WO2014203707A1

WO2014203707A1 - Substrate with decorative material pattern, method for producing same, multilayer material for decorative material formation, and decorative material pattern-containing multilayer material for decorative material formation

Info

Publication number: WO2014203707A1
Application number: PCT/JP2014/064370
Authority: WO
Inventors: 吉成　伸一
Original assignee: 富士フイルム株式会社
Priority date: 2013-06-17
Filing date: 2014-05-30
Publication date: 2014-12-24
Also published as: TW201501921A; JP2015024498A

Abstract

This method for producing a substrate with a decorative material pattern comprises: a step for forming a decorative material pattern by exposing and developing a photosensitive resin layer of a multilayer material for decorative material formation, which has the photosensitive resin layer on a supporting body, and a step for laminating the thus-formed decorative material pattern on a substrate; a step for laminating a photosensitive resin layer of a multilayer material for decorative material formation, which has the photosensitive resin layer on a supporting body, and a step for forming a decorative material pattern by exposing and developing the thus-laminated photosensitive resin layer; or a step for laminating a decorative material pattern of a decorative material pattern-containing multilayer material for decorative material formation on a substrate, said decorative material pattern-containing multilayer material for decorative material formation having a decorative material pattern, which is obtained by exposing and developing a photosensitive resin layer, on a supporting body. In addition, this method for producing a substrate with a decorative material pattern satisfies the following condition (M) or condition (N). Condition (M): A base color layer is arranged between the supporting body and the photosensitive resin layer of the multilayer material for decorative material formation, or between the supporting body and the decorative material pattern of the decorative material pattern-containing multilayer material for decorative material formation. Condition (N): The method comprises a step for laminating a base color layer of another multilayer material for decorative material formation, which has the base color layer on a supporting body, on the decorative material pattern.

Description

Substrate with decorating material pattern and manufacturing method thereof, laminating material for decorating material formation, and laminating material for decorating material containing decorating material pattern

The present invention relates to a substrate with a decorative material pattern, a method for producing the same, a laminated material for forming a decorative material, and a laminated material for forming a decorative material pattern-containing decorative material.

The exterior of electronic devices such as mobile phones and smartphones is generally configured by combining a front exterior and a rear exterior. In recent years, with the trend toward fashion of electronic devices, decorative material patterns such as borders, letters, logo marks, and the like are formed by printing, and decoration has been applied. Such a decorating material pattern is usually provided as a laminate of a decorating material pattern and a base color layer for enhancing the coloring and visibility of the decorating material pattern.

In addition, a touch panel type input device is arranged on the front surface of the liquid crystal device or the like, and a finger or a touch pen is touched on the position where the instruction image is displayed while referring to the instruction image displayed in the image display area of the liquid crystal device. The touch panel that can input information corresponding to the instruction image has been used.

As an example of decorating the exterior of the touch panel, a method of decorating the front exterior is known. For example, Patent Document 1 includes a protective panel body made of a transparent plate, a rectangular lower transparent electrode on the upper surface of the transparent resin film, and a lower circuit provided around the lower transparent electrode, A lower electrode sheet bonded to the upper surface, a rectangular upper transparent electrode on the lower surface of the transparent resin film, and an upper circuit provided around the upper transparent electrode, and a gap is formed between the lower electrode sheet and the electrode An upper electrode sheet bonded to the transparent resin film, and a decorative layer for concealing the lower circuit and the upper circuit to form a transparent window on at least one surface of the transparent resin film, and on the upper surface of the upper electrode sheet Adhering the laminated decorative sheet, the upper electrode sheet and the lower electrode sheet, avoiding the transparent window portion inside the frame-shaped portion and the frame-shaped portion provided along the outer periphery of the frame-shaped portion and the front A glue layer made of a plurality of islands which are distributed extends to the circuit portion, the protection panel with a touch input function for electronic instrument table window having a listed. In Patent Document 1, a decorative film having a printed layer or a combination of a printed layer and a metal thin film layer previously patterned by a printing method on a support is applied to a substrate using a pressure-sensitive adhesive (hereinafter also referred to as PSA). To manufacture decorative substrates. Patent Document 1 also describes that the glue layer of the island-shaped portion is a black dot-shaped or streak-shaped light shielding layer.

On the other hand, there is also known an example in which a decoration material pattern is formed on the surface (rear exterior) opposite to the touch panel and decoration is performed. For example, Patent Document 2 is formed by laminating a glitter layer containing a pearl pigment, a pattern layer laminated by offset printing, and a concealing layer on the surface of a base film formed of a polyethylene terephthalate film or an acrylic film. The disclosed decorative film is disclosed, and can be produced in a small lot and in a short delivery time, and can provide a decorative film and a decorative molded product with a design that requires gradation expression. Has been.

JP 2011-8448 A JP 2012-201006 A

In the conventional method for manufacturing a substrate with a decorative material pattern as described in Patent Documents 1 and 2, a method of printing on a substrate using ink has been mainstream. However, when the present inventor formed a substrate with a decorative material pattern by printing, it is necessary to improve the uniformity of the thickness of the layer formed by printing and the pattern accuracy when printing on the pattern. all right.
In addition, it has been found that in printing on a substrate, multiple layers of coating must be applied to each single substrate, which is inefficient and needs to be improved.
Furthermore, the method of Patent Document 1 that creates a substrate with a decorative material pattern by pasting a decorative film previously patterned on a support by a printing method onto a substrate using PSA requires formation of a PSA layer. It was found that the process was complicated and there was a need for improvement.

The problem to be solved by the present invention is a method for producing a substrate with a decorating material pattern that has a simple process, low production cost, little variation in the thickness of the base color layer, and a highly accurate decorating material pattern. Is to provide.

