JP7152593B2 - Transfer film and patterned substrate manufacturing method - Google Patents

Description

The present disclosure relates to transfer films and methods of manufacturing patterned substrates.

In a display device equipped with a touch panel such as a capacitive input device [organic electroluminescence (EL) display device, liquid crystal display device, etc.], an electrode pattern corresponding to a sensor in the visual recognition part, a peripheral wiring part and a lead-out wiring part A conductive layer pattern such as wiring is provided inside the touch panel.
In general, a method using a photosensitive transfer material is widely used for forming a patterned layer because the number of steps for obtaining a required pattern shape is small. Specifically, a layer of a photosensitive resin composition provided on an arbitrary substrate using a photosensitive transfer material is exposed through a mask having a desired pattern, and then developed. It is possible to obtain a pattern shape that

For example, Japanese Patent Application Laid-Open No. 2018-24225 discloses, on a temporary support, a first transparent layer containing at least a polymerizable monomer and a resin, containing at least metal oxide particles and a resin, and having an average thickness of less than 200 nm. and a second transparent layer having an average thickness thinner than the average thickness of the second transparent layer, and measured by X-ray photoelectron spectroscopy from the outermost surface opposite to the surface in contact with the second transparent layer A transfer film having, in order from the temporary support side, a third transparent layer in which the ratio of metal atoms to all atoms in a 300 μm square area is 2% or less.
In addition, International Publication No. 2017/209002 contains a binder having an I/O value of 0.5 or more and a weight average molecular weight of 25,000 or less, a pigment, a polymerizable monomer, and a polymerization initiator. and a photosensitive resin layer containing the solid content of a photosensitive resin composition in which the content of the pigment is 20% by mass or more relative to the total solid content of the photosensitive resin composition; and a temporary support. A transfer film is disclosed.

By the way, the transfer film is required to be capable of forming a pattern with excellent resolution. As a method for increasing the pattern resolution, there is a method in which the resin layer contains a resin having a large proportion of structural units derived from styrene (so-called binder resin). A resin layer containing a binder resin having a large proportion of structural units derived from styrene is less likely to swell during development, and thus can realize formation of a high-resolution pattern.

However, when the present inventors incorporated a binder resin containing a large proportion of structural units derived from styrene into the resin layer for the purpose of increasing pattern resolution, it was found that the substrate may be discolored. rice field. Conventionally, it has been difficult to suppress discoloration of the substrate while increasing the resolution of the pattern in the transfer film.

Regarding the above point, the transfer films described in JP-A-2018-24225 and WO 2017/209002 each have a resin layer containing a binder resin containing structural units derived from styrene. However, in JP-A-2018-24225 and WO 2017/209002, no attention is paid to the problems that may occur when the resin layer contains a binder resin having a large proportion of structural units derived from styrene. In addition, in a transfer film having a resin layer containing a binder resin having a large proportion of structural units derived from styrene, there is no mention of achieving both improvement in pattern resolution and suppression of discoloration of the substrate.

A problem to be solved by an embodiment of the present invention is to provide a transfer film that is resistant to discoloration of a substrate and capable of forming a pattern with excellent resolution.
Another problem to be solved by another embodiment of the present invention is to provide a method for manufacturing a patterned substrate using the transfer film.

Means for solving the above problems include the following aspects.
<1> a temporary support;
a first resin layer containing an alkali-soluble resin (A) containing structural units derived from a vinylbenzene derivative, a polymerizable compound, and a polymerization initiator;
a second resin layer containing an alkali-soluble resin (B) having an acid value of 130 mgKOH/g or more;
in that order, and
A transfer film, wherein the content of structural units derived from a vinylbenzene derivative in the alkali-soluble resin (A) is 30% by mass or more with respect to all structural units of the alkali-soluble resin (A).
<2> The transfer film according to <1>, wherein the alkali-soluble resin (A) has an acid value of 150 mgKOH/g or more.
<3> The transfer film according to <1> or <2>, wherein the alkali-soluble resin (B) has an acid value of 150 mgKOH/g or more.
<4> The transfer film according to any one of <1> to <3>, wherein the alkali-soluble resin (B) has an acid value of 250 mgKOH/g or less.
<5> The content of structural units derived from a vinylbenzene derivative in the alkali-soluble resin (A) is 70% by mass or less with respect to the total structural units of the alkali-soluble resin (A). The transfer film according to any one of <4>.
<6> The transfer film according to any one of <1> to <5>, wherein the second resin layer has a thickness of 40 nm to 120 nm.
<7> The transfer film according to any one of <1> to <6>, wherein the first resin layer has a thickness of 2 μm to 4 μm.
<8> A step of bonding the substrate and the transfer film according to any one of <1> to <7> by bringing the substrate and the second resin layer of the transfer film into contact with each other;
a step of pattern-exposing the first resin layer of the transfer film;
a step of developing the first resin layer that has undergone the pattern exposure to form a pattern;
A method of manufacturing a patterned substrate, comprising in that order:
<9> The method for manufacturing a patterned substrate according to <8>, including a step of etching the substrate in the region where the pattern is not arranged after the step of forming the pattern.
<10> The method for producing a patterned substrate according to <8> or <9>, wherein at least part of the surface of the substrate that contacts the second resin layer is made of copper.

According to one embodiment of the present invention, there is provided a transfer film that is resistant to discoloration of a substrate and capable of forming a pattern with excellent resolution.
Further, according to another embodiment of the present invention, there is provided a method of manufacturing a patterned substrate using the transfer film.

1 is a schematic cross-sectional view showing an example of the layer structure of a transfer film of the present disclosure; FIG.

The contents of the present disclosure will be described in detail below. The description of the constituent elements described below may be made based on representative embodiments of the present disclosure, but the present disclosure is not limited to such embodiments.

In the present disclosure, a numerical range indicated using "to" means a range including the numerical values before and after "to" as the minimum and maximum values, respectively.
In the numerical ranges described step by step in the present disclosure, upper or lower limits described in a certain numerical range may be replaced with upper or lower limits of other numerical ranges described step by step. In addition, in the numerical ranges described in the present disclosure, upper or lower limits described in a certain numerical range may be replaced with values shown in Examples.
In the present disclosure, a combination of two or more preferred aspects is a more preferred aspect.

Regarding the notation of a group (so-called atomic group) in the present disclosure, the notation that does not describe substitution or unsubstituted includes both those having no substituents and those having substituents. For example, the term "alkyl group" includes not only alkyl groups having no substituents (so-called unsubstituted alkyl groups) but also alkyl groups having substituents (so-called substituted alkyl groups).

In this disclosure, chemical structural formulas may be described as simplified structural formulas omitting hydrogen atoms.

In the present disclosure, "(meth)acrylic acid" is a term that includes both acrylic acid and methacrylic acid, and "(meth)acrylate" is a term that includes both acrylate and methacrylate. "(Meth)acryloyl" is a term that includes both acryloyl and methacryloyl, and "(meth)acryloxy" is a term that includes both acryloxy and methacryloxy. be.

In the present disclosure, when there are multiple substances corresponding to each component in the composition, the amount of each component in the composition is the total amount of the above substances present in the composition unless otherwise specified. means

In the present disclosure, the term "process" includes not only an independent process, but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.

In the present disclosure, the molecular weight when there is a molecular weight distribution represents the weight average molecular weight (Mw; hereinafter the same) unless otherwise specified.

The weight average molecular weight (Mw) in the present disclosure is a value measured by gel permeation chromatography (GPC). For measurement by gel permeation chromatography (GPC), HLC (registered trademark)-8220GPC [manufactured by Tosoh Corporation] is used as a measuring device, and TSKgel (registered trademark) Super HZM-M [4.6 mm ID × 15 cm, manufactured by Tosoh Corporation], Super HZ4000 [4.6 mm ID × 15 cm, manufactured by Tosoh Corporation], Super HZ3000 [4.6 mm ID × 15 cm, manufactured by Tosoh Corporation], Super HZ2000 [4.6 mm ID × 15 cm, manufactured by Tosoh Corporation] manufactured by Tosoh Corporation] are connected in series, and THF (tetrahydrofuran) can be used as an eluent.
As the measurement conditions, the sample concentration is 0.2% by mass, the flow rate is 0.35 mL/min, the sample injection amount is 10 μL, and the measurement temperature is 40° C., and a differential refractive index (RI) detector can be used. can.
The calibration curve is "Standard sample TSK standard, polystyrene" manufactured by Tosoh Corporation: "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500" and 7 samples of "A-1000" can be used.

In the present disclosure, the ratio of structural units in the resin represents mass ratio unless otherwise specified.

In the present disclosure, “transparent” means that the total light transmittance at wavelengths of 380 nm to 780 nm is 85% or higher (preferably 90% or higher, more preferably 95% or higher). The total light transmittance is measured at a temperature of 23° C. using a spectrophotometer [for example, spectrophotometer “U-3310 (trade name)” manufactured by Hitachi, Ltd.].

In the present disclosure, "refractive index" refers to the refractive index at a wavelength of 550 nm unless otherwise specified. In addition, unless otherwise specified, the “refractive index” in the present disclosure means a value measured by ellipsometry at a temperature of 23° C. using visible light with a wavelength of 550 nm.

[Transfer film]
The transfer film of the present disclosure comprises a temporary support and an alkali-soluble resin (A) containing structural units derived from a vinylbenzene derivative (hereinafter also simply referred to as "alkali-soluble resin (A)"). ], a first resin layer containing a polymerizable compound and a polymerization initiator, and an alkali-soluble resin (B) having an acid value of 130 mgKOH/g or more (hereinafter also simply referred to as “alkali-soluble resin (B)”). ], in this order, and the content of structural units derived from the vinylbenzene derivative in the alkali-soluble resin (A) is, with respect to all structural units of the alkali-soluble resin (A), The transfer film of the present disclosure, which has a content of 30% by mass or more, has the configuration as described above, so that the substrate is unlikely to be discolored and a pattern with excellent resolution can be formed.
Although it is not clear why the transfer film of the present disclosure can produce such effects, the present inventors speculate as follows. However, the following assumptions are not intended to restrictively interpret the transfer film of the present disclosure, but are explained as an example.

