tredegar Co., Ltd.) was compression-bonded as a cover film to prepare a photosensitive transfer film. Printed materials. In addition, the total haze of PET (A) was 0.19%. As for the film haze, a haze tester HZ-2 manufactured by Suga Test Instruments Co., Ltd. was used, and the total light haze value (%) of the substrate was measured based on JIS-K-7136. The photosensitive resin composition of Example 19 was formed on a 30 μm-thick polyethylene terephthalate film (hereinafter, referred to as “PET (B)”) as a temporary support using a slit nozzle. Apply so that the dry film thickness becomes 3.0 μm. After that, it was dried in a convection oven at 100 ° C for 2 minutes, and finally a polyethylene film (Tredegar Corporation, OSM-N) was pressure-bonded as a casing film to prepare a photosensitive transfer material. The total light haze of PET (B) was 0.35% by the same measurement method as described above.

<Performance Evaluation> A PET substrate having a copper layer with a copper layer was prepared by a sputtering method on a PET film having a thickness of 188 μm and a thickness of 500 nm.

<Evaluation of lamination suitability> The prepared photosensitive transfer material was cut into 50 cm squares, and the cover film was peeled off. The lamination conditions were 90 ° C, a linear pressure of 0.8 MPa, and a linear speed of 3.0 m / min. On a copper-clad layer. The PET substrate was laminated. The area where the photosensitive resin layer and the copper layer were closely adhered without bubbles or warpage was visually evaluated, and the area ratio of the adhered area was determined by the area where the photosensitive resin layer was in close contact / the area of the transfer material being cut (%). The larger the area (%), the better the lamination adaptability. [Evaluation Criteria] Area (%) is over 95%: 5 Area (%) is over 90% and less than 95%: 4 Area (%) is over 85% and less than 90%: 3 Area (%) is over 80% Less than 85%: 2 area (%) less than 80%: 1

<Resolution evaluation> The prepared photosensitive transfer material was laminated on a PET substrate with a copper layer under a lamination condition of a linear pressure of 0.8 MPa and a linear speed of 3.0 m / min. In addition, in the case where the evaluation result of the lamination suitability at a roll temperature of 90 ° C is 4 or less, the lamination roll temperature was increased until the evaluation result of the lamination suitability became 5 (area (%) is 95% or more). kind. The photosensitive resin layer is exposed with a super-high pressure mercury lamp through a line-and-space pattern (duty ratio 1: 1) mask without peeling the temporary support through a line width of 3 μm to 20 μm. Then, the temporary support was peeled after standing for 1 hour, and development was performed. For development, a 1.0% aqueous sodium carbonate solution at 28 ° C. was used for 30 seconds by spray development. When a 20 μm line and space pattern was formed, a scanning electron microscope (SEM) evaluated the residues in the space portion, and the exposure amount without any residue was set as the optimum exposure amount. Among the line and space patterns obtained by the optimum amount of exposed light, the pattern with the highest resolution is set as the reaching resolution. In addition, when it is determined that the resolution is reached, the pattern is observed by a scanning electron microscope (SEM), and when a large roughness is generated on the side wall portion of the pattern, the analysis is not performed. The smaller the reach resolution, the better the pattern can be obtained. [Evaluation criteria] Less than 6 μm: 5 6 μm or more and less than 8 μm: 4.5 8 μm or more and less than 10 μm: 4 10 μm or more and less than 12 μm: 3.5 12 μm or more and less than 15 μm: 3 15 μm or more and less than 20 μm: 2 No resolution: 1

