TW202236008A - Method for producing laminate, method for producing circuit wiring, transfer film - Google Patents

Abstract

The present invention provides: a method for manufacturing a laminate including a pattern and exhibiting an excellent pattern shape and excellent pattern adhesiveness; a method for manufacturing circuit wiring; and a transfer film. A method for manufacturing a laminate according to the present invention includes: a sticking step for bringing, into contact with a substrate, the surface at the side opposite to a middle layer side of a photosensitive composition layer in a transfer film which has a temporary support, a middle layer, and the photosensitive composition layer in the stated order, and sticking the transfer film and the substrate together; a releasing step for releasing the temporary support between the temporary support and the middle layer; an exposure step for pattern-exposing the photosensitive composition layer; and a development step for developing the exposed photosensitive composition layer by using a developer and forming a pattern. An elastic modulus X calculated through measurement X is 1.0-10.0 Gpa.

Description

Manufacturing method of laminate, manufacturing method of circuit wiring, transfer film

The present invention relates to a method for manufacturing a laminate, a method for manufacturing circuit wiring, and a transfer film.

Since the number of steps for obtaining a predetermined pattern is small, the method of disposing a photosensitive composition layer on an arbitrary substrate using a transfer film, exposing the photosensitive composition layer through a mask, and then developing is widely used. .

For example, Patent Document 1 discloses a photosensitive resin laminate in which an intermediate layer and a photosensitive resin layer are sequentially laminated on a support film.

[Patent Document 1] Japanese Patent Laid-Open No. 2008-175957

As a result of studying a method of manufacturing a laminate using a conventional transfer film or the like described in Patent Document 1, the present inventors found that defects in the shape of the obtained pattern tended to occur. In particular, it has been found that the above-mentioned problems tend to occur when the dummy support is peeled off for exposure in order to obtain a higher-definition pattern. Specifically, after bonding the transfer film to the transfer body and peeling off the dummy support, pattern exposure is performed, and further development is performed to obtain a desired pattern. When the cross-sectional shape of the obtained pattern was observed, it was found that the pattern shape tended to become a shape in which the width of the pattern became wider as it approached the substrate side from the side opposite to the substrate side. That is, the extended hem shape refers to a pattern shape in which the length of the lower bottom surface (on the substrate side) is longer than the length of the upper bottom surface (the side opposite to the substrate) in the obtained pattern shape. More specifically, as shown in FIG. 1, in a pattern 2 arranged on a substrate 1, there is a problem of generating a hem extension 3 as shown in a dotted line portion. Hereinafter, the case where the obtained pattern hardly becomes a hem-spreading shape is also referred to as being excellent in pattern shape.

On the other hand, it is also required that the pattern obtained by transferring the photosensitive composition layer in the transfer film to the transfer body, exposing and developing the photosensitive composition layer is not easy to peel off from the transfer body, and that the pattern Excellent adhesion. In particular, it is excellent in the adhesiveness of the pattern which requires higher definition.

Therefore, the subject of this invention is providing the manufacturing method of the laminated body which contains the pattern excellent in pattern shape, and also excellent in pattern adhesiveness. Moreover, the subject of this invention is providing the manufacturing method of a circuit wiring, and a transfer film.

As a result of intensive studies on the above-mentioned problems, the inventors of the present invention have found that the above-mentioned problems can be solved by the following configurations.

[1] A method of manufacturing a laminate comprising: The substrate is brought into contact with the surface of the photosensitive composition layer on the side opposite to the side of the intermediate layer of a transfer film having a dummy support, an intermediate layer, and a photosensitive composition layer in this order, and the transfer film is bonded. Lamination steps with the above substrate; between the above-mentioned pseudo-support and the above-mentioned intermediate layer, a peeling step of peeling off the above-mentioned pseudo-support; an exposure step of subjecting the photosensitive composition layer to pattern exposure; and A developing step of developing the exposed photosensitive composition layer using a developing solution to form a pattern, The elastic modulus X obtained from the measurement X described later is 1.0 to 10.0 GPa. [2] The method for producing the laminate according to [1], wherein The elastic modulus Y obtained from the measurement Y described later is 3.5 MPa or less. [3] The method for producing the laminate according to [2], wherein The ratio of the elastic modulus X to the elastic modulus Y is 1500-10000. [4] The method for producing a laminate according to any one of [1] to [3], wherein The content of the double bond in the said photosensitive composition layer is 1.0-3.0 mmol/g. [5] The method for producing a laminate according to any one of [1] to [4], wherein The above-mentioned photosensitive composition layer contains resin, The glass transition temperature Tg of the above-mentioned resin is 90-150°C. [6] The method for producing a laminate according to any one of [1] to [5], wherein The acid value of the said photosensitive composition layer is 50-100 mgKOH/g. [7] The method for producing a laminate according to any one of [1] to [6], wherein The photosensitive composition layer contains a bifunctional or higher polymerizable compound and a resin, The mass ratio of the content of the above-mentioned bifunctional or higher polymerizable compound to the content of the above-mentioned resin is 0.60 to 1.00. [8] The method for producing a laminate according to any one of [1] to [7], wherein The above-mentioned intermediate layer contains polyols, oxidation adducts of polyols, phenol derivatives, amide compounds, water-soluble cellulose derivatives, polyether resins, and polyamide resins. At least 1 species. [9] The method for producing a laminate according to any one of [1] to [8], wherein The thickness of the said photosensitive composition layer is 1-20 micrometers. [10] The method for producing a laminate according to any one of [1] to [9], wherein The thickness of the above-mentioned intermediate layer is 3.0 μm or less. [11] The method for producing a laminate according to any one of [1] to [10], wherein The exposing step is an exposing step in which the exposed intermediate layer is brought into contact with a mask to perform pattern exposure. [12] A method of manufacturing a circuit wiring, comprising: a substrate having a conductive layer and a transfer film having a dummy support, an intermediate layer, and a photosensitive composition layer in this order; The surface on the opposite side of the layer side is in contact, and the step of laminating the above-mentioned transfer film and the above-mentioned substrate; the peeling step of peeling the above-mentioned pseudo-support between the above-mentioned pseudo-support and the above-mentioned intermediate layer; Exposing the composition layer to pattern exposure; Developing the exposed photosensitive composition layer using a developer to form a pattern; and Etching the conductive layer in the area where the pattern is not arranged In the etching step, the elastic modulus X obtained from the measurement X is 1.0 to 10.0 GPa. [13] A transfer film comprising a pseudo-support, an intermediate layer, and a photosensitive composition layer in this order, And carry out the exposing step of carrying out pattern exposure to above-mentioned photosensitive composition layer, wherein The elastic modulus X obtained from the measurement X described later is 1.0 to 10.0 GPa. [14] The transfer film according to [13], wherein The elastic modulus Y obtained from the measurement Y described later is 3.5 MPa or less. [15] The transfer film according to [14], wherein The ratio of the elastic modulus X to the elastic modulus Y is 1500-10000. [16] The transfer film according to any one of [13] to [15], wherein The content of the double bond in the said photosensitive composition layer is 1.0-3.0 mmol/g. [17] The transfer film according to any one of [13] to [16], wherein The above-mentioned photosensitive composition layer contains resin, The glass transition temperature Tg of the above-mentioned resin is 90-150°C. [18] The transfer film according to any one of [13] to [17], wherein The acid value of the said photosensitive composition layer is 50-100 mgKOH/g. [19] The transfer film according to any one of [13] to [18], wherein The photosensitive composition layer contains a bifunctional or higher polymerizable compound and a resin, The mass ratio of the content of the above-mentioned bifunctional or higher polymerizable compound to the content of the above-mentioned resin is 0.60 to 1.00. [20] The transfer film according to any one of [13] to [19], wherein The above-mentioned intermediate layer contains polyols, oxidation adducts of polyols, phenol derivatives, amide compounds, water-soluble cellulose derivatives, polyether resins, and polyamide resins. At least 1 species. [21] The transfer film according to any one of [13] to [20], wherein The thickness of the said photosensitive composition layer is 1-20 micrometers. [22] The transfer film according to any one of [13] to [21], wherein The thickness of the above-mentioned intermediate layer is 3.0 μm or less. [Invention effect]

According to the present invention, it is possible to provide a method for producing a laminate including a pattern having an excellent pattern shape and also excellent pattern adhesion. Moreover, according to this invention, the manufacturing method of a circuit wiring, and a transfer film can also be provided.

Hereinafter, the present invention will be described in detail. In this specification, the numerical range represented using "-" shows the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. In the numerical ranges described step by step in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of the numerical range described in other steps. In addition, in the numerical range described in this specification, the upper limit or the lower limit described in a certain numerical range may be replaced with the value shown in an Example.

In this specification, the term "step" includes not only an independent step, but also includes the term as long as the intended function of the step is exerted even if it cannot be clearly distinguished from other steps.

In this specification, "transparent" means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, preferably 90% or more. In this specification, the average transmittance of visible light is a value measured using a spectrophotometer, for example, can be measured using a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

In this manual, unless otherwise specified, TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all are product names manufactured by TOSOH CORPORATION) are used as columns, and as washers, unless otherwise specified. THF (tetrahydrofuran) in the extract, a differential refractometer as a detector, and polystyrene as a standard substance, and converted using polystyrene as a standard substance measured by a gel permeation chromatography (GPC) analysis device value. In this specification, unless otherwise specified, the molecular weight of the compound contained in the molecular weight distribution is a weight average molecular weight (Mw). In this specification, unless otherwise specified, the content of metal elements is a value measured using an Inductively Coupled Plasma (ICP: Inductively Coupled Plasma) spectrometer. In this specification, unless otherwise specified, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm. In this specification, unless otherwise specified, the hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).

In this specification, "(meth)acrylic acid" is a concept that includes both acrylic acid and methacrylic acid, and "(meth)acryloxy" includes both acryloxy and methacryloxy. concept.

In this specification, "alkali solubility" means that the solubility of sodium carbonate in 100 g of 1 mass % aqueous solution is 0.1 g or more on 22 degreeC conditions.

In the present specification, "water solubility" means that the solubility in 100 g of water of pH 7.0 at a liquid temperature of 22° C. is 0.1 g or more. For example, a water-soluble resin refers to a resin satisfying the above solubility conditions.

In this specification, the "solid content" of the composition refers to the components that form the composition layer (photosensitive composition layer, intermediate layer, and thermoplastic resin layer) formed using the composition, and the composition includes solvents (organic solvents, In the case of water, etc.), it means removal of all components of the solvent. Moreover, as long as it is a component which forms a composition layer, a liquid component is also considered as a solid component.

[Manufacturing method of laminated body] The manufacturing method of the laminated body of the present invention has: The substrate is brought into contact with the surface of the photosensitive composition layer of the transfer film having the dummy support, the intermediate layer, and the photosensitive composition layer in this order, which is opposite to the intermediate layer side, and the transfer film and the substrate are bonded together. Fitting step; between the pseudo-support and the intermediate layer, a step of peeling off the pseudo-support; an exposure step of subjecting the photosensitive composition layer to pattern exposure; and A developing step of developing the exposed photosensitive composition layer using a developing solution to form a pattern, The elastic modulus X obtained from the measurement X is 1.0 to 10.0 GPa. As a preferable aspect of the manufacturing method of a laminated body, the aspect which has the above-mentioned bonding process, a peeling process, an exposure process, and a developing process sequentially is mentioned.

The characteristic point of the method for producing the laminate of the present invention is that the elastic modulus X obtained from the measurement X described later is 1.0 to 10.0 GPa. Although the details of the mechanism by which the method for producing a laminate of the present invention exerts the desired effect are not clear, the inventors of the present invention presume as follows. The inventors of the present invention have found that when the modulus of elasticity X is less than 1.0 GPa, the intensity of the pattern (cured layer) obtained by exposing the photosensitive composition layer is too low, so when the elastic modulus X is less than 1.0 GPa, the strength of the pattern (hardened layer) obtained by exposing the photosensitive composition layer is too low. At the time of development, it becomes a hem-expanded shape by the swelling and dissolution of the pattern; and, in the case where the elastic modulus X is greater than 10.0 GPa, due to the pattern (hardened layer) obtained by exposing the photosensitive composition layer to light Since the strength is too high, the adhesion between the cured layer and the transfer body is poor. In view of the above, it can be presumed that in the method for producing a laminate of the present invention, by adjusting the elastic modulus X to a predetermined range, the pattern shape is excellent and the pattern adhesion is also excellent. Hereinafter, when at least one of the effects of a more excellent pattern shape and a more excellent pattern adhesiveness can be obtained, it is also called that the effect of the present invention is more excellent.

Hereinafter, the manufacturing method and each step of the laminated body of the present invention will be described in detail. In addition, the description of the constituent requirements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

〔Elastic modulus〕 ＜Elastic modulus X＞ In the manufacturing method of the laminated body of the present invention, the elastic modulus X obtained from the measurement X is 1.0 to 10.0 GPa, and from the viewpoint of more excellent effect of the present invention, 1.0 to 8.0 GPa is preferable, and 2.0 to 8.0 GPa is more preferred, 3.0-6.0 GPa is further preferred, and 4.0-6.0 GPa is particularly preferred.

The elastic modulus X is a value obtained from the following measurement X. The measurement method for measuring X is as follows: The substrate is brought into contact with the surface of the photosensitive composition layer of the transfer film opposite to the intermediate layer side, and the transfer film and the substrate are bonded together, and the obtained laminate is obtained from the laminated body. Peel off the pseudo-support between the pseudo-support and the intermediate layer, and expose the entire surface of the photosensitive composition layer from the exposed intermediate layer, peel off the exposed intermediate layer, then measure the elastic modulus of the exposed hardened layer, and set is the elastic modulus X. In addition, the exposure conditions (type of light source, exposure amount, etc.) at the time of performing the said whole surface exposure are implemented under the same exposure conditions as the exposure conditions implemented in the exposure process mentioned later. That is, the whole-surface exposure performed in the measurement X corresponds to the exposure of the entire surface of the photosensitive composition layer by changing the exposure range of the pattern exposure performed in the exposure step described later. As a method of measuring the elastic modulus, for example, a rheometer DFR-2 manufactured by TA Instruments can be used to measure under the conditions of a set temperature of 20 to 125°C, a heating rate of 5°C/min, a frequency of 1Hz, and a distortion of 0.5%. . As a method of peeling the exposed intermediate layer, for example, a known peeling method can be mentioned, and tape peeling is preferable. In addition, in the case where the transfer film has a protective film, after peeling the protective film from the transfer film, the measurement of X was carried out. In addition, the substrate used in the measurement X is the substrate used in the method of manufacturing the laminated body, which will be described in detail later.

＜Elastic modulus Y＞ From the standpoint of excellent development residue suppression, the elastic modulus Y obtained by measuring Y is preferably 10.0 MPa or less, more preferably 5.0 MPa or less, still more preferably 3.5 MPa or less, and most preferably 1.0 MPa or less , below 0.8MPa is the best. The lower limit is preferably 0.1 MPa or more.

The elastic modulus Y is the measurement of the elastic modulus of the photosensitive composition layer of the transfer film, and is set as the measurement of the elastic modulus Y. That is, the elastic modulus Y corresponds to the elastic modulus of the non-exposed portion of the photosensitive composition layer that has not been exposed. As a method of measuring the modulus of elasticity, for example, the method of measuring the modulus of elasticity used in the modulus of elasticity X described above can be mentioned. In addition, the measurement of Y may be performed after peeling off the intermediate layer from the transfer film. As a method of peeling off an intermediate layer, a well-known peeling method can be mentioned, for example, Tape peeling is preferable. Also, in the case where the transfer film has a protective film, the measurement Y was performed after the protective film was peeled off from the transfer film.

From the viewpoint of excellent development residue suppression, the ratio of elastic modulus X to elastic modulus Y (elastic modulus X/elastic modulus Y) is preferably 100 or more, more preferably 200 to 10,000, and 1,000 to 10,000 is more preferable, 1,500 to 10,000 is particularly preferable, and 3,000 to 8,000 is most preferable.

As a method of adjusting the elastic modulus X and the elastic modulus Y, for example, changing the kind and content of the resin contained in the photosensitive composition layer is mentioned. Specifically, the following method can be mentioned: Regarding the resin, the method of using the resin whose weight average molecular weight, acid value and Tg (glass transition temperature) are adjusted to the respective preferable aspects described later, and using the resin in each preferable state A method of synthesizing a resin using a monomer having more than three functions and/or an aromatic hydrocarbon group, and a method of combining them.

〔Fitting step〕 The bonding step is to bring the substrate into contact with the surface of the photosensitive composition layer of the transfer film having the dummy support, the intermediate layer, and the photosensitive composition layer in this order, which is opposite to the intermediate layer side, and bond the transfer film. Lamination step of film and substrate. Moreover, when a transfer film has a protective film, you may implement a bonding process after peeling a protective film.

In the bonding step, the surface of the photosensitive composition layer of the transfer film on the side opposite to the intermediate layer side is brought into contact and pressure-bonded. As a bonding method, a well-known transfer method and a lamination method are mentioned, for example. Among them, as a bonding method, it is preferable to overlap the surface of the photosensitive composition layer of the transfer film on the side opposite to the intermediate layer side with the substrate, and to apply pressure and heating with a roller or the like. As a bonding method, the bonding method using a well-known laminator, such as a vacuum laminator and an automatic cutting laminator, is mentioned. As lamination temperature, 70-130 degreeC is preferable.