As a result of intensive research in order to solve the above problems, the inventors have made a decoration as a method for producing a substrate with a decorative material pattern having a decorative material pattern and a base color layer in this order on the substrate. The material pattern is formed by exposure and development using a photolithography technique, and the decorative material pattern and the base color layer are exposed and developed on the support with the photosensitive resin layer, the base color layer, and the photosensitive resin layer being exposed and developed. By laminating using a decorative material forming laminated material provided with at least one layer among the decorative material patterns to be manufactured, the process is simple, the manufacturing cost is low, and the film thickness variation of the base color layer is small, It discovered that the manufacturing method of the board | substrate with a decorating material pattern which has a highly accurate decorating material pattern can be provided.
That is, it has been found that the above-described problems can be solved by the present invention having the following configuration, and the present invention has been completed.

[1] A process of forming a decorative material pattern by exposing and developing a photosensitive resin layer of a decorative material-forming laminated material having a photosensitive resin layer on a support, and the formed decorative material pattern A step of laminating on a substrate; a step of laminating a photosensitive resin layer of a decorative material forming laminate material having a photosensitive resin layer on a support on a substrate; and exposing and developing the laminated photosensitive resin layer Forming a decorating material pattern; or
Any one of the processes of laminating | stacking the decorating material pattern of the decorating material pattern containing laminated material for decorating material pattern containing the decorating material pattern in which the photosensitive resin layer is exposed and developed on a support body on a board | substrate. Including steps,
The manufacturing method of the board | substrate with a decorating material pattern which satisfy | fills the following conditions (M) or conditions (N).
Condition (M): Between the support of the laminate material for decorating material formation and the photosensitive resin layer, or between the support of the laminate material for decorating material pattern-containing decorating material and the decorating material pattern. And a base color layer.
Condition (N): including a step of laminating a base color layer of another decorating material forming laminate material having a base color layer on the support on the decorating material pattern. The laminated material for decorating material does not have a base color layer between the support and the photosensitive resin layer or the decorating material pattern.
[2] The method for manufacturing a substrate with a decorating material pattern according to [1] satisfies the condition (M),
Exposing the photosensitive resin layer of the decorative material-forming laminate material (i) having a base color layer and a photosensitive resin layer in this order on the support;
Developing the exposed photosensitive resin layer to prepare a decorative material pattern-containing decorative material forming laminate material (ii) in which a decorative material pattern is formed; and
It is preferable to include the process of laminating | stacking the decorating material pattern containing laminated material for decorating material formation on the said board | substrate in the state which made the decorating material pattern side face the board | substrate.
[3] The method for manufacturing a substrate with a decorating material pattern according to [1] satisfies the condition (M),
A decorative material pattern-containing decorative material forming laminate material (ii) having a decorative material pattern formed by exposing and developing a base color layer and a photosensitive resin layer on a support in this order, and a decorative material pattern on the substrate It is preferable to include a step of laminating the substrate with the sides facing each other.
[4] The method for manufacturing a substrate with a decorating material pattern according to [1] satisfies the condition (N),
Exposing the photosensitive resin layer of the decorative material-forming laminate material (A) having a photosensitive resin layer on a support;
Developing the exposed photosensitive resin layer to form a decorative material pattern; and
A step of laminating the decorative material pattern of the decorative material forming laminate material (A) on the substrate;
It is preferable to include the process of laminating | stacking the base color layer of the other laminated material for decorating material formation which has a base color layer on a support body on a decorating material pattern.
[5] The method for manufacturing a substrate with a decorating material pattern according to [1] satisfies the condition (N),
Laminating the photosensitive resin layer of the decorative material forming laminate material (A) having a photosensitive resin layer on the support on the substrate;
Peeling the support from the photosensitive resin layer;
Exposing the photosensitive resin layer;
Developing the exposed photosensitive resin layer to form a decorative material pattern; and
It is preferable to include the process of laminating | stacking the base color layer of the other laminated material for decorating material formation which has a base color layer on a support body on a decorating material pattern.
[6] The method for producing a substrate with a decorating material pattern according to any one of [1] to [5] has a light shielding layer between a support and a base color layer, and the base color layer and the light shield layer Are preferably laminated on the substrate in a lump.
[7] In the method for manufacturing a substrate with a decorating material pattern according to any one of [1] to [6], the base color layer is preferably a white layer.
[8] In the method for producing a substrate with a decorating material pattern according to [2] or [3], the base color layer is preferably a metallic luster layer.
[9] The method for producing a substrate with a decorating material pattern according to [8] preferably has a transparent adhesive layer on the surface adjacent to the metallic luster layer and opposite to the support.
[10] In the method for producing a substrate with a decorating material pattern according to [8] or [9], the metallic gloss layer is preferably a metal thin film layer.
[11] In the method for producing a substrate with a decorating material pattern according to any one of [1] to [10], the photosensitive resin layer preferably contains a photopolymerization initiator and an ethylenically unsaturated compound.
[12] In the method for producing a substrate with a decorating material pattern according to any one of [1] to [11], the photosensitive resin layer preferably contains a dye or a pigment.
[13] A substrate with a decorative material pattern manufactured by the method for manufacturing a substrate with a decorative material pattern according to any one of [1] to [12].
[14] A decorative material-forming laminate material having a base color layer and a photosensitive resin layer in this order on a support.
[15] The decorative material forming laminate material according to [14] preferably has a light shielding layer between the support and the base color layer.
[16] In the decorative material-forming laminated material according to [14] or [15], the base color layer is preferably a white layer.
[17] In the decorative material-forming laminate material according to [16], the base color layer is a metallic luster layer, and a transparent adhesive layer is provided adjacent to the metallic luster layer and on the surface opposite to the support. It is preferable to have.
[18] In the decorative material forming laminate material according to [16] or [17], the metallic luster layer is preferably a metal thin film layer.
[19] In the decorative material-forming laminated material according to any one of [14] to [18], the photosensitive resin layer preferably contains a photopolymerization initiator and an ethylenically unsaturated compound.
[20] In the decorative material-forming laminated material according to any one of [14] to [19], the photosensitive resin layer preferably contains a dye or a pigment.
[21] A decorative material pattern-containing decoration having a decorative material pattern in which the photosensitive resin layer of the laminated material for forming a decorative material according to any one of [14] to [20] is exposed and developed. Laminate material for material formation.