The transfer film of the present disclosure includes a temporary support, an alkali-soluble resin (A) having a content of structural units derived from a vinylbenzene derivative of 30% by mass or more, a polymerizable compound, and a polymerization initiator. It has a resin layer and a second resin layer containing an alkali-soluble resin (B) in this order, and when it is attached to a substrate, the second resin layer is in contact with the substrate, which is the object to be transferred. .
Since the first resin layer contains the alkali-soluble resin (A) in which the ratio of structural units derived from a vinylbenzene derivative is 30% by mass or more, it is difficult to swell during development. Therefore, the transfer film of the present disclosure can form patterns with excellent resolution.
On the other hand, the alkali-soluble resin (A) has a large proportion of structural units derived from vinylbenzene derivatives. Therefore, the first resin layer contains residual monomers (so-called unreacted monomers) and/or residual oligomers (so-called reaction products of unreacted monomers) derived from the vinylbenzene derivative. Residual monomers and residual oligomers derived from vinylbenzene derivatives are components that are difficult to remove with a developer, so they are concentrated during development and tend to adhere to the substrate. When residual monomers and/or residual oligomers derived from the vinylbenzene derivative adhere to the substrate, the substrate is discolored.
In contrast, the transfer film of the present disclosure has a configuration in which the second resin layer is interposed between the first resin layer and the substrate when attached to the substrate. Since the second resin layer contains an alkali-soluble resin [that is, alkali-soluble resin (B)] having a relatively high acid value of 130 mgKOH/g or more, it is easily removed by a developer. If the second resin layer can be satisfactorily removed, the first resin layer, which may cause discoloration of the substrate, can also be satisfactorily removed together with the second resin layer. Therefore, it is considered that the transfer film of the present disclosure is less likely to discolor the substrate.
In addition, direct contact of the first resin layer containing the alkali-soluble resin (A) with a large proportion of structural units derived from a vinylbenzene derivative to the substrate may cause discoloration.
In contrast, as described above, the transfer film of the present disclosure has a configuration in which the second resin layer is interposed between the first resin layer and the substrate when bonded to the substrate. , the first resin layer containing the alkali-soluble resin (A) having a large proportion of structural units derived from a vinylbenzene derivative does not come into direct contact with the substrate. Also from this point, it is considered that the transfer film of the present disclosure is unlikely to discolor the substrate.
From the above, it is believed that the transfer film of the present disclosure is capable of forming a pattern with excellent resolution while preventing discoloration of the substrate.

FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of the transfer film of the present disclosure.
The transfer film 100 shown in FIG. 1 has a temporary support 10, a first resin layer 20, and a second resin layer 30 in this order. It should be noted that the elements shown in the drawings of this disclosure are not necessarily drawn to scale.
Each configuration of the transfer film of the present disclosure will be described below.

[Temporary support]
The transfer film of the present disclosure has a temporary support.
The temporary support is a support that supports at least the first resin layer and the second resin layer and is peelable from the adherend.

The temporary support preferably has light transmittance from the viewpoint that pattern exposure through the temporary support is possible.
In the present disclosure, "having optical transparency" means having a transmittance of 50% or more for the dominant wavelength of light used for pattern exposure.
From the viewpoint of improving exposure sensitivity, the transmittance of the dominant wavelength of light used for pattern exposure is preferably 60% or more, more preferably 70% or more.
A method of measuring transmittance includes a method of measuring using a spectrophotometer.
As a spectrophotometer, for example, MCPD-6800 (product name) manufactured by Otsuka Electronics Co., Ltd. can be preferably used. However, the spectrophotometer is not limited to this.

Temporary supports include glass substrates, resin films, and paper.
The temporary support is preferably a resin film from the viewpoint of strength and flexibility.
Examples of the resin film include polyethylene terephthalate film, cellulose triacetate film, polystyrene film, polycarbonate film and the like.
Among these, polyethylene terephthalate film is preferable as the temporary support from the viewpoint of optical properties.

The thickness of the temporary support is not particularly limited, and can be appropriately selected according to the material.
The thickness of the temporary support is preferably 5 μm to 200 μm, more preferably 10 μm to 150 μm, from the viewpoints of ease of handling and versatility.

Preferred aspects of the temporary support are described, for example, in paragraphs [0017] and [0018] of JP-A-2014-85643, and these descriptions are incorporated herein by reference.

[First resin layer]
The transfer film of the present disclosure has a first resin layer containing an alkali-soluble resin (A) containing structural units derived from a vinylbenzene derivative, a polymerizable compound, and a polymerization initiator.

<Alkali-soluble resin (A)>
The first resin layer contains an alkali-soluble resin (A).
Alkali-soluble resin (A) functions as a binder.
The alkali-soluble resin (A) contains structural units derived from a vinylbenzene derivative, and the content of the structural units derived from the vinylbenzene derivative in the alkali-soluble resin (A) is equal to the total structural units of the alkali-soluble resin (A). is 30% by mass or more.

In the present disclosure, "alkali-soluble" means soluble in a 1 mol/L sodium hydroxide solution at 25°C. Moreover, "soluble" refers to dissolving 0.1 g or more in 100 mL of solvent.

(Structural Unit Derived from Vinylbenzene Derivative)
The alkali-soluble resin (A) contains structural units derived from vinylbenzene derivatives.
In the present disclosure, "a structural unit derived from a vinylbenzene derivative" means a structural unit formed by addition polymerization of a vinylbenzene derivative.

A structural unit derived from a vinylbenzene derivative is not particularly limited.
As a structural unit derived from a vinylbenzene derivative, for example, a structural unit represented by the following formula (1) (hereinafter also referred to as “structural unit (1)”) is preferable.

In formula (1), n represents an integer of 0-5.
In formula (1), R ¹ represents a substituent.
When n is 2 or more, two R ^1s may combine with each other to form a condensed ring structure.
In formula (1), ^R2 represents a hydrogen atom or a methyl group.

The substituent represented by R ¹ is not particularly limited, but is preferably, for example, a halogen atom, an alkyl group, an aryl group, an alkoxy group, or a hydroxyl group.

When the substituent represented by R ¹ is a halogen atom, the halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom, a chlorine atom or a bromine atom.

When the substituent represented by R ¹ is an alkyl group, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 12, still more preferably 1 to 6, even more preferably 1 to 3, 1 or 2 is more preferred, and 1 is particularly preferred.

When the substituent represented by R ¹ is an aryl group, the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, still more preferably 6 to 10 carbon atoms, and particularly preferably 6 carbon atoms.

When the substituent represented by R ¹ is an alkoxy group, the number of carbon atoms in the alkoxy group is preferably 1 to 20, more preferably 1 to 12, still more preferably 1 to 6, still more preferably 1 to 3, 1 or 2 is more preferred, and 1 is particularly preferred.

n is particularly preferably an integer of 0-2.
When n is 2 or more, a naphthalene ring structure or an anthracene ring structure is preferable as the condensed ring structure that can be formed by combining two R ¹ s.

Monomers (ie, vinylbenzene derivatives) forming the structural unit (1) include styrene, α-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, vinylbiphenyl, vinylanthracene, 4-hydroxystyrene, and 4-bromo. Styrene, 4-methoxystyrene and the like can be mentioned.
Among these, styrene is particularly preferable as the monomer forming the structural unit (1).

The alkali-soluble resin (A) may contain only one kind of constitutional unit derived from a vinylbenzene derivative, or may contain two or more kinds thereof.

The content of structural units derived from the vinylbenzene derivative in the alkali-soluble resin (A) is relative to all structural units contained in the alkali-soluble resin (A) [that is, all structural units of the alkali-soluble resin (A)]. , 30% by mass or more, preferably 35% by mass or more, and more preferably 40% by mass or more.
When the content of structural units derived from a vinylbenzene derivative in the alkali-soluble resin (A) is 30% by mass or more with respect to the total structural units of the alkali-soluble resin (A), the first resin Since swelling of the layer is suppressed, a pattern with excellent resolution can be formed.
The upper limit of the content of structural units derived from vinylbenzene derivatives in the alkali-soluble resin (A) is not particularly limited.
If the content of the structural unit derived from the vinylbenzene derivative in the alkali-soluble resin (A) is too high, the acid value of the first resin layer becomes excessively low, resulting in the formation of residual monomers derived from the vinylbenzene derivative during development. and/or residual oligomers may be difficult to remove.
From such a viewpoint, the content of structural units derived from a vinylbenzene derivative in the alkali-soluble resin (A) is preferably, for example, 70% by mass or less with respect to the total structural units of the alkali-soluble resin (A). , 65% by mass or less, and even more preferably 60% by mass or less.
If the content of structural units derived from the vinylbenzene derivative in the alkali-soluble resin (A) is 70% by mass or less relative to the total structural units of the alkali-soluble resin (A), discoloration of the substrate is further suppressed.

(Structural Unit Derived from Monomer Having Acid Group)
From the viewpoint of developability, the alkali-soluble resin (A) preferably contains a structural unit derived from a monomer having an acid group.
In the present disclosure, "structural unit derived from a monomer having an acid group" means a structural unit formed by addition polymerization of a monomer having an acid group.

A carboxy group, a sulfonic acid group, a phosphoric acid group, etc. are mentioned as an acid group.
Among these, a carboxy group is preferable as the acid group.

The type of monomer having a carboxy group is not particularly limited as long as it can be copolymerized with the aforementioned vinylbenzene derivative.
Monomers having a carboxy group include (meth)acrylic acid, crotonic acid, maleic anhydride, fumaric acid, itaconic acid, glutaconic acid, citraconic acid, ω-carboxy-polycaprolactone mono(meth)acrylate and the like.
Among these, (meth)acrylic acid is preferable as the monomer having a carboxy group from the viewpoint of copolymerizability.

Monomers having a carboxy group are described in paragraph [0043] of JP-A-2012-8571 and paragraph [0096] of WO2017/043544. This description is incorporated herein by reference.

When the alkali-soluble resin (A) contains a structural unit derived from a monomer having an acid group (preferably a carboxy group; hereinafter the same), it contains only one type of structural unit derived from a monomer having an acid group. may be included, or two or more may be included.

When the alkali-soluble resin (A) contains a structural unit derived from a monomer having an acid group, the content of the structural unit derived from the monomer having an acid group in the alkali-soluble resin (A) is not particularly limited. It can be appropriately set according to the acid value of the alkali-soluble resin (A).
As an example, the content of structural units derived from monomers having an acid group in the alkali-soluble resin (A) is 20% by mass to 40% by mass with respect to all structural units of the alkali-soluble resin (A). be able to.