As the substrate, a substrate having a conductive layer is preferable. Substrate with Conductive Layer Any layer other than the above-mentioned conductive layer may be formed on the substrate as necessary. That is, it is preferable that the substrate is a conductive substrate having at least a conductive layer disposed on the substrate. As a substrate, a resin substrate, a glass substrate, and a semiconductor substrate are mentioned, for example. As the substrate, paragraph [0140] of International Publication No. 2018/155193 is preferable, and these contents are incorporated into this specification. As the material of the resin substrate, cycloolefin polymer or polyimide is preferable. The thickness of the resin substrate is preferably from 5 to 200 μm, more preferably from 10 to 100 μm.

As the conductive layer, at least one selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer from the viewpoint of conductivity and thin line formability A conductive layer is preferred. Only one conductive layer may be arranged on the substrate, or two or more layers may be arranged. When arranging two or more conductive layers, it is preferable that two or more conductive layers are made of different materials. As the conductive layer, paragraph [0141] of International Publication No. 2018/155193 is preferable, and these contents are incorporated into this specification.

〔Peel off step〕 The stripping step is a step of stripping the pseudo-support between the pseudo-support and the intermediate layer. As a method of peeling off the dummy support, for example, known peeling methods can be mentioned. Specifically, there may be mentioned the cover film peeling mechanism described in paragraphs [0161] to [0162] of JP-A-2010-072589.

〔Exposure steps〕 The exposing step is a step of pattern-exposing the photosensitive composition layer. "Pattern exposure" means exposure in a pattern-like form, that is, exposure showing a form in which exposed parts and non-exposed parts exist. The positional relationship between the exposed area and the unexposed area in the pattern exposure is not particularly limited, and can be appropriately adjusted.

The direction of exposure is not particularly limited, and exposure may be performed from the intermediate layer side of the photosensitive composition layer, or may be exposed from the side (substrate side) of the photosensitive composition layer opposite to the intermediate layer side.

As the exposure step, it is preferable to perform pattern exposure by bringing the intermediate layer exposed in the above-mentioned peeling step into contact with a mask. A high-definition pattern is obtained by performing pattern exposure in contact with the above-mentioned mask. Specifically, on the intermediate layer exposed by the peeling of the dummy support, it is preferable to place a mask having a predetermined opening in close contact and perform pattern exposure. The exposing step of bringing the above-mentioned intermediate layer into contact with the mask can cause a hardening reaction of the components contained in the photosensitive composition layer in the exposed region of the photosensitive composition layer (position corresponding to the opening of the mask). . After exposure, an alkali development process is performed, and the non-exposed area|region of a photosensitive composition layer is removed and a pattern is formed. It is preferable that the method for producing a laminate has a peeling step for peeling off the mask used in the exposure step between the exposure step and the development treatment.

As a light source for pattern exposure, any light source capable of irradiating at least a wavelength range capable of curing the photosensitive composition layer (for example, 365 nm and 405 nm) can be appropriately selected and used. Among them, the dominant wavelength of the exposure light for pattern exposure is preferably 365 nm. In addition, the dominant wavelength means the wavelength with the highest intensity.

Examples of light sources include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps. The exposure amount is preferably 5 to 200 mJ/cm ² , more preferably 10 to 200 mJ/cm ² . As a light source, exposure amount, and an exposure method, for example, paragraphs [0146] to [0147] in International Publication No. 2018/155193 can be cited, and these contents are incorporated in this specification.

〔Development step〕 The developing step is a step of developing the exposed photosensitive composition layer using a developing solution to form a pattern. By developing using an alkali developing solution (alkaline aqueous solution), the non-exposed area of the photosensitive composition layer is removed, and a pattern in which the openings of the mask are used as protrusions is formed.

As a developing solution, an alkaline aqueous solution is preferable. Examples of basic compounds (compounds that dissolve in water and exhibit basicity) contained in alkaline aqueous solutions include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, hydrogen Tetramethylammonium Oxide, Tetraethylammonium Hydroxide, Tetrapropylammonium Hydroxide, Tetrabutylammonium Hydroxide and Choline (2-Hydroxyethyltrimethylammonium Hydroxide).

As a developing method, for example, a known developing method can be mentioned. Specifically, flood image development, shower image development, spin image development, and immersion image development are mentioned. As a developing method, the developing method described in paragraph [0195] of International Publication No. 2015/093271 is preferable.

[Post-exposure step and post-baking step] The method for producing a laminate of the present invention may include a step of further exposing the pattern obtained in the developing step (hereinafter also referred to as "post-exposure step") and/or Or a step of heating (hereinafter also referred to as "post-baking step."). When the manufacturing method of a laminate has both a post-exposure process and a post-baking process, it is preferable to implement a post-baking process after implementing a post-exposure process. The exposure amount in the post-exposure step is preferably 100 to 5000 mJ/cm ² , more preferably 200 to 3000 mJ/cm ² . In the post-baking step, the post-baking temperature is preferably 80-250°C, more preferably 90-160°C. In the post-baking step, the post-baking time is preferably 1-180 minutes, more preferably 10-60 minutes.

The position and size of the pattern formed on the substrate obtained by the method of manufacturing the laminate are not particularly limited. Among them, as a pattern, a fine line shape is preferable. Specifically, the width of the pattern is preferably 20 μm or less, more preferably 15 μm or less, still more preferably 10 μm or less, and particularly preferably 5 μm or less. The lower limit is preferably 1 μm or more, more preferably 3 μm or more.

[Use of laminated body] The laminate manufactured by the manufacturing method of the laminate of this invention can be applied to various devices. As a device provided with a laminate, for example, an input device can be mentioned, a touch panel is preferable, and a capacitive touch panel is more preferable. The input device described above can be applied to display devices such as organic EL (organic electroluminescence) display devices and liquid crystal display devices.

[Manufacturing method of circuit wiring] In the method of manufacturing circuit wiring of the present invention, when a conductive substrate is used as the substrate, the conductive layer in the region where the pattern is not arranged in the layered body having the pattern manufactured by the above-mentioned method of manufacturing the layered body is included. An etching step of performing an etching process.

Hereinafter, each step of the manufacturing method of the circuit wiring of this invention is demonstrated in detail. In addition, the description of the constituent requirements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

〔Etching step〕 The etching step is a step of etching the conductive layer in the area where no pattern is arranged. Specifically, in the etching step, the pattern obtained from the photosensitive composition layer in the development step in the above-mentioned method for producing a laminate is used as an etching resist, and the conductive layer is subjected to etching treatment. The board|substrate has the same meaning as the board|substrate in the manufacturing method of the above-mentioned laminated body, and a preferable aspect is also the same.

As a method of etching treatment, for example, a known etching method can be mentioned. Specifically, the method described in paragraphs [0209] to [0210] of JP-A-2017-120435, the method described in paragraphs [0048]-[0054] of JP-A-2010-152155, etc. The described method, wet etching by immersion in an etchant, and dry etching such as plasma etching.

Regarding the etchant used in wet etching, acidic or alkaline etchant can be appropriately selected depending on the object to be etched. As the acidic etchant, for example, an acidic aqueous solution containing one or more acidic compounds, and an acidic compound and at least one selected from the group consisting of ferric chloride, ammonium fluoride, and potassium permanganate Acidic mixed aqueous solutions of salts. As the acidic compound contained in the acidic aqueous solution (a compound that dissolves in water and exhibits acidity), at least one acidic compound selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid is preferred. good. Examples of alkaline etching solutions include alkaline aqueous solutions containing one or more alkaline compounds, and alkaline mixed aqueous solutions of alkaline compounds and salts (for example, potassium permanganate, etc.). As the basic compound contained in the alkaline aqueous solution (compound showing basicity by dissolving in water), for example, selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines and salts of organic amines (for example, hydroxide Tetramethylammonium, etc.) is preferably at least one kind from the group.

[Removal steps] The manufacturing method of the circuit wiring of this invention may have the removal process of removing the remaining pattern. The removal step is preferably performed after the etching step described above. As a method of removing the remaining pattern, for example, a method of removing by chemical treatment is mentioned, and a method of removing using a removing liquid is preferable. As liquid temperature of a removal liquid, 30-80 degreeC is preferable, and 50-80 degreeC is more preferable. As a preferred aspect of the removal method, for example, a method of immersing a substrate having a pattern to be removed in a removal solution having a liquid temperature of 50 to 80° C. under stirring for 1 to 30 minutes is mentioned. As a method of removing the remaining pattern, for example, a method of removing by a known method such as a spraying method, a shower method, and a dipping method using a removing liquid can also be mentioned.

As the removal liquid, for example, dissolving a basic inorganic compound or a basic organic compound in at least 1 remover in solution. Examples of basic inorganic compounds include sodium hydroxide and potassium hydroxide. Examples of basic organic compounds include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[other steps] The manufacturing method of circuit wiring may have other steps besides each step mentioned above. As other steps, for example, the step of reducing the reflectance of visible light described in paragraph [0172] of International Publication No. 2019/022089 and the step of reducing the reflectance of visible light described in paragraph [0172] of International Publication No. The step of forming a new conductive layer on the surface of the film.

＜Steps to reduce the reflectance of visible light＞ The manufacturing method of circuit wiring may have the process of performing the process of reducing the visible light reflectance of some or all of the several conductive layers which a board|substrate has. As a treatment for lowering the reflectance of visible light, for example, oxidation treatment can be mentioned. When the substrate has a conductive layer containing copper, the visible light reflectance of the conductive layer can be reduced by oxidizing the copper to form copper oxide and blackening the conductive layer. As a treatment for reducing the reflectance of visible light, paragraphs [0017] to [0025] of JP-A-2014-150118, and paragraphs [0041], [0042], and [0048] of JP-A-2013-206315 can be cited. ] and [0058] paragraphs, and these contents are incorporated into this specification.

<Step of forming an insulating film, step of forming a new conductive layer on the surface of the insulating film> The method of manufacturing circuit wiring may include the step of forming an insulating film on the surface of the circuit wiring and the step of forming a new conductive layer on the surface of the insulating film. Through the above process, the first electrode pattern and the insulated second electrode pattern can be formed. As a step of forming an insulating film, for example, a method of forming a known permanent film can be mentioned. In addition, an insulating film having a desired pattern can be formed by photolithography using a photosensitive composition having insulating properties. As a step of forming a new conductive layer on the surface of the insulating film, for example, a photosensitive composition having conductivity can be used to form a new conductive layer with a desired pattern by photolithography.

In the method of manufacturing circuit wiring, it is preferable to use a substrate having a plurality of conductive layers on both surfaces of the substrate, and it is also preferable to form circuit wiring sequentially or simultaneously on the conductive layers formed on both surfaces of the substrate. With the above configuration, it is possible to form circuit wiring for a touch panel in which the first conductive pattern is formed on the surface of one substrate and the second conductive pattern is formed on the surface of the other substrate. Moreover, it is also preferable to form the circuit wiring for touch panels of the said structure from both surfaces of a board|substrate by roll-to-roll.

[Use of circuit wiring] The circuit wiring manufactured by the manufacturing method of circuit wiring can be applied to various devices. As a device provided with circuit wiring, for example, an input device is mentioned, and a touch panel is preferable, and an electrostatic capacitance type touch panel is more preferable. The input device described above can be applied to display devices such as organic EL display devices and liquid crystal display devices.

[Transfer film] The transfer film of the present invention has a pseudo-support, an intermediate layer, and a photosensitive composition layer in this order, and is a transfer film subjected to an exposure step of pattern-exposing the photosensitive composition layer, wherein, obtained from the measurement X The elastic modulus X is 1.0～10.0GPa. The meanings of the elastic modulus X in the transfer film, the elastic modulus X to the elastic modulus Y, and the ratio of the elastic modulus Y are the same as those described in the above-mentioned method for producing a laminate, and the preferred ranges are also the same.

The transfer film may have other layers besides the photosensitive composition layer and the intermediate layer. As another layer, the thermoplastic resin layer mentioned later is mentioned, for example. In addition, the transfer film may have a protective film described later on the photosensitive composition layer.

Embodiments of the transfer film are not particularly limited, and examples include the following configurations. (1) "pseudo-support/intermediate layer/photosensitive composition layer/protective film" (2) "pseudo-support/thermoplastic resin layer/intermediate layer/photosensitive composition layer/protective film" As the photosensitive composition layer in each of the above configurations, a negative photosensitive composition layer is preferable. Moreover, a colored resin layer is also preferable as a photosensitive composition layer.

From the viewpoint of suppressing the generation of air bubbles in the above-mentioned bonding step, the maximum width of the ripples of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, still more preferably 60 μm or less. The lower limit is preferably at least 0 μm, more preferably at least 0.1 μm, and still more preferably at least 1 μm. The maximum width of the corrugation of the transfer film is a value measured by the following procedure. First, the transfer film was cut in a direction perpendicular to the main surface to a size of 20 cm long x 20 cm wide to prepare a test sample. Moreover, when a transfer film has a protective film, a protective film is peeled from a transfer film. Next, the above-mentioned test sample was placed on a stage with a smooth and horizontal surface so that the surface of the dummy support faced the stage. After standing still, use a laser microscope (for example, VK-9700SP manufactured by KEYENCE CORPORATION) to scan the surface of the test sample to obtain a three-dimensional surface image of the center of the test sample within a 10 cm square area. From the obtained three-dimensional surface image The maximum convex height observed in the image minus the lowest concave height. The above-mentioned operation was carried out on 10 test samples, and the arithmetic mean thereof was used as the maximum width of corrugations of the transfer film.

From the viewpoint of better adhesion, the transmittance of light having a wavelength of 365 nm of the photosensitive composition layer is preferably at least 10%, more preferably at least 30%, and still more preferably at least 50%. The upper limit is not particularly limited, but is preferably 99.9% or less.

An example of an embodiment of the transfer film will be described. The transfer film 10 shown in FIG. 1 has a dummy support 11 , a composition layer 17 including an intermediate layer 13 and a photosensitive composition layer 15 , and a protective film 19 in this order. In addition, although the transfer film 10 shown in FIG. 1 is the form in which the protective film 19 was arrange|positioned, the protective film 19 may not be arrange|positioned. In addition, in FIG. 1 , each layer other than the protective film 19 that can be disposed on the dummy support 11 is also referred to as a composition layer 17 . Furthermore, the transfer film may have a thermoplastic resin layer in addition to the above layers, and it is preferable that the thermoplastic resin layer is disposed between the dummy support 11 and the intermediate layer 13 .

Hereinafter, each member and each component of the transfer film of the present invention will be described in detail. In addition, the description of the constituent requirements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

〔Pseudo-support body〕 The transfer film has a pseudo-support. The member of the pseudo support system supporting the photosensitive composition layer is finally removed by peeling treatment.

The pseudo-support can be a single-layer structure or a multi-layer structure. As the pseudo-support, a thin film is preferable, and a resin thin film is more preferable. Also, as a pseudo-support, a film that is flexible and does not undergo significant deformation, shrinkage, or elongation under pressure or under pressure and heat is also preferable, and a film that does not cause deformation such as wrinkles and scratches is also preferable. better. As the film, for example, polyethylene terephthalate film (for example, biaxially oriented polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film , polyimide film and polycarbonate film, polyethylene terephthalate film is preferred.

From the viewpoint of enabling pattern exposure through the dummy support, it is preferable that the dummy support has high transparency. Specifically, the transmittance of the pseudo-support at a wavelength of 365 nm is preferably 60% or more, more preferably 70% or more. The upper limit is preferably less than 100%. It is preferable that the haze of the dummy support is small from the viewpoint of the pattern formability at the time of pattern exposure through the dummy support and the transparency of the dummy support. Specifically, the haze of the pseudo-support is preferably 2% or less, more preferably 0.5% or less, and still more preferably 0.1% or less. The lower limit is preferably 0% or more.

From the viewpoint of the pattern formation properties and the transparency of the pseudo-support when pattern exposure is performed through the pseudo-support, it is preferable that the number of fine particles, foreign substances, and defects in the pseudo-support is small. Specifically, the number of particles (for example, particles with a diameter of 1 μm), foreign matter and defects in the pseudo-support is preferably 50 pieces/10mm2 or less, more preferably ¹⁰ pieces/10mm2 or less, and ³ pieces/10mm ² or less is more preferable, and 0 piece/10mm ² is particularly preferable.

The thickness of the pseudo-support is preferably 5-200 μm, more preferably 5-150 μm, further preferably 5-50 μm, and particularly preferably 5-25 μm from the viewpoint of ease of handling and versatility. The thickness of the pseudo-support was calculated as an average value of arbitrary 5 points measured by cross-sectional observation by SEM (Scanning Electron Microscope).

From the viewpoint of handling, the pseudo-support may have a layer (lubricant layer) containing fine particles on one or both surfaces of the pseudo-support. The fine particles contained in the lubricant layer preferably have a diameter of 0.05-0.8 μm. The thickness of the lubricant layer is preferably 0.05 to 1.0 μm.

From the viewpoint of improving the adhesiveness between the pseudo support and the photosensitive composition layer, the surface of the pseudo support that is in contact with the photosensitive composition layer may be subjected to a surface modification treatment. Examples of the surface modification treatment include treatment using UV irradiation, corona discharge, and plasma. The exposure amount during UV irradiation is preferably 10-2000 mJ/cm ² , more preferably 50-1000 mJ/cm ² . As long as the exposure amount is within the above range, the lamp output and illuminance are not particularly limited. Examples of light sources for UV irradiation include pressure-resistance mercury lamps, high-pressure mercury lamps, excess-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, and electrodeless discharge lamps that emit light in a wavelength range of 150 to 450 nm. and light-emitting diodes (LEDs).