According to the present invention, there is provided a method for manufacturing a substrate with a decorating material pattern that has a simple process, low manufacturing cost, little variation in film thickness of a base color layer, and a highly accurate decorating material pattern. Can do.

Hereinafter, the board | substrate with a decorating material pattern of this invention, its manufacturing method, the laminated material for decorating material formation, and the laminated material for decorating material pattern containing decorating material formation are demonstrated in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Method of manufacturing substrate with decorative material pattern]
The manufacturing method of the board | substrate with a decorating material pattern of this invention (henceforth the manufacturing method of this invention) exposes the said photosensitive resin layer of the laminated material for decorating material formation which has a photosensitive resin layer on a support body. And a step of forming a decorative material pattern by developing, and a step of laminating the formed decorative material pattern on a substrate; a photosensitive resin of a laminated material for forming a decorative material having a photosensitive resin layer on a support A step of laminating a layer on a substrate, and a step of exposing and developing the laminated photosensitive resin layer to form a decorating material pattern; or
Laminating the decorative material pattern of a decorative material pattern-containing decorative material forming laminate material having a decorative material pattern formed by exposing and developing a photosensitive resin layer on a support to a substrate;
The following condition (M) or condition (N) is satisfied.
Condition (M): The laminate material for decorating material formation has a base color layer between the support and the photosensitive resin layer or the decorating material pattern.
Condition (N): including a step of laminating the base color layer of another decorating material forming laminated material having a base color layer on the support on the decorating material pattern. In addition, the said lamination material for decorating material formation does not have a base color layer between the said support body and the said photosensitive resin layer or the said decorating material pattern.
With such a configuration, the manufacturing method of the present invention has a simple process, low manufacturing cost, little variation in the thickness of the base color layer, and a substrate with a decorative material pattern having a highly accurate decorative material pattern. Can be manufactured. In the production method of the present invention, high-precision pattern formation by photolithography and high film thickness uniformity are utilized, and a layer for performing photolithography and other underlying color layers are laminated once or a small number of times for decoration. A substrate with a material pattern can be manufactured. These have not been suggested in prior art documents including Japanese Unexamined Patent Application Publication Nos. 2011-8448 and 2012-201006.
Moreover, the manufacturing method of the board | substrate with a decorating material pattern of this invention has small variation in the film thickness of a base color layer. The film thickness variation of the base color layer is preferably within ± 3%, more preferably within ± 2%, particularly preferably within ± 1%, and within ± 0.7%. Is more particularly preferred.
The details and preferred embodiments of the method for producing a substrate with a decorative material pattern of the present invention will be described.

The manufacturing method of the board | substrate with a decorating material pattern of this invention forms the decorating material pattern by exposing and developing the said photosensitive resin layer of the laminated material for decorating material formation which has a photosensitive resin layer on a support body. A step of laminating the formed decorative material pattern on the substrate; a step of laminating the photosensitive resin layer of the decorative material forming laminated material having the photosensitive resin layer on the support; and laminating Exposing and developing the formed photosensitive resin layer to form a decorative material pattern; or
A step of laminating the decorative material pattern of the decorative material pattern-containing laminated material for forming a decorative material pattern having a decorative material pattern formed by exposing and developing a photosensitive resin layer on a support on a substrate.
That is, the manufacturing method of the substrate with a decorative material pattern of the present invention is:
A step of forming a decorating material pattern by photolithography on the photosensitive resin layer laminated on the substrate; or a decorating material pattern previously formed by photolithography on the photosensitive resin layer on the support. A decorative material pattern-containing laminated material for forming a decorative material may be used.

<Specific embodiment>
Specifically, the method for producing a substrate with a decorating material pattern of the present invention is preferably any one of the following first aspect, second aspect, third aspect and fourth aspect.

In the 1st aspect of the manufacturing method of the board | substrate with a decorating material pattern of this invention, the said conditions (M) are satisfy | filled,
Exposing the photosensitive resin layer of the decorative material-forming laminate material (i) having a base color layer and a photosensitive resin layer in this order on the support;
The exposed photosensitive resin layer is developed to form a decorative material pattern laminated material (ii) (hereinafter referred to as “decorative material pattern-containing decorative material forming laminated material (ii)”). Also referred to as)),
It is preferable to include the process of laminating | stacking the said decorating material pattern containing laminated material for decorating material formation on the said board | substrate in the state which made the said decorating material pattern side oppose the board | substrate.

In the 2nd aspect of the manufacturing method of the board | substrate with a decorating material pattern of this invention, the said conditions (M) are satisfy | filled,
A decorative material pattern-containing laminated material for forming a decorative material (ii) having a decorative material pattern formed by exposing and developing a base color layer and a photosensitive resin layer on a support in this order, and the decorative material on a substrate. It is preferable to include a step of laminating the substrate with the pattern sides facing each other.

In the 3rd aspect of the manufacturing method of the board | substrate with a decorating material pattern of this invention, the said conditions (N) are satisfy | filled,
Exposing the photosensitive resin layer of the decorative material-forming laminate material having a photosensitive resin layer on a support;
Developing the exposed photosensitive resin layer to form a decorative material pattern; and
A step of laminating the decorative material pattern side of the decorative material forming laminate material on a substrate;
It is preferable to include a step of laminating the base color layer of another decorative material forming laminate material having a base color layer on the support on the decorating material pattern.

