JP2005292734A - Photosensitive transfer sheet and laminate, image pattern forming method, and wiring pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive transfer sheet and a photosensitive laminate capable of easily forming desired patterns of different thicknesses within an image. <P>SOLUTION: The photosensitive transfer sheet is obtained by sequentially stacking on a support a first photosensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator and a second photosensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator and having relatively higher light sensitivity than the first photosensitive layer, wherein a polymer having a sensitizing functional group is used as a binder in at least one of the first photosensitive layer and the second photosensitive layer. The sensitizing functional group corresponds to an atomic group formed by removing one monovalent atom or group from a sensitizing dye having a molecular weight of ≤1,000. In the light-sensitive laminate, the second photosensitive layer and the first photosensitive layer are stacked in this order on a substrate. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a photosensitive transfer sheet, a photosensitive laminate, an image pattern forming method, and a wiring pattern forming method. The present invention relates to a photosensitive transfer sheet, a laminate, and a method for forming a wiring pattern of a printed wiring board using the photosensitive transfer sheet or laminate particularly useful for producing a printed wiring board.

  Photosensitive transfer sheet with support and photosensitive layer is used for various image formation such as printed wiring boards, color filters, pillars, ribs, spacers, display members such as partition walls, printing plates, holograms, micromachines, and proofs. It is widely used as an image-like pattern forming material for manufacturing materials.

  In the printed wiring board manufacturing field, a wiring pattern is a photosensitive transfer sheet (also referred to as a dry film resist) comprising a transparent support (for example, polyethylene terephthalate) and a photosensitive layer formed on the support. It has been formed by photolithography technology. For example, in the case of manufacturing a printed wiring board having a through hole, a through hole is formed in a printed wiring board forming substrate (for example, a copper clad laminate), and a metal plating layer is formed on the inner side wall portion of the through hole. The photosensitive layer of the photosensitive transfer sheet is superposed and adhered to the surface, and the photosensitive layer is cured by irradiating each of the wiring pattern forming region and the region including the through-hole opening in a predetermined pattern. Next, the support of the photosensitive transfer sheet is peeled off, and a developer is used in the uncured area other than the cured area on the wiring pattern formation area and the cured area (called a tent film) on the through-hole opening area. Then, after dissolution and removal, an exposed metal layer portion is etched, and then a hardened region is removed to generate a wiring pattern on the substrate surface.

  A method of protecting the metal plating layer of the through hole using the tent film is generally called a tenting method. A multilayer printed wiring board may be provided with a hole for interlayer connection called a via hole. In this case as well, when forming a wiring pattern, it is necessary to protect the via hole portion with a tent film.

  In recent years, the demand for higher density in printed wiring boards has increased, and a photoresist film capable of higher resolution has been demanded. In order to increase the resolution of the photoresist film, it is effective to reduce the thickness of the photosensitive layer. However, as described above, the cured layer obtained by curing the photosensitive layer also serves to protect through holes or via holes formed in the printed wiring board. If the thickness of the photosensitive layer is simply reduced, the photosensitive resin composition In the process of dissolving and removing the uncured region of the object and the process of etching the exposed metal layer portion, there arises a problem that the tent film is broken.

  Hitherto, photosensitive transfer sheets that can form a high-resolution pattern and that can form a tent film that is not easily torn have been actively developed, and the results have been disclosed as follows.

  Patent Document 1 describes a photosensitive transfer sheet having a photosensitive layer composed of a binder component having a carboxyl group, a monomer component containing a specific vinylurethane compound and a specific acrylate compound, and a photopolymerization initiator.

  In Patent Document 2, a first photosensitive layer that is alkali-soluble and has low fluidity by heating and is sensitive to active energy rays is provided on a support, and further, it is alkali-soluble and has fluidity by heating. Largely, a photosensitive transfer sheet having a two-layered photosensitive layer provided with a second photosensitive layer sensitive to active energy rays is described. This patent document describes that the metal layer of the through hole can be protected by embedding the second photosensitive layer of the photosensitive transfer sheet in the through hole.

  Patent Document 3 discloses a photosensitive resin laminate having a first photosensitive layer and a second photosensitive layer on a support, the two layers having different vinyl copolymers, and both An example including a specific monofunctional monomer in the layer is described, and as an effect, it is described that adhesion and resolution are improved.

  Patent Document 4 describes a photoresist having a non-adhesive photosensitive layer and an adhesive photosensitive layer on a support, and a method for forming a printed wiring board using the photoresist. It is described that the performance and resolution are improved.

  In Patent Document 5, a printing relief having at least two photopolymerizable layers (having a thickness of 25 μm to 2.5 mm) having different photopolymerization speeds on a base material and having a high polymerization speed on the side close to the base material. A photosensitive plate for production is disclosed, and an example of forming a relief image in which the base of the printing surface is wider than the top is described.

Japanese Patent Laid-Open No. 10-142789 JP-A-8-54732 JP-A-10-111573 Japanese Patent Laid-Open No. 3-17650 Japanese Patent Publication No.37-1306

The subject of this invention is providing the photosensitive transfer sheet and photosensitive laminated body which can form easily the desired pattern from which thickness differs in an image.
Another object of the present invention is to provide a method capable of industrially advantageously forming desired patterns having different thicknesses in an image using a photosensitive transfer sheet or a photosensitive laminate.
An object of the present invention is to provide a photosensitive transfer sheet that is particularly effective for the production of printed wiring boards, can be increased in resolution by thinning, and can form a tent film that is not easily torn.
Another object of the present invention is to provide a method capable of industrially advantageously producing a printed wiring board having a hole portion such as a through hole or a via hole using a photosensitive transfer sheet.

  The present invention firstly includes a first photosensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator on a support, and a photosensitivity of the first photosensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator. A second photosensitive layer having a relatively high photosensitivity is laminated in this order, and at least one binder of the first photosensitive layer and the second photosensitive layer is a polymer having a sensitizing functional group, The group corresponds to an atomic group obtained by removing one monovalent atom or one group from a sensitizing dye having a molecular weight of 1000 or less.

The polymer having a sensitizing functional group preferably has an absorption maximum wavelength in the range of 300 to 500 nm, and preferably has an absorption maximum wavelength in the range of 380 to 450 nm.
The sensitizing dye having a molecular weight of 1000 or less is preferably selected from the group consisting of a cyanine dye, a merocyanine dye, a xanthene dye, a phenothiazine dye, an acridine dye, an anthraquinone dye, an acridone dye, a coumarin dye, an aniline dye, and a squarylium dye.
It is also preferable that the binder of the second photosensitive layer is a polymer having a sensitizing functional group.
The polymer having a sensitizing functional group may be a copolymer having another repeating unit (for example, a repeating unit having a carboxyl group or a repeating unit having an aromatic group) in addition to the repeating unit having a sensitizing functional group. Good.

A preferred embodiment of the first invention is as follows.
(1) A barrier layer is disposed between the first photosensitive layer and the second photosensitive layer.
(2) The barrier layer contains a resin having an affinity for water or a lower alcohol having 1 to 4 carbon atoms as a main component.
(3) The barrier layer contains, as a main component, a resin that is soluble in water or a lower alcohol having 1 to 4 carbon atoms.
(4) The barrier layer has a thickness in the range of 0.1 to 5 μm.
(5) When the photosensitivity of the first photosensitive layer is 1, the photosensitivity of the second photosensitive layer is in the range of 2 to 200.

(6) The ratio expressed by A / B between the amount of light energy A necessary for curing the second photosensitive layer and the amount of light energy B necessary for curing the first photosensitive layer is 0.005. It is in the range of 0.5.
(7) The ratio represented by C / A between the amount of light energy A required to cure the second photosensitive layer and the amount of light energy C required until the first photosensitive layer begins to cure is 1 to 10 It is in the range.
(8) Each of the first photosensitive layer and the second photosensitive layer contains a polymer having a sensitizing functional group.
(9) The number of sensitizing functional groups in the polymer having sensitizing functional groups contained in the second photosensitive layer is the number of sensitizing functional groups in the polymer having sensitizing functional groups contained in the first photosensitive layer More than the number of
(10) The amount of the photopolymerization initiator contained in the second photosensitive layer is larger than the amount of the photopolymerization initiator contained in the first photosensitive layer.

(11) The amount of the polymerizable compound contained in the second photosensitive layer is larger than the amount of the polymerizable compound contained in the first photosensitive layer.
(12) The first photosensitive layer has a thickness in the range of 1 to 100 μm, and the thickness is larger than the thickness of the second photosensitive layer.
(13) The second photosensitive layer has a thickness in the range of 0.1 to 15 μm.
(14) The support is made of synthetic resin and is transparent.
(15) The support is a long support.
(16) A protective film is disposed on the second photosensitive layer.
(17) It is a long body and is wound in a roll shape.
(18) For printed wiring board manufacture.

  Secondly, the present invention includes a second photosensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator on a substrate, and a binder, a polymerizable compound and a photopolymerization initiator. The first photosensitive layer exhibiting relatively low photosensitivity is laminated in this order, and at least one binder of the first photosensitive layer and the second photosensitive layer is a polymer having a sensitizing functional group, and the sensitizer In the photosensitive laminate, the functional group corresponds to an atomic group obtained by removing one monovalent atom or group from a sensitizing dye having a molecular weight of 1000 or less.

A preferred embodiment of the second invention is as follows.
(1) A barrier layer is disposed between the first photosensitive layer and the second photosensitive layer.
(2) The barrier layer contains a resin having an affinity for water or a lower alcohol having 1 to 4 carbon atoms as a main component.
(3) The barrier layer contains, as a main component, a resin that is soluble in water or a lower alcohol having 1 to 4 carbon atoms.
(4) The barrier layer has a thickness in the range of 0.1 to 5 μm.
(5) When the photosensitivity of the first photosensitive layer is 1, the photosensitivity of the second photosensitive layer is in the range of 2 to 200.

(6) The ratio expressed by A / B between the amount of light energy A necessary for curing the second photosensitive layer and the amount of light energy B necessary for curing the first photosensitive layer is 0.005. It is in the range of 0.5.
(7) The ratio represented by C / A between the amount of light energy A required to cure the second photosensitive layer and the amount of light energy C required until the first photosensitive layer begins to cure is 1 to 10 It is in the range.
(8) Each of the first photosensitive layer and the second photosensitive layer contains a polymer having a sensitizing functional group.
(9) The number of sensitizing functional groups in the polymer having sensitizing functional groups contained in the second photosensitive layer is the number of sensitizing functional groups in the polymer having sensitizing functional groups contained in the first photosensitive layer More than the number of
(10) The amount of the photopolymerization initiator contained in the second photosensitive layer is larger than the amount of the photopolymerization initiator contained in the first photosensitive layer.

(11) The amount of the polymerizable compound contained in the second photosensitive layer is larger than the amount of the polymerizable compound contained in the first photosensitive layer.
(12) The first photosensitive layer has a thickness in the range of 1 to 100 μm, and the thickness is larger than the thickness of the second photosensitive layer.
(13) The second photosensitive layer has a thickness in the range of 0.1 to 15 μm.
(14) The substrate is a printed wiring board forming substrate.
(15) A support (in particular, a transparent resin film is preferred) is laminated on the first photosensitive layer.
(16) For printed wiring board manufacture.

Thirdly, the present invention includes the following steps, on which a region where a cured resin layer formed by curing both the first photosensitive layer and the second photosensitive layer is present and a cured resin layer are not present. In this method, an image pattern including regions is formed.
(1) A step of laminating the photosensitive transfer sheet of the first invention on a substrate in a positional relationship such that the second photosensitive layer is on the substrate side;
(2) A step of performing light irradiation of a predetermined image pattern from the side of the first photosensitive layer of the laminate and curing both the first photosensitive layer and the second photosensitive layer in the region irradiated with the light;
(3) removing the support from the laminate; and
(4) The process of developing a laminated body and removing the unhardened part in a laminated body.

Fourthly, the present invention includes the following steps, a region where a resin layer formed by curing both the first photosensitive layer and the second photosensitive layer is present on the substrate, and the second photosensitive layer is cured. There is a method of forming an image pattern composed of a region where a resin layer is formed and a region where a cured resin layer is not present.
(1) A step of laminating the photosensitive transfer sheet of the first invention on a substrate in a positional relationship such that the second photosensitive layer is on the substrate side;
(2) Light irradiation is performed from the first photosensitive layer side of the laminate with an image pattern that defines a region to be irradiated with at least two different levels of irradiation energy amount, and the light irradiation energy amount is relatively large Curing both the first photosensitive layer and the second photosensitive layer in the region irradiated with light, and curing the second photosensitive layer in the region irradiated with light having a relatively small amount of light irradiation energy;
(3) removing the support from the laminate; and
(4) The process of developing a laminated body and removing the unhardened part in a laminated body.

Preferred embodiments of the third and fourth inventions of the present invention are as follows.
(1) The step of removing the support from the laminate of (3) is performed between step (1) and step (2) instead of between step (2) and step (4). .
(2) The light irradiation in the step (2) is performed by laser light irradiation.

Fifthly, the present invention includes a region covered with a cured resin layer formed by curing both the first photosensitive layer and the second photosensitive layer on a printed wiring board forming substrate including the following steps: And a method of forming a wiring pattern composed of a region where the substrate surface is exposed.
(1) A step of laminating the photosensitive transfer sheet of the first invention on a substrate in a positional relationship such that the second photosensitive layer is on the substrate side;
(2) A step of irradiating a predetermined wiring pattern from the first photosensitive layer side of the laminate and curing both the first photosensitive layer and the second photosensitive layer in the irradiated region;
(3) removing the support from the laminate; and
(4) The process of developing a laminated body and removing the unhardened part in a laminated body.

Sixth, the present invention includes a printed wiring board forming substrate having a hole portion, which includes the following steps, and is coated with a cured resin layer formed by curing both the first photosensitive layer and the second photosensitive layer. In this method, a wiring pattern is formed which includes a hole portion, a region covered with a cured resin layer formed by curing the second photosensitive layer, and a region where the substrate surface is exposed.
(1) A step of laminating the photosensitive transfer sheet of the first invention on a substrate in a positional relationship such that the second photosensitive layer is on the substrate side;
(2) From the side of the first photosensitive layer of the laminate, the hole portion is irradiated with light having a relatively large amount of light irradiation energy to cure both the first photosensitive layer and the second photosensitive layer, and wiring A step of irradiating the formation region with light of an image pattern that cures the second photosensitive layer by applying light irradiation with a relatively small amount of light irradiation energy;
(3) removing the support from the laminate; and
(4) The process of developing a laminated body and removing the unhardened part in a laminated body.

Preferred embodiments of the fifth and sixth inventions of the present invention are as follows.
(1) The step of removing the support from the laminate of (3) is performed between step (1) and step (2) instead of between step (2) and step (4). .
(2) The light irradiation in the step (2) is performed by laser light irradiation.

In the photosensitive transfer sheet and the photosensitive laminate of the present invention, a cured layer having a different thickness can be formed in an arbitrary region by changing the light irradiation amount (in other words, the exposure amount). Accordingly, when an image is formed using the photosensitive transfer sheet or photosensitive laminate of the present invention, a cured layer having an arbitrary thickness can be formed in each desired region (forming a three-dimensional image). The amount of transmitted light can be changed for each desired region (the density of the image can be changed), a cured layer showing a desired film strength can be formed for each desired region, etc. There are a number of advantages. For example, it is possible to form a pattern in which the thickness of the cured layer can be increased in a region where the film strength of the cured layer is desired to be increased, and in the region where the resolution is desired to be increased, the thickness of the cured layer is decreased.
The above effect can be obtained by dividing the first photosensitive layer and the second photosensitive layer. However, when the sensitizing dye added to one layer (one of the first photosensitive layer and the second photosensitive layer) diffuses to another layer (the other), the effect of separating the first photosensitive layer from the second photosensitive layer Cannot be obtained sufficiently. According to the study of the present inventors, a polymer having a sensitizing functional group hardly diffuses from an added layer to another layer. Therefore, by using a polymer having a sensitizing functional group, the effect obtained by dividing the first photosensitive layer and the second photosensitive layer can be sufficiently obtained.

  Therefore, when the photosensitive transfer sheet and the photosensitive laminate of the present invention are used for manufacturing a printed wiring board, particularly a printed wiring board having a hole portion such as a through hole or a via hole, In other words, a high-resolution hardened layer having a relatively small thickness can be formed, and a relatively thick and high-strength hardened layer can be formed in the through hole or via hole. Therefore, by using the present invention, a high-resolution printed wiring board can be manufactured by an industrially advantageous tenting method.

[Polymer having sensitized functional group]
In the present invention, a polymer having a sensitizing functional group is used as a binder for the first photosensitive layer or the second photosensitive layer. A polymer having a sensitizing functional group comprises a sensitizing functional group, a main chain, and optionally a linking group (a group that connects the sensitizing functional group and the main chain).
Hereinafter, the sensitizing functional group, the main chain, and the linking group will be described in this order.

The sensitizing functional group corresponds to an atomic group obtained by removing one monovalent atom or group from 1000 or less sensitizing dyes.
The molecular weight of the sensitizing dye is preferably 80 to 900, more preferably 90 to 800, and most preferably 100 to 700.
Sensitizing dyes having a molecular weight of 1000 or less include methine dyes (eg, cyanine dyes, merocyanine dyes), tricyclic condensed ring dyes (eg, xanthene dyes, phenothiazine dyes, acridine dyes, anthraquinone dyes, acridone dyes), coumarin dyes, An aniline dye or squarylium dye is preferred.

Methine dyes can be classified into cyanine dyes, merocyanine dyes, arylidene dyes, styryl dyes and oxonol dyes.
Cyanine dye: Bs = Lo-Bo
Merocyanine dye: Ac = Le = Bs
Arylidene dye: Ac = Lo-Ar
Styryl dye: Bo-Le-Ar
Oxonol dye: Ac = Lo-Ae
In the above formulas, Bs is a basic nucleus; Bo is an onium body of a basic nucleus; Ac is an acidic nucleus; Ae is an enol body of an acidic nucleus; Ar is an aromatic nucleus; Lo Is a methine chain consisting of an odd number of methines; and Le is a methine chain consisting of an even number of methines (including zero).
Cyanine dyes and merocyanine dyes are preferred.

When the sensitizing functional group corresponds to a cyanine dye, for example, an atom bonded to the basic nucleus (or its onium form) of the cyanine dye or an atomic group obtained by removing one monovalent group directly or a linking group A polymer bonded to the main chain via the base chain can be used.
Examples of sensitizing functional groups include the following cyanine dyes:

  The following sensitized functional group (D1) corresponding to the atomic group excluding the 5-position hydrogen atom of the onium body of the basic nucleus can be exemplified.

  Further, the following sensitizing functional group (D2) corresponding to an atomic group obtained by removing the ethyl group bonded to the 3-position nitrogen atom of the basic nucleus from the cyanine dye can also be exemplified.

When the sensitizing functional group corresponds to a merocyanine dye, for example, an atom bonded to the basic nucleus or acidic nucleus of the merocyanine dye or an atomic group excluding one monovalent group is directly or via a linking group A polymer bonded to the main chain can be used.
Examples of sensitizing functional groups include the following merocyanine dyes:

  The following sensitized functional group (D3) corresponding to the atomic group excluding the ethyl group bonded to the 3-position nitrogen atom of the basic nucleus can be exemplified.

  The tricyclic fused ring dye is a dye having a tricyclic fused ring such as a xanthene ring, a phenothiazine ring, an acridine ring, an anthraquinone ring or an acridone ring.

When the sensitizing functional group corresponds to a xanthene dye, for example, an atom bonded to the xanthene ring or a substituent thereof or an atomic group obtained by removing one monovalent group is directly or via a linking group to the main chain. A bound polymer can be used.
Examples of sensitizing functional groups include the following xanthene dyes (fluorescein dyes),

  The following sensitized functional group (D4) corresponding to the atomic group excluding the 4-position hydrogen atom of the phenyl group substituted at the 9-position of the xanthene ring can be exemplified.

When the sensitizing functional group corresponds to a phenothiazine dye, for example, an atomic group bonded to the phenothiazine ring or its substituent or an atomic group excluding one monovalent group is directly or via a linking group to the main chain. A bound polymer can be used.
Examples of sensitizing functional groups include the following phenothiazine dye (methylene blue),

  The following sensitizing functional group (D5) corresponding to the atomic group excluding one methyl group contained in the dimethylamino group substituted at the 9-position of the phenothiazine ring can be exemplified.