As the pseudo support, for example, a biaxially stretched polyethylene terephthalate film with a thickness of 16 μm, a biaxially stretched polyethylene terephthalate film with a thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film with a thickness of 9 μm Stretched polyethylene terephthalate film. In addition, as the pseudo-support, for example, paragraphs [0017] to [0018] of Japanese Patent Application Laid-Open No. 2014-085643, paragraphs [0019] to [0026] of Japanese Patent Application Laid-Open No. 2016-027363, international The descriptions in paragraphs [0041] to [0057] of Publication No. 2012/081680 and paragraphs [0029] to [0040] of International Publication No. 2018/179370 are incorporated into this specification. Commercially available products of the pseudo-support include, for example, Lumirror 16KS40, Lumirror 16FB40 (the above are manufactured by TORAY INDUSTRIES, INC), Cosmo Shine A4100, Cosmo Shine A4300, and Cosmo Shine A8300 (the above are manufactured by TOYOBO CO., LTD. ).

〔Photosensitive composition layer〕 The transfer film of the present invention has a photosensitive composition layer. In a display device (for example, an organic EL display device, a liquid crystal display device, etc.) equipped with a touch panel such as a capacitive input device, the electrode pattern of the sensor corresponding to the visual recognition part and the surrounding area are provided inside the touch panel. Conductive layer patterns such as the wiring part and the wiring of the lead-out wiring part. Generally, in order to form a patterned layer, the following method is widely used: using a transfer film or the like to provide a negative photosensitive composition layer on a substrate, exposing the photosensitive layer through a mask having a desired pattern, and then performing development. Therefore, as the photosensitive composition layer, a negative photosensitive composition layer is preferable. In the case where the photosensitive composition layer is a negative photosensitive composition layer, the formed pattern corresponds to a cured layer.

The photosensitive composition layer preferably contains a resin, a polymerizable compound, and a polymerization initiator, which will be described later. Moreover, in the photosensitive composition layer, it is also preferable that the resin contains an alkali-soluble resin (resin which is an alkali-soluble resin, etc.) as mentioned later. That is, it is preferable that the photosensitive composition layer contains a resin containing an alkali-soluble resin, a polymerizable compound, and a polymerization initiator. The photosensitive composition layer preferably contains 10 to 90% by mass of the resin, 5 to 70% by mass of the polymerizable compound, and 0.01 to 20% by mass of the polymerization initiator, based on the total mass of the photosensitive composition layer.

＜Resin＞ The photosensitive composition layer may contain resin. As the resin, an alkali-soluble resin is preferable. As the resin, an alkali-soluble resin in the thermoplastic resin layer described later can be used.

It is preferable that the resin contains a structural unit derived from a monomer having an aromatic hydrocarbon group from the viewpoint of suppressing thickening of the line width and deterioration of resolution when the focal position shifts during exposure. As said aromatic hydrocarbon group, a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group are mentioned, for example. The content of the structural unit derived from a monomer having an aromatic hydrocarbon group in the resin is preferably at least 10% by mass, more preferably at least 20% by mass, and still more preferably at least 30% by mass, based on the total mass of the resin. The upper limit is preferably 80% by mass or less, more preferably 60% by mass or less, still more preferably 55% by mass or less, and particularly preferably 45% by mass or less, based on the total mass of the resin. Moreover, when the photosensitive composition layer contains some resin, it is preferable that the average value of content of the structural unit derived from the monomer which has an aromatic hydrocarbon group exists in the said range. The above averages use mass averages.

As monomers having an aromatic hydrocarbon group, for example, monomers having an aralkyl group, styrene and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tertiary butoxybenzene ethylene, acetyloxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.), monomers with aralkyl groups or styrene are preferred, and styrene is more preferred. In the case of mono-system styrene having an aromatic hydrocarbon group in the resin, the content of the constituent units derived from styrene is preferably 10 to 80% by mass, more preferably 10 to 60% by mass, based on the total mass of the resin. Preferably, 20-60 mass % is more preferable, 20-55 mass % is especially preferable, and 30-45 mass % is most preferable. Moreover, when the photosensitive composition layer contains some resin, it is preferable that the average value of content of the structural unit which has an aromatic hydrocarbon group exists in the said range. The above averages use mass averages.

As the aralkyl group, for example, a substituted or unsubstituted phenylalkyl group (wherein, the benzyl group is removed) and a substituted or unsubstituted benzyl group, and a substituted or unsubstituted benzyl group is preferred. good.

As a monomer which has a phenylalkyl group, phenethyl (meth)acrylate is mentioned, for example.

Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group such as benzyl (meth)acrylate and benzyl chloride (meth)acrylate; vinylbenzyl chloride and vinylbenzene; Vinyl monomers with benzyl groups such as methanol. Among them, benzyl (meth)acrylate is preferred. When the monomer component having an aromatic hydrocarbon group in the resin is benzyl (meth)acrylate, the content of the structural unit derived from benzyl (meth)acrylate is 50 to 95% by mass based on the total mass of the resin It is more preferable, 60-90 mass % is more preferable, 70-90 mass % is still more preferable, and 75-90 mass % is especially preferable.

A resin comprising a constituent unit derived from a monomer having an aromatic hydrocarbon group is obtained by combining a monomer having an aromatic hydrocarbon group with at least one of the first monomers described below and/or at least one of the second monomers described below. It is better to obtain it through a kind of polymerization.

It is preferable that the resin containing no structural unit derived from a monomer having an aromatic hydrocarbon group is obtained by polymerizing at least one of the first monomers described later, by combining at least one of the first monomers with It is more preferably obtained by copolymerizing at least one of the second monomers described later.

The first monomer system is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid. Acid half ester, (meth)acrylic acid is preferred. The content of the structural unit derived from the first monomer in the resin is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass, and still more preferably from 15 to 30% by mass, based on the total mass of the resin. When the said content is 5 mass % or more, excellent developability, control of edge melting property, etc. can be realizable. When the above-mentioned content is 50% by mass or less, high resolution and edge shape control of the photoresist pattern and high chemical resistance of the photoresist pattern can be realized.

The second monomer system is non-acidic and is a monomer having at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylic acid n-butyl ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid (Meth)acrylic acid esters such as cyclohexyl ester and 2-ethylhexyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; (meth)acrylonitrile. Among them, methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate or n-butyl (meth)acrylate are preferred, methyl methacrylate or Ethyl(meth)acrylate is more preferred. The content of the constituent unit derived from the second monomer in the resin is preferably 5 to 80% by mass, more preferably 15 to 60% by mass, more preferably 20 to 60% by mass, and 20% to the total mass of the resin. ~48% by mass is particularly preferred, and 30-48% by mass is optimal.

In the case where the resin contains a structural unit derived from a monomer having an aralkyl group and/or a structural unit derived from styrene, it is possible to suppress a thickening of the line width and deterioration of the resolution when the focal position shifts during exposure. As the resin, a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from styrene, a structural unit derived from methacrylic acid, a structural unit derived from methacrylic acid A copolymer of a structural unit derived from methyl ester, a structural unit derived from ethyl methacrylate, and a structural unit derived from styrene, or a structural unit derived from methacrylic acid or a structural unit derived from benzyl methacrylate Copolymers are preferred. A preferable aspect of the resin includes 30 to 60 mass % of structural units derived from monomers having an aromatic hydrocarbon group, 10 to 40 mass % of structural units derived from the first monomer, and 10 to 40 mass % of structural units derived from the first monomer. 2 Constituent units of monomers 20 to 48% by mass. Another preferable aspect of the resin includes 70 to 90% by mass of a structural unit derived from a monomer having an aromatic hydrocarbon group and 10 to 25% by mass of a structural unit derived from a first monomer.

The resin may have any of a linear structure, a branched structure, and an alicyclic structure in a side chain. By using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain, a branched structure and an alicyclic structure can be introduced into the side chain of the resin. The group having an alicyclic structure may be either monocyclic or polycyclic. As a monomer containing a group having a branched chain structure in the side chain, for example, isopropyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, ( tertiary butyl methacrylate, isopentyl (meth) acrylate, tertiary pentyl (meth) acrylate, second pentyl (meth) acrylate, 2-octyl (meth) acrylate, (meth) acrylate base) 3-octyl acrylate and tertiary octyl (meth)acrylate. Among them, isopropyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl methacrylate is preferred, and isopropyl methacrylate or tert-butyl methacrylate is more preferred. As a monomer containing a group having an alicyclic structure in a side chain, for example, a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group are mentioned. Moreover, the (meth)acrylate which has the alicyclic hydrocarbon group of 5-20 carbon atoms is mentioned. Specifically, (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylate-1-adamantyl ester, (meth)acrylate-2-adamantyl ester , (meth)acrylate-3-methyl-1-adamantyl ester, (meth)acrylate-3,5-dimethyl-1-adamantyl ester, (meth)acrylate-3-ethyl Adantyl ester, 3-methyl-5-ethyl-1-adamantyl (meth)acrylate, 3,5,8-triethyl-1-adamantyl (meth)acrylate , (meth)acrylate-3,5-dimethyl-8-ethyl-1-adamantyl ester, (meth)acrylate 2-methyl-2-adamantyl ester, (meth)acrylate 2 -Ethyl-2-adamantyl ester, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro-4,7-mentanoindene-5-yl (meth)acrylate, Octahydro-4,7-menthol-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, (meth)acrylic acid -3-Hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl ester, (meth)acrylic acid-3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0 ]heptyl ester, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fenzyl (meth)acrylate, 2,2,5-trimethylcyclo(meth)acrylate Hexyl ester and cyclohexyl (meth)acrylate. Among them, cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-(meth)acrylate Adamantyl ester, (meth) fenzyl ester, (meth) acrylate 1-menthyl ester or (meth) acrylate tricyclodecane are preferred, (meth) acrylate cyclohexyl ester, (meth) ) norbornyl acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate or tricyclodecane (meth)acrylate are more preferred.

The Tg of the resin is preferably 30-150°C, more preferably 60-150°C, still more preferably 90-150°C, particularly preferably 100-150°C, and most preferably 100-120°C.

From the standpoint of more excellent effects of the present invention, the acid value of the resin is preferably 220 mgKOH/g or less, more preferably less than 200 mgKOH/g, more preferably less than 190 mgKOH/g, and particularly preferably less than 170 mgKOH/g. From the standpoint of more excellent effects of the present invention, the lower limit is preferably 10 mgKOH/g or more, more preferably 50 mgKOH/g or more, still more preferably 70 mgKOH/g or more, and particularly preferably 90 mgKOH/g or more. In addition, the acid value (mgKOH/g) refers to the mass (mg) of potassium hydroxide required to neutralize 1 g of the sample. An acid value can be calculated|required according to the method of JISK0070:1992, for example. The acid value of resin can be adjusted by the kind of structural unit which resin has, and/or content of the structural unit containing an acid group.

The weight average molecular weight of the resin is preferably from 5,000 to 500,000, more preferably from 10,000 to 100,000, still more preferably from 20,000 to 50,000, and most preferably from 20,000 to 40,000. When the weight average molecular weight is 500,000 or less, resolution and developability can be improved. Moreover, in the case where the weight average molecular weight is 5,000 or more, properties of the unexposed film such as the property of the developed aggregate and the edge melting property of the transfer film and the wafer dicing property can be controlled. The edge melting property refers to the degree to which the photosensitive composition layer is likely to protrude from the end surface of the roll when the transfer film is wound up into a roll. Chipping refers to the degree to which a wafer is easily scattered when the unexposed film is cut with a dicing knife. If the wafer adheres to the upper surface of the transfer film, etc., it will be transferred to the mask in the subsequent exposure step and the like, causing defective products. The degree of dispersion of the resin is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, still more preferably from 1.0 to 4.0, and particularly preferably from 1.0 to 3.0.

The photosensitive composition layer may contain other resins other than the above-mentioned resins. Examples of other resins include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formaldehyde, polyamide resins, polyester resins, polyamide resins, Epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine and polyalkylene di alcohol.

Resin may be used individually by 1 type, and may use 2 or more types. When two or more resins are used, two resins containing constituent units derived from monomers having aromatic hydrocarbon groups are used in combination, or resins containing constituent units derived from monomers having aromatic hydrocarbon groups are used in combination with A resin that does not contain a constituent unit derived from a monomer having an aromatic hydrocarbon group is preferable. In the latter case, the content of the resin containing a constituent unit derived from a monomer having an aromatic hydrocarbon group is preferably at least 50% by mass, more preferably at least 70% by mass, and at least 80% by mass based on the total mass of the resin. More preferably, 90% by mass or more is particularly preferable. The upper limit is preferably 100% by mass or less.

The resin content is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass, and most preferably 40 to 60% by mass based on the total mass of the photosensitive composition layer. . When content of resin is 90 mass % or less with respect to the gross mass of a photosensitive composition layer, developing time can be controlled. Moreover, when content of resin is 10 mass % or more with respect to the gross mass of a photosensitive composition layer, edge melting resistance can be improved.

As a method for synthesizing the resin, for example, adding an appropriate amount of benzoyl peroxide to a solution obtained by diluting the above-mentioned single or multiple monomers with solvents such as acetone, methyl ethyl ketone, and isopropanol And a radical polymerization initiator such as azoisobutyronitrile, and the method of heating and stirring. The synthesis can be performed while adding a part of the mixture dropwise to the reaction liquid. In addition, after completion of the reaction, a solvent may be further added to adjust to a desired concentration. Moreover, as a synthetic|combination method of resin, block polymerization, suspension polymerization, and emulsion polymerization are mentioned other than the above.

＜Polymerizable compound＞ The photosensitive composition layer preferably contains a polymerizable compound having a polymerizable group. In addition, in this specification, a "polymerizable compound" means the compound which polymerizes by the action|action of the polymerization initiator mentioned later, and shows the compound different from the above-mentioned resin.

The polymerizable group possessed by the polymerizable compound is not particularly limited as long as it is a group related to the polymerization reaction, for example, vinyl group, acryl group, methacryl group, styryl group and cis Groups having ethylenically unsaturated groups such as butenedilimide groups; groups having cationic polymerizable groups such as epoxy groups and oxetanyl groups. Among them, as the polymerizable group, a group having an ethylenically unsaturated group is preferable, and an acryl group or a methacryl group is more preferable.

As the polymerizable compound, a compound (ethylenically unsaturated compound) having one or more ethylenically unsaturated groups is preferable from the viewpoint of better photosensitivity of the photosensitive composition layer, and two or more ethylenically unsaturated groups are present in one molecule. The above ethylenically unsaturated compound (polyfunctional ethylenically unsaturated compound) is more preferable. Also, from the standpoint of more excellent resolving properties and exfoliation properties, the number of ethylenically unsaturated groups in one molecule of the ethylenically unsaturated compound is preferably 1-6, more preferably 1-3, and 2-3. For further preference, 3 is particularly preferable.

From the viewpoint of a better balance between photosensitivity, resolving power, and peelability of the photosensitive composition layer, the polymerizable compound includes bifunctional or trifunctional ethylenic compounds having 2 or 3 ethylenically unsaturated groups in one molecule. An unsaturated compound is preferable, and it is more preferable to contain a trifunctional ethylenically unsaturated compound having three ethylenically unsaturated groups in one molecule. The elastic modulus X can be adjusted by including the above-mentioned trifunctional ethylenically unsaturated compound.

From the viewpoint of excellent releasability, the content of the bifunctional ethylenically unsaturated compound is preferably at least 20% by mass, more preferably at least 40% by mass, and still more preferably at least 55% by mass, based on the total mass of the polymerizable compound. , more than 90% by mass is especially good. The upper limit is not particularly limited, but is preferably 100% by mass or less. That is, all the polymerizable compounds contained in the photosensitive composition layer may be bifunctional ethylenically unsaturated compounds. From the viewpoint of being able to adjust the elastic modulus X, the content of the trifunctional ethylenically unsaturated compound is preferably at least 10% by mass, more preferably at least 20% by mass, based on the total mass of the polymerizable compound. The upper limit is not particularly limited, but is preferably at most 100% by mass, more preferably at most 80% by mass, and still more preferably at most 50% by mass. That is, all the polymerizable compounds contained in the photosensitive composition layer may be trifunctional ethylenically unsaturated compounds. Also, as the ethylenically unsaturated compound, a (meth)acrylate compound having a (meth)acryl group as a polymerizable group is preferable.

(polymerizable compound B1) It is also preferable that the photosensitive composition layer contains the polymerizable compound B1 which has an aromatic ring and 2 ethylenically unsaturated groups. The polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule of the above-mentioned polymerizable compound B.

As the aromatic ring possessed by the polymerizable compound B1, for example, aromatic hydrocarbon rings such as benzene ring, naphthalene ring, and anthracene ring; aromatic hydrocarbon rings such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring, and pyridine ring; An aromatic heterocyclic ring; such condensed rings are preferably aromatic hydrocarbon rings, and more preferably benzene rings. In addition, the above-mentioned aromatic ring may have a substituent. The polymerizable compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

It is preferable that polymerizable compound B1 has a bisphenol structure from a viewpoint of improving resolution by suppressing swelling of the photosensitive composition layer by a developing solution. As the bisphenol structure, for example, a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl) hydroxyphenyl) methane) and bisphenol B structure derived from bisphenol B (2,2-bis (4-hydroxyphenyl) butane), bisphenol A structure is better.

Examples of the polymerizable compound B1 having a bisphenol structure include those having a bisphenol structure and two polymerizable groups (preferably (meth)acryl groups) bonded to both ends of the bisphenol structure. compound. Both ends of the bisphenol structure may be directly bonded to two polymerizable groups, or may be bonded via one or more alkyleneoxy groups. As the alkoxyl group added to both ends of the bisphenol structure, ethoxyl or propoxyl is preferred, and ethoxyl is more preferred. The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16 per molecule, more preferably 6 to 14. Regarding the polymerizable compound B1 having a bisphenol structure, paragraphs [0072] to [0080] of JP-A-2016-224162 can be cited, and these contents are incorporated in this specification.