<Evaluation of Peelability> The produced photosensitive transfer material was laminated on a PET substrate with a copper layer under laminated conditions of a linear pressure of 0.8 MPa and a linear speed of 3.0 m / min. In addition, when the lamination adaptability is 4 or less at a roll temperature of 90 ° C., the lamination roll temperature is increased until the lamination performance becomes 5 to determine a sample. The temporary support is not peeled off, and exposed with an ultra-high pressure mercury lamp through a line and space pattern (Duty ratio 1: 1) with a line width of 3 μm to 20 μm. After being left for 1 hour, the temporary support is peeled and developed. During development, a 1.0% sodium carbonate aqueous solution at 28 ° C. was used for 30 seconds under spray development. Next, the copper layer was etched by a dipping method using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Inc.) at 25 ° C for 60 seconds, and then a 25 ° C ITO etching solution (KANTO CHEMICAL CO., ITO-02 by INC.) The ITO layer was etched for 60 seconds by a dipping method. Regarding the materials (evaluation system 1) that were not analyzed in the above-mentioned resolution evaluation, the same operations were performed in copper and ITO etching solution. The remaining photosensitive resin layer was peeled using a peeling solution. Regarding peeling, peeling by a dipping method was performed using a 10% by mass sodium hydroxide aqueous solution at 50 ° C. The photosensitive resin layer was observed with a scanning electron microscope (SEM), and the time until the photosensitive resin layer on the copper layer could be completely removed was determined. When judging peelability, a peeling time of less than 70 seconds is a practical level, and the shorter the peeling time, the better. [Evaluation criteria] Peel time is 20 seconds or less: 5 Peel time is 20 seconds or more and less than 30 seconds: 4.5 Peel time is 30 seconds or more and less than 40 seconds: 4 Peel time is 40 seconds or more and less than 50 Seconds: 3.5 Peel time is more than 50 seconds and less than 70 seconds: 3 Peel time is more than 70 seconds: 2 Cannot peel: 1

The results are shown in Table 2 below. As shown in Table 2, the photosensitive transfer material of this embodiment obtained a pattern with excellent build-up adaptability and excellent resolution, and a pattern with excellent pattern peelability.

[Table 2]

In Table 2, the description of "-" indicates that the compound is not contained. In Table 2, I / O values, Tg, and Mw were measured by the methods described above. For example, descriptions such as "A-1 / A-4" in the column of type, and "60/40" in the column of addition amount indicate that 60-mass parts of A-1 and 40-mass parts of A-4 are added. Amount used.

(Example 101) On a 100 μm-thick PET substrate, indium tin oxide (ITO) was formed as a conductive layer of the second layer by sputtering to a thickness of 150 nm, and the conductive layer was used as the conductive layer of the first layer. The copper layer was formed into a film with a thickness of 200 nm by a vacuum deposition method to form a circuit-forming substrate. The photosensitive transfer material 1 obtained in Example 1 (line pressure 0.8 MPa, line speed 3.0 m / min, and roll temperature 90 ° C) was laminated on the copper layer. The contact pattern was exposed using a mask provided with a pattern (hereinafter also referred to as "pattern A") shown in FIG. 3 having a structure in which a conductive layer gasket is connected in one direction without peeling off the temporary support. 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 a frame that is supposed to indicate alignment. Thereafter, the temporary support was peeled, developed, and washed with water to obtain a pattern A. Next, the copper layer was etched using a copper etchant (Cu-02 manufactured by Kanto Chemical Co., Inc.), and then the ITO layer was etched using an ITO etchant (ITO-02 manufactured by Kanto Chemical Co., Inc.). In this way, a substrate in which the pattern A was drawn by copper (solid line portion SL) and ITO (gray portion G) was obtained.

Next, pattern exposure, development, and water washing were performed using a mask provided with an opening portion of a pattern shown in FIG. 4 (hereinafter also referred to as "pattern B") in an aligned state. In the pattern B shown in FIG. 4, the gray portion G is a light-shielding portion, and the dotted line portion DL is a frame that is supposed to indicate alignment. Thereafter, the copper layer was etched using Cu-02, and the remaining photosensitive resin layer was peeled off using a stripping solution (10% by mass sodium hydroxide aqueous solution) to obtain a circuit wiring board. Thus, a circuit wiring board was obtained. When observed under a microscope, it is a perfect pattern without peeling or missing.