In the 4th aspect of the manufacturing method of the board | substrate with a decorating material pattern of this invention, the said conditions (N) are satisfy | filled,
A step of laminating the photosensitive resin layer of a decorative material-forming laminate material having a photosensitive resin layer on a support on a substrate;
Peeling the support from the photosensitive resin layer;
Exposing the photosensitive resin layer;
Developing the exposed photosensitive resin layer to form a decorative material pattern; and
It is preferable to include a step of laminating the base color layer of another decorative material forming laminate material having a base color layer on the support on the decorating material pattern.

Among the first aspect, the second aspect, the third aspect, and the fourth aspect of the method for producing a substrate with a decorating material pattern of the present invention described above, the first aspect and the second aspect are the above-mentioned conditions ( It is preferable from the same viewpoint as when M) is satisfied, and the first aspect using the laminated material for forming a decorative material of the present invention having a base color layer and a photosensitive resin layer in this order on a support is more preferable. In addition, when manufacturing the board | substrate with a decorating material pattern of this invention in a 3rd aspect and a 4th aspect, between the support body of the laminated material for decorating material formation and the photosensitive resin layer, or a decorating material. There is no base color layer between the support of the laminated material for pattern-containing decorating material formation and the decorating material pattern (that is, when the condition (N) is satisfied, the condition (M) is overlapped to satisfy the condition (M). It is preferred).

<Types of decorative material forming laminate material, decorative material forming laminate material of the present invention, decorative material pattern-containing decorative material forming laminate material of the present invention>
The production method of the present invention satisfies the following condition (M) or (N).
Condition (M): The laminate material for decorating material formation has a base color layer between the support and the photosensitive resin layer or the decorating material pattern.
Condition (N): including a step of laminating the base color layer of another decorating material forming laminated material having a base color layer on the support on the decorating material pattern.
That is, in the production method of the present invention, as the type of the laminated material used when forming the decorative material pattern and the base color layer,
A decorative material-forming laminate material (i) having a base color layer and a photosensitive resin layer in this order on the support may be used; the base color layer and the photosensitive resin layer are exposed and developed on the support. The decorative material pattern-containing decorative material forming laminate material (ii) having the decorative material patterns in this order may be used; other decorative material forming laminate materials having a base color layer on the support May be used.
The decorative material-forming laminate material (i) having the base color layer and the photosensitive resin layer in this order on the support has a structure that has not been known so far. The base color layer and the photosensitive resin layer are formed on the support. The laminated material for forming a decorative material in order is also referred to as the laminated material for forming a decorative material of the present invention.
The decorative material pattern-containing decorative material forming laminate material (ii) having a decorative material pattern formed by exposing and developing a base color layer and a photosensitive resin layer on a support in this order has a conventionally unknown configuration. The decorative material pattern-containing decorative material forming laminate material (ii) having a decorative material pattern formed by exposing and developing the base color layer and the photosensitive resin layer on the support in this order. It is also called a laminated material for forming a decorative material pattern-containing decorative material.
In addition, in this specification, when there is no notice in particular and it says "a laminated material for decorating material formation", the laminated material for decorating material formation (i) which has a base color layer and a photosensitive resin layer in this order on a support body. In addition, a decorative material pattern-containing decorative material-forming laminate material (ii) having a base color layer and a decorating material pattern on the support, and other decorative material forming having a base color layer on the support Also includes laminated materials.
When satisfy | filling the said condition (M), the manufacturing process of a decoration board | substrate can be simplified and cost-reduced by laminating | stacking the film which has two or more layers which should be laminated | stacked collectively.

According to the production method of the present invention, when producing a substrate with a decorating material pattern having a decorating material pattern and a base color layer on the substrate, pressure sensitivity as described in JP2011-8448A is disclosed. Even without using a heat-sensitive adhesive layer, a decorating material pattern and a base color layer can be laminated on the substrate.
The photosensitive resin layer, the base color layer, and the decorative material formed by exposing and developing the photosensitive resin layer contained in the decorative material-forming laminated material or the decorative material pattern-containing decorative material-forming laminated material By laminating the pattern on the substrate described later (the support may be peeled off after the lamination to transfer only the target layer), the photosensitive resin layer, the base color layer, and the photosensitive layer are formed on the substrate. A decorative material pattern formed by exposing and developing the functional resin layer can be formed.
Note that the photosensitive resin layer, the base color layer, and the decorative resin layer that are included in the decorative material forming laminate material or the decorative material pattern-containing decorative material forming laminate material are exposed and developed. The material pattern preferably has the same composition as the decorative material pattern and the base color layer in the substrate with a decorative material pattern of the present invention, but the decorative material forming laminated material or the decorative material pattern-containing decorative material formation The composition of the decorative resin pattern in which the photosensitive resin layer, the base color layer, and the photosensitive resin layer in the laminated material for exposure are exposed and developed may vary depending on the production process after lamination on the substrate. For example, the decorative material pattern formed by exposing and developing the photosensitive resin layer, the base color layer, and the photosensitive resin layer in the decorative material forming laminated material or the decorative material pattern-containing decorative material forming laminated material. When has a polymeric compound, the content rate of the said polymeric compound may be changing in the decorating material pattern and the base color layer in the board | substrate with a decorating material pattern of this invention.