As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is better. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethyl) Oxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2 ,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methyl 2,2-bis(4-(methacryloxydecamethacryloxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd. Pentaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.) and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.) .

As the polymerizable compound B1, a compound represented by the general formula (B1) is also preferable.

[chemical formula 1]

In formula (B1), R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group. A represents C ₂ H ₄ . B represents C ₃ H ₆ . n1 and n3 each independently represent the integer of 1-39. n1+n3 is an integer of 2-40. n2 and n4 each independently represent the integer of 0-29. n2+n4 is an integer of 0-30. The sequence of the constituent units of -(AO)- and -(BO)- may be random or blocked. In the case of being blocked, both -(AO)- and -(BO)- may be on the side of the bisphenyl group. As n1+n2+n3+n4, 2-20 are preferable, 2-16 are more preferable, 4-12 are still more preferable. Also, n2+n4 is preferably 0-10, more preferably 0-4, still more preferably 0-2, and particularly preferably 0.

The polymerizable compound B1 may be used individually by 1 type, and may use 2 or more types. From the viewpoint of better resolution, the content of the polymerizable compound B1 is preferably at least 10% by mass, more preferably at least 20% by mass, and still more preferably at least 25% by mass, based on the total mass of the photosensitive composition layer. . The upper limit is not particularly limited, but is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of transferability and edge melting (a phenomenon in which the photosensitive resin bleeds from the end of the transfer member).

From the standpoint of better resolution, the content of the polymerizable compound B1 is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 55% by mass or more, and 60% by mass relative to the total mass of the polymerizable compound. More than mass% is especially good. The upper limit is not particularly limited, but from the viewpoint of releasability, 100% by mass or less is more preferred, 99% by mass or less is more preferred, 95% by mass or less is more preferred, 90% by mass or less is particularly preferred, and 85% by mass or less is preferred. Below % is the best.

(other polymeric compounds) The photosensitive composition layer may contain other polymerizable compounds in addition to the above-mentioned polymerizable compound B1. It does not specifically limit as another polymeric compound, It can select suitably from well-known polymeric compounds. Examples include compounds having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compounds), bifunctional ethylenically unsaturated compounds not having an aromatic ring, and trifunctional or higher ethylenically unsaturated compounds. compound.

Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloxyethylsuccinate, polyethylene glycol Glycol Mono(meth)acrylate, Polypropylene Glycol Mono(meth)acrylate and Phenoxyethyl(meth)acrylate.

Examples of bifunctional ethylenically unsaturated compounds having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane ester di(meth)acrylate and trimethylolpropane diacrylate. Examples of alkylene glycol di(meth)acrylates include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), Methanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-Hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate and new Pentylene glycol di(meth)acrylate. Examples of the polyalkylene glycol di(meth)acrylate include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate. )Acrylate. Examples of urethane di(meth)acrylate include propylene oxide modified urethane di(meth)acrylate, ethylene oxide and propylene oxide modified amino Formate di(meth)acrylate. Also, as commercially available products, for example, 8UX-015A (manufactured by TAISEI FINE CHEMICAL CO,. LTD.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.) and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

Examples of ethylenically unsaturated compounds having a trifunctional or higher function include diperythritol (tri/tetra/penta/hexa) (meth)acrylate, neopentylthritol (tri/tetra) (methyl) Acrylates, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate (meth)acrylates, glycerol tri(meth)acrylates and their alkylene oxide modified substances. Here, "(three/four/five/six) (meth)acrylates" include tri(meth)acrylates, tetra(meth)acrylates, penta(meth)acrylates and hexa(meth)acrylates ) the concept of acrylate, "(three/four) (meth)acrylate" includes the concept of three (meth)acrylate and four (meth)acrylate.

Examples of alkylene oxide modified products of trifunctional or higher ethylenically unsaturated compounds include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA manufactured by Nippon Kayaku Co., Ltd. -20, A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide modified (meth)acrylate compound (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., Shin -ATM-35E and A-9300 manufactured by Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by DAI-CELL-ALLNEX LTD., etc.), ethoxylated glycerol triacrylate (Shin-Nakamura A-GLY-9E, etc. manufactured by Chemical Co., Ltd.), ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI CO., LTD.), ARONIX M-520 (manufactured by TOAGOSEI CO., LTD.) and ARONIX M -510 (manufactured by TOAGOSEI CO., LTD.).

In addition, the polymerizable compound may be a polymerizable compound having an acidic group (such as a carboxyl group). The above-mentioned acid groups may form acid anhydride groups. As the polymeric compound having an acid group, for example, ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI CO., LTD.), ARONIX (registered trademark) M-520 (manufactured by TOAGOSEI CO., LTD.) and ARONIX (registered trademark) M-510 (manufactured by TOAGOSEI CO., LTD.). Examples of the polymerizable compound having an acid group include those described in paragraphs [0025] to [0030] of JP-A-2004-239942.

The molecular weight (weight average molecular weight when there is a molecular weight distribution) of the polymerizable compound (including the polymerizable compound B1) is preferably 200 to 3,000, more preferably 280 to 2,200, and still more preferably 300 to 2,200.

A polymeric compound may be used individually by 1 type, and may use 2 or more types. The content of the polymerizable compound is preferably from 10 to 70% by mass, more preferably from 15 to 70% by mass, and still more preferably from 20 to 70% by mass, based on the total mass of the photosensitive composition layer.

From the viewpoint of more excellent effects of the present invention, the mass ratio of the content of the bifunctional or higher polymerizable compound to the content of the resin (content of the bifunctional or higher polymerizable compound/resin content) is preferably 0.10 to 1.00 , 0.50-1.00 is more preferable, 0.60-1.00 is still more preferable, and 0.60-0.80 is especially preferable.

It is also preferable that the photosensitive composition layer contains the above-mentioned polymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and it is more preferable to include the above-mentioned polymerizable compound B1 and two or more kinds of trifunctional or higher ethylenically unsaturated compounds. . The mass ratio of the mass of the polymerizable compound B1 to the mass of the trifunctional or higher ethylenically unsaturated compound is preferably from 1.0 to 5.0, more preferably from 1.2 to 4.0, and still more preferably from 1.5 to 3.0. Moreover, it is preferable that the photosensitive composition layer contains the above-mentioned polymerizable compound B1 and a trifunctional ethylenically unsaturated compound.

＜Polymerization initiator＞ It is also preferable that the photosensitive composition layer contains a polymerization initiator. A polymerization initiator can be selected according to the form of a polymerization reaction, For example, a thermal polymerization initiator and a photopolymerization initiator are mentioned. The polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator.

It is preferable that the photosensitive composition layer contains a photoinitiator. A photopolymerization initiator is a compound that receives activating rays such as ultraviolet rays, visible rays, and X-rays to start polymerization of a polymerizable compound. The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used. As a photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are mentioned, for example, A photoradical polymerization initiator is preferable.

Examples of photoradical polymerization initiators include photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenone structure, and photopolymerization initiators having an α-hydroxyalkylphenone structure. A photopolymerization initiator with a structure, a photopolymerization initiator with an acyl phosphine oxide structure, and a photopolymerization initiator with an N-phenylglycine structure.

In addition, from the viewpoint of photosensitivity, visibility and resolution of exposed and non-exposed parts, the photosensitive composition layer contains a compound selected from the group consisting of 2,4,5-triaryl imidazole dimers and derivatives thereof. At least one of them is preferred as a photoradical polymerization initiator. In addition, the structures of two 2,4,5-triarylimidazoles in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different. Examples of derivatives of 2,4,5-triaryl imidazole dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl )-4,5-bis(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl) -4,5-diphenylimidazole dimer and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

Examples of photoradical polymerization initiators include paragraphs [0031] to [0042] of JP-A-2011-095716 and paragraphs [0064]-[0081] of JP-A-2015-014783. The described polymerization initiator.

Examples of photoradical polymerization initiators include dimethylaminobenzoic acid ethyl ester (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxy benzyl), TAZ-110 (product name: manufactured by Midori Kagaku Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (product name : Manufactured by Midori Kagaku Co., Ltd.) 1-[4-(Phenylthio)]-1,2-octanedione-2-(O-benzoyl oxime) (product name: IRGACURE (registered trademark) OXE-01, manufactured by BASF Corporation), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime ) (product name: IRGACURE OXE-02, manufactured by BASF Corporation), IRGACURE OXE-03 (manufactured by BASF Corporation), IRGACURE OXE-04 (manufactured by BASF Corporation), 2-(dimethylamino)-2-[(4 -methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (product name: Omnirad 379EG, manufactured by IGM Resins B.V.), 2-methyl-1- (4-Methylthiophenyl)-2-morpholinopropan-1-one (product name: Omnirad 907, manufactured by IGM Resins B.V.), 2-hydroxy-1-{4-[4-(2-hydroxy-2 -methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (product name: Omnirad 127, manufactured by IGM Resins B.V.), 2-benzyl-2-dimethylamino-1 -(4-morpholinephenyl)butanone-1 (product name: Omnirad 369, manufactured by IGM Resins B.V.), 2-hydroxy-2-methyl-1-phenylpropan-1-one (product name: Omnirad 1173 , manufactured by IGM Resins B.V.), 1-hydroxycyclohexyl phenyl ketone (product name: Omnirad 184, manufactured by IGM Resins B.V.), 2,2-dimethoxy-1,2-diphenylethan-1-one ( Product name: Omnirad 651, manufactured by IGM Resins B.V.), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (product name: Omnirad TPO H, manufactured by IGM Resins B.V.), bis(2,4 ,6-trimethylbenzoyl)phenylphosphine oxide (product name: Omnirad 819, manufactured by IGM Resins B.V.), oxime ester-based photopolymerization initiator (product name: Lunar 6, manufactured by DKSH Management Ltd.) , 2,2'-double (2 -chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (product name: B- CIM, manufactured by Hampford Research Inc.), 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (product name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.) (product name: BCTB , manufactured by Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyl oxime) (Product name: TR-PBG-305, manufactured by Changzhou Tronly New Electronic Materials CO.,LTD.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furan ylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (product name: TR-PBG-326, manufactured by Changzhou Tronly New Electronic Materials CO., LTD.) and 3-cyclo Hexyl-1-(6-(2-(benzoyloxyimino)hexyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2 -(O-Benzoxime) (product name: TR-PBG-391, manufactured by Changzhou Tronly New Electronic Materials CO., LTD.).

Photocationic polymerization initiators (photoacid generators) are compounds that generate acid upon receiving activated light. As a photocationic polymerization initiator, a compound that generates acid by responding to activating light with a wavelength of 300nm or more (preferably a wavelength of 300-450nm) is preferred. Also, regarding the photocationic polymerization initiator that does not directly respond to activating light with a wavelength of 300 nm or more, if it is a compound that generates an acid by using a sensitizer in combination with activating light with a wavelength of 300 nm or more, it can also be combined with the sensitizer. better use. As the photocationic polymerization initiator, the photocationic polymerization initiator that produces an acid with a pKa of 4 or less is preferred, the photocationic polymerization initiator that produces an acid with a pKa of 3 or less is more preferred, and the photocationic polymerization initiator that produces an acid with a pKa of 2 or less The photocatalytic polymerization initiator of acid is especially preferred. The lower limit of pKa is not particularly limited, but -10.0 or more is preferable.

As a photocationic polymerization initiator, an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator are mentioned. As an ionic photocationic polymerization initiator, for example, onium salt compounds such as diaryliodonium salts and triaryliumium salts, and quaternary ammonium salts are mentioned. As an ionic photocationic polymerization initiator, the ionic photocationic polymerization initiator described in paragraph [0114]-[0133] of Unexamined-Japanese-Patent No. 2014-085643 is mentioned, for example.

Examples of nonionic photocationic polymerization initiators include trichloromethyl-symmetrical trisulfones, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Examples of the trichloromethyl-symmetric trisulfones, diazomethane compounds, and imidesulfonate compounds include compounds described in paragraphs [0083] to [0088] of JP-A-2011-221494. Moreover, examples of the oxime sulfonate compound include compounds described in paragraphs [0084] to [0088] of International Publication No. 2018/179640.

A polymerization initiator may be used individually by 1 type, and may use 2 or more types. The content of the polymerization initiator (preferably a photopolymerization initiator) is preferably at least 0.1% by mass, more preferably at least 0.5% by mass, based on the total mass of the photosensitive composition layer. The upper limit is preferably at most 20 mass %, more preferably at most 15 mass %, and still more preferably at most 10 mass %, with respect to the total mass of the photosensitive composition layer.

＜Pigment＞ From the viewpoint of the visibility of the exposed part and the non-exposed part, and the visibility and resolution of the pattern after development, the photosensitive composition layer includes a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 to 780 nm during color development, and by A dye whose maximum absorption wavelength is changed by acid, alkali or radical (also referred to as "dye N") is also preferable. When the dye N is contained, the detailed mechanism is not clear, but the adhesion with the adjacent layer (for example, the pseudo-water-soluble resin layer) is improved, and the resolution is more excellent.

In this specification, a pigment "changes its maximum absorption wavelength by acid, alkali or free radical" may refer to a state in which a pigment in a color-developed state is decolorized by an acid, alkali or free radical, or in a decolorized state. Any of the state in which the pigment in the pigment develops color by acid, alkali or free radicals and the state in which the pigment in the color state changes to another color state. Specifically, the dye N may be a compound that develops color by changing from a decolorized state by exposure, or may be a compound that decolorizes by changing from a color-developed state by exposure. In the above cases, it may be a pigment that generates acid, alkali or free radicals in the photosensitive composition layer by exposure and acts to change the state of color development or decolorization, or it may be a pigment that is exposed to acid, alkali or free radicals. Free radicals change the state (such as pH) in the photosensitive composition layer to change the state of color development or decolorization. In addition, it may be a pigment that is directly stimulated by an acid, an alkali or a free radical without exposure to light to change the state of color development or decolorization.

Among them, dye N is preferably a dye whose maximum absorption wavelength is changed by acid or radicals, and a dye whose maximum absorption wavelength is changed by radicals from the viewpoint of visibility and resolution of the exposed part and the non-exposed part. for better. From the viewpoint of the visibility and resolution of the exposed portion and the non-exposed portion, the photosensitive composition layer contains both a dye that changes the maximum absorption wavelength by radicals as the dye N and a photoradical polymerization initiator. better. Moreover, from the viewpoint of the visibility of an exposed part and a non-exposed part, it is preferable that the dye N is a dye that develops color with an acid, an alkali or a radical.

As the coloring mechanism of the dye N, for example, an aspect in which a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator) or a photobase generator is added to the photosensitive composition layer is mentioned. , after exposure due to free radicals, acids or bases generated by photoradical polymerization initiators, photocationic polymerization initiators or photobase generators, radical reactive dyes, acid reactive dyes or base reactive dyes (such as colorless pigments) for color development.

From the viewpoint of the visibility of the exposed part and the non-exposed part, as the maximum absorption wavelength in the wavelength range of 400 to 780 nm in the color development of the dye N, 550 nm or more is preferable, 550 to 700 nm is more preferable, and 550 to 650 nm is preferably Further better. In addition, the dye N may have only one maximum absorption wavelength in the wavelength range of 400 to 780 nm at the time of color development, or may have two or more. When the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm for color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.

Regarding the maximum absorption wavelength of dye N, the transmission of a solution (liquid temperature: 25°C) containing dye N can be measured in the range of 400 to 780 nm using a spectrophotometer: UV3100 (manufactured by SHIMADZU CORPORATION) in an atmospheric atmosphere Spectrum, and detect the intensity of light reaches the minimum wavelength (maximum absorption wavelength) and measure.

As a coloring matter which develops or decolorizes by exposure, a colorless compound is mentioned, for example. Examples of dyes that decolorize by exposure include leuco compounds, diarylmethane-based dyes, 㗁𠯤-based dyes, Kuchi Yamaguchi-based dyes, iminonaphthoquinone-based dyes, azomethine-based dyes, and Anthraquinone pigments. As the dye N, a colorless compound is preferable from the viewpoint of the visibility of the exposed portion and the non-exposed portion.

As the colorless compound, for example, a colorless compound having a triarylmethane skeleton (triarylmethane-based dye), a colorless compound having a helicopyran skeleton (helicopyran-based dye), and a colorless compound having a fluorescent yellow mother skeleton (fluorescent yellow matrix pigment), colorless compound with diarylmethane skeleton (diarylmethane pigment), colorless compound with rhodamine lactamide skeleton (rhodamine lactamide pigment), indole A colorless compound with an indolylphthalide skeleton (indolylphthalide pigment) and a colorless compound with a white gold amine skeleton (white gold amine pigment). Among them, triarylmethane-based pigments or fluorescent yellow parent system pigments are preferred, and colorless compounds (triphenylmethane-based pigments) with triphenylmethane skeletons or fluorescent yellow parent system pigments are more preferred.

The colorless compound preferably has a lactone ring, a sultone ring, or a sultone ring from the viewpoint of the visibility of the exposed portion and the non-exposed portion. Thereby, the lactone ring, sultone ring or sultone ring of the colorless compound can be reacted with the free radical generated by the photoradical polymerization initiator or the acid generated by the photocationic polymerization initiator , Change the colorless compound to a ring-closed state to decolorize or change the colorless compound to a ring-opened state to develop color. As a colorless compound, a compound having a lactone ring, a sultone ring or a sultone ring and developing color by free radicals or acids opening the lactone ring, sultone ring or sultone ring is Preferably, it has a lactone ring and is more preferably a compound that develops color by opening the lactone ring with a radical or an acid.