When the sensitizing functional group corresponds to an acridine dye, for example, an atom bonded to an acridine ring or a substituent thereof or an atomic group obtained by removing one monovalent group is bonded to the main chain directly or via a linking group. A bound polymer can be used.
Examples of sensitizing functional groups include the following acridine dyes:

  The following sensitizing functional group (D6) corresponding to an atomic group obtained by removing one hydrogen atom contained in the amino group substituted at the 9-position of the acridine ring can be exemplified.

  From the following acridine dyes,

  The following sensitizing functional group (D7) corresponding to an atomic group obtained by removing one hydrogen atom contained in an amino group substituted at the 3-position of the acridine ring can also be exemplified.

  Furthermore, from the following acridine dyes,

  The following sensitizing functional group (D8) corresponding to the atomic group excluding the methyl group contained in the p-methoxyphenyl group substituted at the 9-position of the acridine ring can also be exemplified.

When the sensitizing functional group corresponds to an anthraquinone dye, for example, an atom group bonded to an anthraquinone ring or a substituent thereof or an atomic group obtained by removing one monovalent group is directly or via a linking group to the main chain. A bound polymer can be used.
Examples of sensitizing functional groups include the following anthraquinone dyes:

  The following sensitizing functional group (D9) corresponding to the atomic group excluding the methyl group contained in the methoxy group substituted at the 1-position of the anthraquinone ring can be exemplified.

  In addition, from the following anthraquinone dyes,

  The following sensitizing functional group (D10) corresponding to the atomic group excluding the methyl group contained in the acetamide group substituted at the 1-position of the anthraquinone ring can also be exemplified.

When the sensitizing functional group corresponds to an acridone dye, for example, an atom group bonded to an acridone ring or a substituent thereof or an atomic group obtained by removing one monovalent group is directly or via a linking group to the main chain. A bound polymer can be used.
Examples of sensitizing functional groups include the following acridone dyes (X is a hydrogen atom, a halogen atom or cyano),

  The following sensitized functional group (D11) corresponding to the atomic group excluding the hydrogen atom bonded to the 5-position nitrogen atom of the acridone ring can be exemplified.

It is particularly preferred that the sensitizing functional group corresponds to an acridone dye, and details will be described later.
The coumarin dye is a dye having a coumarin ring or a condensed ring thereof.
When the sensitizing functional group corresponds to a coumarin dye, for example, a coumarin ring, a condensed ring thereof, or an atom group obtained by removing one atom or monovalent group bonded to the substituent is directly or a linking group A polymer bonded to the main chain via a can be used.
Examples of sensitizing functional groups include the following coumarin dyes:

  The following sensitized functional group (D12) corresponding to the atomic group excluding the hydrogen atom bonded to the 4-position carbon atom of the coumarin ring can be exemplified.

  From the following coumarin dyes,

  The following sensitizing functional group (D13) corresponding to the atomic group excluding the hydrogen atom bonded to the 4-position carbon atom of the coumarin ring can also be exemplified.

It is also particularly preferred that the sensitizing functional group corresponds to a coumarin dye, and details will be described later.
An aniline dye is a dye having an aniline ring or a condensed ring thereof.
When the sensitizing functional group corresponds to an aniline dye, for example, an aniline ring, a condensed ring thereof, or an atomic group obtained by removing one atom or a monovalent group bonded to the substituent is directly or a linking group. A polymer bonded to the main chain via a can be used.
Examples of sensitizing functional groups include the following aniline dyes:

  The following sensitized functional group (D14) corresponding to the atomic group excluding the hydrogen atom bonded to the 4-position carbon atom of the aniline ring can be exemplified.

A squarylium dye is a dye having a squarylium ring.
When the sensitizing functional group corresponds to a squarylium dye, for example, an atomic group bonded to a squarylium ring or a substituent thereof or an atomic group obtained by removing one monovalent group is directly or via a linking group to the main chain. A bound polymer can be used.
Examples of sensitizing functional groups include the following squarylium dyes:

  The following sensitized functional group (D15) corresponding to the atomic group excluding the para-positioned hydrogen atom contained in one of the anilino groups substituting the squarylium ring can be exemplified.

  In addition, from the following squarylium dye,

  The following sensitizing functional group (D16) corresponding to an atomic group excluding one methyl group contained in one of the 4-dimethylamino-2-hydroxyphenyl groups substituting the squarylium ring can also be exemplified.

  The main chain of the polymer is preferably polyolefin, polyurethane, polyamide, polyurea, polyester, or polyether, more preferably polyolefin, polyurethane, or polyamide, and most preferably polyolefin.

  The sensitized functional group and the main chain are preferably bonded via a linking group rather than directly connected. The linking group is preferably a divalent to 10 valent group, more preferably a divalent to 6 valent group, and most preferably a divalent group. In the n-valent linking group, n-1 sensitizing functional groups are bonded to one repeating unit. In other words, it is most preferable that one sensitizing functional group is bonded to one repeating unit.

The linking group is a divalent to decavalent aliphatic group, a divalent to decavalent aromatic hydrocarbon group, a divalent to decavalent heterocyclic group, -O-, -S-, -CO-, -CS. -, - NH -, - N <, - SO -, - SO 2 -, or a combination thereof is preferable.

The aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms in the aliphatic group is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 15, still more preferably 1 to 10, and still more preferably 1 to 6 is most preferred.
The aliphatic group may have a substituent. Examples of substituents are halogen atom, nitro, cyano, hydroxyl, mercapto, carboxyl, amino, carbamoyl, carbamoyloxy, ureido, sulfamoyl, aryl group, substituted aryl group, heterocyclic group, alkoxy group, substituted alkoxy group, aryloxy Group, substituted aryloxy group, alkylthio group, substituted alkylthio group, arylthio group, substituted arylthio group, acyl group, alkoxycarbonyl group, substituted alkoxycarbonyl group, substituted amino group, amide group, substituted carbamoyl group, substituted carbamoyloxy group, alkoxy Carbonylamino group, substituted alkoxycarbonyloxy group, arylcarbonylamino group, substituted arylcarbonylamino group, substituted ureido group, alkylsulfonyl group, substituted alkylsulfonyl group, arylsulfuric group Containing group, substituted arylsulfonyl group, a sulfonamido group and a substituted sulfamoyl group.

The number of carbon atoms of the aryl group is preferably 6 to 30, and more preferably 6 to 20.
The aryl part of the substituted aryl group is the same as the aryl group. Examples of the substituent of the substituted aryl group include an alkyl group and a substituted alkyl group in addition to the examples of the substituent of the aliphatic group.

The alkyl part of the alkoxy group, substituted alkoxy group, alkoxycarbonyl group, and substituted alkoxycarbonyl group is the same as the alkyl group. Examples of the substituent of the substituted alkoxy group and the substituted alkoxycarbonyl group are the same as the examples of the substituent of the substituted alkyl group.
The aryl moiety of the aryloxy group and substituted aryloxy group is the same as the aryl group. The example of the substituent of a substituted aryloxy group is the same as the example of the substituent of a substituted aryl group.
The acyl group is represented by formyl or —CO—R, where R is an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group.
The substituted carbamoyl group is represented by —CO—NH—R or —CO—N (—R) ₂ , and R is an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group.

The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, and more preferably 6 to 20.
The aromatic hydrocarbon group may have a substituent. Examples of the substituent are the same as those of the substituted aryl group.
The heterocyclic group preferably has a 5-membered or 6-membered heterocyclic ring. Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring. The hetero atom of the heterocyclic ring is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The heterocyclic group may have a substituent. Examples of the substituent of the heterocyclic group are the same as the examples of the substituent of the substituted aryl group.

  The polymer having a sensitizing functional group preferably includes a repeating unit having an acridone sensitizing functional group represented by the following formula (I).

In the formula (I), R ¹ and R ² are each independently a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), nitro, cyano, hydroxyl, mercapto, carboxyl, amino, carbamoyl, Carbamoyloxy, ureido, sulfamoyl, alkyl group, substituted alkyl group, aryl group, substituted aryl group, heterocyclic group, alkoxy group, substituted alkoxy group, aryloxy group, substituted aryloxy group, alkylthio group, substituted alkylthio group, arylthio group Substituted arylthio group, acyl group, alkoxycarbonyl group, substituted alkoxycarbonyl group, substituted amino group, amide group, substituted carbamoyl group, substituted carbamoyloxy group, alkoxycarbonylamino group, substituted alkoxycarbonyloxy group, aryloxy Carbonylamino group, a substituted aryloxycarbonylamino group, a substituted ureido group, an alkylsulfonyl group, a substituted alkylsulfonyl group, an arylsulfonyl group, a substituted arylsulfonyl group, a sulfonamido group or a substituted sulfamoyl group.

The alkyl group may have a cyclic structure or a branched structure. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and further preferably 1 to 6 Most preferably.
The alkyl part of the substituted alkyl group is the same as the alkyl group. Examples of the substituent of the substituted alkyl group are halogen atom, nitro, cyano, hydroxyl, mercapto, carboxyl, amino, carbamoyl, carbamoyloxy, ureido, sulfamoyl, aryl group, substituted aryl group, heterocyclic group, alkoxy group, substituted alkoxy Group, aryloxy group, substituted aryloxy group, alkylthio group, substituted alkylthio group, arylthio group, substituted arylthio group, acyl group, alkoxycarbonyl group, substituted alkoxycarbonyl group, substituted amino group, amide group, substituted carbamoyl group, substituted carbamoyl group Oxy group, alkoxycarbonylamino group, substituted alkoxycarbonyloxy group, arylcarbonylamino group, substituted arylcarbonylamino group, substituted ureido group, alkylsulfonyl group, substituted alkylsulfonyl Includes an arylsulfonyl group, a substituted arylsulfonyl group, a sulfonamido group and a substituted sulfamoyl group.

The number of carbon atoms of the aryl group is preferably 6 to 30, and more preferably 6 to 20.
The aryl part of the substituted aryl group is the same as the aryl group. Examples of the substituent of the substituted aryl group include an alkyl group and a substituted alkyl group in addition to the examples of the substituent of the substituted alkyl group.
The heterocyclic group preferably has a 5-membered or 6-membered heterocyclic ring. Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring. The hetero atom of the heterocyclic ring is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The heterocyclic group may have a substituent. Examples of the substituent of the heterocyclic group are the same as the examples of the substituent of the substituted aryl group.

The alkyl part of the alkoxy group and the substituted alkoxy group is the same as the alkyl group. Examples of the substituent of the substituted alkoxy group are the same as the examples of the substituent of the substituted alkyl group.
The aryl moiety of the aryloxy group and substituted aryloxy group is the same as the aryl group. The example of the substituent of a substituted aryloxy group is the same as the example of the substituent of a substituted aryl group.

The alkyl part of the alkylthio group and the substituted alkylthio group is the same as the alkyl group. The example of the substituent of a substituted alkylthio group is the same as the example of the substituent of a substituted alkyl group.
The aryl moiety of the arylthio group and the substituted arylthio group is the same as the aryl group. The example of the substituent of a substituted arylthio group is the same as the example of the substituent of a substituted aryl group.

The acyl group is represented by formyl or -CO-R, where R is an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group.
The alkyl moiety of the alkoxycarbonyl group and the substituted alkoxycarbonyl group is the same as the alkyl group. Examples of the substituent of the substituted alkoxycarbonyl group are the same as the examples of the substituent of the substituted alkyl group.
The aryl moiety of the aryloxycarbonyl group and the substituted aryloxycarbonyl group is the same as the aryl group. Examples of the substituent of the substituted aryloxycarbonyl group are the same as the examples of the substituent of the substituted aryl group.

The substituted amino group is represented by —NH—R or —N (—R) ₂ , and R is an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group.
The amide group is represented by —NH—CO—R, and R is an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group.
The substituted carbamoyl group is represented by —CO—NH—R or —CO—N (—R) ₂ , and R is an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group.
The substituted carbamoyloxy group is represented by —O—CO—NH—R or —O—CO—N (—R) ₂ , and R is an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group.

The alkyl moiety of the alkoxycarbonylamino group and the substituted alkoxycarbonylamino group is the same as the alkyl group. Examples of the substituent of the substituted alkoxycarbonylamino group are the same as the examples of the substituent of the substituted alkyl group.
The aryl moiety of the aryloxycarbonylamino group and the substituted aryloxycarbonylamino group is the same as the aryl group. Examples of the substituent of the substituted aryloxycarbonylamino group are the same as the examples of the substituent of the substituted aryl group.

The substituted ureido group is represented by —NH—CO—NH—R or —NH—CO—N (—R) ₂ , and R is an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group.
The alkyl moiety of the alkylsulfonyl group and the substituted alkylsulfonyl group is the same as the alkyl group. Examples of the substituent of the substituted alkylsulfonyl group are the same as the examples of the substituent of the substituted alkyl group.
The aryl moiety of the arylsulfonyl group and substituted arylsulfonyl group is the same as the aryl group. Examples of the substituent of the substituted arylsulfonyl group are the same as the examples of the substituent of the substituted aryl group.

The sulfonamide group is represented by —NH—SO ₂ —R, and R is an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group.
The substituted sulfamoyl group is represented by —SO ₂ —NH—R or —SO ₂ —N (—R) ₂ , and R is an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group.

In the formula (I), L is a divalent linking group. The divalent linking group includes a divalent aliphatic group, a divalent aromatic hydrocarbon group, a divalent heterocyclic group, —O—, —S—, —CO—, —CS—, —NH—, -NR- (R is a monovalent aliphatic group or a monovalent aromatic hydrocarbon radical of), - SO -, - SO 2 -, or a combination thereof is preferable. The aliphatic group, aromatic hydrocarbon group and heterocyclic group are as described above.

In the formula (I), R ³ is a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) or an alkyl group having 1 to 6 carbon atoms.
R ³ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and is a hydrogen atom or methyl. Is most preferred.
Examples of the repeating unit represented by the formula (I) are shown below. R is a hydrogen atom or methyl.

  The polymer having a sensitizing functional group also preferably contains a repeating unit having a coumarin sensitizing functional group represented by the following formula (II).

In the formula (II), R ¹ , R ² , R ³ and R ⁶ are each independently a hydrogen atom, a halogen atom (F, Cl, Br, I), nitro, cyano, hydroxyl, carboxyl, amino, carbamoyl, An alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkoxy group, a substituted alkoxy group, an aryloxy group, a substituted aryloxy group, a substituted carbamoyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group or an acyl group, and R ⁴ And R ⁵ are each independently a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, or two selected from R ³ , R ⁴ , R ⁵ and R ⁶ are bonded together. A nitrogen-containing heterocycle is formed.

The alkyl group may have a cyclic structure or a branched structure. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and further preferably 1 to 6 Most preferably.
The alkyl part of the substituted alkyl group is the same as the alkyl group. Examples of the substituent of the substituted alkyl group are halogen atom, nitro, cyano, hydroxyl, mercapto, carboxyl, amino, carbamoyl, carbamoyloxy, ureido, sulfamoyl, aryl group, substituted aryl group, heterocyclic group, alkoxy group, substituted alkoxy Group, aryloxy group, substituted aryloxy group, alkylthio group, substituted alkylthio group, arylthio group, substituted arylthio group, acyl group, alkoxycarbonyl group, substituted alkoxycarbonyl group, substituted amino group, amide group, substituted carbamoyl group, substituted carbamoyl group Oxy group, alkoxycarbonylamino group, substituted alkoxycarbonyloxy group, arylcarbonylamino group, substituted arylcarbonylamino group, substituted ureido group, alkylsulfonyl group, substituted alkylsulfonyl Includes an arylsulfonyl group, a substituted arylsulfonyl group, a sulfonamido group and a substituted sulfamoyl group.

The number of carbon atoms of the aryl group is preferably 6 to 30, and more preferably 6 to 20.
The aryl part of the substituted aryl group is the same as the aryl group. Examples of the substituent of the substituted aryl group include an alkyl group and a substituted alkyl group in addition to the examples of the substituent of the substituted alkyl group.

The alkyl part of the alkoxy group, substituted alkoxy group, alkoxycarbonyl group, and substituted alkoxycarbonyl group is the same as the alkyl group. Examples of the substituent of the substituted alkoxy group and the substituted alkoxycarbonyl group are the same as the examples of the substituent of the substituted alkyl group.
The aryl moiety of the aryloxy group and substituted aryloxy group is the same as the aryl group. The example of the substituent of a substituted aryloxy group is the same as the example of the substituent of a substituted aryl group.
The acyl group is represented by formyl or —CO—R, where R is an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group.
The substituted carbamoyl group is represented by —CO—NH—R or —CO—N (—R) ₂ , and R is an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group.

When two selected from R ³ , R ⁴ , R ⁵ and R ⁶ are bonded to form a nitrogen-containing heterocyclic ring, the combination is preferably R ³ and R ⁴ , R ⁵ and R ⁴ or R ⁵ and R ⁶ . The nitrogen-containing heterocyclic ring to be formed is preferably a 5- to 7-membered ring, particularly preferably a 6-membered ring.

In the formula (II), L is a divalent linking group. The divalent linking group includes a divalent aliphatic group, a divalent aromatic hydrocarbon group, a divalent heterocyclic group, —O—, —S—, —CO—, —CS—, —NH—, -NR- (R is a monovalent aliphatic group or a monovalent aromatic hydrocarbon radical of), - SO -, - SO 2 -, or a combination thereof is preferable. The aliphatic group, aromatic hydrocarbon group and heterocyclic group are as described above.

In the formula (II), R ⁷ is a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) or an alkyl group having 1 to 6 carbon atoms.
R ⁷ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and is a hydrogen atom or methyl. Is most preferred.
Examples of the repeating unit represented by the formula (II) are shown below. R is a hydrogen atom or methyl.

The polymer having a sensitizing functional group may be a copolymer having a repeating unit having a sensitizing functional group and another repeating unit. Examples of other repeating units include a repeating unit having an aromatic group and a repeating unit having a carboxyl group. The polymer having a sensitizing functional group is preferably a copolymer of a repeating unit having a sensitizing functional group and a repeating unit having a carboxyl group.
The copolymer preferably contains 0.1 to 30 mol%, more preferably 0.2 to 20 mol%, and more preferably 0.3 to 10 mol% of repeating units having a sensitizing functional group. Most preferred.
The copolymer preferably contains 5 to 50 mol% of repeating units having a carboxyl group, more preferably 10 to 40 mol%, and most preferably 15 to 35 mol%.

The polymer having a sensitizing functional group includes polymerization of a monomer having a sensitizing functional group (corresponding to the above-described repeating unit), or a monomer having a sensitizing functional group and another monomer (preferably a monomer having a carboxyl group). ) And copolymerization.
As the copolymerizable monomer, monomers shown as raw materials for other binders described later can be used.
Examples of combinations of monomers having a sensitizing functional group and other monomers are shown below.

(CP1) methacrylic acid / methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / (11) corresponding monomer (CP2) methacrylic acid / methyl methacrylate / styrene / (11) corresponding monomer (CP3) methacrylic acid / benzyl methacrylate / Monomer corresponding to (11) (CP4) Methacrylic acid / Methyl methacrylate / 2-ethylhexyl acrylate / Monomer corresponding to (1) (CP5) Methacrylic acid / Methyl methacrylate / Styrene / Monomer corresponding to (1) (CP6) Methacrylic acid / benzyl methacrylate / monomer corresponding to (1) (CP7) acrylic acid / styrene / monomer corresponding to (1) (CP8) methacrylic acid / methyl methacrylate / 2-ethylhexyl acetate Relate / benzyl methacrylate / monomer corresponding to (3) (CP9) methacrylic acid / methyl methacrylate / styrene / monomer corresponding to (3) (CP10) methacrylic acid / benzyl methacrylate / monomer corresponding to (3) (CP11) methacryl Monomer corresponding to acid / methyl methacrylate / styrene / benzyl methacrylate / (4)

A polymer having a reactive group can be synthesized by synthesizing a polymer having a reactive group and reacting a polymer having a reactive group with a compound having a sensitizing functional group and a reactive group.
Examples of reactive groups include acid groups (eg, carboxyl, sulfo, acid halide groups), amino, hydroxyl, isocyanate and epoxy groups.
The proportion of the repeating unit having a sensitizing functional group formed in the copolymer by the reaction is preferably 0.1 to 30 mol%, more preferably 0.2 to 20 mol%, more preferably 0. Most preferably, 3 to 10 mol% is contained.
The copolymer preferably contains 5 to 50 mol% of repeating units having a carboxyl group, more preferably 10 to 40 mol%, and most preferably 15 to 35 mol%. When the reactive group of the polymer is a carboxyl group, it is preferable to adjust the ratio of the compound having a sensitizing functional group and a reactive group to the polymer so that the carboxyl group remains in the above ratio after the reaction.
Below, the example of the compound which has a sensitization functional group and a reactive group is shown.