(Structural units derived from other monomers)
The alkali-soluble resin (A) may contain structural units other than structural units derived from vinylbenzene derivatives and structural units derived from monomers having an acid group (so-called structural units derived from other monomers).
In the present disclosure, "structural units derived from other monomers" mean structural units formed by addition polymerization of other monomers.

The type of other monomer is not particularly limited as long as it can be copolymerized with at least a vinylbenzene derivative.
Other monomers include hydroxyl group-containing monomers, amino group-containing monomers, (meth)acrylic acid ester monomers [(meth)acrylic acid alkyl ester, allyl (meth)acrylate, etc.].
As other monomers, unsubstituted (meth)acrylic acid alkyl ester monomers are preferred.
The type of (meth)acrylic acid alkyl ester monomer is not particularly limited.
The alkyl group of the (meth)acrylic acid alkyl ester monomer may be linear, branched, or cyclic.
Although the number of carbon atoms in the alkyl group of the (meth)acrylic acid alkyl ester monomer is not particularly limited, it is preferably 4 to 24, more preferably 4 to 20, for example.

Other monomers are described, for example, in paragraphs [0044] to [0075] of JP-A-2012-8571 and paragraphs [0097] to [0101] of WO 2017/043544. This description is incorporated herein by reference.

The alkali-soluble resin (A) preferably has a structural unit derived from a vinylbenzene derivative, a structural unit derived from a monomer having an acid group, and a structural unit derived from a (meth)acrylic acid ester monomer, and has the formula (1 ) [that is, structural unit (1)], a structural unit derived from a monomer having a carboxy group, and a structural unit derived from a (meth)acrylic acid alkyl ester monomer.

The acid value of the alkali-soluble resin (A) is not particularly limited.
The acid value of the alkali-soluble resin (A) is, for example, preferably 150 mgKOH/g or more, more preferably 160 mgKOH/g or more, even more preferably 170 mgKOH/g or more.
When the acid value of the alkali-soluble resin (A) is 150 mgKOH/g or more, the first resin layer is easily removed by a developer. Further, when the acid value of the alkali-soluble resin (A) is 150 mgKOH/g or more, the dispersibility of the residual monomers and residual oligomers derived from the vinylbenzene derivative into the developer is further improved during development. Residual monomers and residual oligomers derived from benzene derivatives are more easily removed. Therefore, residual monomers and/or residual oligomers derived from the vinylbenzene derivative are less likely to come into direct contact with the substrate, making it more difficult for the substrate to discolor.
In order to improve the rectangularity of the pattern, it is desirable that the alkali-soluble resin (A) contained in the first resin layer be hydrophobic and have a high acid value. However, if the acid value is too high (in other words, the proportion of acid groups is too high), the hydrophobicity will decrease, and good rectangularity may not be maintained.
From such a viewpoint, the acid value of the alkali-soluble resin (A) is, for example, preferably 250 mgKOH/g or less, more preferably 240 mgKOH/g or less, and even more preferably 230 mgKOH/g or less. .
When the acid value of the alkali-soluble resin (A) is 250 mgKOH/g or less, pattern resolution can be further improved.

In the present disclosure, the acid value of the alkali-soluble resin means the theoretical acid value.
The theoretical acid value of the alkali-soluble resin is expressed in milligrams (mg) of potassium hydroxide required to neutralize all the acid components contained in 1 g of the alkali-soluble resin.
How to determine the theoretical acid value is described in paragraph [0070] of JP-A-2012-211228. This description is incorporated herein by reference.

The I/O value of the alkali-soluble resin (A) is not particularly limited. More preferably 0.55 or more.
Although the upper limit of the I/O value of the alkali-soluble resin (A) is not particularly limited, it is preferably 0.9 or less, for example.

In the present disclosure, the “I/O value” is the average I/O value obtained by dividing the inorganic value I based on the organic conceptual diagram by the organic value O.
For the I / O value, Organic Conception Diagram (Yoshio Koda, Sankyo Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, Items 1 to 16 (1954); No. 10, paragraphs 719-725 (1957); Fragrance Journal, No. 34, paragraphs 97-111 (1979); Fragrance Journal, No. 50, paragraphs 79-82 ( 1981);
The concept of the I/O value divides the properties of a compound into organic groups that represent covalent bonding and inorganic groups that represent ionic bonding, and all organic compounds are represented by an organic axis and an inorganic axis. It is shown by positioning one point at a time.

The I/O value when the alkali-soluble resin (A) contains two or more resins can be considered as follows. For example, when the alkali-soluble resin (A) contains three kinds of alkali-soluble resins (A) (resin 1 to resin 3), the I/O value of resin 1 is A1, the mass fraction is M1, and the I/O value of resin 2 is When the O value is A2, the mass fraction is M2, the I/O value of resin 3 is A3, and the mass fraction is M3, the I/O value "Am" of the mixture component can be estimated as follows. be.
Am = A1 x M1 + A2 x M2 + A3 x M3
In addition, when the alkali-soluble resin (A) contains only one kind of alkali-soluble resin (A), the I / O value of the one kind of alkali-soluble resin (A) contained is the I / O in the alkali-soluble resin (A) average value.

Although the weight average molecular weight of the alkali-soluble resin (A) is not particularly limited, it is preferably 2,000 to 200,000 from the viewpoint of the strength, manufacturability, and developability of the first resin layer, More preferably 4,000 to 100,000.

The first resin layer may contain only one type of alkali-soluble resin (A), or may contain two or more types.

The content of the alkali-soluble resin (A) in the first resin layer is not particularly limited. It is more preferably in the range of 80% by mass and even more preferably in the range of 30% by mass to 70% by mass.

The production method (so-called synthesis method) of the alkali-soluble resin (A) is not particularly limited, and known methods can be applied.
Examples of the method for producing the alkali-soluble resin (A) include a method of polymerizing a vinylbenzene derivative, a monomer having a carboxy group, and other monomers in an organic solvent using a polymerization initiator.

<Polymerizable compound>
The first resin layer contains a polymerizable compound.
In the first resin layer, the polymerizable compound contributes to the improvement of pattern formability.
Examples of the polymerizable compound include compounds capable of being polymerized, such as compounds such as radically polymerizable compounds and cationic polymerizable compounds.
The polymerizable compound is preferably a photopolymerizable compound, more preferably an ethylenically unsaturated compound.
An ethylenically unsaturated compound is a compound having one or more ethylenically unsaturated groups.
A (meth)acryloyl group is preferred as the ethylenically unsaturated group.
A (meth)acrylate compound is preferable as the ethylenically unsaturated compound.

The ethylenically unsaturated compound preferably contains a bifunctional or higher functional ethylenically unsaturated compound, more preferably a bifunctional or higher functional ethylenically unsaturated compound.
In the present disclosure, "difunctional or higher ethylenically unsaturated compound" means a compound having two or more ethylenically unsaturated groups in one molecule.

The bifunctional ethylenically unsaturated compound is not particularly limited.
Bifunctional ethylenically unsaturated compounds include tricyclodecanedimethanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylates, polypropylene glycol di(meth)acrylates, and the like.

A commercial item can be used as a bifunctional ethylenically unsaturated compound.
Examples of commercially available bifunctional ethylenically unsaturated compounds include tricyclodecanedimethanol diacrylate [trade name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.] and tricyclodecanedimethanol dimethacrylate. [trade name: NK Ester DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.], 1,9-nonanediol diacrylate [trade name: NK Ester A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.], 1, 6-hexanediol diacrylate [trade name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.], ethoxylated bisphenol A dimethacrylate [trade name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd. ], polypropylene glycol diacrylate [trade name: Aronix (registered trademark) M-270, manufactured by Toagosei Co., Ltd.] and the like.

The tri- or higher functional ethylenically unsaturated compound is not particularly limited.
Examples of tri- or higher ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa) (meth)acrylate, pentaerythritol (tri/tetra) (meth)acrylate, trimethylolpropane tri(meth)acrylate, Ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, glycerol tri(meth)acrylate skeleton (meth)acrylate compounds, and the like.

In the present disclosure, "(tri/tetra/penta/hexa) (meth)acrylate" is a concept that includes tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate. It is the term used. Moreover, "(tri/tetra)(meth)acrylate" is a term used as a concept that includes both tri(meth)acrylate and tetra(meth)acrylate.

The ethylenically unsaturated compound may contain an ethylenically unsaturated compound having an acid group from the viewpoint of improving developability.
Examples of acid groups include phosphoric acid groups, sulfonic acid groups, and carboxy groups.
Among these, a carboxy group is preferable as the acid group.

Examples of ethylenically unsaturated compounds having an acid group include bifunctional or higher ethylenic unsaturated compounds having an acid group (tri- to tetra-functional ethylenic unsaturated compounds having an acid group, 5- to 6-functional ethylenically unsaturated compounds, etc.).
The ethylenically unsaturated compound having an acid group is preferably at least one selected from the group consisting of bifunctional or higher ethylenically unsaturated compounds having a carboxy group and carboxylic acid anhydrides thereof.

A commercial item can be used as a bifunctional or more functional ethylenically unsaturated compound which has a carboxy group.
Examples of commercially available bifunctional or higher ethylenically unsaturated compounds having a carboxy group include Aronix (registered trademark) TO-2349 [manufactured by Toagosei Co., Ltd.], Aronix (registered trademark) M-520 [Toagosei ( Co., Ltd.], Aronix (registered trademark) M-510 [manufactured by Toagosei Co., Ltd.], and the like.

Ethylenically unsaturated compounds having an acid group are described in paragraphs [0025] to [0030] of JP-A-2004-239942. These descriptions are incorporated herein by reference.

The molecular weight (Mw) of the polymerizable compound is preferably 200 to 3,000, more preferably 250 to 2,600, even more preferably 280 to 2,200, and 300 to 2,200. is particularly preferred.

The first resin layer may contain only one type of polymerizable compound, or may contain two or more types.

Although the content of the polymerizable compound in the first resin layer is not particularly limited, for example, it is preferably 1% by mass to 70% by mass, and 10% by mass to It is more preferably 70% by mass, still more preferably 20% to 60% by mass, and particularly preferably 30% to 50% by mass.

<Polymerization initiator>
The first resin layer contains a polymerization initiator.
In the first resin layer, the polymerization initiator contributes to the improvement of pattern formability.
Examples of polymerization initiators include photopolymerization initiators and thermal polymerization initiators.
Among these, photopolymerization initiators are preferred.