Examples of the dye N include dyes and leuco compounds. Examples of dyes include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinaldine red, bengal Rose bengal, metanil yellow, thymol sulfonphthalein, xylenol blue, methyl orange, p-methyl red, Congo red, benzene red purple 4B, α- Naphthyl red, Nile blue 2B, Nile blue A, methyl violet, malachite green, parafuchsin, Victoria pure blue-naphthalene sulfonate, Victoria pure blue BOH (manufactured by Hodogaya Chemical Co., Ltd. ), Oil Blue #603 (manufactured by Orient Chemical Co., Ltd.), Oil Powder #312 (manufactured by Orient Chemical Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Co., Ltd.), oil red OG (manufactured by Orient Chemical Co., Ltd.), oil red RR (manufactured by Orient Chemical Co., Ltd.), oil green #502 (manufactured by Orient Chemical Co., Ltd. manufactured), SPIRON Red BEH SPECIAL (manufactured by Hodogaya Chemical Co., Ltd.), m-cresyl violet, cresyl red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethyl Aminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxy Ethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1-β-naphthalene- 4-p-Diethylaminophenylimino-5-pyrazolone.

Examples of colorless compounds include p,p',p''-hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (manufactured by Ciba Geigy), crystal violet lactone, peacock Green lactone, benzoyl leuco methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)amino fluorescent yellow precursor, 2-aniline Base-3-methyl-6-(N-ethyl-p-toluidine) fluorescent yellow precursor, 3,6-dimethoxy fluorescent yellow precursor, 3-(N,N-diethylamino) -5-methyl-7-(N,N-dibenzylamino) fluorescent yellow precursor, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluorescent Luminous yellow precursor, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorescent yellow precursor, 3-(N,N-diethylamino)-6-methyl -7-stibamidofluorescent yellow precursor, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorescent yellow precursor, 3-(N,N-diethylamino )-6-methoxy-7-amino fluorescent yellow precursor, 3-(N,N-diethylamino)-7-(4-chloroanilino) fluorescent yellow precursor, 3-(N, N-diethylamino)-7-chlorofluorescent yellow precursor, 3-(N,N-diethylamino)-7-benzylamino fluorescent yellow precursor, 3-(N,N-di Ethylamino)-7,8-benzofluorescent yellow precursor, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorescent yellow precursor, 3-(N, N-dibutylamino)-6-methyl-7-stibamidofluorescent yellow precursor, 3-piperidinyl-6-methyl-7-anilinyl fluorescent yellow precursor, 3-pyrrolidinyl- 6-Methyl-7-anilinofluorescent yellow precursor, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butyl -2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethyl Amino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-phthalide, 3-(4-diethylaminophenyl )-3-(1-ethyl-2-methylindol-3-yl)phthalide and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H), 9'-[9H]koustar-3-one.

From the viewpoint of the visibility of the exposed area and the non-exposed area, the visibility of the pattern after development, and the resolution, it is preferable that the pigment N is a pigment whose maximum absorption wavelength is changed by free radicals, and the color is developed by free radicals. The pigment is better. As the dye N, leuco crystal violet, crystal violet lactone, brilliant green or Victoria pure blue-naphthalenesulfonate are preferable.

One type of dye N may be used alone, or two or more types may be used. From the viewpoint of excellent visibility of exposed and non-exposed areas, pattern visibility after development, and excellent resolution, the content of the pigment N is preferably 0.1% by mass or more with respect to the total mass of the photosensitive composition layer, and 0.1 to 0.1% by mass. 10 mass % is more preferable, 0.1-5 mass % is further more preferable, and 0.1-1 mass % is especially preferable.

The content of the dye N shows the content of the dye when all the dye N contained in the total mass of the photosensitive composition layer is in a colored state. Hereinafter, a method for quantifying the content of the dye N will be described by taking a dye that develops color by radicals as an example. A solution obtained by dissolving 0.001 g and 0.01 g of dye N in 100 mL of methyl ethyl ketone was prepared. A photoradical polymerization initiator (Irgacure OXE01, manufactured by BASF Japan Ltd.) was added to each of the obtained solutions, and irradiated with light having a wavelength of 365 nm to generate radicals to bring all the dyes N into a color-developed state. Then, under the air atmosphere, using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), the absorbance of each solution at a liquid temperature of 25° C. was measured to prepare a calibration curve. Next, except for dissolving 3 g of the photosensitive composition layer in methyl ethyl ketone instead of the dye N, the absorbance of the solution in which all the dye was developed was measured by the same method as above. Based on the obtained absorbance of the solution containing the photosensitive composition layer, the content of the pigment N contained in the photosensitive composition layer is calculated according to the calibration curve. In addition, the photosensitive composition layer 3g is the same as the total solid content 3g in the photosensitive resin composition.

＜Heat-crosslinkable compound＞ From the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, the photosensitive composition layer may contain a heat-crosslinkable compound. In addition, in this specification, the heat-crosslinkable compound which has the ethylenically unsaturated group mentioned later is not regarded as a polymeric compound, but is regarded as a heat-crosslinkable compound. As a heat-crosslinkable compound, a methylol compound and a blocked isocyanate compound are mentioned, for example. Among these, blocked isocyanate compounds are preferred from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. Since the blocked isocyanate compound reacts with a hydroxyl group and a carboxyl group, for example, when a resin and/or a polymerizable compound has at least a hydroxyl group and a carboxyl group, There exists a tendency for the hydrophilicity of the formed film to fall, and to harden the photosensitive composition layer and use it as a film to strengthen the function. In addition, the blocked isocyanate compound means "a compound having a structure in which an isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent."

The dissociation temperature of the blocked isocyanate compound is preferably from 100 to 160°C, more preferably from 130 to 150°C. The dissociation temperature of blocked isocyanate refers to "the temperature of the endothermic peak accompanying the deprotection reaction of blocked isocyanate when analyzed and measured by DSC (Differential scanning calorimetry: differential scanning calorimetry) using a differential scanning calorimeter." As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited to this.

As an end-capping agent with a dissociation temperature of 100 to 160°C, for example, active methylene compounds (malonate diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, etc.) Esters and 2-ethylhexyl malonate, etc.), oxime compounds (formaldoxime, acetaldehyde oxime, acetyloxime, methyl ethyl ketoxime and cyclohexanone oxime, etc. have -C ( =N-OH)-compound of the structure represented). Among them, as the blocking agent having a dissociation temperature of 100 to 160° C., for example, at least one selected from oxime compounds is preferred from the viewpoint of storage stability.

For example, it is preferable that the blocked isocyanate compound has an isocyanurate structure from the viewpoint of improving the brittleness of the film and improving the adhesive force with the transfer target. A blocked isocyanate compound having an isocyanurate structure is obtained, for example, by isocyanurating and protecting hexamethylene diisocyanate. Among them, as a blocked isocyanate compound having an isocyanurate structure, it is easier to set the dissociation temperature within a preferable range than a compound not having an oxime structure, and it is easy to reduce development residue. Compounds Compounds with an oxime structure as an end-capping agent are preferred.

The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and known polymerizable groups can be used, and radically polymerizable groups are preferred. Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloxy group, a (meth)acrylamide group, and a styryl group, and groups having an epoxy group such as a glycidyl group. Among them, as the polymerizable group, an ethylenically unsaturated group is preferable, a (meth)acryloxy group is more preferable, and an acryloxy group is still more preferable.

Examples of blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (manufactured by SHOWA DENKO K.K.), blocked type DURANATE series (for example, DURANATE (registered trademark) TPA-B80E, DURANATE (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation.). As a blocked isocyanate compound, the compound of the following structure is also mentioned, for example.

[chemical formula 2]

A heat-crosslinkable compound may be used individually by 1 type, and may use 2 or more types. When the photosensitive composition layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the photosensitive composition layer. good.

＜Pigment＞ The photosensitive composition layer may be a colored resin layer containing a pigment. In recent years, a cover glass in which a black frame-shaped light-shielding layer is formed on the back peripheral portion of a transparent glass substrate or the like is sometimes attached to a liquid crystal display window of an electronic device to protect the liquid crystal display window. In order to form such a light-shielding layer, a colored resin layer can be used. As a pigment, what is necessary is just to select suitably according to desired hue, and can select from black pigment, white pigment, and color pigments other than black and white. Among them, in the case of forming a black-based pattern, a black pigment can be preferably selected as the pigment.

(black pigment) Known black pigments (organic pigments, inorganic pigments, etc.) can be appropriately selected as the black pigment within a range that does not impair the effects of the present invention. Among them, from the viewpoint of optical density, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, or graphite are preferred as the black pigment, and carbon black is more preferred. Carbon black having at least a part of the surface covered with a resin is preferable from the viewpoint of surface resistance.

The particle size (number average particle size) of the black pigment is preferably from 0.001 to 0.1 μm, more preferably from 0.01 to 0.08 μm, from the viewpoint of dispersion stability. In addition, the particle diameter refers to the diameter of a circle when the area of the pigment particle is calculated from the photographic image of the pigment particle taken with an electron microscope and a circle having the same area as the area of the pigment particle is considered, and the number average particle diameter is for any 100 Particles The average value obtained by calculating the above-mentioned particle size and averaging the calculated particle sizes of 100 particles.

Examples of white pigments include inorganic pigments and white pigments described in paragraphs [0015] and [0114] of JP-A-2005-007765. As the inorganic pigment, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide or barium sulfate are preferred, titanium oxide or zinc oxide is more preferred, titanium oxide is further preferred , rutile or anatase titanium oxide is particularly preferred, and rutile titanium oxide is the best. In addition, silica treatment, alumina treatment, titania treatment, zirconia treatment, or organic treatment may be performed on the surface of titanium oxide, or two or more treatments may be performed. Thereby, the catalytic activity of titanium oxide is suppressed, and heat resistance and delustering properties are improved. From the viewpoint of reducing the thickness of the photosensitive composition layer after heating, it is preferable to perform at least one of alumina treatment and zirconia treatment as the surface treatment on the surface of titanium oxide, and perform alumina treatment and zirconia treatment. Zirconium dioxide is better for both.

Moreover, when a photosensitive composition layer is a colored resin layer, it is also preferable that a photosensitive composition layer contains color pigments other than a black pigment and a white pigment from a viewpoint of transferability. When a color pigment is included, the particle diameter of the color pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the viewpoint of better dispersibility. The lower limit is preferably 10 nm or more. Examples of color pigments include Victoria Pure Blue BO (Color Index: Color Index (C.I.) 42595), Goldamine (C.I. 41000), Fat Black HB (C.I. 26150), Monoright Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I. Pigment Yellow 83), Permanent Magenta FBB (C.I. Pigment Red 146), Master Yeast Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH ( C.I. Pigment Red 11), Fastel Powder B Supra (C.I. Pigment Red 81), Monastral Fast Blue (C.I. Pigment Blue 15), Monoright Black B (C.I. Pigment Black 1) Pigment Red 97, C.I. Pigment Red 122, C.I. Pigment Red 149, C.I. Pigment Red 168, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 192, C.I. Pigment Red 215, C.I. Pigment Green 7, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:4, C.I. Pigment Blue 22, C.I. Pigment Blue 60, C.I. Pigment Blue 64, C.I. Pigment Violet 23, C.I. Pigment Red 177 is preferred.

A pigment may be used individually by 1 type, and may use 2 or more types. When the photosensitive composition layer contains a pigment, the content of the pigment is preferably more than 3% by mass and not more than 40% by mass, and more than 3% by mass and not more than 35% by mass relative to the total mass of the photosensitive composition layer More preferably, more than 5 mass % and 35 mass % or less are still more preferable, and 10-35 mass % or less are especially preferable.

When the photosensitive composition layer contains pigments (white pigments and color pigments) other than black pigments, the content of pigments other than black pigments is preferably 30% by mass or less, 1 to 20% by mass, based on the total mass of black pigments % is more preferable, and 3-15 mass % is still more preferable.

When the photosensitive composition layer contains a black pigment, it is preferable to introduce the black pigment (preferably carbon black) into the photosensitive composition in the form of a pigment dispersion. The dispersion liquid may be prepared by adding a mixture obtained by mixing a black pigment and a pigment dispersant in advance to an organic solvent (or vehicle), and dispersing using a disperser. What is necessary is just to select a pigment dispersant according to a pigment and a solvent, For example, a commercially available dispersant can be used. In addition, the vehicle means, in the case of a pigment dispersion, the part of the medium in which the pigment is dispersed, and is liquid, and contains a binder component that holds the black pigment in a dispersed state and a component that dissolves and dilutes the binder component. Solvent composition (organic solvents).

Examples of the dispersing machine include known dispersing machines such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mixer. In addition, fine pulverization can be carried out by mechanical grinding using frictional force. Examples of the dispersing machine and fine pulverization include the descriptions in "Encyclopedia of Pigments" (by Kunizo Asakura, first edition, Asakura Publishing Co., Ltd., 2000, pages 438 and 310).

＜Other additives＞ The photosensitive composition layer may contain known additives (other additives) as needed in addition to the above components. Examples of other additives include radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, sensitizers, surfactants, plasticizers, heterocyclic compounds (triazoles, etc.), Pyridines (isonicotinamide, etc.) and purine bases (adenine, etc.). In addition, other additives include metal oxide particles, antioxidants, dispersants, acid multiplying agents, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic precipitation inhibitors. Agent, paragraphs [0165] to [0184] of Japanese Patent Laid-Open No. 2014-085643, and these contents are incorporated into this specification. One type of other additives may be used alone, or two or more types may be used.

(Free Radical Polymerization Inhibitor) Examples of radical polymerization inhibitors include thermal polymerization inhibitors described in paragraph [0018] of Japanese Patent No. 4502784, among which phenthiazine, phenomethanol, or 4-methoxyphenol is preferable. Examples of the radical polymerization inhibitor include naphthylamine, cuprous chloride, nitrosophenylhydroxylamine aluminum salt, and diphenylnitrosoamine. Among them, nitrosophenylhydroxylamine aluminum salt is preferable from the viewpoint of not impairing the sensitivity of the photosensitive composition layer. A radical polymerization inhibitor may be used individually by 1 type, and may use 2 or more types together. When the photosensitive composition layer contains a radical polymerization inhibitor, the content of the radical polymerization inhibitor is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, based on the total mass of the photosensitive composition layer. Preferably, 0.02 to 2.0 mass % is still more preferable. The content of the radical polymerization inhibitor is preferably from 0.005 to 5.0% by mass, more preferably from 0.01 to 3.0% by mass, and still more preferably from 0.01 to 1.0% by mass, based on the total mass of the polymerizable compound.

(benzotriazoles) Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)amino Methylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole and bis(N-2-hydroxyethyl base) aminomethylene-1,2,3-benzotriazole.

(Carboxybenzotriazoles) As carboxybenzotriazoles, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N- Di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole and N-(N, N-di-2-ethylhexyl)aminoethylenylcarboxybenzotriazole. Specific examples of carboxybenzotriazoles include CBT-1 (JOHOKU CHEMICAL CO., LTD, product name).

The total content of the radical polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles is preferably from 0.01 to 3% by mass, more preferably from 0.05 to 1% by mass, based on the total mass of the photosensitive composition layer. When the said content is 0.01 mass % or more, the storage stability of a photosensitive composition layer becomes more excellent. On the other hand, when the above content is 3% by mass or less, the maintenance of sensitivity and the suppression of decolorization of the dye are more excellent.

(sensitizer) As a sensitizer, a well-known sensitizer, dye, and a pigment are mentioned, for example. Examples of sensitizers include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, tiostatone compounds, and acridone compounds. , azole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (for example, 1,2,4-triazole), stilbene compounds, trioxazole compounds, thiophene compounds, naphthalene dicarboxamides Amine compounds, triarylamine compounds and aminoacridine compounds.

In the case where the photosensitive composition layer contains a sensitizer, the content of the sensitizer relative to the content of the photosensitive composition layer should be considered from the viewpoint of improving the sensitivity to the light source and increasing the hardening speed based on the balance between the polymerization speed and chain transfer. The total mass is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass.

(surfactant) Examples of the surfactant include those described in paragraph [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of Japanese Patent Application Laid-Open No. 2009-237362.

As the surfactant, a nonionic surfactant, a fluorine-based surfactant, or a silicone-based surfactant is preferable. Examples of commercially available fluorine-based surfactants include MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F -144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557 , F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, EXP.MFS-578, EXP .MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-603, R-41, R-41 -LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, and DS-21 (manufactured by DIC CORPORATION), Fluorad FC430, FC431, FC171 (Above are manufactured by Sumitomo 3M Limited), SurflonS-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (Above Manufactured for AGC INC.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc. above), FTERGENT 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (manufactured by NEOS Corporation), U-120E (UNICHEM CO., LTD.), etc.

Also, as a fluorine-based surfactant, an acrylic compound having a molecular structure having a functional group containing a fluorine atom, and the functional group containing a fluorine atom being partly cut off when heat is applied can also be preferably used. And the fluorine atom volatilizes. Examples of such fluorine-based surfactants include MEGAFACE DS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016) and Nikkei Sangyo Shimbun (February 23, 2016)). Furthermore, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorine-based surfactant. In addition, as the fluorine-based surfactant, a blocked polymer can also be used. In addition, as the fluorine-based surfactant, a fluorine-containing polymer compound including a constituent unit derived from a (meth)acrylate compound having a fluorine atom and a unit derived from a (meth)acrylate compound having two A constituent unit of the (meth)acrylate compound of the above (preferably 5 or more) alkoxyl groups (preferably ethylenyloxy, propoxyl groups). Moreover, as a fluorine-based surfactant, for example, a fluorine-containing polymer having a group having an ethylenically unsaturated bond in a side chain can also be used, and MEGAFACE RS-101, RS-102, RS-718K, and RS -72-K (the above is manufactured by DIC Corporation).