  Below, the example of the copolymer obtained by reaction of the polymer which has a reactive group, and the compound which has a sensitization functional group and a reactive group is shown.

(CP21) Addition reaction product of methacrylic acid / methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate copolymer and (d2) (CP22) Addition reaction product of methacrylic acid / methyl methacrylate / styrene copolymer and (d2) (CP23) Methacryl Addition reaction product of acid / benzyl methacrylate copolymer and (d2) (CP24) Addition reaction product of methacrylic acid / methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate copolymer and (d4) (CP25) Methacrylic acid / methyl methacrylate / styrene Addition reaction product of copolymer and (d4) (CP26) Addition reaction product of methacrylic acid / benzyl methacrylate copolymer and (d4) (CP27) Acrylic acid / styrene copolymer (d9) (CP28) methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate copolymer and (d6) addition reaction product (CP29) methacrylic acid / methyl methacrylate / isocyanatoethyl methacrylate / benzyl methacrylate copolymer and (d1) Addition reaction product (CP30) of methacrylic acid / methyl methacrylate / isocyanatoethyl methacrylate / benzyl methacrylate copolymer and (d5) addition reaction product (CP31) methacrylic acid / methyl methacrylate / isocyanatoethyl methacrylate / benzyl methacrylate copolymer (d10) ) Addition reaction product

The polymer may have two or more types of sensitizing functional groups. Two or more kinds of polymers having a sensitizing functional group may be used in combination.
In the present invention, the second photosensitive layer preferably contains a polymer having a sensitizing functional group. Furthermore, the first photosensitive layer can also contain a polymer having a sensitizing functional group.
The content of the polymer having a sensitizing functional group in the photosensitive layer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and most preferably 40 to 80% by mass.
When both the first photosensitive layer and the second photosensitive layer contain a polymer having a sensitizing functional group, the number of sensitizing functional groups contained in the second photosensitive layer is the number of sensitizing functional groups contained in the first photosensitive layer. It is preferable that there are more than the number of functional groups. The sensitizing functional group contained in the second photosensitive layer is preferably 1.5 to 100 times the number of sensitizing functional groups contained in the first photosensitive layer, and preferably 1.8 to 50 times. Is more preferable, and most preferably 2 to 20 times.

[Other binders]
The photosensitive layer containing a polymer having a sensitizing functional group may further contain another polymer (having no sensitizing functional group) as a binder. In addition, the photosensitive layer different from the photosensitive layer containing a polymer having a sensitizing functional group can contain only another polymer (having no sensitizing functional group) as a binder.
The binder used in each photosensitive layer is preferably soluble in an alkaline aqueous solution, or preferably has at least swelling property. Examples of such binders include those having an acidic group (eg, carboxyl group, sulfonic acid group, phosphoric acid group), and particularly binders having a carboxyl group are typical, for example, a carboxyl group-containing vinyl. Copolymers, carboxyl group-containing polyurethane resins, polyamic acid resins, modified epoxy resins, etc. are mentioned. From the viewpoints of solubility in coating solvents, solubility in alkaline developers, suitability for synthesis, and ease of adjustment of film properties. A carboxyl group-containing vinyl copolymer is preferred.

  The carboxyl group-containing vinyl copolymer can be obtained by copolymerization of at least (1) a carboxyl group-containing vinyl monomer and (2) a monomer copolymerizable therewith.

  Examples of the carboxyl group-containing vinyl monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and the like. Further, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Of these, (meth) acrylic acid is particularly preferred from the viewpoints of copolymerizability, cost, solubility, and the like.

  Other copolymerizable monomers that can be used for the synthesis of the above copolymer are not particularly limited, and examples of such monomers include (meth) acrylic acid esters, crotonic acid esters, Vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes, (meth) acrylonitrile and the like are preferred. Examples of such a compound include the following compounds.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth). Acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t-octyl (meth) acrylate, dodecyl (Meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, -Ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol Monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol mono Ethyl ether (meth) acrylate, β-phenoxyethoxyethyl acrylate, nonyl phen Noxypolyethylene glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) Examples thereof include acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, and tribromophenyloxyethyl (meth) acrylate.

  Examples of crotonic acid esters include butyl crotonate and hexyl crotonate. Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.

  Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate. Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate. Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, etc. are mentioned.

  Examples of styrenes (styrene and styrene derivatives) are styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene , Bromostyrene, chloromethylstyrene, hydroxystyrene protected with a group deprotectable by an acidic substance (for example, t-Boc, etc.), methyl vinylbenzoate, and α-methylstyrene. Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

  In addition to the above compounds, (meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (eg, vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinyl Caprolactone and the like can also be used.

  In addition, 2-acrylamido-2-methylpropanesulfonic acid, mono (2-acryloyloxyethyl ester) phosphate, mono (1-methyl-2-acryloyloxyethyl ester) phosphate, and the like can also be used.

  In addition to the above compounds, vinyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used. Such a monomer having a urethane group or a urea group can be appropriately synthesized using, for example, an addition reaction of an isocyanate group and a hydroxyl group or an amino group. Specifically, an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or primary or secondary amino group containing It can be appropriately synthesized by an addition reaction between a monomer and monoisocyanate.

Specific examples of the isocyanate group-containing monomer include the following compounds (R ¹ represents a hydrogen atom or a methyl group).

  Specific examples of the monoisocyanate include cyclohexyl isocyanate, n-butyl isocyanate, toluyl isocyanate, benzyl isocyanate, and phenyl isocyanate.

Specific examples of the hydroxyl group-containing monomer include the following compounds (R ¹ represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more).

  Examples of the compound containing one hydroxyl group include alcohols (methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol, t-butanol, n-hexanol, 2-ethylhexanol, n-decanol, n-dodecanol, n-octadecanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenylethyl alcohol, etc.), phenols (phenol, cresol, naphthol, etc.), and further containing substituents such as fluoroethanol, tri Examples include fluoroethanol, methoxyethanol, phenoxyethanol, chlorophenol, dichlorophenol, methoxyphenol, and acetoxyphenol.

  Examples of the primary or secondary amino group-containing monomer include, for example, vinylbenzylamine.

  Specific examples of compounds containing one primary or secondary amino group include alkylamines (methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, sec-butylamine, t-butylamine, hexyl). Amine, 2-ethylhexylamine, decylamine, dodecylamine, octadecylamine, dimethylamine, diethylamine, dibutylamine, dioctylamine), cyclic alkylamine (cyclopentylamine, cyclohexylamine, etc.), aralkylamine (benzylamine, phenethylamine, etc.), Arylamine (aniline, toluylamine, xylylamine, naphthylamine, etc.), a combination thereof (N-methyl-N-benzylamine, etc.), and an amine further containing a substituent (trifluoroethyl) Min, hexafluoro isopropyl amine, methoxyaniline, and methoxy propylamine, etc.) and the like.

  The above compounds may be used alone or in combination of two or more. Examples of other particularly preferred monomers are methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, styrene, chlorostyrene. , Bromostyrene, and hydroxystyrene.

  Such a vinyl copolymer can be obtained by copolymerizing corresponding monomers according to a conventional method by a known method. For example, it can be obtained by using a method (solution polymerization method) in which these monomers are dissolved in a suitable solvent and a radical polymerization initiator is added thereto to polymerize in a solution. Further, polymerization may be carried out by so-called emulsion polymerization or the like in a state where the above monomer is dispersed in an aqueous medium.

  Examples of suitable solvents used in the solution polymerization method can be arbitrarily selected depending on the monomers used and the solubility of the copolymer to be produced. For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, and toluene can be mentioned. These solvents may be used as a mixture of two or more. Examples of radical polymerization initiators include azo compounds such as 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile), benzoyl par Peroxides such as oxides, and persulfates such as potassium persulfate and ammonium persulfate can be used.

  The content of the repeating unit derived from the polymerizable compound having a carboxyl group in the vinyl copolymer obtained from these monomers is preferably 5 to 50 mol% in all the repeating units of the copolymer for each photosensitive layer, More preferably, it is 10-40 mol%, and 15-35 mol% is especially preferable. If the content is less than 5 mol%, the developability to alkaline water may be insufficient, and if it exceeds 50 mol%, the developer resistance of the cured portion (image portion) may be insufficient.

  The molecular weight of the binder having a carboxyl group can be arbitrarily adjusted, but the weight average molecular weight of each photosensitive layer is preferably 2000 to 300000, particularly preferably 4000 to 150,000. When the mass average molecular weight is less than 2000, the strength of the film tends to be insufficient, and stable production tends to be difficult. On the other hand, if the molecular weight exceeds 300,000, the developability tends to decrease.

  These binders having a carboxyl group may be used alone or in combination of two or more binders in each photosensitive layer. Examples of using two or more binders in combination include two or more binders composed of different copolymerization components, two or more binders having different mass average molecular weights, and two or more binders having different dispersities. .

  In the binder having a carboxyl group, part or all of the carboxyl group may be neutralized with a basic substance. As the binder, resins having different structures such as polyester resin, polyamide resin, polyurethane resin, epoxy resin, polyvinyl alcohol, and gelatin may be used in combination.

  Examples of the binder include resins soluble in an alkaline aqueous solution described in Japanese Patent No. 2873889 and the like.

  The content of the binder in the photosensitive layer (the total amount of the polymer having a sensitizing functional group and other binders used in combination as necessary) is usually 10 to 90% by mass for each photosensitive layer, preferably It is 20-80 mass%, Most preferably, it is 40-80 mass%. When the content of the polymer having a sensitizing functional group (and the total amount with other binders used in combination as needed) is small, alkali developability and a printed wiring board forming substrate (for example, copper-clad laminate) The adhesiveness of the film tends to decrease, and if it increases too much, the stability with respect to the development time and the strength of the cured film (tent film) tend to decrease. In order to adjust the sensitivity, the content of the binder contained in the second photosensitive layer within the above range is lower than the content of the binder contained in the first photosensitive layer (the content of the polymerizable compound is increased). You may make adjustments.

[Basic configuration]
As an example of the photosensitive transfer sheet of the present invention, schematic sectional views of a constitution having two photosensitive layers are shown in FIGS.

  In FIG. 1, a photosensitive transfer sheet 10 includes a support 11, a first photosensitive layer 12, and a second photosensitive layer 14 laminated in this order. The first photosensitive layer 12 and the second photosensitive layer 14 are each composed of a photosensitive resin composition containing a binder, a polymerizable compound, and a photopolymerization initiator, and are cured by light irradiation. The photosensitive transfer sheet of the present invention is mainly characterized in that the second photosensitive layer 14 has relatively higher photosensitivity than the first photosensitive layer 12. Here, the photosensitivity corresponds to the amount of light energy required to cure each photosensitive layer, and the high photosensitivity means that the second photosensitive layer 14 is cured less than the first photosensitive layer 12. It means that starting with a light irradiation amount or curing of the second photosensitive layer 14 is completed with a light irradiation amount smaller than that of the first photosensitive layer 12.

  In the photosensitive transfer sheet of the present invention, a barrier layer may be disposed between the first photosensitive layer and the second photosensitive layer, and a photosensitive transfer sheet in which this barrier layer is disposed is preferable. FIG. 2 shows a photosensitive transfer sheet further having a barrier layer 13 between the first photosensitive layer 12 and the second photosensitive layer 14.

  3 and 4 are photosensitive transfer sheets obtained by further laminating a protective film 15 on the photosensitive transfer sheets of FIGS. 1 and 2, respectively.

  The thicknesses of the first photosensitive layer, the barrier layer and the second photosensitive layer can be arbitrarily set according to the purpose. However, the first photosensitive layer preferably has a thickness in the range of 1 to 100 μm, more preferably in the range of 5 to 80 μm, and particularly preferably in the range of 10 to 50 μm. When the thickness of the first photosensitive layer is less than 1 μm, it may be inappropriate to increase the film strength, and when the thickness exceeds 100 μm, development problems such as development residue remaining easily occur. There is. The thickness of the first photosensitive layer is preferably larger than the thickness of the second photosensitive layer.

  The barrier layer preferably has a thickness in the range of 0.1 to 5 μm, more preferably in the range of 0.5 to 4 μm, and particularly preferably in the range of 1 to 3 μm. If the thickness of the barrier layer is less than 0.1 μm, sufficient barrier properties may not be obtained. If the thickness exceeds 5 μm, it takes a long time for development. The second photosensitive layer preferably has a thickness in the range of 0.1 to 15 μm, more preferably in the range of 1 to 12 μm, and particularly preferably in the range of 3 to 10 μm. If the thickness of the second photosensitive layer is less than 0.1 μm, uneven thickness is likely to occur during coating, and if the thickness exceeds 15 μm, the resolution is lowered.

  The layer structure of the photosensitive transfer sheet of the present invention is not limited to the layer structure illustrated in FIGS. 1 to 4 described above, and may have layers other than the layers illustrated in FIGS. 1 to 4. . For example, between the support 11 and the first photosensitive layer 12, or between the protective film 15 and the second photosensitive layer 14, a layer for adjusting the peelability and adhesion between the support and the substrate, an antihalation layer, Alternatively, a barrier layer or the like may be provided. In this case, the barrier layer has a role to prevent or suppress external influences such as oxygen and humidity, and the like, and prevention of migration of substances contained in the photosensitive layer, the support or the protective film.

  Next, the relationship between the light irradiation amount and the photosensitive layer curing amount in the photosensitive transfer sheet and photosensitive laminate of the present invention will be described with reference to FIG. In FIG. 5, for example, the photosensitive transfer sheet shown in FIG. 1 or the photosensitive transfer sheet from which the protective film is peeled off from the photosensitive transfer sheet shown in FIG. 3 is transferred onto a substrate to form a laminate. In the case where the photosensitive layer is irradiated with light from the opposite side of the substrate from the side opposite to the substrate through the support, or if necessary, the support is peeled off. 2 is a graph (sensitivity curve) showing the relationship between the light irradiation amount, the irradiation (exposure), and the thickness of the cured layer generated by the subsequent development processing. In FIG. 5, the horizontal axis represents the amount of light irradiation, and the vertical axis represents the thickness of the cured layer obtained after being cured by light irradiation and developed. D on the vertical axis is the thickness of the cured layer formed from the second photosensitive layer, and E is the sum of the thickness of the cured layer formed from the first photosensitive layer and the thickness of the cured layer formed from the second photosensitive layer. Represents the thickness.

  As shown in FIG. 5, in the photosensitive transfer sheet of the present invention, the light irradiated from the support side, in the case of having the support, proceeds in the order of the support, the first photosensitive layer, and the second photosensitive layer. The curing of the second photosensitive layer starts with a small amount of light energy prior to the first photosensitive layer. Then, after the entire second photosensitive layer is cured, when the amount of light energy is increased, curing of the first photosensitive layer starts, and when the amount of light energy is further increased, the entire first photosensitive layer is cured.

  Regarding the relationship between the sensitivity of the first photosensitive layer and the sensitivity of the second photosensitive layer, when the photosensitivity of the first photosensitive layer is 1, the photosensitivity of the second photosensitive layer is preferably in the range of 2 to 200. More preferably, it is in the range of 2.5 to 100, and particularly preferably in the range of 3 to 50.

  The amount of light energy C required until the curing of the first photosensitive layer may be the same as the amount of light energy A necessary to cure the second photosensitive layer, but is greater than the amount of light energy A. Is preferred.

  Even when a barrier layer is provided between the first photosensitive layer and the second photosensitive layer as in the photosensitive transfer sheet shown in FIGS. 2 and 4, the light irradiation amount and the thickness of the cured layer are the same as those in FIG. This relationship is obtained. However, the film thickness E in this case represents the thickness obtained by adding the thickness of the barrier layer to the thickness of the cured layer formed from the first photosensitive layer and the thickness of the cured layer formed from the second photosensitive layer.

  The photosensitive transfer sheet of the present invention may have two or more photosensitive layers. As an example, FIG. 6 shows a cross-sectional view when the photosensitive layer has three layers. FIG. 7 shows a case where a barrier layer is provided between the photosensitive layers, FIG. 8 shows a case where a protective film is provided on the photosensitive layer in FIG. 6, and FIG. 7 shows a case where a protective film is provided on the photosensitive layer in FIG. 9 shows.

  In the photosensitive transfer sheet 50 of FIGS. 6 to 9, the support is represented by 51, on which the first photosensitive layer 52, the second photosensitive layer 54, and the third photosensitive layer. 55 are sequentially stacked. In the photosensitive transfer sheet 50 of FIG. 7, a barrier layer 53 is provided between the first photosensitive layer 52 and the second photosensitive layer 54 and between the second photosensitive layer 54 and the third photosensitive layer 55. ing. 8 shows a configuration in which the protective film 56 is provided on the photosensitive transfer sheet of FIG. 6, and FIG. 9 shows a configuration in which the protective film 56 is provided on the photosensitive transfer sheet of FIG.

  Even in the case of these three photosensitive layer configurations, each photosensitive layer has relatively higher sensitivity of the photosensitive layer on the side away from the support than the sensitivity of the photosensitive layer on the side closer to the support. That is, the sensitivity of the photosensitive layer is the highest for the third photosensitive layer, then the second photosensitive layer is the highest, and the sensitivity of the first photosensitive layer is the lowest.

  Using the photosensitive transfer sheet having the configuration shown in FIGS. 6 to 9, the amount of light energy used for pattern formation is set to a light energy amount X for curing only the third photosensitive layer, and the third photosensitive layer. By changing the amount of light energy Y for curing the second photosensitive layer, the amount of light energy Z for curing all of the third photosensitive layer, the second photosensitive layer, and the first photosensitive layer, and the amount of light irradiation. As shown in FIG. 10, the region having a thickness in which only the third photosensitive layer is cured, the region having the thickness in which the third photosensitive layer and the second photosensitive layer are cured, the third photosensitive layer, It is possible to form a pattern having three different thicknesses, that is, a region having a cured thickness of all of the second photosensitive layer and the first photosensitive layer, with one type of photosensitive transfer sheet.

  Similarly, the photosensitive layer has N layers (the number of photosensitive layers is N), and the sensitivity of the photosensitive layer on the side away from the support is relatively higher than the sensitivity of the photosensitive layer on the side close to the support. If a transfer sheet is used, it becomes possible to form a cured layer pattern having different thicknesses in N stages with one type of photosensitive transfer sheet.

  As described above, in the photosensitive transfer sheet of the present invention, the thickness of the cured layer obtained by exposure and development processing can be set to a desired thickness according to the exposure amount (so-called light energy amount). It is possible to change the pattern of exposure amount as necessary, so that it can be made separately from the area where only the photosensitive layer closest to the substrate is cured to the area where all the photosensitive layers are cured by changing the thickness sequentially. Is possible. Therefore, one type of three-dimensional modeling with different thicknesses inside the image, a cured resin image with characteristics such as increasing the strength of the film only in the desired region, or increasing the image density only in the desired region, etc. It can be formed with a photosensitive transfer sheet.

  Therefore, when the photosensitive transfer sheet of the present invention is used for the production of a printed wiring board, particularly for the production of a printed wiring board having a through hole or a via hole, the wiring pattern formation region is relatively thin and has a high resolution. A hardened layer is formed, and a high-strength hardened layer having a relatively thick thickness can be formed in the through hole or via hole. Therefore, by using the photosensitive transfer sheet of the present invention, it is possible to easily form a cured resin pattern having sufficient tent film strength that can be used as a tenting method and having sufficient resolution in a portion that requires high resolution. Can do.

  According to the present invention, the photosensitive transfer sheet having the sensitivity curve as described above can be realized by relatively increasing the sensitivity of each photosensitive layer in order from the side closer to the support to the side away from the support. found. Any known high sensitivity technology can be used as a method of making the photosensitive layer into two or more layers and sequentially increasing the sensitivity of the photosensitive layers. That is, for example, use of a highly sensitive initiator, use of a sensitizer, increase in the content of a photopolymerization initiator and / or sensitizer, or increase the content of a polymerizable compound in the photosensitive layer, polymerization inhibition It can be obtained by a technique such as reducing the ratio of the agent or the polymerization inhibitor. In particular, when the photosensitive layer has two layers, for example, a high-sensitivity initiator is used, and a sensitizer is added to the second photosensitive layer, and a photopolymerization initiator and / or sensitizer in the second photosensitive layer. Can be obtained by a technique such as increasing the content of the first photosensitive layer or increasing the content of the polymerizable compound in the second photosensitive layer than that of the first photosensitive layer.