A photoinitiator is not specifically limited.
As the photopolymerization initiator, a photopolymerization initiator having an oxime ester structure (hereinafter also referred to as an “oxime photopolymerization initiator”), a photopolymerization initiator having an α-aminoalkylphenone structure (hereinafter, “α- Also referred to as "aminoalkylphenone-based photopolymerization initiator".), a photopolymerization initiator having an α-hydroxyalkylphenone structure (hereinafter also referred to as an "α-hydroxyalkylphenone-based polymerization initiator"), an acylphosphine oxide structure A photopolymerization initiator having a ), a photopolymerization initiator having a hexaarylbiimidazole structure (hereinafter also referred to as a “hexaarylbiimidazole-based photopolymerization initiator”), and the like.

As the photopolymerization initiator, a hexaarylbiimidazole-based photopolymerization initiator is preferred.
Examples of hexaarylbiimidazole-based photopolymerization initiators include 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole.

For the photopolymerization initiator, for example, paragraphs [0031] to [0034] of JP-A-2011-95716, paragraphs [0064] to [0081] of JP-A-2015-014783, and JP-A-2010-015062 It is described in paragraphs [0132] to [0135] of the publication. These descriptions are incorporated herein by reference.

A commercial item can be used as a photoinitiator.
Examples of commercially available photopolymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) [trade name: IRGACURE (registered trademark) OXE-01 , manufactured by BASF], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) [trade name: IRGACURE (registered trademark) OXE -02, manufactured by BASF], IRGACURE (registered trademark) OXE-03 [trade name, manufactured by BASF], IRGACURE (registered trademark) OXE-04 [trade name, manufactured by BASF], 2-(dimethylamino)-2 -[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [trade name: IRGACURE (registered trademark) 379EG, manufactured by BASF], 2-methyl-1-( 4-methylthiophenyl)-2-morpholinopropan-1-one [trade name: IRGACURE (registered trademark) 907, manufactured by BASF], 2-hydroxy-1-{4-[4-(2-hydroxy-2- methyl-propionyl)benzyl]phenyl}-2-methylpropan-1-one [trade name: IRGACURE (registered trademark) 127, manufactured by BASF], 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl )-butanone-1 [trade name: IRGACURE (registered trademark) 369, manufactured by BASF], 2-hydroxy-2-methyl-1-phenyl-propan-1-one [trade name: IRGACURE (registered trademark) 1173, BASF company], 1-hydroxycyclohexylphenyl ketone [trade name: IRGACURE (registered trademark) 184, manufactured by BASF], 2,2-dimethoxy-1,2-diphenylethan-1-one [trade name: IRGACURE (registered trademark) ) 651, manufactured by BASF], 2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole [trade name: B-CIM, manufactured by Hodogaya Chemical Industry Co., Ltd. ] etc. are mentioned.

The first resin layer may contain only one polymerization initiator, or may contain two or more polymerization initiators.

The content of the polymerization initiator in the first resin layer is not particularly limited. It is more preferably 1.0% by mass or more, and even more preferably 1.0% by mass or more.
Moreover, the content of the polymerization initiator in the first resin layer is preferably 10% by mass or less, more preferably 8% by mass or less, relative to the total mass of the first resin layer.

<Polymerization inhibitor>
The first resin layer may contain a polymerization inhibitor.
When the first resin layer contains a polymerization inhibitor, the resolution of the formed pattern can be further improved. In addition, the polymerization inhibitor can contribute to anti-fogging.

A polymerization inhibitor is not specifically limited.
As the polymerization initiator, for example, a thermal polymerization inhibitor described in paragraph [0018] of Japanese Patent No. 4502784 can be used.
The polymerization initiator is preferably at least one selected from the group consisting of phenothiazine, phenoxazine and 4-methoxyphenol, more preferably phenoxazine.

When the first resin layer contains a polymerization inhibitor, it may contain only one polymerization inhibitor, or may contain two or more polymerization inhibitors.

When the first resin layer contains a polymerization inhibitor, the content of the polymerization initiator in the first resin layer is not particularly limited, but for example, 0.01 mass with respect to the total mass of the first resin layer. % to 3% by mass, more preferably 0.01% to 1% by mass, even more preferably 0.01% to 0.5% by mass.

<Surfactant>
The first resin layer may contain a surfactant.
When the first resin layer contains a surfactant, the thickness uniformity of the first resin layer can be improved.

Surfactants are not particularly limited.
Examples of surfactants include anionic surfactants, cationic surfactants, nonionic (that is, nonionic) surfactants, and amphoteric surfactants.
For surfactants, paragraph [0017] of Patent No. 4502784, paragraphs [0060] to [0071] of JP-A-2009-237362, and paragraphs [0085] to [0087 of JP-A-2018-189754 ] is described. These descriptions are incorporated herein by reference.

A nonionic surfactant is preferable as the surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ether compounds, polyoxyethylene higher alkylphenyl ether compounds, higher fatty acid diester compounds of polyoxyethylene glycol, silicone surfactants, fluorine surfactants, and the like. .
Among these, fluorine-based surfactants are preferred as nonionic surfactants.

A commercially available product can be used as the surfactant.
Examples of commercially available surfactants include KP [manufactured by Shin-Etsu Chemical Co., Ltd.], Polyflow [manufactured by Kyoeisha Chemical Co., Ltd.], F-top (manufactured by JEMCO), Megafac (registered trademark) [product examples: F551A, F444, etc., manufactured by DIC Corporation], Florado [manufactured by Sumitomo 3M Co., Ltd.], Asahi Guard (registered trademark) [manufactured by AGC Corporation], Surflon (registered trademark) [manufactured by AGC Seichemical Co., Ltd.] , PolyFox (manufactured by OMNOVA), Surfynol (manufactured by Nissin Chemical Industry Co., Ltd.), SH-8400 (manufactured by Dow Corning Toray Co., Ltd.), and the like. All of the above series are nonionic surfactants.

When the first resin layer contains a surfactant, it may contain only one type of surfactant, or may contain two or more types.

When the first resin layer contains a surfactant, the content of the surfactant in the first resin layer is not particularly limited, but for example, 0.05 mass with respect to the total mass of the first resin layer. % to 10% by mass, more preferably 0.05% to 5% by mass.

<Sensitizer>
The first resin layer may contain a sensitizer.
The sensitizer has actions such as improving the sensitivity of the photopolymerization initiator to actinic rays and suppressing inhibition of polymerization of the polymerizable compound by oxygen.

A sensitizer is not particularly limited.
Examples of the sensitizer include known sensitizing dyes, dyes, pigments and the like.

Examples of sensitizing dyes include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds, stilbene compounds, triazine compounds, and thiophenes. compounds, naphthalimide compounds, triarylamine compounds, aminoacridine compounds, acridone compounds (eg, 2-chloro-N-butylacridone), N-phenylglycine compounds, and the like.

Dyes or pigments include fuchsine, phthalocyanine green, auramine base, chalcoxide green S, paramagenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, basic blue 20, malachite green [for example, Hodogaya Chemical Industry Co., Ltd. Eisen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Industry Co., Ltd.], Diamond Green [for example, Eisen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Industry Co., Ltd.], and the like.

Sensitizers are described in paragraphs [0069] to [0074] of JP-A-2018-189754. These descriptions are incorporated herein by reference.

When the first resin layer contains a sensitizer, it may contain only one sensitizer, or may contain two or more sensitizers.

When the first resin layer contains a sensitizer, the content of the sensitizer in the first resin layer is not particularly limited, but for example, 0.01 mass with respect to the total mass of the first resin layer. % to 5% by mass, more preferably 0.03% to 3% by mass, even more preferably 0.05% to 1% by mass.

<Other ingredients>
The first resin layer may contain components other than the above components (hereinafter also referred to as "other components").
Other components are not particularly limited, and can be appropriately selected according to the purpose and the like.
Other components include coloring agents [eg, Victoria Pure Blue NAPS manufactured by Hodogaya Chemical Industry Co., Ltd.], printing agents [eg, Leuco Crystal Violet], ultraviolet absorbers, development accelerators, and the like.

(thickness of the first resin layer)
The thickness of the first resin layer is not particularly limited.
For example, the thickness of the first resin layer is preferably 1 μm or more, more preferably 1.5 μm or more, and even more preferably 2 μm or more.
When the thickness of the first resin layer is 1 μm or more, lamination properties can be further improved.
The thinner the first resin layer, the less the amount of residual monomers and/or residual oligomers derived from the vinylbenzene derivative, and the less the substrate is discolored.
From such a viewpoint, the upper limit of the thickness of the first resin layer is, for example, preferably 5 μm or less, more preferably 4.5 μm or less, and even more preferably 4 μm or less.
Further, the thickness of the first resin layer is particularly preferably 2 μm to 4 μm, for example, from the viewpoint of achieving well-balanced suppression of discoloration of the substrate and improvement of lamination properties.

The thickness of the first resin layer is measured by the following method.
In the cross-sectional observation image in the thickness direction of the first resin layer, the arithmetic average value of the thickness of the first resin layer measured at five randomly selected locations is obtained, and the obtained value is the first resin Let it be the thickness of the layer.
A cross-sectional observation image in the thickness direction of the first resin layer can be obtained using a scanning electron microscope (SEM).

(Minimum transmittance of the first resin layer)
The minimum transmittance of the first resin layer at a wavelength of 400 nm to 700 nm is preferably 80% or more, more preferably 90% or more.
A method of measuring the minimum transmittance of the first resin layer includes a method of measuring using a spectrophotometer.
As a spectrophotometer, for example, MCPD-6800 manufactured by Otsuka Electronics Co., Ltd. can be preferably used. However, the spectrophotometer is not limited to this.

(Method for forming first resin layer)
A method for forming the first resin layer is not particularly limited, and a known method can be applied.
As the first resin layer, for example, a method of applying the coating liquid for forming the first resin layer containing the components described above onto an object to be coated and drying it can be used.

A coating method is not particularly limited, and a known coating method can be applied.
Examples of coating methods include slit coating, spin coating, curtain coating, inkjet coating, and the like.

The drying temperature is not particularly limited, and can be appropriately set according to the type of volatile component such as solvent.
The drying temperature can be set to 60° C. to 120° C., for example.

The coating liquid for forming the first resin layer can be prepared, for example, by mixing each component described above and a solvent in an arbitrary ratio.