Fluorine-based surfactants derived from compounds having a straight-chain perfluoroalkyl group with a carbon number of 7 or more, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), from the viewpoint of improving environmental adaptability The surfactant of the alternative material is preferred.

Examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerin propoxylate, glycerin Ethoxylates, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol Alcohol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; PLURONIC (registered trademark) L10, L31, L61, L62, 10R5, 17R2 and 25R2 (manufactured by BASF); TETRONIC 304, 701, 704, 901, 904 and 150R1, HYDROPALAT WE 3323 (the above are manufactured by BASF); SOLSPERSE 20000 (the above are manufactured by Lubrizol Japan Ltd.); NCW-101, NCW-1001 and NCW-1002 (the above are FUJIFILM Wako Pure Chemical Corporation); Pionin D-1105, D-6112, D-6112-W, and D-6315 (the above are manufactured by TAKEMOTO OIL & FAT Co., Ltd.); OLFIN E1010, Surfynol 104, 400, 440 (The above are manufactured by Nissin Chemical Industry Co., Ltd.).

Examples of silicone-based surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers having organic groups introduced into side chains and/or terminals.

Specific examples of silicone-based surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, and EXP.S-505-2 (manufactured by DIC CORPORATION ), DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA and Toray Silicone SH8400 (manufactured by X-Chemie GmbH above); -4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22 -4515, KF-6004, KP-341, KF-6001 and KF-6002, KP-101KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP -120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369 , KP-611, KP-620, KP-621, KP-626 and KP-652 (the above are manufactured by Shin-Etsu Chemical Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF-4460及TSF-4452（以上為Momentive Performance Materials Inc.製造）；BYK300、BYK306、BYK307、BYK310、BYK320、BYK323、BYK325、BYK330、BYK313、BYK315N、BYK331、BYK333、BYK345、BYK347、BYK348、BYK349、BYK370、BYK377 , BYK378 and BYK323 (the above are manufactured by BYK Chemie GmbH).

When the photosensitive composition layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and 0.05 to 1.0% by mass relative to the total mass of the photosensitive composition layer. 0.8 mass % is more preferable.

Examples of plasticizers and heterocyclic compounds include compounds described in paragraphs [0097] to [0103] and paragraphs [0111] to [0118] of International Publication No. 2018/179640.

＜Impurities＞ The photosensitive composition layer may contain impurities. Examples of impurities include metal impurities or ions thereof, halide ions, residual organic solvents, residual monomers, and water.

(Metal impurities and halide ions) Examples of metal impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin and their ions and halide ions. Among them, since sodium ions, potassium ions, and halide ions are easily mixed, it is preferable to set the following content. The metal impurities are compounds different from the above-mentioned particles (for example, metal oxides).

The content of metal impurities is preferably at most 80 mass ppm, more preferably at most 10 mass ppm, and still more preferably at most 2 mass ppm, relative to the total mass of the photosensitive composition layer. The lower limit is not particularly limited, and is preferably at least 1 mass ppm, more preferably at least 0.1 mass ppm, based on the total mass of the photosensitive composition layer.

As a method of adjusting the content of impurities, for example, a method of selecting a material with a low content of impurities as a raw material of the photosensitive composition layer, a method of preventing the mixing of impurities when forming a photosensitive composition layer, and cleaning by cleaning method of removal. The content of impurities can be quantified by known methods such as ICP emission spectrometry, atomic absorption spectrometry, and ion chromatography.

(residual organic solvent) Examples of residual organic solvents include benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylformamide Acetamide and hexane. The content of the residual organic solvent is preferably at most 100 mass ppm, more preferably at most 20 mass ppm, and still more preferably at most 4 mass ppm, relative to the total mass of the photosensitive composition layer. The lower limit is not particularly limited, but it is preferably at least 10 mass ppb, and more preferably at least 100 mass ppb. The content of the residual organic solvent can be prepared by the same method as the metal impurity mentioned above. Moreover, content of a residual organic solvent can be quantified by well-known methods, such as gas chromatography, for example.

(residual monomer) The photosensitive composition layer may contain residual monomers of each constituent unit of the resin described above. From the viewpoint of patternability and reliability, the content of the residual monomer is preferably at most 5000 mass ppm, more preferably at most 2000 mass ppm, and still more preferably at most 500 mass ppm, based on the total mass of the resin. The lower limit is not particularly limited, but is preferably 1 mass ppm or more, more preferably 10 mass ppm or more, based on the total mass of the resin. From the viewpoint of patternability and reliability, the residual monomer of each constituent unit of the alkali-soluble resin is preferably 3000 mass ppm or less, more preferably 600 mass ppm or less, and 100 mass ppm with respect to the total mass of the photosensitive composition layer It is still more preferably below ppm. The lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more, based on the total mass of the photosensitive resin composition layer.

It is also preferable that the residual monomer amount of the monomer when synthesizing the alkali-soluble resin by a polymer reaction be within the above-mentioned range. For example, when synthesizing an alkali-soluble resin by reacting glycidyl acrylate in a carboxylic acid side chain, it is preferable to make content of glycidyl acrylate into the said range. The amount of residual monomers can be measured by known methods such as liquid chromatography and gas chromatography.

The content of water in the photosensitive composition layer is preferably from 0.01 to 1.0% by mass, more preferably from 0.05 to 0.5% by mass, from the viewpoint of improving reliability and lamination.

[Characteristics of photosensitive composition layer] The thickness (film thickness) of the photosensitive composition layer is often 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, still more preferably 0.5 to 30 μm, and most preferably 1 to 20 μm. Thereby, the developability of a photosensitive composition layer improves, and resolution can be improved.

The content of the double bond in the photosensitive composition layer is preferably from 0.8 to 3.0 mmol/g, more preferably from 1.0 to 3.0 mmol/g, and still more preferably from 1.2 to 2.0 mmol/g.

The acid value of the photosensitive composition layer is preferably from 10 to 150 mgKOH/g, more preferably from 40 to 100 mgKOH/g, and still more preferably from 50 to 100 mgKOH/g. From the viewpoint of better effects of the present invention, 50 to 100 mgKOH/g is more preferable. 90mgKOH/g is particularly good, and 70-90mgKOH/g is the best. As the method of measuring the above-mentioned acid value, for example, the method of measuring the acid value in the above-mentioned resin and the method of calculating the acid value from the known content of the resin are mentioned.

〔middle layer〕 The transfer film of the present invention has an intermediate layer. Examples of the intermediate layer include a water-soluble resin layer and an oxygen barrier layer having an oxygen barrier function described as "separation layer" in JP-A-5-072724. As the intermediate layer, an oxygen barrier layer is preferable from the viewpoint of improving the sensitivity at the time of exposure, reducing the time load of the exposure machine, and improving productivity. When the transfer film has an oxygen barrier layer, when the photosensitive composition layer of the transfer film is exposed to light, the polymerization reaction proceeds easily and smoothly, and the elastic modulus X of the cured layer can be brought into a preferable range. As a result, the obtained pattern shape became favorable. As the said oxygen barrier layer, it can select suitably from the well-known layer described in the said gazette etc. Among them, an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkaline solution (1% by mass of sodium carbonate at 22°C) is preferred. Hereinafter, each component which can be contained in a water-soluble resin layer (intermediate layer) is demonstrated.

＜Water-soluble resin＞ It is preferable that the intermediate layer contains a water-soluble resin. Examples of water-soluble resins include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, polyether-based resins, gelatin, and polyamide resins.

Examples of cellulose-based resins include water-soluble cellulose derivatives. Examples of water-soluble cellulose derivatives include hydroxyethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, methylcellulose, and ethylcellulose.

Examples of polyether resins include polyethylene glycol, polypropylene glycol, and their alkylene oxide adducts, and vinyl ether resins. Examples of polyamide-based resins include acrylamide-based resins, vinylamine-based resins, and allylamine-based resins. Among these, water-soluble cellulose derivatives or polyamide-based resins are preferred as the water-soluble resin.

Moreover, as a water-soluble resin, the copolymer of (meth)acrylic acid/vinyl compound is also mentioned, for example. As a copolymer of (meth)acrylic acid/vinyl ester compound, a copolymer of (meth)acrylic acid/allyl (meth)acrylic acid is preferable, and a copolymer of methacrylic acid/allyl methacrylate is more preferable. good. In the case of a water-soluble resin-based (meth)acrylic acid/vinyl compound copolymer, the composition ratio (mole %) is preferably 90/10 to 20/80, and 80/20 to 30/70 better.

The weight average molecular weight (Mw) of the water-soluble resin is preferably at least 5,000, more preferably at least 7,000, and still more preferably at least 10,000. The upper limit is preferably at most 200,000, more preferably at most 100,000, and still more preferably at most 50,000. The degree of dispersion (Mw/Mn) of the water-soluble resin is preferably 1-10, more preferably 1-5.

The water-soluble resin may be used alone or in combination of two or more. The content of the water-soluble resin is preferably 50% by mass or more, more preferably 70% by mass or more, based on the total mass of the intermediate layer from the viewpoint of better effects of the present invention and/or better oxygen barrier capability. The upper limit is preferably 100% by mass or less, more preferably 99.9% by mass or less, still more preferably 99.8% by mass or less, and particularly preferably 99% by mass or less.

＜Other ingredients＞ The intermediate layer may contain other components in addition to the above-mentioned resins. The molecular weight of other components is preferably less than 5,000, more preferably less than 4,000, still more preferably less than 3,000, particularly preferably less than 2,000, and most preferably less than 1,500. The lower limit is preferably 60 or more.

As other components, polyols, alkylene oxide adducts of polyols, phenol derivatives, or amide compounds are preferable, and polyols, phenol derivatives, or amide compounds are more preferable.

As polyhydric alcohols, glycerol, diglycerol, and diethylene glycol are mentioned, for example. The number of hydroxyl groups containing polyols is preferably 2-10. Examples of the alkylene oxide adducts of polyols include compounds obtained by adding ethylene oxide, propylene oxide, and the like to the above-mentioned polyols. In addition, the average addition number is preferably 1-100, more preferably 2-50, and more preferably 2-20. As a phenol derivative, bisphenol A and bisphenol S are mentioned, for example. N-methylpyrrolidone is mentioned as an amide compound.

The intermediate layer contains at least 1 is better.

The thickness of the intermediate layer is preferably 3.0 μm or less, more preferably 2.0 μm or less. The lower limit is preferably 1.0 μm or more.

The other components may be used individually by 1 type, and may use 2 or more types. The content of other components is preferably at least 0.1% by mass, more preferably at least 0.5% by mass, and still more preferably at least 1% by mass, based on the total mass of the intermediate layer. The upper limit is preferably less than 30 mass %, more preferably 10 mass % or less, and still more preferably 5 mass % or less.

〔Thermoplastic resin layer〕 The transfer film of the present invention may have a thermoplastic resin layer. The thermoplastic resin layer is usually placed between the dummy support and the photosensitive composition layer. The transfer film is provided with a thermoplastic resin layer, thereby improving the followability to the substrate in the step of laminating the transfer film and the substrate, and suppressing the mixing of air bubbles between the substrate and the transfer film. As a result, the adhesiveness of the layer adjacent to the thermoplastic resin layer (for example, a dummy support) can be ensured. Moreover, as a thermoplastic resin layer, for example, paragraphs [0189] to [0193] of JP-A-2014-085643 can be mentioned, and these contents are incorporated in this specification.

The thickness (layer thickness) of the thermoplastic resin layer is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of adhesiveness with adjacent layers. From the viewpoint of developability and resolution, the upper limit is preferably 20 μm or less, more preferably 10 μm or less, and still more preferably 8 μm or less.

＜Thermoplastic resin＞ The thermoplastic resin layer preferably contains a thermoplastic resin. As the thermoplastic resin, an alkali-soluble resin is preferable. Examples of alkali-soluble resins include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formaldehyde, polyamide resins, and polyester resins. , polyamide resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine and polyalkylene glycols.

As the alkali-soluble resin, an acrylic resin is preferable from the viewpoint of developability and adhesiveness with an adjacent layer. Here, the acrylic resin refers to a resin having a composition selected from the group consisting of (meth)acrylic acid-derived constituent units, (meth)acrylate-derived constituent units, and (meth)acrylamide-derived constituent units. At least one resin constituting the unit. In the acrylic resin, the total content of the structural unit derived from (meth)acrylic acid, the structural unit derived from (meth)acrylate, and the structural unit derived from (meth)acrylamide relative to the total mass of the acrylic resin , more than 50% by mass is preferred. The upper limit is preferably 100% by mass or less with respect to the total mass of the acrylic resin. Among them, the total content of structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylate is preferably 30 to 100% by mass, and 50 to 100% by mass based on the total mass of the acrylic resin. better.

As the alkali-soluble resin, polymers having acid groups are preferred. Examples of the acid group include carboxyl group, sulfo group, phosphoric acid group and phosphonic acid group, and carboxyl group is preferred. From the viewpoint of developability, the acid value of the alkali-soluble resin is preferably 60 mgKOH/g or more. The upper limit is preferably 300 mgKOH/g or less, more preferably 250 mgKOH/g or less, still more preferably 200 mgKOH/g or less, and particularly preferably 150 mgKOH/g or less. Among them, as the alkali-soluble resin, an alkali-soluble resin of 60 mgKOH/g or more is preferable, and an acrylic resin containing a carboxyl group having an acid value of 60 mgKOH/g or more is more preferable.

The carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more is not particularly limited, but can be appropriately selected from known resins and used. For example, an acrylic resin containing a carboxyl group, that is, an alkali-soluble resin having an acid value of 60 mgKOH/g or more in the polymer described in paragraph [0025] of JP-A-2011-095716, JP-A-2010- Carboxyl group-containing acrylic resins described in paragraphs [0033] to [0052] of Japanese Patent Application Laid-Open No. 2016-224162 and paragraphs [0053] to [0068] of Japanese Patent Laid-Open No. Carboxyl group-containing acrylic resins with an acid value of 60 mgKOH/g or more in the resins described in the paragraphs. The copolymerization ratio of the constituent units having a carboxyl group in the above-mentioned carboxyl group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 12 to 30% by mass, based on the total mass of the acrylic resin. good. As the alkali-soluble resin, an acrylic resin having a structural unit derived from (meth)acrylic acid is particularly preferable from the viewpoint of developability and adhesiveness with an adjacent layer.

Alkali-soluble resins may have reactive groups. As the reactive group, as long as it is a group capable of addition polymerization, examples include ethylenically unsaturated groups; polycondensation groups such as hydroxyl groups and carboxyl groups; polyaddition reactive groups such as epoxy groups and (blocked) isocyanate groups. base.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably at least 1,000, more preferably 10,000 to 100,000, and still more preferably 20,000 to 50,000.

Alkali-soluble resin may be used individually by 1 type, and may use 2 or more types. From the viewpoint of developability and adhesion to adjacent layers, the content of the alkali-soluble resin is preferably 10-99% by mass, more preferably 20-90% by mass, and 40-90% by mass relative to the total mass of the thermoplastic resin layer. 80 mass % is more preferable, and 50-75 mass % is especially preferable.

＜Pigment＞ The thermoplastic resin layer contains a pigment whose maximum absorption wavelength is 450nm or more in the wavelength range of 400-780nm during color development, and whose maximum absorption wavelength is changed by acid, alkali or free radicals (hereinafter also referred to as "pigment B"). is better. A preferred aspect of the dye B is the same as that of the aforementioned preferred aspect of the dye N except for the points described later.

As the dye B, a dye whose maximum absorption wavelength is changed by an acid or a radical is preferable from the viewpoint of visibility and resolution of the exposed part and the non-exposed part, and a dye whose maximum absorption wavelength is changed by an acid is more preferable. good. From the viewpoint of the visibility and resolving power of the exposed part and the non-exposed part, the thermoplastic resin layer contains: as the dye B, a dye whose maximum absorption wavelength is changed by an acid, and a compound which generates an acid by light as described later. Whichever is better.

The dye B may be used individually by 1 type, and may use 2 or more types. From the viewpoint of the visibility of the exposed portion and the non-exposed portion, the content of the pigment B is preferably at least 0.2% by mass, more preferably 0.2 to 6.0% by mass, and further preferably 0.2 to 5.0% by mass, based on the total mass of the thermoplastic resin. More preferably, 0.25 to 3.0% by mass is particularly preferred.

Here, the content of the dye B means the content of the dye when all the dye B contained in the thermoplastic resin layer is in a colored state. Hereinafter, a method for quantifying the content of the dye B will be described by taking a dye that develops color by radicals as an example. A solution in which 0.001 g and 0.01 g of the dye B were dissolved in 100 mL of methyl ethyl ketone was prepared. A photoradical polymerization initiator (Irgacure OXE01, manufactured by BASF Japan Ltd.) was added to each of the obtained solutions, and irradiated with light having a wavelength of 365 nm to generate radicals to bring all the dyes B into a color-developed state. Then, under the air atmosphere, using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), the absorbance of each solution at a liquid temperature of 25° C. was measured to prepare a calibration curve. Next, except for dissolving 0.1 g of the thermoplastic resin layer in methyl ethyl ketone instead of the dye B, the absorbance of the solution in which all the dye was developed was measured by the same method as above. Based on the obtained absorbance of the solution containing the thermoplastic resin layer, the amount of the pigment B contained in the thermoplastic resin layer was calculated according to the calibration curve. In addition, the thermoplastic resin layer 3g is the same as the solid content 3g of the composition.

<Compounds that generate acids, bases or free radicals by light> The thermoplastic resin layer may contain a compound (hereinafter, also simply referred to as "compound C") that generates acid, base, or radical by light. As compound C, a compound that generates acid, base or free radical by receiving activating light such as ultraviolet light and visible light is preferable. As compound C, a well-known photoacid generator, a photobase generator, and a photoradical polymerization initiator (photoradical generator) are mentioned, for example.