The first photosensitive layer comprising a photosensitive resin composition containing a binder, a polymerizable compound, and a photopolymerization initiator on a support of the present invention, and a photosensitivity containing a binder, a polymerizable compound, and a photopolymerization initiator. A photosensitive transfer sheet comprising a resin composition and a second photosensitive layer having a higher photosensitivity than the first photosensitive layer and laminated in this order, or a first photosensitive layer and a second photosensitive layer, In the case where an image pattern (cured resin pattern) is formed using a photosensitive transfer sheet in which a barrier layer is disposed between, a light energy amount S at which curing of the second photosensitive layer starts is 0.05 to 10 mJ / cm. it is preferably in the ² range, still preferably in the range of 0.1~5mJ / cm ^2, preferably in the range particularly 0.15~2.5mJ / cm ^2. The amount of light energy A necessary for curing the second photosensitive layer is preferably in the range of 0.1~20mJ / cm ^2, that further the range of 0.2~15mJ / cm ² preferably In particular, the range of 0.4 to 10 mJ / cm ² is preferable.

The ratio (A / B) of the amount of light energy A required to cure the second photosensitive layer and the amount of light energy B necessary to cure the first photosensitive layer is in the range of 0.005 to 0.5. It is preferably in the range of 0.01 to 0.4, and more preferably in the range of 0.02 to 0.35. The ratio (C / A) of the amount of light energy A required to cure the second photosensitive layer and the amount of light energy C necessary until the first photosensitive layer begins to be cured (C / A) is in the range of 1 to 10. Is more preferable, and it is preferable that it exists in the range of 1.1-9, and it is especially preferable that it is the range of 1.3-8. The optical energy C is preferably in the range of 0.1~200mJ / cm ^2, that further in the range of 1 to 100 mJ / cm ² is preferred, particularly from 2~50mJ / cm ² It is preferable.

  Next, each material used for the photosensitive transfer sheet of this invention and the photosensitive layer of a photosensitive laminated body is demonstrated.

[Polymerizable compound]
The polymerizable compound is a compound having at least one polymerizable functional group. Polymerizable compounds are classified into polymerizable urethane compounds, monofunctional polymerizable aromatic compounds, polyfunctional polymerizable aromatic compounds, and other (aliphatic non-urethane) polymerizable compounds from the viewpoint of functions in the photosensitive layer. it can.

(Polymerizable urethane compound)
The polymerizable urethane compound is a compound having at least one polymerizable functional group and at least one urethane bond (—NH—CO—O—) in the molecule. The polymerizable urethane compound includes a high molecular compound (oligomer or polymer) in addition to the low molecular compound (monomer).
The polymerizable functional group is preferably a ring-opening polymerizable group or an addition polymerizable group, and more preferably an addition polymerizable group. The addition polymerizable group is particularly preferably an ethylenically unsaturated group.

Polymerizable urethane compounds are disclosed in JP-B-48-41708, JP-A-51-37193, JP-B-5-50737, JP-A-7-7208, JP-A-2001-154346 and 2001-356476. There is a description.
Urethane bonds are generally formed by the reaction of isocyanates with alcohols or phenols. The alcohol or phenol preferably has a polymerizable group.

  The isocyanate is preferably a polyisocyanate having two or more isocyanate groups per molecule. Examples of diisocyanates are hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate, phenylene diisocyanate, norbornene diisocyanate, diphenyl diisocyanate, Diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-diphenyl diisocyanate. A polyaddition product of a diisocyanate and a bifunctional alcohol (in this case, both ends are isocyanate groups) can also be used as the diisocyanate. Diisocyanate trimers (eg, burettes and isocyanurates), and adducts of diisocyanates and polyfunctional alcohols (eg, trimethylolpropane, pentaerythritol, glycerin) can also be used as polyisocyanates. An alkylene oxide (eg, ethylene oxide) may be added to the polyfunctional alcohol.

  Examples of alcohols having a polymerizable group are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyalkylene glycol mono (meth) acrylate, trimethylolpropane di (Meth) acrylate, pentaerythritol tri (meth) acrylate is included. Examples of polyalkylene glycol mono (meth) acrylates are diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, octaethylene glycol mono (meth) acrylate, dipropylene glycol mono (Meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate, dibutylene glycol mono (meth) acrylate, tributylene glycol mono (meth) acrylate, Tetrabutylene glycol mono (meth) acrylate, octabutylene glycol mono (meth) acrylate). The polyalkylene glycol moiety of the polyalkylene glycol mono (meth) acrylate may be a copolymer of different alkylene oxide units (eg, ethylene oxide and propylene oxide). Copolymerization may be random, block, or alternating.

Further, as a monomer containing a urethane group, a compound having an isocyanurate ring such as tri ((meth) acryloyloxyethyl) isocyanurate, di (meth) acrylated isocyanurate, or tri (meth) acrylate of ethylene oxide-modified isocyanuric acid Can also be used.
The polymerizable urethane compound is preferably represented by the following formula (I).

In the formula (I), R ¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or methyl.
In the formula (I), p is an integer of 1 to 10. p is preferably an integer of 2 to 6, and more preferably 2 or 3.
C _p H _2p in the formula (I) means a chain alkylene group which may have a branch.

  In the formula (I), m1 is an integer of 1 to 60. m1 is preferably an integer of 2 to 30, more preferably an integer of 3 to 20, and most preferably an integer of 4 to 15. When m1 is an integer of 2 or more, the plurality of chain alkylene groups may be different from each other. For example, it may be a combination of ethylene and propylene. When a plurality of chain alkylene groups are different, a partial structure in which alkylene oxide units are copolymerized exists in the polymerizable urethane compound. Copolymerization may be random, block, or alternating.

In formula (I), n1 is an integer of 2 to 6, and L ¹ is a divalent to hexavalent (n1-valent) linking group.
If n1 is 2, ^{L 1} represents a divalent linking group. The divalent linking group is an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group, an arylene group, a substituted arylene group, or a combination thereof, or Between these combinations, an oxygen atom (—O—), a sulfur atom (—S—), a carbonyl (—CO—), an imino (—NH—), a substituted imino group (—NR—, R is a substituent) ) Or sulfonyl (—SO ₂ —) is preferred. The divalent linking group is particularly preferably composed of an alkylene group, an arylene group, a substituted arylene group, or a combination thereof.

The alkylene group may have a cyclic structure or a branched structure. The number of carbon atoms in the alkylene group is preferably 1 to 18, more preferably 2 to 14, and most preferably 4 to 10.
Examples of alkylene groups are methylene, ethylene, trimethylene, propylene, tetramethylene, 1-methyltrimethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, cyclohexylene, heptamethylene, octamethylene 2-ethylhexamethylene, nonamethylene, decamethylene, dodecamethylene, dicyclohexylmethylene, octadecamethylene. The following cyclic alkylene groups are also included in the examples of the alkylene group.

The alkylene part of the substituted alkylene group is the same as the above alkylene group. Examples of the substituent of the substituted alkylene group include a halogen atom (F, Cl, Br, I), an aryl group, an alkoxy group (eg, methoxy, ethoxy, 2-ethoxyethoxy), an aryloxy group (eg, phenoxy), acyl Groups (eg, acetyl, propionyl), acyloxy groups (eg, acetoxy, butyryloxy), alkoxycarbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl) and aryloxycarbonyl groups (eg, phenoxycarbonyl).
Examples of substituted alkylene groups include diphenylmethylene.

The alkenylene group and the alkynylene group may have a cyclic structure or a branched structure.
The alkenylene part of the substituted alkenylene group is the same as the above alkenylene group. The alkynylene part of the substituted alkynylene group is the same as the above alkynylene group. Examples of the substituent of the substituted alkylene group and the substituted alkynylene group are the same as the examples of the substituent of the substituted alkylene group.

Examples of arylene groups include phenylene, biphenyldiyl and naphthylene.
The arylene part of the substituted arylene group is the same as the above arylene group. Examples of the substituent of the substituted arylene group include an alkyl group in addition to the examples of the substituent of the substituted alkylene group.
Examples of substituted arylene groups include methylphenylene and dimethylphenylene.

A divalent linking group comprising a combination of an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group, an arylene group or a substituted arylene group is a xylylene group (eg, xylene-α, α′- Diyl) and substituted xylylene groups are particularly preferred.
A combination of an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group, an arylene group or a substituted arylene group includes an oxygen atom, a sulfur atom, a carbonyl group, an imino group, a substituted imino group, or a sulfonyl group. It may be interposed. Examples of the substituent of the substituted imino group include an alkyl group and an aryl group. The alkyl group preferably has 1 to 18 carbon atoms, and more preferably 1 to 10 carbon atoms. The number of carbon atoms in the aryl group is preferably 6 to 18, and more preferably 6 to 10.

When n1 is an integer of 3 to 6, L ¹ is a trivalent to hexavalent linking group. The trivalent to hexavalent linking group is a trivalent to hexavalent aliphatic group, a trivalent to hexavalent aromatic group, a trivalent to hexavalent heterocyclic group or a combination thereof, or an alkylene group thereof. , Substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group, arylene group, substituted arylene group, oxygen atom (—O—), sulfur atom (—S—), carbonyl (—CO—), imino It is preferably composed of a combination with (—NH—), a substituted imino group (—NR—, R is a substituent) or sulfonyl (—SO ₂ —), and a trivalent to hexavalent aliphatic group, trivalent to 6 And further comprising a combination of a valent aromatic group, a trivalent to hexavalent heterocyclic group or a combination thereof, or an alkylene group, a substituted alkylene group or an oxygen atom (—O—) thereof. Masui. The definitions and examples of the alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group, arylene group, substituted arylene group, and substituted imino group are the same as those for the divalent linking group.

When n1 is an integer of 3 to 6, the number of carbon atoms of L ¹ is preferably 1 to 100, more preferably 2 to 50, and most preferably 3 to 30.
It may have a trivalent to hexavalent aliphatic group, a branched structure or a cyclic structure. The aliphatic group has preferably 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and most preferably 3 to 10 carbon atoms.
The aliphatic group may have a substituent. The example of a substituent is the same as the substituent of the substituted alkylene group mentioned above.
The number of carbon atoms of the trivalent to hexavalent aromatic group is preferably 6 to 100, more preferably 6 to 50, and most preferably 6 to 30.
The aromatic group may have a substituent. The example of a substituent is the same as the substituent of the substituted arylene group mentioned above.
The trivalent to hexavalent heterocyclic group preferably has a 5-membered or 6-membered heterocyclic ring. The heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring.
The heterocyclic group may have a substituent. The example of a substituent is the same as the substituent of the substituted arylene group mentioned above.

  A particularly preferred polymerizable urethane compound is represented by the following formula (Ia).

式（Ｉａ）において、Ｒ^１１は、水素原子または炭素原子数が１乃至６のアルキル基である。Ｒ^１１は、水素原子または炭素原子数が１乃至３のアルキル基であることが好ましく、水素原子またはメチルであることがさらに好ましい。

In the formula (Ia), R ¹¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ¹¹ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or methyl.

In formula (Ia), L ¹¹ is a divalent linking group comprising an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group, an arylene group, a substituted arylene group, or a combination thereof. Or an oxygen atom (—O—), a sulfur atom (—S—), a carbonyl (—CO—), an imino (—NH—), a substituted imino group (—NR—, R) Is a divalent linking group intervening by a substituent) or sulfonyl (—SO ₂ —). L ¹¹ is particularly preferably a divalent linking group composed of an alkylene group, an arylene group, a substituted arylene group, or a combination thereof. The alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group, arylene group, and substituted arylene group are as described in Formula (I).

  The divalent linking group comprising a combination of an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group, an arylene group or a substituted arylene group preferably has 7 to 25 carbon atoms. 7 to 18 is more preferable, and 7 to 15 is most preferable. An example of a divalent linking group comprising a combination includes xylene-α, α'-diyl.

  A combination of an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group, an arylene group or a substituted arylene group includes an oxygen atom, a sulfur atom, a carbonyl group, an imino group, a substituted imino group, or a sulfonyl group. It may be interposed. Examples of the substituent of the substituted imino group include an alkyl group and an aryl group. The alkyl group preferably has 1 to 18 carbon atoms, and more preferably 1 to 10 carbon atoms. The number of carbon atoms in the aryl group is preferably 6 to 18, and more preferably 6 to 10.

In the formula (Ia), t and u are each independently an integer of 1 to 10. t and u are each independently preferably an integer of 1 to 6, more preferably 2, 3 or 4, and most preferably 2 or 3.
-C t _H 2t _- is good number of carbon atoms which may have a branch means a chain unsubstituted alkylene group is a t.
(—O—C _t H _2t —) When a plurality of oxyalkylenes (—O—C _t H _2t —) contained in _m11 are different, the polyoxyalkylene moiety serving as a copolymer is random, alternating, or block Either is acceptable.
-C u _H 2u _- are good number of carbon atoms which may have a branch means a chain unsubstituted alkylene group is u.
If _(-C u _H 2u _-O-) a plurality of oxyalkylene included in _{m12 (-C u} H 2u -O-) are different, polyoxyalkylene moiety which is a copolymer, a random, alternating, block Either may be sufficient.

In formula (Ia), m11 and m12 are each independently an integer of 1 to 50.
m11 is preferably an integer of 1 to 14, more preferably an integer of 4 to 14, and most preferably an integer of 4 to 10.
m12 is preferably an integer of 1 to 30, more preferably an integer of 1 to 20, and most preferably an integer of 1 to 10.

_{Below, - (- O-C t} H 2t -) m11 - shows an example of. m5 and m6 are integers from 1 to 49 that satisfy m5 + m6 = m11. _{- (- -O- C u H 2u} ) m12 - ( except the left and right are reversed) is also an example of the same.
_{L01: - (- O-CH} 2 -CH 2 -) m11 -
L02: — (— O—CH ₂ —CH (CH ₃ ) —) _m11 −
_{L03: - (- O-CH} 2 -CH 2 -CH 2 -) m11 -
L04: — (— O—CH ₂ —CH ₂ —CH ₂ —CH ₂ —) _m11 −
L05: — (— O—CH ₂ —CH ₂ —) _m5 −
_{- (- O-CH 2 -CH} (CH 3) -) m6 -
L06: — (— O—CH ₂ —CH ₂ —) _m5 −
_{- (- O-CH 2 -CH} 2 -CH 2 -CH 2 -) m6 -
L07: — (— O—CH ₂ —CH (CH ₃ ) —) _m5 −
_{- (- O-CH 2 -CH} 2 -CH 2 -CH 2 -) m6 -

  In formula (Ia), n11 is each independently an integer of 3 to 6. n11 is preferably 3, 4 or 6.

In the formula (Ia), L ¹² is a trivalent to hexavalent aliphatic group or a trivalent to hexavalent aromatic group, or an alkylene group, a substituted alkylene group, an alkenylene group, or a substituted alkenylene group. , Alkynylene group, substituted alkynylene group, arylene group, substituted arylene group, oxygen atom (—O—), sulfur atom (—S—), carbonyl (—CO—), imino (—NH—), substituted imino group (— NR-, R is a substituent) or a sulfonyl (-SO ₂ - is a combination of). L ¹² is particularly preferably a trivalent to hexavalent aliphatic group. The definition and examples of each group are as described in formula (I).

Polymerizable urethane compound represented by formula (Ia), for ^{_{example, [OCN-L 11 -NH-}} CO-O - (- C u H 2u -O-) m12 -] polyisocyanates corresponding to n11 ^{L 12} And CH ₂ ═C (—R ¹¹ ) —CO — (— O—C _t H _2t —) _m11 —OH.
The polyisocyanate, for _{example, HO - (- C u H} 2u -O-) m12 -] reaction of alkylene oxide adducts corresponding to n11 ^{L 12,} a diisocyanate corresponding to ^OCN-L 11 -NCO Can be synthesized. It said alkylene oxide adducts, for _example, be synthesized by reaction of a polyhydric (trivalent to hexavalent) alcohol corresponding to _(HO-) n11 ^{L 12.}

  Two or more kinds of polymerizable urethane compounds may be used in combination. When the polymerizable urethane compound represented by the formula (I) is synthesized by a general production method, a mixture having different degrees of polymerization of alkylene oxide units is often obtained. In the present invention, the obtained mixture can be used as it is.

Two or more kinds of polymerizable urethane compounds may be used in combination.
The polymerizable urethane compound is preferably contained in the range of 5 to 90% by mass in the layer used in combination, more preferably in the range of 15 to 60% by mass, and in the range of 20 to 50% by mass. Is more preferable.
When the polymerizable urethane compound and the polymerizable aromatic compound are used in combination, 10 to 90% by mass of the total polymerizable compound is preferably a polymerizable urethane compound, and 20 to 80% by mass is a polymerizable urethane compound. Is more preferable, and 30 to 70% by mass is most preferably a polymerizable urethane compound.

(Monofunctional polymerizable aromatic compound)
The monofunctional polymerizable aromatic compound is a compound having one polymerizable functional group and at least one aromatic ring in the molecule.
The polymerizable functional group is preferably a ring-opening polymerizable group or an addition polymerizable group, and more preferably an addition polymerizable group. The addition polymerizable group is particularly preferably an ethylenically unsaturated group.

  Examples of monofunctional polymerizable aromatic compounds include esters of phenol and (meth) acrylic acid (eg, phenyl (meth) acrylate, tribromophenyl (meth) acrylate), aromatic alcohol and (meth) acrylic acid Esters (eg, benzyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate), N-aryl substituted ( (Meth) acrylamide (eg, N-phenyl (meth) acrylamide), N-aralkyl-substituted (meth) acrylamide (eg, N-benzyl (meth) acrylamide), styrene, substituted styrene (eg, methylstyrene, dimethylstyrene, trimethylstyrene) , Ethylstyrene, isopropylstyrene , Butyl styrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichloro styrene, bromostyrene, chloromethylstyrene, methyl vinyl benzoate, alpha-methyl styrene). The hydroxyl group of hydroxystyrene may be protected with a group (eg, t-Boc) that can be removed by an acidic substance.

  Urethane or urea having one polymerizable functional group and at least one aromatic ring in one molecule can also be used as the monofunctional polymerizable aromatic compound. Urethane or urea is generally synthesized by a condensation reaction between an isocyanate and an alcohol, phenol or amine (primary amine or secondary amine). In order to synthesize a monofunctional polymerizable aromatic compound, either isocyanate or alcohol, phenol or amine has a polymerizable group, and either isocyanate or alcohol, phenol or amine is used. It is an aromatic compound.

The monofunctional polymerizable aromatic compound is preferably an ester of an aromatic alcohol and (meth) acrylic acid. An ester of an aromatic alcohol and (meth) acrylic acid is defined by the following formula.
_{CH 2 = CR-CO-O} - (- L-O-) n -Ar
[Wherein, R is a hydrogen atom or an alkyl group; L is an alkylene group having 2 to 6 carbon atoms; n is an integer of 1 to 20, and when n is 2 or more, a plurality of ( -L-O-) may be different from each other; and Ar is an aryl or substituted aryl group].
R is preferably a hydrogen atom or methyl.
The alkylene group of L preferably has a chain structure rather than a cyclic structure. The chain alkylene group may have a branch. Examples of the alkylene group include ethylene, propylene, tetramethylene, pentamethylene and hexamethylene.
When a plurality of (—L—O—) are different from each other, an example of a combination of a plurality of alkylene groups includes a combination of ethylene and propylene.

  Examples of aryl groups and substituted aryl groups are phenyl, naphthyl, tolyl, xylyl, ethylphenyl, methoxyphenyl, propylphenyl, butylphenyl, t-butylphenyl, octylphenyl, nonylphenyl, chlorophenyl, cyanophenyl, dibromophenyl, tri Including bromophenyl, biphenylyl, benzylphenyl, α-dimethyl-benzylphenyl.

Two or more types of monofunctional polymerizable aromatic compounds may be used in combination.
The monofunctional polymerizable aromatic compound is preferably included in the layer to be added in a range of 5 to 90% by mass, more preferably in a range of 15 to 60% by mass, and in a range of 20 to 50% by mass. More preferably it is included.