(Example 102) On a 100 μm-thick PET substrate, ITO was formed as a second conductive layer by sputtering to a thickness of 150 nm, and copper was used as the first conductive layer to form copper. A film was formed in a thickness of 200 nm by a vacuum evaporation method, thereby producing a circuit-forming substrate. The photosensitive transfer material 1 obtained in Example 1 (line pressure 0.8 MPa, line speed 3.0 m / min, and roll temperature 90 ° C) was laminated on the copper layer. The photosensitive resin layer was subjected to pattern exposure using a photomask provided with a pattern A shown in FIG. 3 having a structure in which a conductive layer gasket was connected in one direction without peeling the temporary support. Thereafter, the temporary support was peeled, developed, and washed with water to obtain a pattern A. Next, the copper layer was etched using a copper etchant (Cu-02 manufactured by Kanto Chemical Co., Inc.), and then the ITO layer was etched using an ITO etchant (ITO-02 manufactured by Kanto Chemical Co., Inc.). In this way, a substrate in which the pattern A was drawn by copper (solid line portion SL) and ITO (gray portion G) was obtained. Next, a PET (A) protective layer was laminated on the remaining resist. In this state, pattern exposure was performed using a mask provided with an opening portion of the pattern B shown in FIG. 4 in the state of the alignment mark, and the PET (A) was peeled and developed and washed with water. Thereafter, the copper wiring was etched using Cu-02, and the remaining photosensitive resin layer was peeled using a stripping solution (KP-301 manufactured by Kanto Chemical Co., Inc.) to obtain a circuit wiring board. When observed under a microscope, it is a perfect pattern without peeling or missing.

12‧‧‧temporary support

14‧‧‧ photosensitive resin layer

14A‧‧‧The first pattern

14B‧‧‧The second pattern

16‧‧‧ Covering film

20‧‧‧Circuit forming substrate

22‧‧‧ Substrate

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‧‧‧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‧‧‧ dotted line

FIG. 1 is a schematic diagram showing an example of a layer structure of a photosensitive transfer material of the present disclosure. (A)-(h) is a schematic diagram which shows an example of the manufacturing method of the circuit wiring for touch panels using the photosensitive transfer material of this indication. FIG. 3 is a schematic view showing a pattern A. FIG. FIG. 4 is a schematic view showing a pattern B. FIG.

Claims (7)

A photosensitive transfer material comprising: a temporary support; and a photosensitive resin layer containing a polymer component and a photoacid generator. The polymer component contains an acidic group which is protected in the form of an acetal. The average value of the I / O value of the polymer based on the organic conceptual diagram of the polymer component based on the organic concept diagram of the polymer component and the polymer unit having an acid group is 0.55 or more and 0.65 or less. The content of the structural unit having an acid group with respect to the total mass of the polymer component is 0.5% by mass or more and 15% by mass or less, and the average value of the glass transition temperature is -20 ° C to 90 ° C. The photosensitive transfer material according to item 1 of the scope of patent application, wherein the constitutional unit having an acid group protected in the form of an acetal is a constitutional unit represented by the following formula A, In Formula A, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R ³¹ and R ³² is an alkyl group or an aryl group, R ³³ represents an alkyl group or an aryl group, R ³¹ or R ³² may be bonded to R ³³ to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ is a single bond or a divalent linking group. The photosensitive transfer material according to item 1 or 2 of the scope of patent application, wherein the content of the constituent unit having an acid group with respect to the total mass of the polymer component is 1 mass relative to the total mass of the polymer component % To 10% by mass. The photosensitive transfer material according to claim 1 or claim 2, wherein the acid group-containing carboxyl group contained in the constituent unit having an acid group. The photosensitive transfer material according to item 1 or item 2 of the patent application range, wherein the weight average molecular weight of the polymer component is 2,000 to 60,000. A method for manufacturing a circuit wiring includes the following steps: On a substrate, a photosensitive transfer material according to any one of claims 1 to 5 on the side of the substrate opposite to the temporary support A step of laminating the outermost layer in contact with the substrate; a step of pattern exposing the photosensitive resin layer of the photosensitive transfer material after the step of laminating; a photosensitive resin layer after the step of exposing the pattern A step of developing to form a pattern; and a step of etching a substrate in a region where the pattern is not arranged. A method for manufacturing a touch panel includes the following steps: On a substrate, the side of the photosensitive transfer material according to any one of claims 1 to 5 of the scope of patent application, which is opposite to the temporary support A step of bonding the outermost layer of the substrate in contact with the substrate; a step of pattern exposing the photosensitive resin layer of the photosensitive transfer material after the step of bonding; a photosensitive resin after the step of exposing the pattern A step of developing a layer to form a pattern; and a step of etching a substrate in a region where the pattern is not arranged.