(photoacid generator) From the analytical viewpoint, the thermoplastic resin layer may contain a photoacid generator. As a photoacid generator, the photocationic polymerization initiator which can be contained in the above-mentioned photosensitive composition layer is mentioned, for example, The preferable aspect is the same except the point mentioned later.

As the photoacid generator, it is preferable to include at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds from the viewpoints of sensitivity and resolution. From a viewpoint, it is more preferable to contain an oxime sulfonate compound. Moreover, the photoacid generator which has the following structures is also preferable as a photoacid generator.

[chemical formula 3]

(photoradical polymerization initiator) The thermoplastic resin layer may contain a photoradical polymerization initiator. As a photoradical polymerization initiator, the photoradical polymerization initiator which can be contained in the said photosensitive composition layer is mentioned, for example, and a preferable aspect is also the same.

(photobase generator) The thermoplastic resin composition may contain a photobase generator. As a photobase generator, a well-known photobase generator is mentioned, for example. Specifically, 2-nitrobenzylcyclohexylcarbamate, trityl alcohol, O-aminoformyl axamide, O-aminoformyl oxime, [[(2,6-di Nitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinebenzoyl)-1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrole Pyridine, hexammonium cobalt(III) chloride tris(trityl borate), 2-benzyl-2-dimethylamino-1-(4-morpholinephenyl)-butanone, 2,6 -Dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine and 2,6-dimethyl-3,5-diacetyl- 4-(2,4-Dinitrophenyl)-1,4-dihydropyridine.

Compound C may be used alone or in combination of two or more. From the viewpoint of the visibility and resolution of the exposed portion and the non-exposed portion, the content of the compound C is preferably from 0.1 to 10% by mass, more preferably from 0.5 to 5% by mass, based on the total mass of the thermoplastic resin layer.

＜Plasticizer＞ It is preferable that a thermoplastic resin layer contains a plasticizer from a viewpoint of resolution, the adhesiveness with the adjacent layer, and a developability. The molecular weight of the plasticizer (when it is an oligomer or a polymer and has a molecular weight distribution, the weight average molecular weight) is preferably smaller than that of the alkali-soluble resin. The molecular weight (weight average molecular weight) of the plasticizer is preferably 200-2,000. The plasticizer is not limited as long as it is compatible with the alkali-soluble resin and exhibits plasticity. However, from the viewpoint of imparting plasticity, the plasticizer preferably has an alkeneoxy group in the molecule. Polyalkylene glycol compounds are more preferable. It is more preferable that the alkyleneoxy group contained in the plasticizer has a polyethylene oxide structure or a polypropylene oxide structure.

Moreover, it is preferable that a plasticizer contains a (meth)acrylate compound from a viewpoint of analytical property and storage stability. From the viewpoint of compatibility, resolution, and adhesiveness with adjacent layers, the alkali-soluble resin is more preferably an acrylic resin, and the plasticizer includes a (meth)acrylate compound. Examples of (meth)acrylate compounds that can be used as plasticizers include (meth)acrylate compounds described as polymerizable compounds that can be contained in the above-mentioned photosensitive composition layer. In the transfer film, when the thermoplastic resin layer and the photosensitive composition layer are laminated in direct contact, it is preferable that both the thermoplastic resin layer and the photosensitive composition layer contain the same (meth)acrylate compound. This is because when the thermoplastic resin layer and the photosensitive composition layer each contain the same (meth)acrylate compound, component diffusion between layers is suppressed and storage stability is improved.

In the case where the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, from the viewpoint of the adhesion between the thermoplastic resin layer and the adjacent layer, even in the exposed portion after exposure, the (meth)acrylic acid It is also preferable that the ester compound is not polymerized. Moreover, as a (meth)acrylate compound which can be used as a plasticizer, it has two or more (meth)acrylic acid ester compounds in one molecule from the point of view of resolution of a thermoplastic resin layer, adhesiveness with an adjacent layer, and developability. (Meth)acryl polyfunctional (meth)acrylate compounds are preferred. Furthermore, as a (meth)acrylate compound which can be used as a plasticizer, the (meth)acrylate compound or urethane (meth)acrylate compound which has an acidic group is also preferable.

A plasticizer may be used individually by 1 type, and may use 2 or more types. From the standpoint of resolution of the thermoplastic resin layer, adhesiveness to adjacent layers, and developability, the content of the plasticizer is preferably 1 to 70% by mass, and 10 to 60% by mass relative to the total mass of the thermoplastic resin layer. % is more preferable, and 20 to 50% by mass is still more preferable.

＜Sensitizer＞ The thermoplastic resin layer may contain a sensitizer. It does not specifically limit as a sensitizer, The sensitizer which can be contained in the said photosensitive composition layer is mentioned.

A sensitizer may be used individually by 1 type, and may use 2 or more types. The content of the sensitizer is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of improving the sensitivity to the light source and the visibility of the exposed portion and the non-exposed portion. good.

＜Other additives＞ The thermoplastic resin layer may contain other additives as needed in addition to the above components. As another additive, the other additive which can be contained in the said photosensitive composition layer is mentioned, for example.

＜Impurities＞ The thermoplastic resin layer may contain impurities. As an impurity, the impurity which can be contained in the above-mentioned photosensitive composition layer is mentioned, for example.

[other components] The transfer film of the present invention may have other members in addition to the above-mentioned members. As other members, for example, a protective film can be mentioned.

(protective film) As the protective film, a heat-resistant and solvent-resistant resin film can be used, for example, polyolefin films such as polypropylene film and polyethylene film, polyester film such as polyethylene terephthalate film, polycarbonate film, etc. film and polystyrene film. In addition, as the protective film, a resin film made of the same material as that of the above-mentioned dummy support can also be used. Among these, as a protective film, a polyolefin film is preferable, a polypropylene film or a polyethylene film is more preferable, and a polyethylene film is still more preferable.

The thickness of the protective film is preferably from 1 to 100 μm, more preferably from 5 to 50 μm, still more preferably from 5 to 40 μm, and particularly preferably from 15 to 30 μm. From the viewpoint of excellent mechanical strength, the thickness of the protective film is preferably 1 μm or more, and from the viewpoint of relatively low cost, it is preferably 100 μm or less.

In the protective film, the number of fish eyes with a diameter of 80 μm or more included in the protective film is preferably 5 or less/m ² . "Fish eye" refers to the foreign matter, undissolved matter, and oxidative deterioration of the material that are incorporated into the film when the film is produced by thermal melting, kneading, extrusion, biaxial stretching, and casting methods. into the thin film.

The number of particles with a diameter of 3 μm or more contained in the protective film is preferably 30 particles/mm ² or less, more preferably 10 particles/mm ² or less, still more preferably 5 particles/mm ² or less. The lower limit is preferably 0 pieces/mm ² or more. In the case of these ranges, it is possible to suppress defects caused by transfer of unevenness caused by particles contained in the protective film to the photosensitive composition layer or the conductive layer.

From the viewpoint of imparting rollability, the arithmetic average roughness Ra of the surface opposite to the surface in contact with the photosensitive composition layer of the protective film is preferably 0.01 μm or more, more preferably 0.02 μm or more, and 0.03 μm The above are further preferred. The upper limit is preferably less than 0.50 μm, more preferably 0.40 μm or less, and still more preferably 0.30 μm or less. From the viewpoint of suppressing defects during transfer, the surface roughness Ra of the surface of the protective film in contact with the composition layer is preferably at least 0.01 μm, more preferably at least 0.02 μm, and still more preferably at least 0.03 μm. The upper limit is preferably less than 0.50 μm, more preferably 0.40 μm or less, and still more preferably 0.30 μm or less.

[Manufacturing method of transfer film] The method for producing the transfer film is not particularly limited, and known methods can be used. As a method of manufacturing the above-mentioned transfer film 10, for example, a method including the steps of: coating a water-soluble resin composition on the surface of the dummy support 11 to form a coating film, and further drying the coating film to form an intermediate layer Step 13; and a step of coating a photosensitive composition on the surface of the intermediate layer 13 to form a coating film, and further drying the coating film to form a photosensitive composition layer 15 . In addition, before the step of forming the above-mentioned intermediate layer 13, a step of coating a thermoplastic resin composition on the surface of the dummy support 11 to form a coating film, and further drying the coating film to form a thermoplastic resin layer may be included.

The photosensitive composition layer 15 of the laminate manufactured by the above-mentioned manufacturing method is pressure-bonded with the protective film 19 to manufacture the transfer film 10 . As a method of manufacturing a transfer film, a film having a dummy support 11, an intermediate layer, and a film having a dummy support 11 are manufactured by including the step of providing a protective film 19 so as to be in contact with the surface of the photosensitive composition layer 15 opposite to the side having the dummy support 11. 13. The photosensitive composition layer 15 and the transfer film 10 of the protective film 19 are preferred. In addition, as a method of manufacturing a transfer film, a film having a dummy support 11 is produced by including a step of providing a protective film 19 so as to be in contact with the surface of the photosensitive composition layer 15 opposite to the side having the dummy support 11. Transfer film for thermoplastic resin layer, intermediate layer 13 , photosensitive composition layer 15 and protective film 19 . After the transfer film 10 is produced by the above-mentioned production method, the transfer film 10 is wound up, whereby the transfer film in the form of a roll can be produced and stored. The transfer film in the form of a roll can be provided as it is in the bonding step with the substrate in the roll-to-roll system described later.

In addition, as a method of manufacturing the transfer film 10 described above, after the photosensitive composition layer 15 and the intermediate layer 13 are formed on the protective film 19 , a thermoplastic resin layer is formed on the surface of the intermediate layer 13 .

[Method for forming photosensitive composition and photosensitive composition layer] It is preferable to form by the coating method using the photosensitive composition containing the components (for example, resin, a polymerizable compound, a polymerization initiator, etc.) which comprise the said photosensitive composition layer, and a solvent. As a method for producing the transfer film, it is preferable to apply a photosensitive composition on the intermediate layer to form a coating film, and dry the coating film at a predetermined temperature to form a photosensitive composition layer. In addition, the residual solvent amount was adjusted by drying the coating film.

As a photosensitive composition, it is preferable to contain various components and a solvent which form the said photosensitive composition layer. In addition, in the photosensitive composition, the preferable range of the content of each component relative to the total solid content of the photosensitive composition is the same as the preferable range of the content of each component relative to the total mass of the above-mentioned photosensitive composition layer. . The solvent is not particularly limited as long as it can dissolve or disperse components other than the solvent, and known solvents can be used. Specifically, for example, alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol and ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), Aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N,N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents (n-propyl acetate, etc.), amide solvents , lactone solvents, and mixed solvents containing two or more of these.

It is preferable that the solvent contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. Among them, at least 1 selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least 1 selected from the group consisting of ketone solvents and cyclic ether solvents More preferably, a mixed solvent of at least one of at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, ketone solvents, and cyclic ether solvents A mixed solvent is further preferred.

Examples of alkylene glycol ether solvents include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (for example, propylene glycol monomethyl ether acetate, etc.), propylene glycol dialkyl ether, Alkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, and dipropylene glycol dialkyl ethers. Examples of alkylene glycol ether acetate solvents include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and diethylene glycol monoalkyl ether acetate. Propylene Glycol Monoalkyl Ether Acetate. As the solvent, for example, the solvents described in paragraphs [0092] to [0094] of International Publication No. 2018/179640 and the solvents described in paragraph [0014] of JP 2018-177889 A, and These contents are incorporated into this manual. A solvent may be used individually by 1 type, and may use 2 or more types. The content of the solvent is preferably from 50 to 1900 parts by mass, more preferably from 100 to 1200 parts by mass, and still more preferably from 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

Examples of coating methods for the photosensitive composition include printing, spray coating, roll coating, bar coating, curtain coating, spin coating, and die coating (slit coating).

As a method of drying the coating film of the photosensitive composition, heat drying and reduced-pressure drying are preferable. The drying temperature is preferably at least 90°C, more preferably at least 100°C, and still more preferably at least 110°C. The upper limit is preferably 130°C or lower, more preferably 120°C or lower. In addition, drying can also be performed by continuously changing the temperature. Moreover, as a drying time, 20 seconds or more are preferable, 40 seconds or more are more preferable, and 60 seconds or more are still more preferable. The upper limit is preferably at most 600 seconds, more preferably at most 450 seconds, and still more preferably at most 300 seconds.

Furthermore, a transfer film can be manufactured by bonding a protective film to a photosensitive composition layer. As a method of bonding a protective film to a photosensitive composition layer, a well-known method is mentioned, for example. Known laminators, such as a vacuum laminator and an automatic cutting laminator, are mentioned as an apparatus which bonds a protective film to a photosensitive composition layer. It is preferable that the laminator is equipped with any heatable roll such as a rubber roll, and can be pressurized and heated.

[Method for forming water-soluble resin composition and intermediate layer (water-soluble resin layer)] The water-soluble resin composition preferably contains various components and a solvent that form the above-mentioned intermediate layer (water-soluble resin layer). In addition, in the water-soluble resin composition, the preferable range of the content of each component relative to the total solid content of the composition is the same as the preferable range of the content of each component relative to the total mass of the above-mentioned water-soluble resin layer. The solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin. At least one selected from the group consisting of water and water-miscible organic solvents is preferred. Water or water-water-miscible organic solvents A mixed solvent is better. Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, among which alcohols having 1 to 3 carbon atoms are preferred, and methanol or ethanol is more preferred. A solvent may be used individually by 1 type, and may use 2 or more types. The content of the solvent is preferably from 50 to 2500 parts by mass, more preferably from 50 to 1900 parts by mass, and still more preferably from 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

The method for forming the water-soluble resin is not particularly limited as long as it is a method capable of forming a layer comprising the above-mentioned components, for example, known coating methods (slit coating, spin coating, curtain coating and ink-jet coating) can be mentioned. cloth).

[The composition for forming a thermoplastic resin layer and the method for forming a thermoplastic resin layer] The method of forming the thermoplastic resin layer on the dummy support is not particularly limited, and known methods can be used. For example, it can be formed by applying a composition for forming a thermoplastic resin layer on a dummy support and drying it as necessary. The composition for forming a thermoplastic resin layer preferably contains various components and a solvent for forming the above-mentioned thermoplastic resin layer. In addition, in the composition for forming a thermoplastic resin layer, the preferable range of the content of each component relative to the total solid content of the composition is the same as the preferable range of the content of each component relative to the total mass of the above-mentioned thermoplastic resin layer. The solvent is not particularly limited as long as it can dissolve or disperse components other than the solvent, and known solvents can be used. As a solvent, the thing same as the solvent contained in the photosensitive composition mentioned later is mentioned, and a preferable aspect is also the same. The content of the solvent is preferably from 50 to 1900 parts by mass, more preferably from 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.

The method for forming the thermoplastic resin is not particularly limited as long as it is a method capable of forming a layer containing the above-mentioned components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, and inkjet coating). Wait). [Example]

Hereinafter, the present invention will be described in more detail based on examples. The materials, usage amounts, proportions, processing contents, processing steps and the like shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the Examples shown below. In addition, "parts" and "%" are based on mass unless otherwise specified. In addition, in the following examples, the weight average molecular weight of resin is the weight average molecular weight (Mw) calculated|required based on the polystyrene conversion of the gel permeation chromatography (GPC) mentioned above. In addition, the theoretical acid value was used for the acid value.

[resin] ＜Synthesis of Resin A1＞ Propylene glycol monomethyl ether acetate (PGMEA, 67.0 parts by mass) was added to the three-necked flask, and the temperature was raised to 90° C. under a nitrogen atmosphere. Added MAA (20.0 parts by mass), St (52.0 parts by mass), MMA (28.0 parts by mass), V-601 (4.0 parts by mass) and PGMEA (33.0 parts by mass) dropwise over 2 hours to maintain the temperature at 90 ℃ ± 2 ℃ in the above flask solution. After completion of the dropwise addition, the solution in the above-mentioned flask was stirred at 90°C±2°C for 1 hour. A solution containing V-601 (1.0 parts by mass) and PGMEA (33.0 parts by mass) was added dropwise to the solution in the flask maintained at 90°C±2°C over 30 minutes. After completion of the dropwise addition, the solution in the flask was stirred at 90°C±2°C for 1 hour, and PGMEA (100.0 parts by mass) was added and diluted to obtain resin A1 (solid content concentration: 30.0% by mass). Also, referring to the synthesis method of the above-mentioned resin A1, resins A2 to A6 (solid content concentration of any resin: 30.0% by mass) were obtained.

Resins A1 to A6 are shown in Table 1 below. In Table 1, monomers used to form each constituent unit (mass %) are indicated by abbreviations. Resins A1 to A6 correspond to alkali-soluble resins.

[Table 1] resin constituent unit molecular weight acid value Tg MAA MMA EMA St. BYZGR mw mgKOH/g ℃ Resin A1 20 28 0 52 0 25,000 130 130 Resin A2 20 48 0 32 0 25,000 130 110 Resin A3 27 twenty three 0 50 0 40,000 176 110 Resin A4 20 28 20 32 0 24,000 130 84 Resin A5 25 50 0 25 0 50,000 166 110 Resin A6 20 0 0 0 80 25,000 130 110

In Table 1, each description is shown below. MAA: methacrylic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation) MMA: methyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation) EMA: ethyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation) St: Styrene (manufactured by FUJIFILM Wako Pure Chemical Corporation) BzMA: Benzyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

〔Photosensitive composition〕 The components shown in Table 2 below and each photosensitive composition to be blended were prepared. In Table 2, the numerical value described in the column of each component shows content (parts by mass) of each component. However, the amount of each resin in the column of "resin" represents the amount of a resin solution (solid content concentration: 30% by mass).