(Photosensitive resin layer)
In the manufacturing method of this invention, the laminated material for decorating material formation which has a photosensitive resin layer on a support body contains the photosensitive resin layer.
The photosensitive resin layer is not particularly limited. For example, the photosensitive resin layer is used as a coloring composition for a color filter in the photosensitive composition described in JP2010-237589A or [0071] in JP2010-237589A. Materials, that is, coloring compositions described in [0046] to [0059] of JP-A-2004-347831 can be used, and the contents described in these publications are incorporated in the present invention.
Specifically, the photosensitive resin layer preferably contains a resin (A) having an acidic group in the side chain.
The photosensitive resin layer preferably contains a polymerizable compound (B) and a photopolymerization initiator (C), more preferably contains a photopolymerization initiator and an ethylenically unsaturated compound, and photopolymerization. It is particularly preferable that the initiator contains at least dipentaerythritol acrylate compound B1 (below) and tripentaerythritol acrylate compound B2 (below).

(X represents a hydrogen atom or H ₂ C═CR—CO—, and at least four of X in the molecule represent H ₂ C═CR—CO—. R represents a hydrogen atom or a carbon number of 1 to 4 Represents a hydrocarbon group of

(X represents a hydrogen atom or H ₂ C═CR—CO—, and at least 6 of X in the molecule represents H ₂ C═CR—CO—. R represents a hydrogen atom or 1 to 4 carbon atoms. Represents a hydrocarbon group of
In addition, the photosensitive resin layer may be configured using other components such as a colorant such as a pigment or a dye (a white pigment such as a black pigment or rutile titanium oxide), a surfactant, or the like, if necessary. it can. The preferable range of the white pigment used for the photosensitive resin layer is the same as the preferable range of the white pigment used for the base color layer described later.
Other colorants used in the photosensitive resin layer and preferred ranges thereof are described in [0049] to [0059] of JP-A-2004-347831 cited in [0071] of JP-A-2010-237589. The colorant and the preferred range thereof are the same, and the contents described in these publications are incorporated in the present invention. For example, as a coloring agent for forming a green decorative material pattern, at least C.I. I. PG-36 (C.I. Pigment Green 36) and C.I. I. PY-138 (CI Pigment Yellow 138), C.I. I. PY-139 (CI Pigment Yellow 139), C.I. I. Those containing any of PY-150 (CI Pigment Yellow 150) are preferred.
These colorants can be changed according to the design and color of the desired decorative material pattern.

-Resin (A)-
Resin (A) has an acidic group in the side chain. Having an acidic group in the side chain means having a structural unit (group) having an acidic group in the side chain. Even if the acidic group is directly bonded to the main chain, it has an acidic group described later. As shown in the specific examples of the monomer, it includes that an acidic group may be bonded via a linking group.
The resin (A) can have an ethylenically unsaturated group in the side chain. Even in the form in which the ethylenically unsaturated group is directly bonded to the main chain, as shown in the specific example of the monomer having an ethylenically unsaturated group described later, the ethylenically unsaturated group is connected via a linking group. May be combined.
The resin (A) is more preferably a group having an acidic group (structural unit): Y (y mol%), and a group having a branched and / or alicyclic structure in the side chain (structural unit): X (x Mol%) and a group having an ethylenically unsaturated group (structural unit): Z (z mol%), and having other groups (L) (1 mol%) as necessary. Also good. A plurality of X, Y, and Z may be combined in one group in the resin (A).

The acidic group is not particularly limited and may be appropriately selected from known ones, and examples thereof include a carboxyl group, a sulfonic acid group, a sulfonamide group, a phosphoric acid group, and a phenolic hydroxyl group. Among these, a carboxy group and a phenolic hydroxyl group are preferable from the viewpoint of excellent developability and water resistance of the cured film.

The monomer used for having an acidic group in the side chain is not particularly limited, and examples thereof include styrenes, (meth) acrylates, vinyl ethers, vinyl esters, (meth) acrylamides, (Meth) acrylates, vinyl esters and (meth) acrylamides are preferred, and (meth) acrylates are more preferred.

Specific examples of the monomer having an acidic group in the side chain can be appropriately selected from known ones, such as (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, Fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, acrylic acid dimer, addition reaction product of monomer having hydroxyl group and cyclic acid anhydride, ω-carboxy-polycaprolactone mono ( And (meth) acrylate. As these, those produced as appropriate may be used, or commercially available products may be used.

Examples of the monomer having a hydroxyl group used in the addition reaction product of the monomer having a hydroxyl group and a cyclic acid anhydride include 2-hydroxyethyl (meth) acrylate. Examples of the cyclic acid anhydride include maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride. Among these, (meth) acrylic acid and the like are preferable in terms of excellent developability and low cost.

There is no restriction | limiting in particular as a monomer which has the said "ethylenically unsaturated group in a side chain", As a ethylenically unsaturated group, a (meth) acryloyl group is preferable. The connection between the ethylenically unsaturated group and the monomer is not particularly limited as long as it is a divalent linking group such as an ester group, an amide group, or a carbamoyl group.
The method of introducing an ethylenically unsaturated group into the side chain can be appropriately selected from known ones, for example, a method of adding a (meth) acrylate having an epoxy group to a group having an acidic group, or having a hydroxyl group Examples include a method of adding a (meth) acrylate having an isocyanate group to the group, a method of adding a (meth) acrylate having a hydroxy group to a group having an isocyanate group, and the like.
Among these, the method of adding (meth) acrylate having an epoxy group to a repeating unit having an acidic group is most preferable because it is the easiest to produce and is low in cost.

The (meth) acrylate having an ethylenically unsaturated bond and an epoxy group is not particularly limited as long as it has these.

Other monomers are not particularly limited, for example, (meth) acrylic acid ester groups, styrene groups, vinyl ether groups, dibasic acid anhydride groups, vinyl ester groups having no branched and / or alicyclic structures, And monomers having a hydrocarbon alkenyl group.
There is no restriction | limiting in particular as said vinyl ether group, For example, a butyl vinyl ether group etc. are mentioned.