The solvent is not particularly limited, and known solvents can be applied.
Examples of solvents include ethylene glycol monoalkyl ether compounds, ethylene glycol dialkyl ether compounds, ethylene glycol monoalkyl ether acetate compounds, propylene glycol monoalkyl ether compounds, propylene glycol dialkyl ether compounds, propylene glycol monoalkyl ether acetate compounds, and diethylene glycol dialkyl ether compounds. , diethylene glycol monoalkyl ether acetate compounds, dipropylene glycol monoalkyl ether compounds, dipropylene glycol dialkyl ether compounds, dipropylene glycol monoalkyl ether acetate compounds, ester compounds, ketone compounds, amide compounds, lactone compounds, alcohol compounds and the like. .

Preferable examples of the solvent include the following ester compounds, ether compounds, ketone compounds, alcohol compounds, and the like.
Ester compounds include ethyl acetate, propyl acetate, isobutyl acetate, sec-butyl acetate, t-butyl acetate, isopropyl acetate, n-butyl acetate, 1-methoxy-2-propyl acetate and the like.
Ether compounds include diisopropyl ether, 1,4-dioxane, 1,2-dimethoxyethane, 1,3-dioxolane, propylene glycol dimethyl ether, 1-methoxy-2-propanol, tetrahydrofuran and the like.
Examples of ketone compounds include methyl n-butyl ketone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl n-propyl ketone, methyl isopropyl ketone and the like.
Methanol etc. are mentioned as an alcohol compound.

In the first resin layer, the solvent contained in the coating liquid for forming the first resin layer need not be completely removed.
The solvent content in the first resin layer is preferably 1% by mass or less, more preferably 0.5% by mass or less, relative to the total mass of the first resin layer.

The solid content concentration of the coating liquid for forming the first resin layer is not particularly limited.
The solid content concentration of the coating liquid for forming the first resin layer is preferably 1% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, from the viewpoint of coating suitability.

In the present disclosure, the “solid content concentration of the first resin layer-forming coating liquid” refers to the total mass of the first resin layer-forming coating liquid. It means the ratio of residue excluding sexual components.

[Second resin layer]
The transfer film of the present disclosure has a second resin layer containing an alkali-soluble resin (B) having an acid value of 130 mgKOH/g or more.

<Alkali-soluble resin (B)>
The second resin layer contains an alkali-soluble resin (B).
Alkali-soluble resin (B) functions as a binder.
The acid value of the alkali-soluble resin (B) is 130 mgKOH/g or more.

The acid value of the alkali-soluble resin (B) is 130 mgKOH/g or more, preferably 140 mgKOH/g or more, more preferably 150 mgKOH/g or more.
When the acid value of the alkali-soluble resin (B) is 130 mgKOH/g or more, the second resin layer is easily removed with a developer. Therefore, during development, the first resin layer can be effectively removed, and the substrate is more resistant to discoloration.
The upper limit of the acid value of the alkali-soluble resin (B) is not particularly limited. more preferably 230 mgKOH/g or less.

The I/O value of the alkali-soluble resin (B) is not particularly limited. It is more preferable that it is above.
Although the upper limit of the I/O value of the alkali-soluble resin (B) is not particularly limited, it is preferably 0.9 or less, for example.

The type of alkali-soluble resin (B) is not particularly limited as long as it has an acid value of 130 mgKOH/g or more.
A resin having an acid group is preferably used as the alkali-soluble resin (B).
A carboxy group, a sulfonic acid group, a phosphoric acid group, etc. are mentioned as an acid group.
Among these, a carboxy group is preferable as the acid group.

As the alkali-soluble resin (B), for example, a resin having a hydroxyl group such as an acrylic copolymer having an acrylic monomer having a carboxyl group as a structural unit, cellulose ether, polyhydroxyethyl methacrylate, etc., is added with maleic anhydride or phthalic anhydride. Examples include polymers obtained by reacting substances.

As the acrylic copolymer having an acrylic monomer having a carboxy group as a structural unit, a copolymer of a monomer having a carboxy group and another copolymerizable monomer (so-called other monomer) is preferable.
Specific examples and preferred embodiments of the monomer having a carboxy group in the alkali-soluble resin (B) are synonymous with the specific examples and preferred embodiments of the monomer having a carboxy group described in the section "Alkali-soluble resin (A)". Description is omitted here.

Specific examples and preferred embodiments of the other monomers in the alkali-soluble resin (B) are synonymous with specific examples and preferred embodiments of the other monomers described in the section "Alkali-soluble resin (A)", and therefore will not be described here. omitted.

The alkali-soluble resin (B) preferably has a structural unit derived from a monomer having an acid group and a structural unit derived from a (meth)acrylic acid ester monomer, and a structural unit derived from a monomer having a carboxy group and a (meth) ) It is more preferable to have a structural unit derived from allyl acrylate.

Although the weight average molecular weight of the alkali-soluble resin (B) is not particularly limited, it is preferably 2,000 to 100,000 from the viewpoint of the strength, manufacturability, and developability of the second resin layer, More preferably 4,000 to 50,000.

The second resin layer may contain only one type of alkali-soluble resin (B), or may contain two or more types.

The content of the alkali-soluble resin (B) in the second resin layer is not particularly limited. It is more preferably from 70% by mass to 96% by mass, and even more preferably from 70% by mass to 94% by mass.

The production method (so-called synthesis method) of the alkali-soluble resin (B) is not particularly limited, and known methods can be applied.
Examples of the method for producing the alkali-soluble resin (B) include a method of polymerizing a monomer forming the alkali-soluble resin (B) in an organic solvent using a polymerization initiator.

<Polymerizable compound>
The second resin layer may contain a polymerizable compound.
Examples of the polymerizable compound include compounds capable of being polymerized, such as compounds such as radically polymerizable compounds and cationic polymerizable compounds.
The polymerizable compound is preferably a photopolymerizable compound, more preferably an ethylenically unsaturated compound.
When the second resin layer contains a polymerizable compound that is an ethylenically unsaturated compound, the adhesion between the first resin layer and the second resin layer can be improved.
A (meth)acryloyl group is preferred as the ethylenically unsaturated group.
A (meth)acrylate compound is preferable as the ethylenically unsaturated compound.

The ethylenically unsaturated compound preferably contains a bifunctional or higher functional ethylenically unsaturated compound, more preferably a bifunctional or higher functional ethylenically unsaturated compound.
Specific examples and commercial products of the bifunctional or higher functional ethylenically unsaturated compound in the second resin layer are the specific examples of the bifunctional or higher functional ethylenically unsaturated compound described in the section "First resin layer" and Since it is synonymous with an example of a commercial product, the explanation is omitted here.

The ethylenically unsaturated compound may contain an ethylenically unsaturated compound having an acid group from the viewpoint of improving adhesion to the substrate.
The ethylenically unsaturated compound having an acid group in the second resin layer is synonymous with the ethylenically unsaturated compound having an acid group described in the section "First resin layer", so the description is omitted here. .

The molecular weight (Mw) of the polymerizable compound is preferably 200 to 3,000, more preferably 250 to 2,600, even more preferably 280 to 2,200, and 300 to 2,200. is particularly preferred.

When the second resin layer contains a polymerizable compound, it may contain only one polymerizable compound, or may contain two or more polymerizable compounds.

When the second resin layer contains a polymerizable compound, the content of the polymerizable compound in the second resin layer is not particularly limited. It is preferably 30% by mass, more preferably 2% by mass to 25% by mass, even more preferably 3% by mass to 20% by mass, and particularly preferably 5% by mass to 15% by mass. .

<Surfactant>
The second resin layer may contain a surfactant.
When the second resin layer contains a surfactant, the thickness uniformity of the second resin layer can be improved.

Specific examples, preferred embodiments, and commercial products of the surfactant in the second resin layer are the specific examples, preferred embodiments, and commercial products of the surfactant described in the section "First resin layer". is synonymous with , so the description is omitted here.

When the second resin layer contains a surfactant, it may contain only one type of surfactant, or may contain two or more types.

When the second resin layer contains a surfactant, the content of the surfactant in the second resin layer is not particularly limited, but for example, 0.05 mass with respect to the total mass of the second resin layer % to 10% by mass, more preferably 0.05% to 5% by mass.

<Other ingredients>
The second resin layer may contain components other than the above components (hereinafter also referred to as “other components”).
Other components are not particularly limited, and can be appropriately selected according to the purpose and the like.
Other components include polymerization initiators, polymerization inhibitors, sensitizers, ultraviolet absorbers, development accelerators and the like.

(Thickness of second resin layer)
The thickness of the second resin layer is not particularly limited.
For example, the thickness of the second resin layer is preferably 30 nm or more, more preferably 35 nm or more, and even more preferably 40 nm or more.
When the thickness of the second resin layer is 30 nm or more, the first resin layer can be removed more satisfactorily during development, so that the substrate is more resistant to discoloration.
The thickness of the second resin layer is, for example, preferably 150 nm or less, more preferably 135 nm or less, and even more preferably 120 nm or less.
When the thickness of the second resin layer is 150 nm or less, side etching of the pattern is suppressed, and the resolution can be further improved.
Further, the thickness of the second resin layer is particularly preferably 40 nm to 120 nm, for example, from the viewpoint of achieving well-balanced suppression of discoloration of the substrate and improvement of pattern resolution.

The thickness of the second resin layer is measured by the following method.
In the cross-sectional observation image in the thickness direction of the second resin layer, the arithmetic average value of the thickness of the second resin layer measured at five randomly selected locations is obtained, and the obtained value is the second resin Let it be the thickness of the layer.
A cross-sectional observation image in the thickness direction of the second resin layer can be obtained using a scanning electron microscope (SEM).

(Minimum transmittance of second resin layer)
The minimum transmittance of the second resin layer at a wavelength of 400 nm to 700 nm is preferably 80% or more, more preferably 90% or more.
A method of measuring the minimum transmittance of the second resin layer includes a method of measuring using a spectrophotometer.
As a spectrophotometer, for example, MCPD-6800 manufactured by Otsuka Electronics Co., Ltd. can be preferably used. However, the spectrophotometer is not limited to this.

(Method for forming second resin layer)
A method for forming the second resin layer is not particularly limited, and a known method can be applied.
As the second resin layer, for example, a method of applying a coating liquid for forming a second resin layer containing the components described above onto an object to be coated and drying the coating liquid can be used.

A coating method is not particularly limited, and a known coating method can be applied.
Examples of coating methods include slit coating, spin coating, curtain coating, inkjet coating, and the like.

The drying temperature is not particularly limited, and can be appropriately set according to the type of volatile component such as solvent.
The drying temperature can be set to 60° C. to 120° C., for example.