(Polyfunctional polymerizable aromatic compound)
The polyfunctional polymerizable aromatic compound is a compound having at least two polymerizable functional groups and at least one aromatic ring in the molecule. The polyfunctional polymerizable aromatic compound includes a high molecular compound (oligomer, polymer) in addition to a low molecular compound (monomer).
The polymerizable functional group is preferably a ring-opening polymerizable group or an addition polymerizable group, and more preferably an addition polymerizable group. The addition polymerizable group is particularly preferably an ethylenically unsaturated group.
The polyfunctional polymerizable aromatic compound includes an ester of a carboxylic acid having an ethylenically unsaturated group and a polyhydric phenol or a polyhydric alcohol, an amide of a carboxylic acid having an ethylenically unsaturated group and a polyvalent amine, a polyhydric alcohol. And urethane of ethylenically unsaturated isocyanate, carboxylic acid adduct having ethylenically unsaturated group of polyvalent glycidyl compound, ethylenically unsaturated alcohol adduct of polyvalent isocyanate, polyvalent acid and ethylenically unsaturated Preferred are esters with alcohols, divinyl ethers, aromatic compounds having a plurality of ethylenically unsaturated groups, and esters of carboxylic acids having ethylenically unsaturated groups with alcohols having ethylenically unsaturated groups.
The polyfunctional polymerizable aromatic compound is an ester of a carboxylic acid having an ethylenically unsaturated group and a polyhydric phenol or a polyhydric alcohol (an ester of a carboxylic acid having an ethylenically unsaturated group and a polyhydric phenol, an ethylenically unsaturated group). Ester of carboxylic acid having saturated group and polyvalent aromatic alcohol, ester of aromatic carboxylic acid having ethylenically unsaturated group and polyhydric alcohol), carboxylic acid having ethylenically unsaturated group and polyvalent amine The amide (an amide of a carboxylic acid having an ethylenically unsaturated group and a polyvalent aromatic amine, an amide of an aromatic carboxylic acid having an ethylenically unsaturated group and a polyvalent amine) is more preferable.

  The polyfunctional polymerizable aromatic compound is an ester of a carboxylic acid having an ethylenically unsaturated group and a polyhydric phenol, an ester of a carboxylic acid having an ethylenically unsaturated group and a polyvalent aromatic alcohol, or an ethylenically unsaturated group. Most preferred is an amide of a carboxylic acid having a polyvalent aromatic amine.

  Examples of polyhydric phenols and polyhydric aromatic alcohols are polystyrene oxide, xylylene diol, di- (β-hydroxyethoxy) benzene, 1,5-dihydroxy-1,2,3,4-tetrahydronaphthalene, 2,2 -Diphenyl-1,3-propanediol, hydroxybenzyl alcohol, hydroxyethyl resorcinol, 1-phenyl-1,2-ethanediol, 2,3,5,6-tetramethyl-p-xylene-α, α'-diol 1,1,4,4-tetraphenyl-1,4-butanediol, 1,1,4,4-tetraphenyl-2-butyne-1,4-diol, 1,1′-bi-2-naphthol , Dihydroxynaphthalene, 1,1′-methylene-di-2-naphthol, 1,2,4-benzenetriol, biphenol, 2,2 -Bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (hydroxyphenyl) methane, catechol, 4-chlororesorcinol, hydroquinone, hydroxybenzyl alcohol, methylhydroquinone, methylene-2, 4,6-trihydroxybenzoate, phloroglicinol, pyrogallol, resorcinol, α- (1-aminoethyl) -p-hydroxybenzyl alcohol, α- (1-aminoethyl) -p-hydroxybenzyl alcohol, 3-amino- Contains 4-hydroxyphenyl sulfone.

  The polymerizable aromatic compound comprising an ester of a carboxylic acid having an ethylenically unsaturated group and a polyvalent aromatic alcohol is preferably represented by the following formula (II).

In the formula (II), R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ² is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or methyl.
In the formula (II), q is an integer of 1 to 10. q is preferably an integer of 2 to 6, and more preferably 2 or 3.
C _q H _2q in the formula (II) means a chain alkylene group which may have a branch.

  In the formula (II), m2 is an integer of 1 to 60. m2 is preferably an integer of 2 to 30, more preferably an integer of 3 to 20, and most preferably an integer of 4 to 15. When m2 is an integer of 2 or more, the plurality of chain alkylene groups may be different from each other. For example, it may be a combination of ethylene and propylene. When a plurality of chain alkylene groups are different, a partial structure in which alkylene oxide units are copolymerized exists in the polymerizable aromatic compound. Copolymerization may be random, block, or alternating.

In the formula (II), Ar is an arylene group or a substituted arylene group. Ar is preferably an arylene group, more preferably phenylene, and most preferably p-phenylene. The definitions and examples of the arylene group and the substituted arylene group are as described in the formula (I).
In the formula (II), n2 is an integer of 2 to 6. n2 is preferably 2, 3 or 4, more preferably 2 or 3, and most preferably 2. L ² is a divalent to hexavalent (n2 valent) linking group. The definition and examples of the divalent to hexavalent linking group are as described in the formula (I).

Examples of esters of a carboxylic acid having an ethylenically unsaturated group and a polyvalent aromatic alcohol are 2,2-bis [4- (3- (meth) acryloxy-2-hydroxypropoxy) phenyl] propane, 2, 2-bis [4-((meth) acryloxyethoxy) phenyl] propane, 2,2-bis (4-((meth) acryloyloxypoly (2-20) ethoxy) phenyl) propane, 2,2-bis [ 4-((meth) acryloxypropoxy) phenyl] propane, 2,2-bis (4-((meth) acryloyloxypoly (2-20) propoxy) phenyl) propane.
Examples of 2,2-bis (4-((meth) acryloyloxypoly (2-20) ethoxy) phenyl) propane are 2,2-bis (4-((meth) acryloyloxydiethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxypentaethoxy) phenyl) propane, 2,2-bis (4- ((Meth) acryloyloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxypentadecaethoxy) phenyl) propane.

Examples of 2,2-bis (4-((meth) acryloyloxypoly (2-20) propoxy) phenyl) propane are 2,2-bis (4-((meth) acryloyloxydipropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxypentapropoxy) phenyl) propane, 2,2-bis (4- ((Meth) acryloyloxydecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxypentadecapropoxy) phenyl) propane.
The polyalkylene oxide moiety contained in the polyvalent aromatic alcohol may contain a polyethylene oxide chain and a polypropylene oxide chain (for example, described in WO 01/98832 pamphlet). Commercially available products (eg, BPE-200, BPE-500, BPE-1000, manufactured by Shin-Nakamura Chemical Co., Ltd.) can also be obtained as esters of carboxylic acids having an ethylenically unsaturated group and polyvalent aromatic alcohols.

An example of an amide of an aliphatic carboxylic acid having an ethylenically unsaturated group and a polyvalent aromatic amine includes xylylene bis (meth) acrylamide.
Examples of urethanes of polyvalent aromatic alcohols and ethylenically unsaturated isocyanates include alkylene oxide (eg, ethylene oxide, propylene oxide) adducts of bisphenol and 2-isocyanatoethyl (meth) acrylate or α, α-dimethyl- Contains urethane with vinylbenzyl isocyanate.
Examples of the carboxylic acid adduct having an ethylenically unsaturated group of the polyvalent glycidyl aromatic compound include a novolac type epoxy resin and bisphenol A diglycidyl ether.

The ethylenically unsaturated alcohol adducts of polyvalent aromatic isocyanates are disclosed in JP-B-48-41708, JP-A-51-37193, JP-B-5-50737, JP-A-7-7208, and JP-A-2001-154346. No. 2001-356476.
Examples of polyvalent aromatic isocyanates are xylene diisocyanate, toluene diisocyanate, phenylene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-diphenyl diisocyanate. Including naruto. These burettes, these trimers, adducts thereof with polyhydric alcohols (eg, trimethylolpropane, pentaerythritol, glycerin), and these ethylene oxide adducts are also included in the polyvalent aromatic isocyanate.

The ester of the polyvalent aromatic acid and the ethylenically unsaturated alcohol is preferably an allyl alcohol ester or a vinyl alcohol ester.
Examples of esters of allyl alcohol include diallyl phthalate, triallyl trimellitate, diallylbenzene disulfonate.
Examples of esters of vinyl alcohol include divinyl phthalate, divinyl terephthalate, divinyl benzene-1,3-disulfonate.

Examples of aromatic divinyl ethers include bisphenol A divinyl ether. In addition, although an ethylenically unsaturated polymerizable compound is generally radically polymerizable, divinyl ether is cationically polymerizable like a ring-opening polymerizable compound (eg, epoxy compound).
Examples of the aromatic compound having a plurality of ethylenically unsaturated groups include divinylbenzene, 4-allylstyrene, and 4-isopropenestyrene.

  Polyfunctional polymerizable aromatic compounds other than ethylenically unsaturated polymerizable compounds include epoxy compounds (eg, novolac-type epoxy resins, bisphenol A diglycidyl ether), oxetane compounds (eg, 1,4-bis [(3- Ethyl-3-oxetanylmethoxy) methyl] benzene). Epoxy compounds and oxetane compounds are described in WO 01/22165.

Two or more polyfunctional polymerizable aromatic compounds may be used in combination.
The polyfunctional polymerizable aromatic compound is preferably included in the added layer in a range of 5 to 90% by mass, more preferably in a range of 15 to 60% by mass, and in a range of 20 to 50% by mass. More preferably it is included.
When the polymerizable urethane compound and the polyfunctional polymerizable aromatic compound are used in combination, 10 to 90% by mass of the total polymerizable compound is preferably a polyfunctional polymerizable aromatic compound, and 20 to 80% by mass is polyfunctional. It is more preferably a polymerizable aromatic compound, and most preferably 30 to 70% by mass is a polyfunctional polymerizable aromatic compound.

(Other polymerizable compounds)
The photosensitive layer can contain other polymerizable compounds in addition to the polymerizable urethane compound or the polymerizable aromatic compound. Another polymerizable compound is a polymerizable aliphatic compound that does not contain a urethane bond.
The polymerizable functional group of the other polymerizable compound is preferably a ring-opening polymerizable group or an addition polymerizable group, and more preferably an addition polymerizable group. The addition polymerizable group is particularly preferably an ethylenically unsaturated group.
Other polymerizable compounds can be classified into monofunctional aliphatic polymerizable compounds and polyfunctional aliphatic polymerizable compounds. The monofunctional aliphatic polymerizable compound is the same as the monomer exemplified as the raw material of the above-described carboxyl group-containing vinyl copolymer. A polyfunctional aliphatic polymerizable compound is more preferable than a monofunctional aliphatic polymerizable compound.

The polyfunctional aliphatic polymerizable compound is an ester of an aliphatic carboxylic acid having an ethylenically unsaturated group and a polyhydric alcohol, an amide of an aliphatic carboxylic acid having an ethylenically unsaturated group and a polyvalent aliphatic amine, An aliphatic carboxylic acid adduct having an ethylenically unsaturated group of a polyvalent aliphatic glycidyl compound, an ethylenically unsaturated alcohol adduct of a polyvalent aliphatic isocyanate, a polyvalent aliphatic acid and an ethylenically unsaturated alcohol An ester of an ester, divinyl ether, an aliphatic carboxylic acid having an ethylenically unsaturated group and an alcohol having an ethylenically unsaturated group is preferable.
The polyfunctional aliphatic polymerizable compound is an ester of an aliphatic carboxylic acid having an ethylenically unsaturated group (unsaturated fatty acid) and a polyhydric aliphatic alcohol, or an aliphatic carboxylic acid having an ethylenically unsaturated group (unsaturated). More preferred is an amide of a (fatty acid) and a polyvalent aliphatic amine.

Examples of the aliphatic carboxylic acid (unsaturated fatty acid) having an ethylenically unsaturated group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid and maleic acid.
Examples of polyhydric aliphatic alcohols are ethylene glycol, poly (2-18) ethylene glycol di (meth) acrylate, propylene glycol, poly (2-18) propylene glycol, neopentyl glycol, ethylene oxide modified neopentyl glycol, propylene oxide Modified neopentyl glycol, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (hydroxypropyl) ether, trimethylolethane, 1,3-propanediol, 1,3-butanediol 1,4-butanediol, 1,6-hexanediol, tetramethylene glycol, 1,4-cyclohexanediol, 1,2,4-butanetriol, 1,5-pentanediol Pentaerythritol, dipentaerythritol, sorbitol, dimethylol dicyclopentane, tricyclodecane diol, neopentyl glycol, neopentyl glycol-modified trimethylol propane, trimethylol propane and ethylene oxide addition, polybutylene glycol, glycerin.

  Examples of esters of (meth) acrylic acid and polyhydric aliphatic alcohols include ethylene glycol di (meth) acrylate, poly (2-18) ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, poly ( 2-18) Propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified neopentyl glycol di (meth) acrylate, propylene oxide modified neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) ) Acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, trimethylolethane tri (meth) acrylate, 1,3- Lopandiol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate 1,4-cyclohexanediol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, 1,5-pentanediol (meth) acrylate, pentaerythritol di, tri or tetra (meth) acrylate, Dipentaerythritol penta or hexa (meth) acrylate, sorbitol tri, tetra, penta or hexa (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclodecane di (meth) acrylate, ne Neopentyl glycol di (meth) acrylate, neopentyl glycol-modified trimethylolpropane di (meth) acrylate.

  Examples of poly (2-18) ethylene glycol di (meth) acrylate are diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate , Dodecaethylene glycol di (meth) acrylate, tetradecaethylene glycol di (meth) acrylate). Examples of poly (2-18) propylene glycol di (meth) acrylate are dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, dodecapropylene glycol di (meth) ) Acrylate, ethylene oxide added trimethylolpropane tri (meth) acrylate ester, polybutylene glycol di (meth) acrylate, glycerin di or tri (meth) acrylate.

Esters of (meth) acrylic acid and polyhydric aliphatic alcohols also include di (meth) acrylates of alkylene glycol containing an ethylene glycol chain and a propylene glycol chain (described in WO 01/98832 pamphlet).
Esters of (meth) acrylic acid and polyhydric aliphatic alcohols are ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethylene glycol Dialkylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol triacrylate, pentaerythritol di (meth) acrylate, dipentaerythritol pentane (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, diglycerin di (meth) Acrylate, 1,3-propanediol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 1,5-pentanediol (meth) acrylate , Neopentyl glycol di (meth) acrylate, and tri (meth) acrylic acid ester of trimethylolpropane added with ethylene oxide are preferable.

The polyhydric aliphatic alcohol may have a molecular structure having hydroxyl groups at both ends of the polyester chain. Polyester (meth) acrylates and oligomers thereof are described in JP-A-48-64183, JP-B-49-43191, and JP-A-52-30490.
The polyhydric aliphatic alcohol includes an alcohol of an aliphatic heterocyclic compound. Examples of esters of (meth) acrylic acid and aliphatic heterocyclic alcohols are tri ((meth) acryloyloxyethyl) isocyanurate, isocyanuric acid tri (meth) acrylate, ethylene oxide modified isocyanuric acid tri (meth) acrylate. Including.

Examples of esters of itaconic acid and polyhydric aliphatic alcohols are ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol Diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate.
Examples of esters of crotonic acid and polyhydric aliphatic alcohols include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate.

  Examples of esters of isocrotonic acid and polyhydric aliphatic alcohols include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate.

  Examples of esters of maleic acid and polyhydric aliphatic alcohols include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate.

  Examples of amides of an aliphatic carboxylic acid having an ethylenically unsaturated group and a polyvalent aliphatic amine are methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, 1,6-hexamethylene bis (meth) acrylamide, octa Including methylene bis (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, diethylenetriamine bis (meth) acrylamide.

  Examples of the aliphatic carboxylic acid adduct having an ethylenically unsaturated group of the polyvalent glycidyl compound include butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, Dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether.

The ester of the polyvalent aliphatic acid and the ethylenically unsaturated alcohol is preferably an allyl alcohol ester or a vinyl alcohol ester.
Examples of esters of allyl alcohol include diallyl adipate, diallyl malonate, triallyl isocyanurate.
Examples of esters of vinyl alcohol include divinyl succinate, divinyl adipate, divinyl butane-1,4-disulfonate.

  Examples of the aliphatic divinyl ether include butanediol-1,4-divinyl ether, cyclohexanedimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, dipropylene glycol divinyl ether, hexanediol divinyl ether, trimethylolpropane trivinyl ether, Contains pentaerythritol tetravinyl ether and glycerin trivinyl ether. In addition, although an ethylenically unsaturated polymerizable compound is generally radically polymerizable, divinyl ether is cationically polymerizable like a ring-opening polymerizable compound (eg, epoxy compound).

  Examples of esters of an aliphatic carboxylic acid having an ethylenically unsaturated group and an aliphatic alcohol having an ethylenically unsaturated group are N-β-hydroxyethyl-β- (methacrylamide) ethyl acrylate, N, N-bis. (Β-methacryloyloxyethyl) acrylamide and allyl methacrylate are included.

A polyfunctional polymerizable aliphatic compound other than the ethylenically unsaturated polymerizable compound is an epoxy compound (eg, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl). Ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether). Epoxy compounds are described in WO 01/22165.
The polyfunctional polymerizable aliphatic compound is described as a photocurable monomer and oligomer in Journal of Japan Adhesion Association Vol. 20, No. 7, pp. 300-308 (1984).

[Photopolymerization initiator]
As the photopolymerization initiator used in the photosensitive transfer sheet of the present invention, any compound having the ability to initiate the polymerization of the above-described monomer components can be used, and is particularly sensitive to visible light from the ultraviolet region. Any material can be suitably used. The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm). The photopolymerization initiator may be an activator that generates an active radical by generating an action with a photoexcited sensitizer, and is an initiator that initiates cationic polymerization depending on the type of monomer. May be.

  Examples of the photopolymerization initiator preferably used in the photosensitive layer include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), hexaarylbiimidazoles, organic peroxides, thios. Examples include compounds, ketone compounds, aromatic onium salts, ketoxime ethers, and the like. Of these, the use of a halogenated hydrocarbon having a triazine skeleton, an oxime derivative, hexaarylbiimidazole, and a ketone compound is particularly sensitive to the sensitivity and storability of the photosensitive layer and the adhesion between the photosensitive layer and the printed wiring board forming substrate. From the viewpoint of the above.

Examples of the halogenated hydrocarbon compound having a triazine skeleton include the following compounds.
Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), for example, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4 -Chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-tolyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2 -(4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -1, 3,5-triazine, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- n-nonyl-4,6-bis (trichloromethyl) -1,3 - triazine, and 2-(alpha, alpha, beta-trichloroethyl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

  Compounds described in GB 1388492, for example, 2-styryl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylstyryl) -4,6-bis (trichloro) Methyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and 2- (4-methoxystyryl) -4- Amino-6-trichloromethyl-1,3,5-triazine.

  Compounds described in JP-A-53-133428, for example, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4 -Ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6 -Bis (trichloromethyl) -1,3,5-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and 2- (Acenaphtho-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

  Compounds described in DE 33 37 024, for example, 2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-methoxystyryl) ) Phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (1-naphthylvinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2-chlorostyrylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-thiophen-2-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3 , 5-triazine, 2- (4-thiophene-3-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-furan-2-vinylenef Nyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and 2- (4-benzofuran-2-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5 -Triazine.

  FC Schaefer et al., J. Org. Chem .; 29, 1527 (1964) described compounds such as 2-methyl-4,6-bis (tribromomethyl) -1,3,5-triazine, 2,4,4 6-tris (tribromomethyl) -1,3,5-triazine, 2,4,6-tris (dibromomethyl) -1,3,5-triazine, 2-amino-4-methyl-6-tri (bromomethyl) ) -1,3,5-triazine and 2-methoxy-4-methyl-6-trichloromethyl-1,3,5-triazine.

  Compounds described in JP-A-62-258241, for example, 2- (4-phenylethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-naphthyl-1) -Ethynylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-tolylethynyl) phenyl) -4,6-bis (trichloromethyl) -1,3 5-triazine, 2- (4- (4-methoxyphenyl) ethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-isopropylphenylethynyl) phenyl ) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-ethylphenylethynyl) phenyl) -4,6-bis (trichloromethyl) -1, , 5-triazine.

  Compounds described in JP-A-5-281728, for example, 2- (4-trifluoromethylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,6-difluorophenyl) ) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,6-dichlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,6-Dibromophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

  2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl] -1,3,5-triazine described in JP-A-5-34920, Trihalomethyl-s-triazine compounds described in U.S. Pat. No. 4,239,850, 2,4,6-tris (trichloromethyl) -s-triazine, 2- (4-chlorophenyl) -4,6-bis (Tribromomethyl) -s-triazine and the like.