The dibasic acid anhydride group is not particularly limited, and examples thereof include a maleic anhydride group and an itaconic anhydride group.
There is no restriction | limiting in particular as said vinyl ester group, For example, a vinyl acetate group etc. are mentioned.
There is no restriction | limiting in particular as said hydrocarbon alkenyl group, For example, a butadiene group, an isoprene group, etc. are mentioned.

As the content of other monomers in the resin (A), the molar composition ratio is preferably 0 to 30 mol%, and more preferably 0 to 20 mol%.

Specific examples of the resin (A) include compounds represented by compounds P-1 to P-35 described in paragraph numbers [0057] to [0063] of JP-A-2008-146018.
Further, specific examples of the resin (A) include carboxylic acid groups in the side chain described in [0047] and [0048] of JP-A-2004-347831 cited in [0071] of JP-A-2010-237589. Examples thereof include polymers having polar groups such as carboxylic acid groups, and examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, croton as described in JP-A-25-25957, JP-A-59-53836, and JP-A-59-71048 Examples thereof include an acid copolymer, a maleic acid copolymer, and a partially esterified maleic acid copolymer. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned. In addition, a polymer having a hydroxyl group added to a cyclic acid anhydride can also be preferably used. In particular, a copolymer of benzyl (meth) acrylate and (meth) acrylic acid or a multicomponent copolymer of benzyl (meth) acrylate, (meth) acrylic acid and other monomers described in US Pat. No. 4,139,391 Can be mentioned. These binder polymers having a polar group may be used alone, or may be used in the state of a composition used in combination with an ordinary polymer having film-forming ability.
In addition, the content described in the publications cited as specific examples of these resins (A) is incorporated in the present invention.

The resin (A) is made from a two-stage process including a monomer (co) polymerization reaction process and an ethylenically unsaturated group introduction process. First, the (co) polymerization reaction is made by a (co) polymerization reaction of various monomers, and is not particularly limited and can be appropriately selected from known ones. For example, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization and the like can be appropriately selected for the active species of polymerization. Among these, radical polymerization is preferable from the viewpoint of easy synthesis and low cost. Moreover, there is no restriction | limiting in particular also about the polymerization method, It can select suitably from well-known things. For example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method and the like can be appropriately selected. Among these, the solution polymerization method is more desirable.

The weight average molecular weight of the copolymer suitable as the resin (A) is preferably 10,000 to 100,000, more preferably 12,000 to 60,000, and particularly preferably 15,000 to 45,000. When the weight average molecular weight is within the above range, it is desirable from the viewpoint of production suitability and developability of the copolymer. Moreover, it is preferable at the point that the shape formed by the fall of melt viscosity is hard to be crushed, it is hard to become a crosslinking defect, and there is no residue in development.

The glass transition temperature (Tg) suitable for the resin (A) is preferably 40 to 180 ° C, more preferably 45 to 140 ° C, and particularly preferably 50 to 130 ° C. When the glass transition temperature (Tg) is within the preferred range, good developability and mechanical strength can be obtained.

The preferred range of the acid value suitable for the resin (A) varies depending on the molecular structure that can be taken, but generally it is preferably 20 mgKOH / g or more, more preferably 50 mgKOH / g or more, and 70 to 130 mgKOH / g. It is particularly preferred that When the acid value is within the preferred range, good developability and mechanical strength can be obtained.

The resin (A) preferably has a glass transition temperature (Tg) of 40 to 180 ° C. and a weight average molecular weight of 10,000 to 100,000, from the viewpoint of obtaining good developability and mechanical strength.
Furthermore, the preferable example of the said resin (A) has more preferable each combination of the said preferable molecular weight, glass transition temperature (Tg), and an acid value.

Resin (A) has a group having a branched and / or alicyclic structure in the side chain: X (x mol%), a group having an acidic group: Y (y mol%), and an ethylenically unsaturated group. From the viewpoint of deformation recovery rate, development residue, vibration resistance, and reticulation, it is preferably a copolymer of at least ternary copolymer having the group: Z (z mol%) in different copolymer units. . Specifically, a copolymer obtained by copolymerizing at least one of the monomers constituting the X, Y, and Z is preferable.
The copolymer composition ratio of the respective components of the resin (A) is determined in consideration of the glass transition temperature and the acid value, and cannot be generally stated, but “group having a branched and / or alicyclic structure in the side chain” "Is preferably 10 to 70 mol%, more preferably 15 to 65 mol%, and particularly preferably 20 to 60 mol%. When the group having a branched and / or alicyclic structure in the side chain is within the above range, good developability is obtained and the developer resistance of the image area is also good.
The “group having an acidic group in the side chain” is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and particularly preferably 20 to 50 mol%. When the group having an acidic group in the side chain is within the above range, good curability and developability can be obtained.
The “group having an ethylenically unsaturated group in the side chain” is preferably 10 to 70 mol%, more preferably 20 to 70 mol%, particularly preferably 30 to 70 mol%. When the group having an ethylenically unsaturated group in the side chain is within the above range, the pigment dispersibility is excellent, and the developability and curability are also good.

The content of the resin (A) is preferably 5 to 70% by mass and more preferably 10 to 50% by mass with respect to the total solid content of the photosensitive composition. The resin (A) can contain other resins described later, but only the resin (A) is preferable.

The other resin that can be used in combination with the resin (A) is preferably a compound that shows swelling property with respect to an alkaline aqueous solution, and more preferably a compound that is soluble in the alkaline aqueous solution.
As the resin exhibiting swellability or solubility with respect to an alkaline aqueous solution, for example, those having an acidic group are preferably mentioned. Specifically, an ethylenically unsaturated double bond and an acidic group are introduced into an epoxy compound. Compound (epoxy acrylate compound), vinyl copolymer having (meth) acryloyl group and acidic group in side chain, epoxy acrylate compound and vinyl copolymer having (meth) acryloyl group and acidic group in side chain A mixture, a maleamic acid copolymer, and the like are preferable.
The acidic group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, the availability of raw materials, etc. From the viewpoint, a carboxyl group is preferable.