The coating liquid for forming the second resin layer can be prepared, for example, by mixing each component described above and a solvent in an arbitrary ratio.

Although the solvent is not particularly limited, for example, it is preferably a water-based solvent.
Solvents include water (ion-exchanged water, pure water, etc.), 1% by mass to 5% by mass ammonia water, lower alcohols (methanol, ethanol, 1-propanol, 2-propanol, etc.), 1-methoxy-2-propanol, etc. is mentioned.

In the second resin layer, the solvent contained in the coating liquid for forming the second resin layer need not be completely removed.
The solvent content in the second resin layer is preferably 1% by mass or less, more preferably 0.5% by mass or less, relative to the total mass of the second resin layer.

The solid content concentration of the coating liquid for forming the second resin layer is not particularly limited.
The solid content concentration of the coating liquid for forming the second resin layer is preferably 1% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, from the viewpoint of coating suitability.

In the present disclosure, the “solid content concentration of the second resin layer-forming coating liquid” refers to the volatilization of the solvent or the like from the second resin layer-forming coating liquid with respect to the total mass of the second resin layer-forming coating liquid. It means the ratio of residue excluding sexual components.

〔Protective film〕
The transfer film of the present disclosure may have a protective film on the surface of the second resin layer opposite to the first resin layer.
Protective films include polyethylene terephthalate film, polypropylene film, polystyrene film, polycarbonate film and the like.
Protective films are described, for example, in paragraphs [0083] to [0087] and [0093] of JP-A-2006-259138. These descriptions are incorporated herein by reference.

[Method for manufacturing patterned substrate]
The method for manufacturing a patterned substrate of the present disclosure includes a step of bonding a substrate and a transfer film of the present disclosure by bringing the substrate and the second resin layer of the transfer film into contact (hereinafter, “bonding ), a step of exposing the first resin layer of the transfer film in a pattern (hereinafter also referred to as an “exposure step”), and developing the first resin layer that has undergone the pattern exposure. and a step of forming a pattern (hereinafter also referred to as a “development step”) in this order.
According to the method for manufacturing a patterned substrate of the present disclosure, it is possible to manufacture a patterned substrate that suppresses discoloration of the substrate and has excellent pattern resolution.
Details of each step will be described below.

Note that the transfer film in the method for manufacturing a patterned substrate of the present disclosure is as described in the above-mentioned “Transfer Film” section, and preferred embodiments are also the same, so description thereof will be omitted here.

[Lamination process]
The method for manufacturing a patterned substrate of the present disclosure includes a step of bonding a substrate and a transfer film of the present disclosure by bringing the substrate and the second resin layer of the transfer film into contact (i.e., a bonding step). )including.

The substrate may be a substrate itself such as glass, silicon, film, or the like, or may be a substrate provided with an optional layer such as a conductive layer on a substrate such as glass, silicon, film, etc., if necessary. may Preferably, the substrate is a substrate having a conductive layer on a substrate.

The substrate is preferably transparent.
Transparent substrates are described, for example, in JP-A-2010-86684, JP-A-2010-152809, and JP-A-2010-257492. These descriptions are incorporated herein by reference.
The refractive index of the substrate is preferably 1.50-1.52.

The substrate is preferably a glass substrate or a film substrate, more preferably a film substrate.

Examples of glass substrates include tempered glass.
As the tempered glass, for example, Corning Gorilla Glass can be applied.

It is preferable that the film substrate has low optical distortion and high transparency.
A resin film is preferable as the film substrate.
Materials for the resin film include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, cycloolefin polymer, and the like.

Examples of the conductive layer include any conductive layer used for general circuit wiring, touch panel wiring, and the like. Examples of conductive layers include metal layers and conductive metal oxide layers.
In the present disclosure, "conductive" means having a volume resistivity of less than 1 x ¹⁰⁶ Ωcm (preferably less than ¹ x 104 Ωcm).

Materials for the metal layer include Al (aluminum), Zn (zinc), Cu (copper), Fe (iron), Ni (nickel), Cr (chromium), Mo (molybdenum), Ag (silver), and the like. .
The metal forming the metal layer may be a single metal consisting of one metal element, a metal mixture containing two or more metal elements, or an alloy containing at least one metal element. There may be.
Conductive metal oxides forming the conductive metal oxide layer include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), SiO ₂ and the like.

The conductive layer is preferably at least one layer selected from the group consisting of a metal layer and a conductive metal oxide layer, more preferably a metal layer, from the viewpoint of conductivity and fine line formation, and copper A layer is more preferred.
That is, at least part of the surface of the substrate in contact with the second resin layer is preferably at least one selected from the group consisting of metals and conductive metal oxides, more preferably metal, copper is more preferable.

It is preferable that the conductive layer is an electrode pattern corresponding to the sensor of the visual recognition portion used in the capacitive touch panel or the wiring of the peripheral extracting portion.

In the bonding step, the substrate and the transfer film are bonded together by bringing the substrate and the second resin layer of the transfer film into contact with each other.
The bonding of the substrate and the transfer film can be performed using a known laminator such as a vacuum laminator and an autocut laminator.

Lamination temperature is not particularly limited.
The lamination temperature is, for example, preferably 80°C to 150°C, more preferably 90°C to 150°C, even more preferably 100°C to 150°C.
When using a laminator with rubber rollers, the lamination temperature refers to the temperature of the rubber rollers.

The substrate temperature during lamination is not particularly limited.
The substrate temperature during lamination is, for example, preferably 10°C to 150°C, more preferably 20°C to 150°C, even more preferably 30°C to 150°C.
When the substrate is a resin film, the substrate temperature during lamination is preferably 10°C to 80°C, more preferably 20°C to 60°C, and further preferably 30°C to 50°C. preferable.

The linear pressure during lamination is not particularly limited.
The linear pressure during lamination is, for example, preferably 0.5 N/cm to 20 N/cm, more preferably 1 N/cm to 10 N/cm, and further preferably 1 N/cm to 5 N/cm. preferable.

The transport speed during lamination (so-called lamination speed) is not particularly limited.
The conveying speed during lamination is, for example, preferably 0.5 m/min to 5 m/min, more preferably 1.5 m/min to 3 m/min.

[Exposure process]
The method for manufacturing a patterned substrate of the present disclosure includes a step of pattern-exposing the first resin layer of the transfer film (that is, an exposure step) after the bonding step.
In the exposure step, the first resin layer of the transfer film is pattern-exposed to form an exposed portion and a non-exposed portion in the first resin layer.
In the exposure step, the exposed first resin layer (so-called exposed portion) is cured. Moreover, when the second resin layer contains a polymerizable compound, the exposed second resin layer can also be cured.

The method of pattern exposure may be exposure through a mask (also referred to as a “photomask”) or digital exposure using a laser or the like.

A light source for exposure is not particularly limited.
The light source for exposure can be appropriately selected according to the components contained in the first resin layer.
Examples of the light source include a light source capable of irradiating light in a wavelength range (for example, 365 nm or 405 nm) that can cure the exposed portion.
Specific examples of light sources include various lasers, light-emitting diodes (LEDs), ultrahigh-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and the like.

The amount of exposure is not particularly limited.
The exposure dose is, for example, preferably 5 mJ/cm ² to 200 mJ/cm ² , more preferably 10 mJ/cm ² to 200 mJ/cm ² .

In the exposure step, after the temporary support is peeled off from the transfer film bonded to the substrate, the first resin layer may be pattern-exposed, and the first resin layer is pattern-exposed while leaving the temporary support. may

[Development process]
The method for manufacturing a patterned substrate of the present disclosure includes a step of developing the first resin layer that has undergone pattern exposure to form a pattern (that is, a developing step).
In the development step, a pattern can be formed by removing the non-exposed portion of the transfer film with a developer.
In the developing step, the second resin layer is also developed using the pattern of the first resin layer as a mask, so a pattern can be formed on the second resin layer at the same time.

The developer is not particularly limited, and known developers can be used.
Examples of the developer include the developer described in JP-A-5-72724.

The developer is preferably an alkaline aqueous solution.
Alkaline compounds that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline (2-hydroxyethyltrimethylammonium hydroxide) and the like.

The pH of the alkaline aqueous solution is not particularly limited.
The pH of the alkaline aqueous solution at 25° C. is, for example, preferably 8-13, more preferably 9-12, even more preferably 10-12.

Although the content of the alkaline compound in the alkaline aqueous solution is not particularly limited, for example, it is preferably 0.1% by mass to 5% by mass, and 0.1% by mass to 3% by mass, relative to the total mass of the alkaline aqueous solution. is more preferable.

The liquid temperature of the developer is not particularly limited.
The liquid temperature of the developer is preferably 20° C. to 40° C., for example.

Development methods include, for example, paddle development, shower development, spray development, shower and spin development, and dip development.

Pattern exposure, development and the like are described, for example, in paragraphs [0035] to [0051] of JP-A-2006-23696. These descriptions are incorporated herein by reference.

[Etching process]
The method for manufacturing a patterned substrate according to the present disclosure may include, after the developing step, a step of etching the substrate in a region where no pattern is arranged (hereinafter also referred to as an “etching step”).
In the etching process, etching is performed using the pattern formed from the first resin layer as an etching resist.

The etching method is not particularly limited, and known methods can be applied.
For example, as an etching treatment method, there is a commonly used wet etching method in which the substrate is immersed in an etchant.
As for the etchant used for wet etching, an acidic type or an alkaline type etchant may be appropriately selected according to the object to be etched.
Examples of acidic etching solutions include aqueous solutions containing only acidic components such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid. Moreover, as an acidic type etchant, a mixed aqueous solution of the above-described acidic component and a salt such as ferric chloride, ammonium fluoride, or potassium permanganate can be used. The acidic component may be a combination of multiple acidic components.
Examples of the alkaline type etchant include aqueous solutions of alkaline components alone, such as sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines such as tetramethylammonium hydroxide. Further, examples of the alkaline type etchant include a mixed aqueous solution of the above alkaline component and a salt such as potassium permanganate. The alkaline component may be a component obtained by combining a plurality of alkaline components.

Although the temperature of the etching solution is not particularly limited, it is preferably 45° C. or lower.
In the present disclosure, it is preferable that the pattern used as the etching mask exhibits particularly excellent resistance to the etchant in the temperature range of 45° C. or lower. As a result, the first resin layer is prevented from being peeled off during the etching process, and the portions where the first resin layer does not exist are selectively etched.