[Table 2] Components (Numerical value of each component: parts by mass) photosensitive composition B1 B2 B3 B4 B5 B6 B7 B8 resin Resin A1 (solid content concentration: 30% by mass) 200 230 200 Resin A2 (solid content concentration: 30% by mass) 200 Resin A3 (solid content concentration: 30% by mass) 200 Resin A4 (solid content concentration 30% by mass) 200 Resin A5 (solid content concentration 30% by mass) 200 Resin A6 (solid content concentration 30% by mass) 200 polymeric compound Ethoxylated bisphenol A dimethacrylate 30 30 25 30 30 30 30 30 Ethoxylated (3) Trimethylolpropane Triacrylate 12 12 10 12 12 4-n-octylphenoxypentaethylene glycol monopropylene glycol acrylate 5 5 Ethylene Oxide Propylene Oxide Modified Urethane Dimethacrylate 12 10 10 Photopolymerization initiator 2-(o-chlorophenyl)-4,5-diphenylimidazole 3 3 3 3 3 3 3 3 Sensitizer 4,4-bis(diethylamino)benzophenone 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Reagent colorless crystal violet 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 solvent acetone 10 10 10 10 10 10 10 10 toluene 10 10 10 10 10 10 10 10 Methanol 3 3 3 3 3 3 3 3

＜Polymerizable compound＞ Ethoxylated bisphenol A dimethacrylate Ethoxylated (3) Trimethylolpropane Triacrylate 4-n-octylphenoxypentaethylene glycol monopropylene glycol acrylate Ethylene Oxide Propylene Oxide Modified Urethane Dimethacrylate

＜Photopolymerization Initiator＞ 2-(o-chlorophenyl)-4,5-diphenylimidazole

＜Sensitizer＞ 4,4-bis(diethylamino)benzophenone

＜Color developer＞ colorless crystal violet

<Solvent> acetone Toluene Methanol

〔Composition for intermediate layer formation〕 Composition 1 for forming an intermediate layer was prepared using the following components. ・4-88 LA (67.86% by mass): manufactured by KURARAY CO.,LTD., polyvinyl alcohol ・PVP K30 (31.06% by mass): manufactured by FUJIFILM CORPORATION, polyvinylpyrrolidone ・METOLOSE 60SH03 (1.00% by mass): manufactured by Shin-Etsu Chemical Co., Ltd., water-soluble cellulose derivative ・F444 (0.08% by mass): manufactured by DIC Corporation, surfactant

〔Transfer film〕 Each transfer film composed of a dummy support, an intermediate layer, and a photosensitive composition layer was produced to have the configuration shown in Table 3. The specific system is as follows. First, on a dummy support (a polyethylene terephthalate film with a thickness of 16 μm (Lumirer 16KS40, manufactured by TORAY INDUSTRIES, INC)), a bar coater was used to coat the intermediate layer forming agent used to form the above intermediate layer. Composition 1 was dried in an oven at 90° C. to have a thickness of 1.0 μm after drying to form an intermediate layer. Furthermore, using a bar coater, the photosensitive composition for forming the photosensitive composition layer shown in Table 3 was applied on the intermediate layer so as to have the thickness after drying shown in Table 3, and an oven , dried at 80° C. to form a negative photosensitive composition layer. On the obtained negative photosensitive composition layer, polyethylene terephthalate (16KS40, manufactured by TORAY INDUSTRIES, INC) with a thickness of 16 μm was pressure-bonded to prepare transfer films of Examples and Comparative Examples.

〔Measurement and evaluation〕 ＜Elastic modulus＞ The elastic modulus X and the elastic modulus Y are measured by the method mentioned above.

<Pattern shape (shape of extended hem)> Peel off the protective film of the transfer film produced above, and laminate the exposed surface of the photosensitive composition layer (lamination conditions: substrate temperature 80°C, rubber roller temperature 110°C , linear pressure 3N/cm, conveying speed 2m/min) onto a substrate having a conductive layer on which Ni plating (thickness 100nm) was applied on glass to obtain a laminate. Next, the dummy support was peeled off from the obtained laminate, and a photomask having a pattern of line (μm)/space (μm) 1/1 was brought into close contact with the surface of the obtained laminate on the side of the intermediate layer. The photosensitive composition layer was exposed at 100 mJ/cm ² by irradiating light with a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by apan Science Engineering Co., Ltd., dominant wavelength: 365 nm). Then, a pattern was formed by performing shower image development for 30 seconds using a sodium carbonate aqueous solution having a liquid temperature of 25°C. The cross-sectional shape of the pattern obtained by observing the pattern with a scanning electron microscope, on the side surface of each pattern, the length of the portion protruding from the upper surface (the surface opposite to the substrate side) of the pattern (the bottom extended portion in Fig. 1 ) was set as The longest hem length was used as the hem length, and the pattern shape was evaluated based on the following evaluation criteria. A: The hem length is 0.3 μm or less B: The hem length is more than 0.3 μm and 0.5 μm or less C: The hem length is more than 0.5 μm

<Pattern Adhesion> The protective film of the transfer film produced above was peeled off, and the surface of the exposed photosensitive composition layer was laminated (lamination conditions: substrate temperature 80°C, rubber roller temperature 110°C, linear pressure 3N /cm, conveying speed 2m/min) onto a conductive substrate on which Ni plating (thickness 100nm) was applied on glass to obtain a laminate. Next, the dummy support was peeled off from the obtained laminate, and a photomask having a pattern of line (μm)/space (μm) 1/1 was brought into close contact with the surface of the obtained laminate on the side of the intermediate layer. The photosensitive composition layer was exposed at 100 mJ/cm ² by irradiating light with a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by apan Science Engineering Co., Ltd., dominant wavelength: 365 nm). Then, a pattern was formed by performing shower image development for 30 seconds using a sodium carbonate aqueous solution having a liquid temperature of 25°C. The obtained pattern was observed with a scanning electron microscope, and the pattern adhesiveness (μm) was evaluated as the minimum line width at which no pattern peeling and edge lift did not occur.

<Resolution> Peel off the protective film of the transfer film produced above, and laminate the surface of the exposed photosensitive composition layer (lamination conditions: substrate temperature 80°C, rubber roller temperature 110°C, linear pressure 3N/ cm, conveying speed 2m/min) onto a conductive substrate on which Ni plating (thickness 100nm) was applied on glass to obtain a laminate. Next, the dummy support was peeled off from the obtained laminate, and a photomask having a pattern of line (μm)/space (μm) 1/1 was brought into close contact with the surface of the obtained laminate on the side of the intermediate layer. The photosensitive composition layer was exposed at 100 mJ/cm ² by irradiating light with a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by apan Science Engineering Co., Ltd., dominant wavelength: 365 nm). Then, a pattern was formed by performing shower image development for 30 seconds using a sodium carbonate aqueous solution having a liquid temperature of 25°C. The resolution (μm) was defined as the minimum line width at which the obtained pattern could be resolved, and the resolving power was evaluated.

＜Development residue inhibition＞ A pattern was formed in the same manner as above <Resolution>, and the obtained line/space pattern was measured and visually observed for the residue thickness of the space part based on the scanning electron microscope observation, and the development residue was evaluated according to the following criteria Inhibitory. A: The thickness of the residue in the space is 50 nm or less, and no residue is observed visually B: The residue thickness of the space part is 50 nm or less, and the residue is visually observed C: The thickness of the residue in the space part is more than 50nm

Table 3 shows the evaluation results. Table 3 shows each description. The "M/B" column shows the mass ratio of the content of the bifunctional or higher polymerizable compound to the content of the resin (content of the bifunctional or higher polymerizable compound/resin content). The "X/Y" column shows the ratio of the modulus of elasticity X to the modulus of elasticity Y (modulus of elasticity X/modulus of elasticity Y). "Tg" represents the Tg of the resin contained in the photosensitive composition layer. "M/B", "content of a double bond", and "acid value" represent each value of a photosensitive composition layer.

[table 3] Transfer film middle layer Photosensitive composition layer Elastic modulus X (GPa) Elastic modulus Y (MPa) X/Y Evaluation results resin photosensitive composition M/B Double bond content (mmol/g) Acid value (mgKOH/g) Thickness (μm) pattern shape Pattern adhesion (μm) Resolution (μm) Development residue inhibition Composition for intermediate layer formation Thickness (μm) type Tg (°C) Example 1 1 1 1.0 A1 130 B1 0.70 1.5 74 5 5.5 4.0 1375 A 3.5 3.0 B Example 2 2 1 1.0 A2 110 B2 0.70 1.5 74 5 4.5 0.8 5625 A 3.0 3.0 A Example 3 3 1 1.0 A1 130 B3 0.50 1.2 83 5 4.0 0.8 5000 B 4.5 4.0 A Example 4 4 1 1.0 A3 110 B4 0.70 1.5 100 5 4.0 0.8 5000 B 4.0 4.0 A Example 5 5 1 1.0 A1 130 B5 0.70 0.9 83 5 4.0 0.8 5000 B 5.0 4.5 A Example 6 6 1 1.0 A4 84 B6 0.70 1.5 74 5 4.0 0.8 5000 B 4.0 4.0 A Example 7 7 1 1.0 A1 130 B1 0.70 1.5 74 20 5.5 4.0 1375 A 4.5 4.0 B Comparative example 1 8 1 1.0 A5 110 B7 0.75 1.1 106 5 0.8 5.0 160 C 6.5 6.0 C Comparative example 2 9 1 1.0 A6 110 B8 0.75 1.1 70 5 12.0 1.0 12000 B 8.0 6.0 C

From the results in Table 3, it was confirmed that the method for producing the laminate of the present invention was excellent in pattern shape and also excellent in pattern adhesion. When the elastic modulus Y obtained from the above-mentioned measurement Y was 3.5 MPa or less, it was confirmed that the development residue suppression property was more excellent (comparison between Example 2 and Example 1). When it was confirmed that the ratio of the elastic modulus X to the elastic modulus Y was 1,500 to 10,000, the development residue suppression was more excellent (comparison between Example 2 and Example 1). When it was confirmed that the content of double bonds in the photosensitive composition layer was 1.0 to 3.0 mmol/g, the pattern shape was more excellent (comparison between Examples 1 and 2 and Example 5) When the glass transition temperature Tg of resin is 90-150 degreeC, it confirmed that a pattern shape is more excellent (comparison of Examples 1-2 and Example 6). When it was confirmed that the acid value of the photosensitive composition layer was 50 to 90 mgKOH/g, the pattern shape was more excellent (comparison between Examples 1 and 2 and Example 4) When it was confirmed that the mass ratio of the content of the bifunctional or higher polymerizable compound to the content of the resin was 0.60 to 1.00, the pattern shape was more excellent (comparison between Examples 1 and 2 and Example 3)

1: Substrate 2: Pattern (hardened layer) 3: Hem extension 10: Transfer film 11: Pseudo-support 13: middle layer 15: Photosensitive composition layer 17: Composition layer 19: Protective film

FIG. 1 is a schematic diagram showing an example of a hem spread shape. Fig. 2 is a schematic diagram showing an example of the structure of a transfer film.

none.

Claims (22)

A method of manufacturing a laminate comprising: The substrate is brought into contact with the surface of the photosensitive composition layer opposite to the intermediate layer side of the transfer film having a dummy support, an intermediate layer, and a photosensitive composition layer in this order, and the transfer film and the photosensitive composition layer are bonded together. Laminating steps of the aforementioned substrates; between the aforementioned dummy support and the aforementioned intermediate layer, a step of peeling off the aforementioned dummy support; an exposure step of subjecting the aforementioned photosensitive composition layer to pattern exposure; and A developing step of developing the exposed photosensitive composition layer using a developing solution to form a pattern, The elastic modulus X obtained from the measurement X is 1.0～10.0Gpa, Measurement X: The substrate was brought into contact with the surface of the photosensitive composition layer of the transfer film opposite to the intermediate layer side, and the transfer film and the substrate were bonded together. From the obtained laminate and Peel off the dummy support between the dummy support and the intermediate layer, and expose the entire surface of the photosensitive composition layer from the exposed intermediate layer side, peel off the exposed intermediate layer, and then measure the exposed cured layer The modulus of elasticity is set as the modulus of elasticity X. The manufacturing method of the laminated body as described in claim 1, wherein The elastic modulus Y obtained from the measurement Y is below 3.5MPa, Measurement Y: The elastic modulus of the photosensitive composition layer of the transfer film was measured and set as elastic modulus Y. The manufacturing method of the laminated body as described in claim 2, wherein The ratio of the elastic modulus X to the elastic modulus Y is 1500-10000. The method for manufacturing a laminate according to any one of claim 1 to claim 3, wherein The content of the double bond in the said photosensitive composition layer is 1.0-3.0 mmol/g. The method for manufacturing a laminate according to any one of claim 1 to claim 3, wherein The aforementioned photosensitive composition layer contains a resin, The glass transition temperature Tg of the aforementioned resin is 90-150°C. The method for manufacturing a laminate according to any one of claim 1 to claim 3, wherein The acid value of the said photosensitive composition layer is 50-100 mgKOH/g. The method for manufacturing a laminate according to any one of claim 1 to claim 3, wherein The photosensitive composition layer contains a bifunctional or higher polymerizable compound and a resin, The mass ratio of the content of the above-mentioned bifunctional or higher polymerizable compound to the content of the above-mentioned resin is 0.60 to 1.00. The method for manufacturing a laminate according to any one of claim 1 to claim 3, wherein The above-mentioned intermediate layer contains polyols, oxidation adducts of polyols, phenol derivatives, amide compounds, water-soluble cellulose derivatives, polyether resins, and polyamide resins. At least 1 species. The method for manufacturing a laminate according to any one of claim 1 to claim 3, wherein The thickness of the said photosensitive composition layer is 1-20 micrometers. The method for manufacturing a laminate according to any one of claim 1 to claim 3, wherein The thickness of the intermediate layer is 3.0 μm or less. The method for manufacturing a laminate according to any one of claim 1 to claim 3, wherein The exposure step is an exposure step in which the exposed intermediate layer is brought into contact with a mask to perform pattern exposure. A method of manufacturing circuit wiring, comprising: The substrate having the conductive layer is brought into contact with the surface of the photosensitive composition layer opposite to the side of the intermediate layer side of the transfer film having a dummy support, an intermediate layer, and a photosensitive composition layer in this order, and the aforementioned Lamination step of the transfer film and the aforementioned substrate; between the aforementioned dummy support and the aforementioned intermediate layer, a step of peeling off the aforementioned dummy support; an exposure step of subjecting the aforementioned photosensitive composition layer to pattern exposure; A developing step of developing the exposed photosensitive composition layer using a developing solution to form a pattern; and an etching step of performing etching treatment on the aforementioned conductive layer in the region where the aforementioned pattern is not arranged, The elastic modulus X obtained from the measurement X is 1.0～10.0GPa, Measurement X: The substrate was brought into contact with the surface of the photosensitive composition layer of the transfer film opposite to the intermediate layer side, and the transfer film and the substrate were bonded together. From the obtained laminate and Peel off the dummy support between the dummy support and the intermediate layer, and expose the entire surface of the photosensitive composition layer from the exposed intermediate layer side, peel off the exposed intermediate layer, and then measure the exposed cured layer The modulus of elasticity is set as the modulus of elasticity X. A transfer film, which sequentially has a pseudo-support, an intermediate layer and a photosensitive composition layer, and performing an exposure step of subjecting the aforementioned photosensitive composition layer to pattern exposure, wherein The elastic modulus X obtained from the measurement X is 1.0～10.0GPa, Measurement X: The substrate was brought into contact with the surface of the photosensitive composition layer of the transfer film opposite to the intermediate layer side, and the transfer film and the substrate were bonded together. Peel off the dummy support between the dummy support and the middle layer, and expose the entire surface of the photosensitive composition layer from the side of the exposed middle layer, peel off the exposed middle layer, and then measure the elasticity of the exposed cured layer Modulus, set to elastic modulus X. The transfer film as described in claim 13, wherein The elastic modulus Y obtained from the measurement Y is below 3.5MPa, Measurement Y: The elastic modulus of the photosensitive composition layer of the transfer film was measured and set as elastic modulus Y. The transfer film as described in claim 14, wherein The ratio of the elastic modulus X to the elastic modulus Y is 1500-10000. The transfer film according to any one of claim 13 to claim 15, wherein The content of the double bond in the said photosensitive composition layer is 1.0-3.0 mmol/g. The transfer film according to any one of claim 13 to claim 15, wherein The aforementioned photosensitive composition layer contains a resin, The glass transition temperature Tg of the aforementioned resin is 90-150°C. The transfer film according to any one of claim 13 to claim 15, wherein The acid value of the said photosensitive composition layer is 50-100 mgKOH/g. The transfer film according to any one of claim 13 to claim 15, wherein The photosensitive composition layer contains a bifunctional or higher polymerizable compound and a resin, The mass ratio of the content of the above-mentioned bifunctional or higher polymerizable compound to the content of the above-mentioned resin is 0.60 to 1.00. The transfer film according to any one of claim 13 to claim 15, wherein The above-mentioned intermediate layer contains polyols, oxidation adducts of polyols, phenol derivatives, amide compounds, water-soluble cellulose derivatives, polyether resins, and polyamide resins. At least 1 species. The transfer film according to any one of claim 13 to claim 15, wherein The thickness of the said photosensitive composition layer is 1-20 micrometers. The transfer film according to any one of claim 13 to claim 15, wherein The thickness of the intermediate layer is 3.0 μm or less.

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