The total content of the resin (A) and other resins that can be used in combination is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, based on the total solid content of the photosensitive composition. preferable. When the solid content is less than 5% by mass, the film strength of the photosensitive layer described later tends to be weak, and the tackiness of the surface of the photosensitive layer may be deteriorated. Sensitivity may decrease. In addition, the said content has shown that solid content.

-Polymerizable compound (B)-
The polymerizable compound (B) preferably contains at least the compounds B1 and B2.
In the photosensitive composition, the contents W1 (% by mass) and W2 (% by mass) with respect to the total amount of the polymerizable compound (B) of the compound B1 and the compound B2 are represented by the following formulas (1) and (2). It is preferable to satisfy them simultaneously. Here, the content of compound B1 with respect to the total amount of polymerizable compound (B) is W1 (mass%), and the content of compound B2 with respect to the total amount of polymerizable compound (B) is W2 (mass%). .

0.6 ≦ W2 / W1 ≦ 3.0 (1)
63% ≦ W1 + W2 ≦ 100% (2)

By satisfy | filling said Formula (1) and (2), the said photosensitive composition will be able to provide the decorating material pattern with high dynamic strength which can endure the vibration with a high frequency. .

X in compound B1 represents a hydrogen atom or H ₂ C═CR—CO—, and at least 4 of X in the molecule represents H ₂ C═CR—CO—, more preferably 5 or more, The number is preferably 5.5 and 6.
R represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms, and most preferably a hydrogen atom or a methyl group. is there. Specific examples of compound B1 are specifically dipentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and their A mixture is mentioned. Of these, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and mixtures thereof are more preferred.

X in compound B2 represents a hydrogen atom or H ₂ C═CR—CO—, and at least 6 of X in the molecule represents H ₂ C═CR—CO—, more preferably 7 or more, Most preferred are 7.5 and 8.
R represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms, and most preferably a hydrogen atom or a methyl group. is there. Specific examples of compound B2 are specifically tripentaerythritol hexamethacrylate, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate, tripentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate and their A mixture is mentioned. Of these, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, and mixtures thereof are more preferred.

It is preferable that the contents W1 (%) and W2 (%) of the compounds B1 and B2 with respect to the total amount of the polymerizable compound (B) satisfy the above formulas (1) and (2) at the same time. %) And W2 (%) are preferably 65% to 95%, more preferably 70% to 90% from the viewpoint of vibration resistance. If it is less than 63%, vibration resistance may deteriorate.

On the other hand, the ratio W2 / W1 of the contents W1 (%) and W2 (%) is preferably 0.6 or more and 3.0 or less, more preferably 0.62 or more and 2.95 or less, and still more preferably 0. 7 or more and 2.6 or less. If it is less than 0.6, the adhesion between the decorative material pattern and the substrate when developed is lowered, and at the same time, the vibration resistance is deteriorated. If it exceeds 3.0, the development residue is deteriorated and at the same time the vibration resistance is deteriorated.

Other polymerizable compounds that can be used in combination include the components described in paragraph No. [0011] of JP-A-2006-23696 and the components described in paragraph Nos. [0040] to [0049] of JP-A-2006-64921. Can be used together.

In the relationship with the resin (A), the mass ratio of the polymerizable compound (B) to the resin (A) ((B) / (A) ratio) is preferably 0.5 to 2.0, and It is more preferably 6 to 1.4, and particularly preferably 0.7 to 1.2. When the ratio (B) / (A) is within the preferred range, good developability and mechanical strength can be obtained.

-Photopolymerization initiator (C) and other components-
As the photopolymerization initiator (C), other components that constitute a known composition can be suitably used. For example, as described in paragraphs [0012] to [0020] Ingredients and ingredients described in paragraph numbers [0050] to [0053] of JP-A-2006-64921 are exemplified.

The content of the photopolymerization initiator (C) is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass with respect to the resin (A).

In the production method of the present invention, the photosensitive resin layer is preferably soft so as to be easily laminated at the time of lamination, and therefore a negative type containing a photopolymerization initiator and an ethylenically unsaturated compound also called a monomer is preferable.
Further, since the positive photosensitive resin layer is a hard film, the problem of powder falling off easily when the film is cut is also a reason why the negative photosensitive resin layer is preferable.

-Thickness of photosensitive resin layer-
When the photosensitive resin layer is a photosensitive resin layer other than white, the thickness is not particularly limited, but from the viewpoint of thinning, the thickness of the photosensitive resin layer is 0.1 to 10 μm. Is more preferable, 0.5 to 7 μm is more preferable, and 1 to 5 μm is particularly preferable.
Usually, when a white layer is provided, sufficient hiding power and whiteness cannot be obtained unless the thickness is several tens of μm or more.
On the other hand, in the present invention, when the photosensitive resin layer is a white photosensitive resin layer, a white photosensitive resin layer is provided on a metallic luster layer (for example, a metal thin film layer such as an aluminum vapor deposition layer). Thus, even if the thickness of the white photosensitive resin layer is several tens of μm or less, sufficient hiding power and whiteness can be obtained. When the white photosensitive resin layer is provided on the metallic gloss layer, the thickness of the white photosensitive resin layer is preferably 0.5 to 20 μm from the viewpoint of thinning and hiding power, and preferably 1 to 10 μm. More preferably, it is 3 to 5 μm.
In addition, the preferable range of the thickness of the decorating material pattern mentioned later is the same as the preferable range of the thickness of the photosensitive resin layer.