The etching method is described, for example, in paragraphs [0048] to [0052] of JP-A-2010-152155. These descriptions are incorporated herein by reference.

[Other processes]
The method for manufacturing a patterned substrate of the present disclosure may include processes other than the bonding process, the exposure process, the development process, and the etching process process (so-called other processes).
The method of manufacturing a patterned substrate according to the present disclosure may include, for example, a step of cleaning the substrate (so-called cleaning step) as necessary to prevent contamination of the process line after the etching process.
As a method of cleaning the substrate, for example, there is a method of cleaning the substrate by pouring pure water at room temperature (that is, 10° C. to 35° C.) onto the substrate.
Further, the method of manufacturing a patterned substrate according to the present disclosure may include, for example, a step of drying the substrate after the cleaning step (so-called drying step).
As a method for drying the substrate, for example, there is a method of drying the substrate by air blowing. Although the air blow pressure is not particularly limited, it may be set to about 0.1 kg/cm ² to 5 kg/cm ² , for example.

The method for manufacturing a patterned substrate of the present disclosure may include, for example, a step of peeling off the first resin layer and the second resin layer using a peeling solution after the etching treatment step (so-called peeling step). good.
After the etching step, the patterned first resin layer and second resin layer remain. If the first resin layer and the second resin layer are unnecessary, all the remaining first resin layer and second resin layer may be removed.
As a method for peeling using a stripping solution, for example, the first resin layer and the second resin layer are added to the stripping solution that is being stirred at preferably 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. A method of immersing the substrate having the liquid for 5 minutes to 30 minutes can be mentioned.
As the stripping solution, inorganic alkali components such as sodium hydroxide and potassium hydroxide, or organic alkali components such as tertiary amines and quaternary ammonium salts, are combined with water, dimethylsulfoxide, N-methylpyrrolidone, or and a stripping solution dissolved in a mixed solution of
Examples of the method of peeling using a peeling liquid include methods such as a spray method, a shower method, and a paddle method.

[Manufacturing method of touch panel]
The manufacturing method of the touch panel of the present disclosure includes the manufacturing method of the patterned substrate of the present disclosure. That is, the manufacturing method of the patterned substrate of the present disclosure can be applied to the manufacturing method of the touch panel of the present disclosure.

The method for manufacturing a patterned substrate in the method for manufacturing a touch panel of the present disclosure has the same meaning as the method for manufacturing a patterned substrate described in the section "Method for manufacturing a patterned substrate", and the preferred embodiments are also the same. , the description is omitted here.

[Touch panel]
The touch panel of the present disclosure has a patterned substrate manufactured by the patterned substrate manufacturing method of the present disclosure.
Since the touch panel of the present disclosure has the patterned substrate manufactured by the patterned substrate manufacturing method of the present disclosure, discoloration of the substrate is suppressed. Moreover, since the touch panel of the present disclosure includes the patterned substrate manufactured by the patterned substrate manufacturing method of the present disclosure, it has excellent resolution.

Detection methods in the touch panel of the present disclosure include a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, an optical method, and the like.
Among these, the capacitance method is preferable as the detection method.

As the touch panel type, the so-called in-cell type (for example, those described in FIGS. 5, 6, 7, and 8 of JP-A-2012-517051), the so-called on-cell type (for example, JP 2013-168125 The one described in FIG. 19 of the publication and those described in FIGS. 1 and 5 of Japanese Patent Application Laid-Open No. 2012-89102), OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example , those described in FIG. 2 of JP-A-2013-54727), other configurations (for example, those described in FIG. 6 of JP-A-2013-164871), various out-cell types (so-called GG, G1 G2 , GFF, GF2, GF1, G1F, etc.).
As the touch panel of the present disclosure, "Latest touch panel technology" [July 6, 2009, published by Techno Times Co., Ltd.], supervised by Yuji Mitani, "Technology and development of touch panel", CMC Publishing (2004, 12), The configurations disclosed in FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, etc. can be applied.

EXAMPLES Hereinafter, the present disclosure will be described more specifically with reference to Examples.
Materials, usage amounts, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present disclosure. Accordingly, the scope of the present disclosure is not limited to the specific examples shown below.

Tables 1 and 2 show the details of each resin used in this example.
Resins A1 to A7 shown in Table 1 are alkali-soluble resins used for preparing the first resin layer-forming coating solution. Further, resins B1 to B5 shown in Table 2 are alkali-soluble resins used for preparing the second resin layer-forming coating liquid.

The theoretical acid value (unit: mgKOH/g) and I/O value of each resin in Tables 1 and 2 were obtained by the method described above. Moreover, the weight average molecular weight (Mw) of each resin in Tables 1 and 2 was measured by the method described above.

In Table 1, "-" means that the corresponding component is not included.

In Table 1, the following abbreviations represent the following compounds, respectively.
"St": styrene "α-MeSt": α-methylstyrene "MAA": methacrylic acid "MMA": methyl methacrylate

In Table 2, the following abbreviations represent the following compounds, respectively.
"MAA": methacrylic acid

[Preparation of coating solution for forming first resin layer]
[Material 1-1 to Material 1-7]
Each component was mixed so as to have the composition shown in Table 1, and Material 1-1 to Material 1-7, which are coating liquids for forming a first resin layer, were prepared.

[Preparation of coating solution for forming second resin layer]
[Material 2-1 to Material 2-5]
Each component was mixed so as to have the composition shown in Table 2, and materials 2-1 to 2-5, which are coating liquids for forming a second resin layer, were prepared.

In Table 3, "-" means that the corresponding component is not included.

Details of the following components listed in Table 3 are as follows.
Polypropylene glycol diacrylate [trade name: Aronix (registered trademark) M-270, manufactured by Toagosei Co., Ltd.]: Bifunctional ethylenically unsaturated compound ethoxylated bisphenol A dimethacrylate [trade name: BPE-500, Shin-Nakamura Chemical Kogyo Co., Ltd.]: Bifunctional ethylenically unsaturated compound 2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole [trade name: B-CIM, Tsuchiya Chemical Industry Co., Ltd.]: Hexaarylbiimidazole-based photopolymerization initiator Megafac (registered trademark) F551A [trade name; Tsuchiya Chemical Industry Co., Ltd.]: Naphthalene sulfonate of Victoria Pure Blue

Compound A: an N-phenylglycine compound having the structure below

In Table 4, "-" means that the corresponding component is not included.

Details of the following components listed in Table 4 are as follows.
A monomer having a carboxy group [trade name: Aronix (registered trademark) TO-2349, manufactured by Toagosei Co., Ltd.]: a mixture of a pentafunctional ethylenically unsaturated compound and a hexafunctional ethylenically unsaturated compound Megafac (registered Trademark) F444" [trade name; manufactured by DIC Corporation]: fluorine-based surfactant

[Production of transfer film]
[Examples 1 to 16, Comparative Example 1, and Comparative Example 2]
On a temporary support [trade name: Lumirror (registered trademark) 16QS62, polyethylene terephthalate film, thickness: 16 μm, manufactured by Toray Industries, Inc.], a coating solution for forming the first resin layer was applied using a slit nozzle. A certain material (that is, one of materials 1-1 to 1-7) was applied to form a coating film. The coating amount of each material 1-1 to material 1-7 was such that the thickness of the layer after drying would be the thickness shown in Table 5. Next, the formed coating film was dried for 2 minutes in a convection oven set at 100° C. to form a first resin layer.
Next, on the first resin layer, using a slit-shaped nozzle, a material (that is, any of materials 2-1 to 2-5), which is the coating liquid for forming the second resin layer, is applied. , to form a coating film. The coating amount of each material 2-1 to material 2-5 was such that the thickness of the layer after drying would be the thickness shown in Table 5. Next, the formed coating film was dried for 2 minutes in a convection oven set at 100° C. to form a second resin layer.
Next, a protective film [trade name: Torayfan (registered trademark) BO, model number: 12D, type KW37 polypropylene film, thickness: 12 μm, manufactured by Toray Industries, Inc.] was crimped onto the second resin layer. .
As described above, the transfer films of Examples 1 to 16 and Comparative Examples 1 and 2 were produced.

[Comparative Example 3]
On a temporary support [trade name: Lumirror (registered trademark) 16QS62, polyethylene terephthalate film, thickness: 16 μm, manufactured by Toray Industries, Inc.], a coating solution for forming the first resin layer was applied using a slit nozzle. A certain material 1-1 was applied to form a coating film. The amount of material 1-1 applied was such that the thickness of the layer after drying would be the thickness shown in Table 5. Next, the formed coating film was dried for 2 minutes in a convection oven set at 100° C. to form a first resin layer.
Next, a protective film [trade name: Torayphan (registered trademark) BO, model number: 12D, type KW37 polypropylene film, thickness: 12 μm, manufactured by Toray Industries, Inc.] was crimped onto the first resin layer.
A transfer film of Comparative Example 3 was produced as described above.

[Preparation of substrate for circuit pattern formation]
A plurality of particles with a diameter of 3 μm [trade name: SSX103, manufactured by Sekisui Plastics Co., Ltd.] was applied to both sides of a cycloolefin polymer film with a thickness of 100 μm [trade name: Zeonor Film (registered trademark) ZF16, manufactured by Nippon Zeon Co., Ltd.]. product] and a plurality of particles with a diameter of 2 μm [trade name: SSX102, manufactured by Sekisui Plastics Co., Ltd.], a binder resin (trade name: Unidic 17-824-9, manufactured by DIC) per 100 parts by mass , 0.05 parts by mass and 0.02 parts by mass, respectively, were applied using a bar coater to form a coating film. Next, the formed coating film was dried for 1 minute in an oven set at 80 ° C., and then irradiated with ultraviolet rays (light source: ultra-high pressure mercury lamp) at an integrated light amount of 500 mJ / cm ² to obtain an anti-blocking film of 70 nm on both surfaces. A film having layers was formed (hereinafter referred to as "COP substrate").
Next, a refractive index adjusting agent [trade name: OPSTAR (registered trademark) K7415, manufactured by JSR Corporation] was applied to one side of the COP substrate using a bar coater to form a coating film. Next, the formed coating film was dried in an oven set at 80° C. for 1 minute, and then irradiated with ultraviolet rays (light source: high-pressure mercury lamp) at an integrated light amount of 300 mJ/cm ² to obtain a thickness of 100 nm and a refractive index of 1. A refractive index adjusting layer of 0.65 was formed.
Next, an indium tin oxide (ITO) layer having a thickness of 23 nm was laminated as a second conductive layer on the surface of the refractive index adjusting layer of the COP substrate using a winding-type sputtering device. Next, on the ITO layer, a copper film was formed to a thickness of 200 nm as the first conductive layer by vacuum deposition, and a substrate for forming a circuit pattern having a copper layer (hereinafter simply referred to as "substrate") was obtained. Obtained.