  In addition, compounds having an oxadiazole skeleton described in US Pat. No. 4,221,976 can be used. Examples of the compound having an oxadiazole skeleton include 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadi Azole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (2-naphthyl) -1,3,4-oxadiazole, 2- Tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxy) Styryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) ) -1,3,4-oxadiazole, 2-tripromemethyl-5-styryl-1,3,4-oxadiazole, and the like.

  Examples of the oxime derivative that can be suitably used in the present invention include compounds represented by the following general formula.

  Examples of the hexaarylbiimidazole that can be used in the present invention include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2 -Fluorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-bromophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2, 2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (3-methoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (4-methoxyphenyl) biimidazole, 2,2′-bis (4- Methoxypheni ) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (2-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-methylphenyl) -4,4', 5,5'-tetraphenylbiimidazole Examples include imidazole, 2,2′-bis (2-trifluoromethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and compounds described in WO 00/52529.

  The above biimidazoles can be easily synthesized by, for example, the methods disclosed in Bull. Chem. Soc. Japan, 33,565 (1960), and J. Org. Chem, 36 (16) 2262 (1971). it can.

  Examples of ketone compounds include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxy. Carbonyl benzolphenone, benzophenone tetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bisdicyclohexylamino) Benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzophenone 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro-thioxanthone 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1 -Propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (eg benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether) Ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - chloro acridone and the like.

  In addition, acridine derivatives (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine, and the like, polyhalogen compounds (for example, carbon tetrabromide, phenyltribromo, etc.) Methylsulfone, phenyltrichloromethyl ketone, etc.), coumarins (eg, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7 -Diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3'-carbonylbis (5,7-di-n-propoxy) Coumarin), 3,3′-carbonylbis (7-diethylaminocoumarin) ), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridyl) Carbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, and the like, and in addition, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206. No., JP-A No. 2002-363207, JP-A No. 2002-363208, JP-A No. 2002-363209, etc.), amines (for example, ethyl 4-dimethylaminobenzoate, 4-dimethyl N-butyl aminobenzoate, phenethyl 4-dimethylaminobenzoate, 4-dimethyla Minobenzoic acid 2-phthalimidoethyl, 4-dimethylaminobenzoic acid 2-methacryloyloxyethyl, pentamethylenebis (4-dimethylaminobenzoate), phenethyl and pentamethylene ester of 3-dimethylaminobenzoic acid, 4-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-dimethylaminobenzoyl) acetate, 4-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl-4-toluidine, N, N-diethyl-3-phenetidine, tribenzylamine, dibenzylphenylamine, N-methyl-N-phenylbenzylamine, 4-bromo-N, N-dimethylaniline, tridodecylamine, aminophen Luolans (ODB, ODBII, etc.), crystal violet lactone, leuco crystal violet, etc.), acylphosphine oxides (eg bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H -Pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.), JP-A-53-133428, JP 57-1819, 57-6096, and Such as the compounds disclosed in U.S. Patent No. 3,615,455 may also be mentioned.

  Furthermore, the vicinal polyketaldonyl compound disclosed in US Pat. No. 2,367,660, the acyloin ether compound described in US Pat. No. 2,448,828, the α-form described in US Pat. No. 2,722,512 Aromatic acyloin compounds substituted with hydrocarbons, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, organoboron compounds described in JP-A-2002-229194, and other exemplified radicals Generators, phosphonium salt compounds (effective as a cationic polymerization initiator) such as triarylsulfonium salts (salts with hexafluoroantimony or hexafluorophosphate), (phenylthiophenyl) diphenylsulfonium salts, WO01 / 71428 Onium in the publication And compounds can also be used.

  One or two or more photopolymerization initiators can be used in combination. As such a combination, for example, a combination of hexaarylbiimidazole and 4-aminoketone described in US Pat. No. 3,549,367, a benzothiazole compound described in Japanese Patent Publication No. 51-48516, and trihalomethyl-s- Combinations of triazine compounds, combinations of aromatic ketone compounds such as thioxanthone and hydrogen donors (eg dialkylamino-containing compounds, phenol compounds, etc.), combinations of hexaarylbiimidazole and titanocene, coumarins, titanocene and phenylglycines Combination with can also be used.

  The use amount of the photopolymerization initiator is generally in the range of 0.1 to 30% by mass, preferably in the range of 0.5 to 20% by mass with respect to all components of the photosensitive layer in each photosensitive layer. It is particularly preferably in the range of 0.5 to 15% by mass. Further, when adjusting the sensitivity difference of each photosensitive layer by the content of the photopolymerization initiator, the photopolymerization property that the amount of the photopolymerization initiator contained in the second photosensitive layer is contained in the first photosensitive layer. The amount may be larger than the amount of initiator. The content of the photopolymerization initiator in the second photosensitive layer is preferably 1.5 to 100 times the content of the photopolymerization initiator in the first photosensitive layer, and more preferably 1.8 to 50 times. The amount is preferably 2 to 20 times.

[Other ingredients]
If necessary, the photosensitive layer may be a thermal polymerization inhibitor, a plasticizer, a color former, a colorant, an adhesion promoter for the substrate surface, and other auxiliary agents (for example, pigments, conductive particles, fillers, antifoaming agents). , Flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, thermal cross-linking agents, surface tension modifiers, chain transfer agents, etc.) may be used in combination, thereby stabilizing the intended photosensitive transfer sheet It is possible to adjust properties such as photographic properties, printout properties and film properties. The above-described components can be added to both the first photosensitive layer and the second photosensitive layer, and the addition amount may be determined according to the purpose, and the addition amount to each photosensitive layer is the same or different. Also good.

[Thermal polymerization inhibitor]
A thermal polymerization inhibitor may be added in order to prevent thermal polymerization or polymerization over time of the polymerizable compound in the photosensitive layer. Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, Chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-Toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

  The addition amount of the thermal polymerization inhibitor is preferably in the range of 0.001 to 5 mass%, more preferably in the range of 0.005 to 2 mass%, particularly preferably relative to the polymerizable compound of the photosensitive layer. Is in the range of 0.01 to 1% by mass. When the addition amount of the thermal polymerization inhibitor exceeds this range, the sensitivity to active energy rays tends to decrease, and when it exceeds this range, the stability during storage tends to decrease.

[Plasticizer]
A plasticizer may be added to control the film physical properties (flexibility) of the photosensitive layer. Examples of plasticizers include dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diphenyl phthalate, diallyl phthalate, octyl capryl phthalate, etc. Acid esters: triethylene glycol diacetate, tetraethylene glycol diacetate, dimethylglycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, triethylene glycol dicabrylate, etc. Glycol esters; phosphates such as tricresyl phosphate and triphenyl phosphate Ters; Amides such as 4-toluenesulfonamide, benzenesulfonamide, Nn-butylbenzenesulfonamide, Nn-butylacetamide; diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dioctyl sebacate Dibasic acid esters such as dioctyl azelate and dibutyl malate; triethyl citrate, tributyl citrate, glycerin triacetyl ester, butyl laurate, dioctyl 4,5-diepoxycyclohexane-1,2-dicarboxylate And glycols such as polyethylene glycol and polypropylene glycol.

  The addition amount of the plasticizer is preferably in the range of 0.1 to 50% by mass, more preferably in the range of 0.5 to 40% by mass, and particularly preferably 1 to 30% by mass with respect to all components of the photosensitive layer. % Range.

[Coloring agent]
The color former may be added to give a visible image (printing function) to the exposed photosensitive layer. Examples of the color former include tris (4-dimethylaminophenyl) methane (leuco crystal violet), tris (4-diethylaminophenyl) methane, tris (4-dimethylamino-2-methylphenyl) methane, and tris (4-diethylamino). -2-methylphenyl) methane, bis (4-dibutylaminophenyl)-[4- (2-cyanoethyl) methylaminophenyl] methane, bis (4-dimethylaminophenyl) -2-quinolylmethane, tris (4-dipropyl) Aminotriarylmethanes such as aminophenyl) methane; 3,6-bis (dimethylamino) -9-phenylxanthine, 3-amino-6-dimethylamino-2-methyl-9- (2-chlorophenyl) xanthine, etc. Aminoxanthines; 3,6-bis (diethylamino) ) -9- (2-ethoxycarbonylphenyl) thioxanthene, 3,6-bis (dimethylamino) thioxanthene and other aminothioxanthenes; 3,6-bis (diethylamino) -9,10-dihydro-9-phenyl Acridine, amino-9,10-dihydroacridines such as 3,6-bis (benzylamino) -9,10-dihydro-9-methylacridine; aminophenoxazines such as 3,7-bis (diethylamino) phenoxazine Aminophenothiazines such as 3,7-bis (ethylamino) phenothiazone; aminodihydrophenazines such as 3,7-bis (diethylamino) -5-hexyl-5,10-dihydrophenazine; bis (4-dimethylaminophenyl); ) Aminophenylmethanes such as anilinomethane; 4-amino-4'-di Aminohydrocinnamic acids such as methylaminodiphenylamine, 4-amino-α, β-dicyanohydrocinnamic acid methyl ester; hydrazines such as 1- (2-naphthyl) -2-phenylhydrazine; 1,4-bis ( Ethylamino) -2,3-dihydroanthraquinones amino-2,3-dihydroanthraquinones; phenethylanilines such as N, N-diethyl-4-phenethylaniline; 10-acetyl-3,7-bis (dimethylamino) ) An acyl derivative of a leuco dye containing basic NH such as phenothiazine; a leuco-like compound that does not have oxidizable hydrogen such as tris (4-diethylamino-2-tolyl) ethoxycarbonylmentane, but can be oxidized to a coloring compound; Id dyes; U.S. Pat. Nos. 3,042,515 and 3,042,5 Organic amines that can be oxidized to a colored form as described in No. 7 (eg, 4,4′-ethylenediamine, diphenylamine, N, N-dimethylaniline, 4,4′-methylenediamine triphenylamine, N-vinylcarbazole). Particularly preferred are triarylmethane compounds such as leuco crystal violet.

  Furthermore, it is known to combine with a halogen compound for the purpose of coloring these leuco bodies. Examples of halogen compounds are halogenated hydrocarbons (eg carbon tetrabromide, iodoform, ethylene bromide, methylene bromide, amyl bromide, isoamyl bromide, amyl iodide, isobutylene bromide, butyl iodide, diphenyl bromide). Methyl, hexachloroethane, 1,2-dibromoethane, 1,1,2,2-tetrabromoethane, 1,2-dibromo-1,1,2-trichloroethane, 1,2,3 tribromopropane, 1-bromo -4-chlorobutane, 1,2,3,4-tetrabromobutane, tetrachlorocyclopropene, hexachlorocyclopentadiene, dibromocyclohexane, 1,1,1-trichloro-2,2-bis (4-chlorophenyl) ethane Halogenated alcohol compounds (for example, 2,2,2-trichloroethanol, tribromoethane, etc.) 1,3-dichloro-2-propanol, 1,1,1-trichloro-2-propanol, di (iodohexamethylene) aminoisopropanol, tribromo-t-butyl alcohol, 2,2,3-trichlorobutane 1,4-diol and the like; halogenated carbonyl compounds (for example, 1,1-dichloroacetone, 1,3-dichloroacetone, hexachloroacetone, hexabromoacetone, 1,1,3,3-tetrachloroacetone, 1,1 , 1-trichloroacetone, 3,4-dibromo-2-butanone, 1,4-dichloro-2-butanone-dibromocyclohexanone, etc.); halogenated ether compounds (eg 2-bromoethyl methyl ether, 2-bromoethyl ethyl ether) , Di (2-bromoethyl) ether, 1,2-dichloroe Halogenated ester compounds (eg, bromoethyl acetate, ethyl trichloroacetate, trichloroethyl trichloroacetate, homopolymers and copolymers of 2,3-dibromopropyl acrylate, trichloroethyl dibromopropionate, α, β-dichloro) Halogenated amide compounds (such as chloroacetamide, bromoacetamide, dichloroacetamide, trichloroacetamide, tribromoacetamide, trichloroethyltrichloroacetamide, 2-bromoisopropionamide, 2,2,2-trichloropropionamide, N-chlorosuccinimide, N-bromosuccinimide, etc.); compounds having sulfur or phosphorus (for example, tribromomethylphenylsulfone, 4-nitrophenyltoxin) Bromomethyl sulfone, 4-chlorophenyl tribromomethyl sulfone, tris (2,3-dibromopropyl) phosphate, etc.), 2,4-bis (such as trichloromethyl) 6-phenyl triazole and the like. Of the organic halogen compounds, a halide having two or more halogen atoms bonded to the same carbon atom is preferable, and a halide having three halogen atoms in one carbon atom is particularly preferable. The organic halogen compounds may be used alone or in combination of two or more. Of these, particularly preferred organic halogen compounds are tribromomethylphenylsulfone and 2,4-bis (trichloromethyl) -6-phenyltriazole.

  The addition amount of the color former is preferably in the range of 0.01 to 20% by mass, more preferably in the range of 0.05 to 10% by mass, and particularly preferably 0.1 to 20% by mass with respect to all the components of the photosensitive layer. It is in the range of 5% by mass. The amount of the halogen compound is generally in the range of 0.001 to 5 mass%, preferably 0.005 to 1 mass%, based on all components of the photosensitive layer.

[dye]
In the photosensitive layer, a dye can be used for the purpose of coloring the photosensitive resin composition for improving handleability or imparting storage stability. Examples of suitable dyes include brilliant green (eg sulfate thereof), eosin, ethyl violet, erythrosine B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymol. Phthalein, Methyl Violet 2B, Quinaldine Red, Rose Bengal, Methanyl-Yellow, Thymolsulfophthalein, Xylenol Blue, Methyl Orange, Orange IV, Diphenyltylocarbazone, 2,7-Dichlorofluorescein, Paramethyl Red, Congo Red , Benzopurpurin 4B, α-naphthyl-red, Nile blue A, phenacetalin, methyl violet, malachite green, parafuchsin, oil blue # 603 (Ori Cement Chemical Industry Co., Ltd.), mention may be made of rhodamine B, and Rotamin 6G, such as Victoria Pure Blue BOH. The counter anion of the cationic dye may be a residue of an organic acid or an inorganic acid. For example, a residue (anion) such as bromic acid, iodic acid, sulfuric acid, phosphoric acid, oxalic acid, methanesulfonic acid, and toluenesulfonic acid. Can be given. Preferred dyes are cationic dyes, such as malachite green oxalate and malachite green sulfate.

  A preferable addition amount of the dye is an amount in the range of 0.001 to 10% by mass with respect to all components of the photosensitive layer. More preferably, it is the range of 0.01-5 mass%, Most preferably, it is the range of 0.1-2 mass%.

[Adhesion promoter]
In order to improve the adhesion between the layers or the adhesion between the photosensitive transfer sheet and the substrate, a known so-called adhesion promoter can be used for each layer.

  As the adhesion promoter, adhesion promoters described in JP-A-5-11439, JP-A-5-341532, and JP-A-6-43638 can be suitably used. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 3-morpholino Methyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinomethyl-thiadiazole-2-thione, and 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole , Amino group-containing benzotriazole, silane coupling agent and the like.

  A preferable addition amount of the adhesion promoter is in the range of 0.001% by mass to 20% by mass with respect to all components of the photosensitive layer. More preferably, it is the range of 0.01-10 mass%, Most preferably, it is the range of 0.1 mass%-5 mass%.

  The photosensitive layer is, for example, J.I. Contains organic sulfur compounds, peroxides, redox compounds, azo and diazo compounds, photoreducible dyes, and organic halogen compounds as described in Chapter 5 of “Light Sensitive Systems” by Korser Also good. Examples of organic sulfur compounds include di-n-butyl disulfide, dibenzyl disulfide, 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, thiophenol, ethyltrichloromethane sulfenate, and 2-mercaptobenzimidazole. be able to. Examples of the peroxide include di-t-butyl peroxide, benzoyl peroxide, and methyl ethyl ketone peroxide. The redox compound is a combination of a peroxide and a reducing agent, and examples thereof include ferrous ions and persulfate ions, ferric ions and peroxides. Examples of the azo and diazo compounds include α, α'-azobisiributyronitrile, 2-azobis-2-methylbutyronitrile, and diaminonium of 4-aminodiphenylamine. Examples of the photoreductive dye include rose bengal, erythrosine, eosin, acriflavine, lipoflavin, and thionine.

[Surfactant]
A known surfactant can be added in order to improve the surface unevenness that occurs when manufacturing the photosensitive transfer sheet. Examples of the surfactant can be appropriately selected from anionic and cationic surfactants, nonionic surfactants, amphoteric surfactants, fluorine-containing surfactants, and the like. The addition amount is preferably 0.001 to 10% by mass with respect to the solid content of the photosensitive resin composition, and if it is less than 0.001% by mass, the effect of improving the surface condition cannot be obtained. It is easy to generate a problem of lowering. Fluoroaliphatic group having fluorine chain with hydrogen atoms bonded to at least 3 carbon atoms counted from the non-bonding end as a fluorosurfactant containing 40 mass% or more of carbon atoms with 3 to 20 carbon chains A polymer surfactant having an acrylate or methacrylate having a copolymer as a copolymer component is also preferred.

[Barrier layer]
In the photosensitive transfer sheet or photosensitive laminate of the present invention, a barrier layer is preferably disposed between the first photosensitive layer and the second photosensitive layer. The barrier layer has a role of preventing or suppressing migration of substances contained in the photosensitive layer, support, and protective film, and preventing and suppressing external influences such as oxygen and humidity. For example, the installation of the barrier layer has an effect of preventing the sensitivity and film physical properties from changing due to the components of each photosensitive layer moving to another layer.

  The barrier layer preferably contains a resin, and preferably contains a resin having an affinity for water or a lower alcohol having 1 to 4 carbon atoms as a main component. The affinity means that the solvent has emulsification, dispersion, swelling, partial dissolution, and wettability. Moreover, it is preferable that a barrier layer contains resin soluble as a main component with respect to water or a C1-C4 lower alcohol.

  In the production of the barrier layer, a binder similar to that for the photosensitive layer may be used, but a layer made of a different binder is preferable. Examples of such a polymer include various alcohol-soluble, water-soluble polymers, alcohol-dispersible, water-dispersible, emulsifiable or alkali-soluble polymers, such as polyvinyl alcohol (including modified polyvinyl alcohols), polyvinyl pyrrolidone, Examples thereof include water-soluble polyamide, gelatin, cellulose, and derivatives thereof. These polymers may be used alone or in combination of two or more. Furthermore, various polymers such as an acrylic polymer, an amide polymer, and an ester polymer may be added as long as water solubility and alkali water solubility are not impaired. For the barrier layer, the thermoplastic resin described in Japanese Patent No. 2794242 and compounds used in the intermediate layer can also be used.

[Production of photosensitive transfer sheet]
The photosensitive transfer sheet of the present invention can be produced, for example, as follows.
First, the above various materials are dissolved, emulsified or dispersed in water or a solvent to form a first photosensitive resin composition solution for forming a first photosensitive layer and a second photosensitive resin composition for forming a second photosensitive layer. Prepare each solution. In the case of having a barrier layer, a solution for forming the barrier layer is prepared.

  Examples of the solvent for the first photosensitive resin composition solution and the second photosensitive resin composition solution include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, and n-hexanol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate Esters; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, monochlorobenzene Ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, and the like. You may mix and use. A known surfactant may be added to the first photosensitive resin composition solution and the second photosensitive resin composition solution.

  As the solvent of the polymer solution for forming the barrier layer, a coating solvent similar to that for the photosensitive layer may be used, or water or a mixed solvent of water and a solvent may be used. As the solvent, the above-mentioned hydrophilic solvents such as alcohols such as methanol, ethanol, n-propanol, isopropanol, and n-butanol can be used. The solvent may be used so that the coating liquid has a solid content of 10% to 90%.

  Next, a 1st photosensitive resin composition solution is apply | coated on a support body, and a 1st photosensitive layer is formed by drying. In the case of having a barrier layer, a coating solution for forming a barrier layer is applied onto the first photosensitive layer and dried. A second photosensitive resin composition solution is applied thereon and dried to form a second photosensitive layer. As described above, the application in the case of multilayering may be sequential coating or simultaneous multilayer coating. The coating method of the photosensitive resin composition solution is not particularly limited. For example, spray method, roll coating method, spin coating method, slit coating method, extrusion coating method, curtain coating method, die coating method, gravure coating method, wire Various methods such as a bar coating method and a knife coating method can be employed. As drying conditions, although it changes also with each component, the kind of solvent, a use ratio, etc., it is about 30 seconds-15 minutes normally at the temperature of 60-110 degreeC.