[evaluation]
Using the transfer films of Examples 1 to 16 and Comparative Examples 1 to 3, the following evaluations were performed. Table 5 shows the results.

1. Discoloration of Substrate A laminate was obtained by laminating a transfer film from which the protective film was peeled off onto the copper layer of the substrate prepared above (hereinafter referred to as “laminating”).
The lamination was performed under the conditions of a linear pressure of 0.8 MPa, a linear velocity of 4.0 m/min, and a roll temperature of 100°C. In the lamination process, the surface exposed by peeling the protective film from the transfer film was brought into contact with the surface of the copper layer of the substrate.
The resulting laminate is patterned from the temporary support using a pattern forming device at line/space = 1:1, with a line width of 4 μm to 20 μm in increments of 1 μm, and a line width of 20 μm to 50 μm in increments of 5 μm. Then, each line width was exposed. The pattern forming apparatus is an apparatus having a laser light source of 405 nm as light irradiation means. The exposure dose was 55 mJ/cm ² . In the laminates produced using the transfer films of Examples 1 to 16, Comparative Example 1, and Comparative Example 2, the exposed portion of the first resin layer and the second resin layer were exposed by the above exposure. The exposed part of was cured. In addition, in the laminate formed using the transfer film of Comparative Example 3, the exposed portion of the first resin layer was cured by the above exposure.
After peeling the temporary support from the exposed laminate, development processing was performed. The development treatment was carried out by spraying a 1 mass % sodium carbonate aqueous solution at a liquid temperature of 30° C. for 37 seconds at a spray pressure of 0.10 MPa on the entire surface of the first resin layer exposed by peeling the temporary support. In the development process, the non-exposed area [that is, the uncured area (when using each transfer film of Examples 1 to 16, Comparative Example 1, and Comparative Example 2: the uncured area of the first resin layer and the The uncured region of the second resin layer, when the transfer film of Comparative Example 3 was used: the uncured region of the first resin layer)] was dissolved and removed.
After the development treatment, the substrate on which the pattern was formed was sprayed with pure water to remove residues on the substrate.
Air was blown to the substrate from which the residue was removed, and the substrate was dried to obtain a patterned substrate.

Reflectance (X) at a wavelength of 550 nm of the surface on which the copper layer of the substrate before lamination is formed, and the surface on which the patterned substrate obtained above is not formed (i.e., the surface on which the copper layer is exposed) ) and the reflectance (Y) at a wavelength of 550 nm are measured using a spectrophotometer [product name: UV-visible and near-infrared spectrophotometer V-570, manufactured by JASCO Corporation], and the reflectance of both A difference [reflectance (X) - reflectance (Y), unit: %] was obtained.
The difference in reflectance is preferably as small as possible. When the difference in reflectance was 4.0% or less, it was judged that the transfer film was difficult to discolor the substrate.

2. Resolution A patterned substrate was obtained in the same manner as in the evaluation of “1. Discoloration of substrate” above.
The surface of the patterned substrate obtained above was observed with an optical microscope (magnification: 50 times) to confirm the minimum line width in which there were no abnormalities such as clumps or twists in the pattern lines. This minimum line width was defined as the resolution, and evaluation was made according to the following evaluation criteria.
If the evaluation result was "A", "B" or "C", it was judged to be a transfer film capable of forming a pattern with excellent resolution.
In the following evaluation criteria, "A" indicates the best resolution, and "E" indicates the worst resolution.

(Evaluation criteria)
A: The resolution is 4 μm or less.
B: The resolution exceeds 4 μm and is 8 μm or less.
C: The resolution exceeds 8 μm and is 15 μm or less.
D: The resolution exceeds 15 μm and is 25 μm or less.
E: Resolution exceeds 25 μm.

3. Lamination Property A laminate was obtained by laminating a transfer film from which the protective film was peeled off onto the copper layer of the substrate prepared above (that is, laminating). The lamination was performed under the conditions of a linear pressure of 0.8 MPa, a linear velocity of 4.0 m/min, and a roll temperature of 100°C. In the lamination process, the surface exposed by peeling the protective film from the transfer film was brought into contact with the surface of the copper layer of the substrate.
After peeling the temporary support from the laminate obtained above, the laminate is observed from the first resin layer side using an optical microscope (magnification: 50 times), and the copper layer and the second resin layer (between the copper layer and the first resin layer in Comparative Example 3) was measured. Specifically, the number of bubbles in an arbitrarily selected area (size: 9 cm x 9 cm) was measured 100 times at different locations. After averaging the values obtained by 100 measurements, the values were rounded off to the second decimal place. Then, the obtained value was defined as "the number of air bubbles", and the lamination property was evaluated according to the following evaluation criteria.
In addition, "bubbles" may be generated by entrainment of air during lamination.
If the evaluation result was "A", "B" or "C", it was determined that the transfer film had excellent lamination properties.
In the following evaluation criteria, "A" indicates the best lamination property, and "E" indicates the worst lamination property.

(Evaluation criteria)
A: The number of bubbles is 0.1 or less.
B: The number of bubbles exceeds 0.1 and is 0.2 or less.
C: The number of bubbles exceeds 0.2 and is 0.3 or less.
D: The number of bubbles exceeds 0.3 and is 1.3 or less.
E: The number of bubbles exceeds 1.3.

As shown in Table 5, it was confirmed that the transfer films of Examples 1 to 16 were less likely to discolor the substrate. It was also confirmed that the transfer films of Examples 1 to 16 could form patterns with excellent resolution. Further, it was confirmed that the transfer films of Examples 1 to 16 are excellent in lamination properties.

On the other hand, a first resin layer containing a temporary support, an alkali-soluble resin containing structural units derived from a vinylbenzene derivative, a polymerizable compound, and a polymerization initiator, and an alkali-soluble resin having an acid value of 130 mgKOH/g or more and a second resin layer containing in this order, the content of structural units derived from a vinylbenzene derivative in the alkali-soluble resin contained in the first resin layer is less than 30% by mass with respect to all structural units It was confirmed that the resolution of the pattern formed using the transfer film of Comparative Example 1 is inferior to the resolution of the patterns formed using the transfer films of Examples 1 to 16. .
In addition, the transfer film of Comparative Example 2, in which the acid value of the alkali-soluble resin contained in the second resin layer is less than 130 mgKOH/g, discolored the substrate as compared with the transfer films of Examples 1 to 16. confirmed to be easy.
It was also confirmed that the transfer film of Comparative Example 3, which does not have the second resin layer, causes the substrate to discolor more easily than the transfer films of Examples 1 to 16.

[Production of circuit pattern board]
Using the transfer films of Examples 1 to 16, circuit pattern boards were produced by the following method.
A patterned substrate was obtained in the same manner as in the evaluation of “1. Discoloration of substrate” above.
On the resulting patterned substrate, the copper layer was etched using a copper etchant [trade name: Cu-02, manufactured by Kanto Kagaku Co., Ltd.], and an ITO etchant [trade name: ITO-02, Kanto Kagaku ( Co., Ltd.] was used to etch the ITO layer. The first resin layer and the second resin layer remaining after these etchings are peeled off using a peeling solution [trade name: KP-301, manufactured by Kanto Kagaku Co., Ltd.], thereby separating the copper layer and the ITO layer. were patterned together (so-called circuit pattern substrate).
When the obtained circuit pattern substrate was observed with a microscope (magnification: 50 times), it was confirmed that there were no defects such as peeling and chipping, and that the patterning could be performed satisfactorily.

The disclosure of Japanese Patent Application No. 2019-061577 filed on March 27, 2019 is incorporated herein by reference in its entirety.
All publications, patent applications and technical standards mentioned herein are to be used as if each individual publication, patent application or technical standard were specifically and individually indicated to be incorporated by reference. To the extent they are incorporated herein by reference.

Claims (11)

a temporary support;
a first resin layer containing an alkali-soluble resin (A) containing structural units derived from a vinylbenzene derivative, a polymerizable compound, and a polymerization initiator;
a second resin layer containing an alkali-soluble resin (B) having an acid value of 130 mgKOH/g or more;
in that order, and
The content of structural units derived from a vinylbenzene derivative in the alkali-soluble resin (A) is 30% by mass or more with respect to all structural units of the alkali-soluble resin (A),
The transfer film , wherein the second resin layer has a thickness of 40 nm to 120 nm . The transfer film according to claim 1, wherein the alkali-soluble resin (A) has an acid value of 150 mgKOH/g or more. 3. The transfer film according to claim 1, wherein the alkali-soluble resin (B) has an acid value of 150 mgKOH/g or more. According to claim 1 or claim 2, wherein the alkali-soluble resin (B) has an acid value of 150 mgKOH/g or more and a weight average molecular weight of 36,000 to 100,000. Transfer film as described. The acid value of the alkali-soluble resin (B) is 150 mgKOH/g or more, and the content of the alkali-soluble resin (B) in the second resin layer is relative to the total mass of the second resin layer. , 60% by mass to 96% by mass, the transfer film according to claim 1 or 2. The transfer film according to any one of claims 1 to 5 , wherein the alkali-soluble resin (B) has an acid value of 250 mgKOH/g or less. Claims 1 to 6 , wherein the content of structural units derived from a vinylbenzene derivative in said alkali-soluble resin (A) is 70% by mass or less with respect to all structural units of said alkali-soluble resin (A). The transfer film according to any one of . The transfer film according to any one of claims 1 to 7 , wherein the first resin layer has a thickness of 2 µm to 4 µm. a step of bonding a substrate and the transfer film according to any one of claims 1 to 8 by bringing the substrate and the second resin layer of the transfer film into contact;
a step of pattern-exposing the first resin layer of the transfer film;
a step of developing the first resin layer that has undergone the pattern exposure to form a pattern;
A method of manufacturing a patterned substrate, comprising in that order: 10. The method of manufacturing a patterned substrate according to claim 9 , further comprising the step of etching the substrate in the region where the pattern is not arranged after the step of forming the pattern. 11. The method of manufacturing a patterned substrate according to claim 9 , wherein at least part of the surface of said substrate that contacts said second resin layer is made of copper.

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