  Even when there are more photosensitive layers than two layers, a desired photosensitive transfer sheet can be produced by repeating the same operation. By making the photosensitive layer into two or more layers, the total thickness of the photosensitive layers can be in the range of 10 μm to 1 mm.

[Support and protective film]
It is desirable that the support is capable of peeling the photosensitive layer, has good light transmittance, and has good surface smoothness. The support is preferably made of synthetic resin and transparent. Examples of the support include polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly (meth) acrylic acid ester copolymer, polyvinyl chloride, Various plastics such as polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, cellulosic film, nylon film, etc. A film can be mentioned. Furthermore, a composite material composed of two or more of these can also be used. Of these, polyethylene terephthalate is particularly preferred. The thickness of the support is preferably 2 to 150 μm, more preferably 5 to 100 μm, and particularly preferably 8 to 50 μm. The support is preferably a long support. The length of the long support used for producing the photosensitive transfer sheet of the present invention may be arbitrarily determined, and for example, a length of 10 m to 20000 m can be used.

  In the photosensitive transfer sheet of the present invention, a protective film can be disposed on the second photosensitive layer. Examples of the protective film include those used for the support and paper or paper laminated with polyethylene or polypropylene. In particular, polyethylene film and polypropylene film are preferable. The thickness of the protective film is preferably in the range of 5 to 100 μm, more preferably in the range of 8 to 50 μm, particularly preferably in the range of 10 to 30 μm. At that time, it is necessary that the adhesive force A between the photosensitive layer and the support and the adhesive force B between the photosensitive layer and the protective film satisfy the relationship of adhesive force A> adhesive force B. Examples of the support / protective film combination include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. Moreover, the above adhesive force relationship can be satisfied by surface-treating at least one of the support and the protective film. The surface treatment of the support may be performed in order to increase the adhesive strength with the photosensitive layer. For example, coating of an undercoat layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow discharge irradiation treatment , Active plasma irradiation treatment, laser beam irradiation treatment and the like. The coefficient of static friction between the support and the protective film is also important. These static friction coefficients are preferably 0.3 to 1.4, particularly preferably 0.5 to 1.2. If it is less than 0.3, it slips too much, so that when it is made into a roll, a winding deviation occurs. Moreover, when it exceeds 1.4, it will become difficult to wind in a favorable roll shape.

  The photosensitive transfer sheet of the present invention is wound, for example, on a cylindrical core, wound into a roll with a long body, and stored. What is necessary is just to determine the length of this elongate body arbitrarily, for example, what is necessary is just to select in the range of 10 m to 20000 m. The slit may be processed so as to be easy for the user to use, and it may be a long body in the range of 100 m to 1000 m and may be formed into a roll. In this case, it is preferable to wind the support so that the support is on the outermost side. The roll-shaped photosensitive transfer sheet may be slit into a sheet shape. When storing, it is preferable to install a separator (especially moisture-proof and desiccant-containing) on the end surface from the viewpoint of protecting the end surface and preventing edge fusion, and use low moisture-permeable materials for packaging. Is preferred.

  The protective film may be surface treated. The surface treatment is performed to adjust the adhesion between the protective film and the photosensitive layer. For example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, and polyvinyl alcohol is provided on the surface of the protective film. The undercoat layer is generally formed by applying the polymer coating solution onto the surface of the protective film and then drying at 30 to 150 ° C. (especially 50 to 120 ° C.) for 1 to 30 minutes. In addition to the photosensitive layer, the barrier layer, the support, and the protective film, a cushion layer, a release layer, an adhesive layer, a light absorption layer, a surface protective layer, and the like may be included.

[Substrate]
The substrate to which the photosensitive transfer sheet of the present invention is transferred can be arbitrarily selected from those having high surface smoothness to those having an uneven surface. Preferably, a plate-like substrate, a so-called substrate is used. Specific examples include a substrate for producing a known printed wiring board, a glass plate (such as a soda glass plate), a synthetic resin film, paper, and a metal plate.

  The substrate comprises a second photosensitive layer comprising a photosensitive resin composition containing a binder, a polymerizable compound, and a photopolymerization initiator, and a photosensitive resin composition comprising a binder, a polymerizable compound, and a photopolymerization initiator. A photosensitive laminate is formed by laminating a first photosensitive layer exhibiting a light sensitivity relatively lower than that of the second photosensitive layer in this order. Furthermore, it is preferable to form a photosensitive laminate in which a barrier layer is disposed between the first photosensitive layer and the second photosensitive layer.

  The photosensitive transfer sheet of the present invention is widely used as printed wiring boards, color filters, pillar materials, rib materials, spacers, display members such as partition walls, various image forming materials such as holograms, micromachines, and proofs, and pattern forming materials. Is possible. Among these, application to a printed wiring board and a display member is preferable, and application to a printed wiring board is particularly preferable.

[Pattern formation method]
The photosensitive transfer sheet of the present invention comprises (1) a step of obtaining a laminate by laminating the second photosensitive layer on the substrate so as to be on the substrate side, and (2) the first photosensitive layer of the laminate. Irradiating a predetermined image pattern from the side, curing both the first photosensitive layer and the second photosensitive layer in the irradiated region, (3) removing the support from the laminate, and (4) A cured resin formed by curing the first photosensitive layer and the second photosensitive layer on the substrate, including a step of developing the laminate and removing an uncured portion in the laminate. A desired pattern can be formed by a method of forming an image pattern composed of an existing area and an area where no cured resin exists.

  The photosensitive transfer sheet of the present invention includes (1) a step of laminating a second photosensitive layer on a substrate in a positional relationship on the substrate side to obtain a laminate, and (2) a first photosensitive of the laminate. The first of the regions irradiated with light having an image pattern defining a region to be irradiated with light of at least two different levels of irradiation energy amount from the side of the layer, and receiving a relatively large amount of light irradiation energy amount A step of curing both the photosensitive layer and the second photosensitive layer, and curing the second photosensitive layer in a region irradiated with light having a relatively small amount of light irradiation energy; (3) removing the support from the laminate. A resin formed by curing both the first photosensitive layer and the second photosensitive layer on the substrate, including a step and (4) developing the laminate to remove an uncured portion in the laminate. The area where there is, formed by curing the second photosensitive layer Region resin is present which, and by a method for forming an image pattern composed of areas which the cured resin is not present, it is also possible to form a desired pattern.

  However, in the above method, instead of performing the step (3) of removing the support from the laminated body between the step (2) and the step (4), the step (1) and the step (2) You may go between.

  As a light source for light irradiation in the step (2), when light irradiation is performed through a support, an electromagnetic wave that transmits the support and activates a photopolymerization initiator or a sensitizer used, and a wavelength of 300 are used. A light source that generates ultraviolet to visible light in the range of ˜1500 nm, preferably 320 to 800 nm, particularly preferably a light source in the range of 330 nm to 650 nm is used. For example, a known light source such as a (super) high pressure mercury lamp, a xenon lamp, a carbon arc lamp, a halogen lamp, a fluorescent tube for a copying machine, an LED, a semiconductor laser, or the like can be used. In addition, an electron beam or an X-ray may be used. Even when light irradiation is performed after the support is peeled off, a similar light source can be used. Among these, the light irradiation is preferably performed by laser light irradiation, and the laser wavelength is preferably in the range of 200 to 1500 nm, more preferably in the range of 300 to 800 nm, particularly preferably in the range of 370 nm to 650 nm, and 400 nm to The range of 450 nm is most preferable.

[Method of manufacturing printed wiring board]
The photosensitive transfer sheet of the present invention can be suitably used for the production of a printed wiring board, particularly for the production of a printed wiring board having a hole such as a through hole or a via hole.

  The photosensitive transfer sheet of the present invention comprises (1) a step of obtaining a laminate by laminating the second photosensitive layer on the substrate so as to be on the substrate side, and (2) the first photosensitive layer of the laminate. Irradiating a predetermined wiring pattern from the side, curing both the first photosensitive layer and the second photosensitive layer in the irradiated region, (3) removing the support from the laminate, and (4) The first photosensitive layer and the second photosensitive layer are cured together on the printed wiring board forming substrate, including a step of developing the laminate and removing an uncured portion in the laminate. A desired pattern can be formed by a method of forming a wiring pattern composed of a region covered with the formed cured resin and a region where the substrate surface is exposed.

  The photosensitive transfer sheet of the present invention includes (1) a step of laminating a second photosensitive layer on a substrate in a positional relationship on the substrate side to obtain a laminate, and (2) a first photosensitive of the laminate. From the side of the layer, the hole portion is irradiated with light having a relatively large amount of light irradiation energy to cure both the first photosensitive layer and the second photosensitive layer, and the wiring formation region has a light irradiation energy amount. A step of irradiating an image pattern that cures the second photosensitive layer by applying a relatively small amount of light, (3) a step of removing the support from the laminate, and (4) developing the laminate. And a cured resin formed by curing both the first photosensitive layer and the second photosensitive layer on the printed wiring board forming substrate having a hole portion, including a step of removing an uncured portion in the laminate. Formed by hardening the hole part and the second photosensitive layer covered with Region is coated with the cured resin, and the method of forming the composed wiring pattern and a region where the substrate surface is exposed, it is also possible to form a desired pattern.

  In the above method, instead of performing the step of removing the support from the laminate of (3) between step (2) and step (4), between step (1) and step (2) You may go.

  As the light source for light irradiation in the step (2), a light source similar to the above is used when light is irradiated through the support, which is transmitted through the support. The light source is preferably performed by laser light irradiation.

  Thereafter, in order to obtain a printed wiring board, a method of etching or plating the printed wiring board forming substrate on which the wiring pattern is formed, for example, a known subtractive method or additive method (semi-additive method, full additive method). Method). For the purpose of forming a printed wiring board with industrially advantageous tenting according to the present invention, it is preferable to use a subtractive method by etching. The cured resin remaining on the substrate for forming a printed wiring board after the treatment may be peeled off. In the case of the semi-additive method, the copper thin film portion may be further etched after the peeling, and a desired printed wiring board can be formed. Moreover, a multilayer printed wiring board can also be manufactured similarly to the manufacturing method of the said printed wiring board.

  Next, the manufacturing method of the printed wiring board which has a through hole using the photosensitive transfer sheet of this invention is demonstrated, referring FIG. 11 of an accompanying drawing. FIG. 11 shows the case where the photosensitive transfer sheet shown in FIG. 2 or the photosensitive transfer sheet shown in FIG. 4 is used. Even when the photosensitive transfer sheet shown in FIG. 1 or 3 is used, This is the same except that the barrier layer 13 is not included.

  First, as shown in FIG. 11A, a printed wiring board forming substrate 21 having a through hole 22 and having a surface covered with a metal plating layer 23 is prepared. As the printed wiring board forming substrate 21, a copper-clad laminated substrate and a substrate in which a copper plating layer is formed on an insulating base material such as glass-epoxy, or an interlayer insulating film is laminated on these substrates to form a copper plating layer. A substrate (laminated substrate) can be used.

Next, as shown in FIG. 11B, when the photosensitive transfer sheet 10 has a protective film, the protective film is peeled off, and the second photosensitive layer 14 is printed on the printed wiring board forming substrate 21. The pressure roller 31 is used for pressure bonding so as to be in contact with the surface (lamination process). Thereby, a laminate in which the printed wiring board forming substrate 21, the second photosensitive layer 14, the barrier layer 13, the first photosensitive layer 12, and the support 11 are laminated in this order is obtained. Lamination of the photosensitive transfer sheet can be performed at room temperature (15 to 30 ° C.) or under heating (30 to 180 ° C.). In particular, it is preferable to carry out under heating at 60 to 140 ° C. The roll pressure of the pressure-bonding roll is preferably in the range of 1 to 10 kg / cm ² . The crimping speed is preferably 1 to 3 m / min. Further, the printed wiring board forming substrate 21 may be preheated. Moreover, you may laminate | stack under reduced pressure.

  Instead of using the photosensitive transfer sheet, the second photosensitive resin composition solution, the barrier layer solution, and the first photosensitive resin composition solution for manufacturing the photosensitive transfer sheet are arranged on the surface of the printed wiring board forming substrate in this order. By directly applying and drying, a laminate in which the printed wiring board forming substrate, the second photosensitive layer, the barrier layer, and the first photosensitive layer are laminated in this order can also be obtained.

  Next, as shown in FIG. 11C, the photosensitive layer is cured by irradiating light from the surface of the laminate on the support 11 side. At this time, if necessary (for example, when the light transmittance of the support is insufficient), light irradiation may be performed after the support is peeled off. The wiring pattern forming region of the printed wiring board forming substrate 21 is irradiated with light having a light energy amount necessary for curing the second photosensitive layer 14 in a predetermined pattern, and the wiring pattern forming cured layer 16 is thus formed. Are formed (wiring part exposure step). The opening portion of the through hole 22 of the printed wiring board forming substrate and the periphery thereof are irradiated with light having an amount of light energy necessary for curing the first photosensitive layer 12 and the second photosensitive layer 14, respectively. The region of the hardened layer 17 for protecting the metal layer of the hole is formed (hole part exposure step). The wiring portion exposure step and the hole portion exposure step may be performed independently, but are preferably performed in parallel. The exposure is performed by irradiating light through a photomask, or by irradiating laser light using a laser exposure apparatus. In particular, the latter method using a laser exposure apparatus can be formed without using an expensive mask, which eliminates the process problems caused by the mask, and is suitable for the production of a small variety of products. Yes.

  In the case of irradiating light through a photomask, the amount of light energy for curing only the second photosensitive layer is irradiated through the photomask for forming the region of the hardened layer 16 for wiring pattern formation, and the metal of the through hole It is also possible to use a method in which the exposure is performed twice so as to irradiate a light energy amount for curing both the second photosensitive layer and the first photosensitive layer through a photomask for forming the region of the hardened layer 17 for protecting the layer. Alternatively, the phototransmission created so that the light transmittance corresponding to the region portion of the hardened layer 16 for wiring pattern formation is low and the light transmittance corresponding to the region portion of the hardened layer 17 for protecting the metal layer of the through hole is high. Batch exposure can also be performed using a mask. On the other hand, when irradiating laser light using a laser exposure apparatus, it is preferable to perform scanning exposure while changing the light irradiation amount in each necessary region.

  If the support has not yet been peeled off, the support 11 is peeled off from the laminate as shown in FIG. 11D (support peeling step).

  Next, as shown in FIG. 11 (E), the uncured regions of the first photosensitive layer 12, the barrier layer 13 and the second photosensitive layer 14 on the printed wiring board forming substrate 21 are dissolved with an appropriate developer. The pattern of the hardened layer 16 for forming the wiring pattern and the hardened layer 17 for protecting the metal layer of the through hole is formed by removing, and the metal plating layer 23 on the substrate surface is exposed (developing step). As the developer, a developer corresponding to the photosensitive resin composition such as an alkaline aqueous solution, an aqueous developer, or an organic solvent may be used. The developer is preferably a weak alkaline aqueous solution. Base components of this weak alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, potassium phosphate Sodium pyrophosphate, potassium pyrophosphate, borax and the like. The pH of the weak alkaline aqueous solution used for development is preferably about 8 to 12, particularly about 9 to 11. Specifically, 0.1-5 mass% sodium carbonate aqueous solution, potassium carbonate aqueous solution, etc. can be used. The temperature of the developer can be adjusted according to the developability of the photosensitive layer, but is generally preferably about 25 to 40 ° C. In addition, the developer contains a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) and a developing agent. Organic solvents (alcohols, ketones, esters, ethers, amides, lactones, etc.) may be used in combination. As the developer, an aqueous developer obtained by mixing water or an alkaline aqueous solution and an organic solvent may be used, or an organic solvent alone may be used.

  Moreover, you may perform the process which further accelerates | stimulates the hardening reaction of a hardening part by post-heat processing or post-exposure processing as needed after image development. Development may be performed by the wet development method as described above or by a dry development method.

  Next, as shown in FIG. 11F, the exposed metal plating layer 23 on the substrate surface is dissolved and removed with an etching solution (etching step). Since the opening of the through hole 22 is covered with the cured resin composition (tent film) 17, the metal plating of the through hole is performed without the etching solution entering the through hole and corroding the metal plating in the through hole. It will remain in a predetermined shape. Thus, the wiring pattern 24 is formed on the printed wiring board forming substrate 21. When the metal plating layer 23 is made of copper, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, a hydrogen peroxide-based etching solution, or the like can be used as the etching solution. Among these, a ferric chloride solution is particularly preferable from the viewpoint of etching factor.

  Next, as shown in FIG. 11G, the hardened layers 16 and 17 are removed from the printed wiring board forming substrate as a release piece 18 with a strong alkaline aqueous solution or the like (hardened product removing step). Examples of the basic component of the strong alkaline aqueous solution include sodium hydroxide and potassium hydroxide. The pH of the strong alkaline aqueous solution used is preferably about 12 to 14, particularly about 13 to 14. Specifically, 1-10 mass% sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, etc. can be used.

  The printed wiring board may be a multilayer printed wiring board. Moreover, you may use the photosensitive transfer sheet of this invention not only for said etching process but for a plating process. Examples of plating methods include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, hard gold plating, There are gold plating such as soft gold plating.

[Example 1]
A first photosensitive resin composition solution having the following composition was applied to a 20 μm thick polyethylene terephthalate film and dried to form a 25 μm thick first photosensitive layer.

────────────────────────────────────────
First photosensitive resin composition solution ------------------------------
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymer composition (molar ratio): 55 / 11.7 / 4.5 / 28.8, mass average molecular weight: 90000, Tg: 70 parts by mass Dodeca polypropylene glycol diacrylate 6.5 parts by mass Tetraethylene glycol dimethacrylate 1.5 parts by mass 4,4′-bis (diethylamino) benzophenone 0.04 parts by mass Benzophenone 1.0 parts by mass Malachite Green Shu 0.02 parts by weight of acid salt Leuco Crystal Violet 0.2 parts by weight Tribromomethylphenylsulfone 0.1 part by weight Methyl ethyl ketone 60 parts by weight ───────────────────── ───────────────────

  On the 1st photosensitive layer, the 2nd photosensitive resin composition solution which consists of the following composition was apply | coated, and it dried and formed the 2 micrometers photosensitive 2nd photosensitive layer.

────────────────────────────────────────
Second photosensitive resin composition solution ────────────────────────────────────────
Polymer (1) having the following sensitizing functional group 15.45 parts by mass Dodeca polypropylene glycol diacrylate 6.5 parts by mass Tetraethylene glycol dimethacrylate 1.5 parts by mass 2,2′-bis (2-chlorophenyl) -4 , 4 ', 5,5'-Tetraphenylbiimidazole 1.04 parts by weight Malachite green oxalate 0.02 parts by weight Leuco Crystal Violet 0.2 parts by weight Tribromomethylphenylsulfone 0.1 parts by weight Methyl ethyl ketone 40 parts by weight 1-Methoxy-2-propanol 20 parts by mass -----------------------------

Polymer having sensitized functional group (1)
Mass average molecular weight: 60,000 Copolymerization ratio: mol%

A 20 μm thick polyethylene film was laminated on the second photosensitive layer to obtain a photosensitive transfer sheet. In all the layers, the layer thickness unevenness was within ± 5%.
When the sensitivity of the photosensitive transfer sheet was measured by the method described later, the shortest development time was 25 seconds, and the amount of light energy A required to cure the second photosensitive layer was ² mJ / cm ^2. The amount of light energy B required for curing was 40 mJ / cm ² , and the amount of light energy C required until curing of the first photosensitive layer was 14 mJ / cm ² .

[Example 2]
A photosensitive transfer sheet was prepared in the same manner as in Example 1 except that the polymer (2) having the following sensitizing functional group was used instead of the polymer (1) having the sensitizing functional group.

Polymer having sensitized functional group (2)
Mass average molecular weight: 42,000 Copolymerization ratio: mol%

When the sensitivity of the photosensitive transfer sheet was measured by the method described later, the shortest development time was 25 seconds, and the amount of light energy A required to cure the second photosensitive layer was ² mJ / cm ^2. The amount of light energy B required for curing was 40 mJ / cm ² , and the amount of light energy C required until curing of the first photosensitive layer was 14 mJ / cm ² .

[Example 3]
A photosensitive transfer sheet was prepared in the same manner as in Example 1 except that the polymer (3) having the following sensitizing functional group was used instead of the polymer (1) having the sensitizing functional group.

Polymer having sensitized functional group (3)
Mass average molecular weight: 38,000 Copolymerization ratio: mol%

When the sensitivity of the photosensitive transfer sheet was measured by the method described later, the shortest development time was 25 seconds, and the amount of light energy A required to cure the second photosensitive layer was ² mJ / cm ^2. The amount of light energy B required for curing was 40 mJ / cm ² , and the amount of light energy C required until curing of the first photosensitive layer was 14 mJ / cm ² .

[Example 4]
On the first photosensitive layer formed in Example 1, a water-soluble polymer solution having the following composition was applied and dried to form a 1.6 μm thick barrier layer.

────────────────────────────────────────
Water-soluble polymer solution ────────────────────────────────────────
Polyvinyl alcohol (PVA205, manufactured by Kuraray Co., Ltd.) 13 parts by mass Polyvinylpyrrolidone 6 parts by mass Water 200 parts by mass Methanol 180 parts by mass
────────────────────────────────────────

A second photosensitive layer was formed on the barrier layer in the same manner as in Example 1.
A 20 μm thick polyethylene film was laminated on the second photosensitive layer to obtain a photosensitive transfer sheet. In all the layers, the layer thickness unevenness was within ± 5%.

[Comparative Example 1]
A photosensitive transfer sheet was prepared in the same manner as in Example 1 except that the film thickness of the first photosensitive layer in Example 1 was changed to 30 μm and the barrier layer and the second photosensitive layer were not applied.
When the sensitivity of the photosensitive transfer sheet thus obtained was measured by the method described later, the shortest development time was 25 seconds, and the amount of light energy B required to cure the photosensitive layer was 40 mJ / cm ^2. The amount of light energy C required until the curing of was started was 14 mJ / cm ² .

[Comparative Example 2]
The first photosensitive layer and the barrier layer in Example 1 were not applied, and a photosensitive transfer sheet consisting only of the second photosensitive layer having a layer thickness of 5 μm was prepared. When the sensitivity of the photosensitive transfer sheet thus obtained was measured by the method described later, the shortest development time was 10 seconds or less, and the amount of light energy B required to cure the second photosensitive layer was 4 mJ / cm ² .

[Measurement method of sensitivity]
(1) Measuring method of shortest development time The second photosensitive layer of the photosensitive transfer sheet while peeling the protective film of the photosensitive transfer sheet on the surface of a copper clad laminate (without through-holes) that has been polished, washed and dried. The photosensitive transfer sheet is pressure-bonded using a laminator (MODEL8B-720-PH, manufactured by Taisei Laminator Co., Ltd.) so as to be in contact with the substrate, and a copper-clad laminate, a second photosensitive layer (in Example 4, further) Barrier layer), first photosensitive layer, and polyethylene terephthalate film are laminated in this order. The pressure bonding conditions were a pressure roll temperature of 105 ° C., a pressure roll pressure of 3 kg / cm ² , and a pressure bonding speed of 1 m / min. The polyethylene terephthalate film is peeled off from the laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed at a pressure of 0.15 MPa over the entire surface of the photosensitive layer on the copper clad laminate. The time required from the start of spraying of the aqueous sodium carbonate solution until the photosensitive layer on the copper clad laminate is dissolved and removed is measured, and this is taken as the shortest development time.

(2) Measurement of sensitivity A photosensitive transfer sheet is laminated on a substrate in the same manner as the measurement of the shortest development time. The photosensitive transfer sheet photosensitive layer, polyethylene terephthalate using an exposure apparatus having the phthalate film side of the laser light source of 405 nm, 0.1 mJ / cm ² from 2.5 times intervals until 100 mJ / cm ² light energy of different light To cure the photosensitive layer. After standing at room temperature for 10 minutes, the polyethylene terephthalate film is peeled off from the laminate. On the entire surface of the resin composition layer on the copper clad laminate, a 1% by mass aqueous sodium carbonate solution at 30 ° C. was sprayed at a spray pressure of 0.15 MPa for a time twice as long as the shortest development time obtained in (1) above. The cured resin composition is dissolved and removed, and the thickness of the remaining cured layer is measured. Next, a sensitivity curve is obtained by plotting the relationship between the light irradiation amount and the thickness of the cured layer. From the sensitivity curve thus obtained, the amount of light energy (light energy amount A) when the thickness of the cured layer was 5 μm, and the thickness of the cured layer was 30 μm (31.6 μm in Examples 4 to 7). The light energy amount (light energy amount B) and the light energy amount (light energy amount C) when the thickness of the cured layer exceeds 5 μm are read.

[Measurement method of resolution]
A laminate in which a copper-clad laminate, a second photosensitive layer, a barrier layer, a first photosensitive layer, and a polyethylene terephthalate film are laminated in this order under the same conditions as the evaluation method for the shortest development time in (1) above is prepared. And let stand at room temperature (23 ° C., 55% RH) for 10 minutes. From the top of the polyethylene terephthalate film of the obtained laminate, an exposure apparatus having a laser light source of 405 nm is used to expose each line width in increments of 5 μm from 10 μm to 50 μm with a line width / space = 1/1. The exposure amount at this time is the amount of light energy that cures the second photosensitive layer of each photosensitive transfer sheet. After standing at room temperature for 10 minutes, the polyethylene terephthalate film is peeled off from the laminate. An uncured resin is sprayed on the entire surface of the resin composition layer on the copper-clad laminate by spraying a 1% by mass sodium carbonate aqueous solution at 30 ° C. at a spray pressure of 0.15 MPa for twice the shortest development time obtained above. Dissolve the composition. The surface of the copper-clad laminate with the cured resin pattern thus obtained was observed with an optical microscope, and the minimum line width without any abnormalities such as tsumari and twisting was measured on the cured resin pattern line. To do. The smaller the numerical value, the better the resolution.

[Evaluation of sensitivity fluctuation over time]
The photosensitive transfer sheet was stored at 60 ° C. for 3 days, and the sensitivity was measured in the same manner as described above.

Table 1 ─────────────────────────────────────────
Photosensitive transfer sheet Resolution Tents Sensitivity variation over time ────────────────────────────────────── ──
Example 1 20 μm Good None Example 2 20 μm Good None Example 3 20 μm Good None Example 4 20 μm Good None Comparative Example 1 40 μm Good None Comparative Example 2 20 μm Defect None ──────────── ──────────────────────────

It is a schematic cross section of an example of the photosensitive transfer sheet according to the present invention. It is a schematic cross section of the other example of the photosensitive transfer sheet according to the present invention. It is a schematic cross section of the other example of the photosensitive transfer sheet according to the present invention. It is a schematic cross section of the other example of the photosensitive transfer sheet according to the present invention. It is a graph which shows the sensitivity curve showing the relationship between the irradiation amount of light, and the thickness of a hardening layer when light is irradiated to the photosensitive transfer sheet of this invention from the support body side. It is a schematic cross section of an example of the photosensitive transfer sheet according to the present invention. It is a schematic cross section of the other example of the photosensitive transfer sheet according to the present invention. It is a schematic cross section of the other example of the photosensitive transfer sheet according to the present invention. It is a schematic cross section of the other example of the photosensitive transfer sheet according to the present invention. It is a schematic diagram which shows the example of an image (hardened layer pattern) which can be formed using the photosensitive transfer sheet whose photosensitive layer according to this invention is three layers. It is process drawing which shows the manufacturing process of the printed wiring board which has a through hole according to this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Photosensitive transfer sheet 11 Support body 12 1st photosensitive layer 13 Barrier layer 14 2nd photosensitive layer 15 Protective film 16 Hardened layer for wiring pattern formation 17 Hardened layer for metal layer protection of through-hole 18 Release piece 21 Printed wiring board formation Substrate 22 Through hole 23 Metal plating layer 24 Wiring pattern 31 Pressure roller 50 Photosensitive transfer sheet 51 Support body 52 First photosensitive layer 53 Barrier layer 54 Second photosensitive layer 55 Third photosensitive layer 56 Protective film 57 Substrate

Claims (47)

  A first photosensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator on the support, and a photosensitivity relatively higher than the photosensitivity of the first photosensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator. The second photosensitive layer is laminated in this order, and at least one binder of the first photosensitive layer and the second photosensitive layer is a polymer having a sensitizing functional group, and the sensitizing functional group has an increase in molecular weight of 1000 or less. A photosensitive transfer sheet, which corresponds to an atomic group obtained by removing one monovalent atom or group from a dye-sensitive dye.   The photosensitive transfer sheet according to claim 1, wherein the polymer having a sensitizing functional group has an absorption maximum wavelength in the range of 300 to 500 nm.   The sensitizing dye having a molecular weight of 1000 or less is selected from the group consisting of a cyanine dye, a merocyanine dye, a xanthene dye, a phenothiazine dye, an acridine dye, an anthraquinone dye, an acridone dye, a coumarin dye, an aniline dye, and a squarylium dye. Photosensitive transfer sheet.   The photosensitive transfer sheet according to claim 1, wherein the binder of the second photosensitive layer is a polymer having a sensitizing functional group.   The photosensitive transfer sheet according to claim 1, wherein the polymer having a sensitizing functional group is a copolymer having a repeating unit having a sensitizing functional group and a repeating unit having a carboxyl group.   6. The photosensitive transfer sheet according to claim 5, wherein the polymer having a sensitizing functional group is a copolymer having a repeating unit having a sensitizing functional group, a repeating unit having a carboxyl group, and a repeating unit having an aromatic group.   The photosensitive transfer sheet according to claim 1, wherein a barrier layer is disposed between the first photosensitive layer and the second photosensitive layer.   The photosensitive transfer sheet according to claim 7, wherein the barrier layer contains, as a main component, water or a resin having an affinity for a lower alcohol having 1 to 4 carbon atoms.   The photosensitive transfer sheet according to claim 7 or 8, wherein the barrier layer contains, as a main component, a resin soluble in water or a lower alcohol having 1 to 4 carbon atoms.   The photosensitive transfer sheet according to any one of claims 7 to 9, wherein the barrier layer has a thickness in the range of 0.1 to 5 µm.   The photosensitive transfer sheet according to any one of claims 1 to 10, wherein when the photosensitivity of the first photosensitive layer is 1, the photosensitivity of the second photosensitive layer is in the range of 2 to 200.   The ratio expressed by A / B between the amount of light energy A required to cure the second photosensitive layer and the amount of light energy B necessary to cure the first photosensitive layer is 0.005 to 0.5. The photosensitive transfer sheet according to any one of claims 1 to 11, which is in the range of.   The ratio represented by C / A between the amount of light energy A required to cure the second photosensitive layer and the amount of light energy C required until the first photosensitive layer begins to be cured is in the range of 1-10. The photosensitive transfer sheet according to any one of claims 1 to 12.   The photosensitive transfer sheet according to any one of claims 1 to 13, wherein each of the first photosensitive layer and the second photosensitive layer contains a polymer having a sensitizing functional group.   The number of sensitizing functional groups in the polymer having sensitizing functional groups contained in the second photosensitive layer is equal to the number of sensitizing functional groups in the polymer having sensitizing functional groups contained in the first photosensitive layer. The photosensitive transfer sheet of Claim 14 more than.   The amount of the photopolymerization initiator contained in the second photosensitive layer is greater than the amount of the photopolymerization initiator contained in the first photosensitive layer. Transfer sheet.   The photosensitive transfer according to any one of claims 1 to 16, wherein the amount of the polymerizable compound contained in the second photosensitive layer is larger than the amount of the polymerizable compound contained in the first photosensitive layer. Sheet.   The photosensitive transfer sheet according to claim 1, wherein the first photosensitive layer has a thickness in the range of 1 to 100 μm, and the thickness is larger than the thickness of the second photosensitive layer.   The photosensitive transfer sheet according to claim 1, wherein the second photosensitive layer has a thickness in the range of 0.1 to 15 μm.   The photosensitive transfer sheet according to any one of claims 1 to 19, wherein the support is made of a synthetic resin and is transparent.   The photosensitive transfer sheet according to any one of claims 1 to 20, wherein the support is a long support.   The photosensitive transfer sheet according to any one of claims 1 to 21, wherein a protective film is disposed on the second photosensitive layer.   The photosensitive transfer sheet according to any one of claims 1 to 22, which is a long body and is wound in a roll shape.   The photosensitive transfer sheet according to any one of claims 1 to 23, wherein the photosensitive transfer sheet is used for producing a printed wiring board.   A second photosensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator on the substrate, and a photosensitivity relatively lower than the photosensitivity of the second photosensitive layer, comprising a binder, a polymerizable compound and a photopolymerization initiator. The first photosensitive layer is laminated in this order, and at least one binder of the first photosensitive layer and the second photosensitive layer is a polymer having a sensitizing functional group, and the sensitizing functional group has an increase in molecular weight of 1000 or less. A photosensitive transfer sheet, which corresponds to an atomic group obtained by removing one monovalent atom or group from a dye-sensitive dye.   The photosensitive laminate according to claim 25, wherein the polymer having a sensitizing functional group has an absorption maximum wavelength in the range of 300 to 500 nm.   The sensitizing dye having a molecular weight of 1000 or less is selected from the group consisting of a cyanine dye, a merocyanine dye, a xanthene dye, a phenothiazine dye, an acridine dye, an anthraquinone dye, an acridone dye, a coumarin dye, an aniline dye, and a squarylium dye. Photosensitive laminate.   The photosensitive laminate according to claim 25, wherein the binder of the second photosensitive layer is a polymer having a sensitizing functional group.   The photosensitive laminate according to claim 25, wherein the polymer having a sensitizing functional group is a copolymer having a repeating unit having a sensitizing functional group and a repeating unit having a carboxyl group.   30. The photosensitive laminate according to claim 29, wherein the polymer having a sensitizing functional group is a copolymer having a repeating unit having a sensitizing functional group, a repeating unit having a carboxyl group, and a repeating unit having an aromatic group.   The photosensitive laminate according to claim 25, wherein a barrier layer is disposed between the first photosensitive layer and the second photosensitive layer.   32. The photosensitive laminate according to claim 31, wherein the barrier layer contains, as a main component, a resin having an affinity for water or a lower alcohol having 1 to 4 carbon atoms.   The photosensitive laminated body of Claim 31 or 32 in which a barrier layer contains resin soluble as a main component with respect to water or a C1-C4 lower alcohol.   The photosensitive laminate according to any one of claims 25 to 33, wherein the substrate is a printed wiring board forming substrate.   The photosensitive laminate according to any one of claims 25 to 34, wherein a support is laminated on the first photosensitive layer. An image comprising a region where a cured resin layer formed by curing both the first photosensitive layer and the second photosensitive layer on a substrate and a region where no cured resin layer is present, including the following steps: How to form a pattern:
(1) A step of laminating the photosensitive transfer sheet according to claim 1 on a substrate in a positional relationship such that the second photosensitive layer is on the substrate side;
(2) A step of performing light irradiation of a predetermined image pattern from the side of the first photosensitive layer of the laminate and curing both the first photosensitive layer and the second photosensitive layer in the region irradiated with the light;
(3) removing the support from the laminate; and
(4) The process of developing a laminated body and removing the unhardened part in a laminated body. An image comprising a region where a cured resin layer formed by curing both the first photosensitive layer and the second photosensitive layer on a substrate and a region where no cured resin layer is present, including the following steps: How to form a pattern:
A step of laminating the photosensitive transfer sheet according to claim 1 on a substrate in a positional relationship such that the second photosensitive layer is on the substrate side;
Removing the support from the laminate;
Irradiating a predetermined image pattern with light from the first photosensitive layer side of the laminate, and curing both the first photosensitive layer and the second photosensitive layer in the irradiated region; and
The process which develops a laminated body and removes the unhardened part in a laminated body.   The method according to claim 36 or 37, wherein the light irradiation is performed by laser light irradiation. A region including a resin layer formed by curing the first photosensitive layer and the second photosensitive layer on the substrate, including the following steps: a resin layer formed by curing the second photosensitive layer A method of forming an image pattern composed of a region in which a cured resin layer does not exist:
(1) A step of laminating the photosensitive transfer sheet according to claim 1 on a substrate in a positional relationship such that the second photosensitive layer is on the substrate side;
(2) Light irradiation is performed from the first photosensitive layer side of the laminate with an image pattern that defines a region to be irradiated with at least two different levels of irradiation energy amount, and the light irradiation energy amount is relatively large Curing both the first photosensitive layer and the second photosensitive layer in the region irradiated with light, and curing the second photosensitive layer in the region irradiated with light having a relatively small amount of light irradiation energy;
(3) removing the support from the laminate; and
(4) The process of developing a laminated body and removing the unhardened part in a laminated body. A region including a resin layer formed by curing the first photosensitive layer and the second photosensitive layer on the substrate, including the following steps: a resin layer formed by curing the second photosensitive layer A method of forming an image pattern composed of a region in which a cured resin layer does not exist:
A step of laminating the photosensitive transfer sheet according to claim 1 on a substrate in a positional relationship such that the second photosensitive layer is on the substrate side;
Removing the support from the laminate;
Light irradiation is performed from the first photosensitive layer side of the laminate in an image pattern that defines a region to be irradiated with light of at least two different levels of irradiation energy, and light irradiation with a relatively large amount of light irradiation energy is performed. Curing both the first photosensitive layer and the second photosensitive layer in the received area, and curing the second photosensitive layer in the area subjected to light irradiation with a relatively small amount of light irradiation energy; and
The process which develops a laminated body and removes the unhardened part in a laminated body.   The method according to claim 39 or 40, wherein the light irradiation is performed by laser light irradiation. The area covered with the cured resin layer formed by curing the first photosensitive layer and the second photosensitive layer on the printed wiring board forming substrate including the following steps and the substrate surface are exposed. A method of forming a wiring pattern composed of a region including:
(1) A step of laminating the photosensitive transfer sheet according to claim 1 on a substrate in a positional relationship such that the second photosensitive layer is on the substrate side;
(2) A step of irradiating a predetermined wiring pattern from the first photosensitive layer side of the laminate and curing both the first photosensitive layer and the second photosensitive layer in the irradiated region;
(3) removing the support from the laminate; and
(4) The process of developing a laminated body and removing the unhardened part in a laminated body. The area covered with the cured resin layer formed by curing the first photosensitive layer and the second photosensitive layer on the printed wiring board forming substrate including the following steps and the substrate surface are exposed. A method of forming a wiring pattern composed of a region including:
A step of laminating the photosensitive transfer sheet according to claim 1 on a substrate in a positional relationship such that the second photosensitive layer is on the substrate side;
Removing the support from the laminate;
Irradiating a predetermined wiring pattern from the first photosensitive layer side of the laminate, and curing both the first photosensitive layer and the second photosensitive layer in the irradiated region; and
The process which develops a laminated body and removes the unhardened part in a laminated body.   44. The method according to claim 42 or 43, wherein the light irradiation is performed by laser light irradiation. A hole part covered with a cured resin layer formed by curing both the first photosensitive layer and the second photosensitive layer on a printed wiring board forming substrate having a hole part, including the following steps: A method of forming a wiring pattern composed of a region covered with a cured resin layer formed by curing a photosensitive layer and a region where a substrate surface is exposed:
(1) A step of laminating the photosensitive transfer sheet according to claim 1 on a substrate in a positional relationship such that the second photosensitive layer is on the substrate side;
(2) From the side of the first photosensitive layer of the laminate, the hole portion is irradiated with light having a relatively large amount of light irradiation energy to cure both the first photosensitive layer and the second photosensitive layer, and wiring A step of irradiating the formation region with light of an image pattern that cures the second photosensitive layer by applying light irradiation with a relatively small amount of light irradiation energy;
(3) removing the support from the laminate; and
(4) The process of developing a laminated body and removing the unhardened part in a laminated body. A hole part covered with a cured resin layer formed by curing both the first photosensitive layer and the second photosensitive layer on a printed wiring board forming substrate having a hole part, including the following steps: A method of forming a wiring pattern composed of a region covered with a cured resin layer formed by curing a photosensitive layer and a region where a substrate surface is exposed:
A step of laminating the photosensitive transfer sheet according to claim 1 on a substrate in a positional relationship such that the second photosensitive layer is on the substrate side;
Removing the support from the laminate;
From the side of the first photosensitive layer of the laminate, the hole portion is irradiated with light having a relatively large amount of light irradiation energy to cure both the first photosensitive layer and the second photosensitive layer, and to the wiring formation region. Applying a light irradiation of an image pattern that cures the second photosensitive layer by applying a light irradiation with a relatively small amount of light irradiation energy; and
The process which develops a laminated body and removes the unhardened part in a laminated body.   The method according to claim 45 or 46, wherein the light irradiation is performed by laser light irradiation.

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