(Support)
The said laminated material for decorating material formation or the laminated material for decorating material pattern containing decorating material formation has a support body.
The support is preferably flexible and does not cause significant deformation, shrinkage or elongation even under pressure, or under pressure and heat. Examples of such a support include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film, and among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.
The thickness of the support is not particularly limited, but is preferably 5 to 300 μm, more preferably 20 to 200 μm.
Further, the support may be transparent or may contain dyed silicon, alumina sol, chromium salt, zirconium salt, or the like.
Further, the support can be provided with conductivity by a method described in JP-A-2005-221726.

(Background color layer)
The decorative material-forming laminated material or the decorative material pattern-containing decorative material-forming laminated material used in the method for producing a substrate with a decorative material pattern of the present invention includes a base color layer.

In the method for producing a substrate with a decorating material pattern of the present invention, the base color layer is preferably a white layer from the viewpoint of reflecting the color of the photosensitive resin layer. Further, the base color layer may be required to be a metallic luster layer from the viewpoint of a preferable design.
Hereinafter, the case where the background color layer is a white layer and a metallic luster layer will be described. However, the present invention is not limited to the following embodiments, and the base color layer may have other colors other than the white layer and the metal luster layer. It may be a layer.

-Resin with siloxane bond in the main chain-
The white layer preferably contains a resin having a siloxane bond in the main chain. However, the board | substrate with a decorating material pattern of this invention may contain components other than the said pigment in the said white layer, unless it is contrary to the meaning of this invention.

The resin having a siloxane bond in the main chain is not particularly limited, but a silicone resin is preferable.
Known silicone resins can be used. A methyl-based straight silicone resin, a methylphenyl-based straight silicone resin, an acrylic resin-modified silicone resin, a polyester resin-modified silicone resin, an epoxy resin-modified silicone resin, an alkyd resin, a modified silicone resin, and a rubber-based silicone resin can be used.
More preferred are methyl straight silicone resin, methylphenyl straight silicone resin, and acrylic resin-modified silicone resin, and particularly preferred are methyl straight silicone resin and methylphenyl straight silicone resin.
The resin having a siloxane bond in the main chain may be used alone or in combination of two or more. The film physical properties can be controlled by mixing these at an arbitrary ratio.
As the resin having a siloxane bond in the main chain, a commercially available resin may be used, and for example, KR300, KR311, KR251, X40-9246 (manufactured by Shin-Etsu Silicone Co., Ltd.) can be used. Among these, KR251 and X40-9246 (manufactured by Shin-Etsu Silicone Co., Ltd.) are more preferable from the viewpoint of adhesion and workability when slitting the material. KR251 and X40-9246 (manufactured by Shin-Etsu Silicone Co., Ltd.) Two types of mixtures of these are especially preferable.
As the resin having a siloxane bond in the main chain, a resin dissolved in an organic solvent or the like may be used. For example, a resin dissolved in a xylene solution may be used.
Moreover, it is preferable to add a known compound as a polymerization catalyst to the resin having a siloxane bond in the main chain, and more preferable to add a zinc-based polymerization catalyst. A commercially available catalyst may be used as the polymerization catalyst, for example, D-15 (manufactured by Shin-Etsu Silicone Co., Ltd.) or the like can be used.

The component other than the pigment that may be contained in the white layer is not particularly limited, but in addition to the known binder resin and the resin having the siloxane bond in the main chain, a known pigment dispersion stabilizer, However, it is desirable that the color of the white layer does not change or changes to a desired color.
The ratio of the resin having the siloxane bond in the main chain to the components other than the pigment contained in the white layer is preferably 80% by mass or more from the viewpoint of obtaining the effects of the present invention, and is 90% by mass or more. Is more preferable.

The content of the component other than the resin having the siloxane bond in the main chain and the pigment in the white layer is preferably 30% by mass or more based on the total solid content of the white layer. When the content of the component other than the resin having the siloxane bond in the main chain and the pigment is within the above range, the color of the white layer of the present invention can be favorably affected.
The content of the resin having the siloxane bond in the main chain and the components other than the pigment in the white layer is preferably 30 to 60% by mass, more preferably 35 to 55% by mass, and 40 to 50% by mass. More particularly preferred.

-Coloring material for base color layer-
Since the base color layer is particularly easy to see, it is preferable to use the following color material for the white layer. The color material for the white layer is preferably a pigment, and more preferably a white inorganic pigment. In addition, when the base color layer is a metallic luster layer, from the viewpoint of a preferable design, a metal thin film layer (preferably a metal deposition layer such as aluminum, chromium, silver, etc.) such as aluminum, chromium, silver, aluminum flakes, etc. It is also preferable to use metallic pigments. As a means for providing a metallic luster layer, a layer containing a material such as a metallic pigment having a metallic luster, a method of laminating by metal vapor deposition, metal sputtering, or plating on a support used in the production method of the present invention is manufactured according to the present invention. A transfer material in which a layer containing a material such as a metallic pigment having a metallic luster is formed separately by a known method such as coating on a support used in the method is prepared, and then used in the manufacturing method of the present invention. A method of transferring or laminating the transfer material on a support can be mentioned. When the base color layer is a metallic luster layer, a substrate and a metallic luster layer integrated may be used. For example, a commercially available 25 μm PET base with an aluminum vapor deposition layer (product name: Diastar) Can be used.
As the white inorganic pigment, white pigments described in paragraphs [0015] and [0114] of JP-A-2005-7765 can be used.
Specifically, the white inorganic pigment is preferably titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate, more preferably titanium oxide or zinc oxide. The white layer is particularly preferably titanium oxide, among which rutile type or anatase type titanium oxide is more particularly preferred, and rutile type titanium oxide is even more particularly preferred.

The surface of titanium oxide can be used in combination with silica treatment, alumina treatment, titania treatment, zirconia treatment, organic matter treatment and the like.
Thereby, the catalytic activity of titanium oxide can be suppressed, and heat resistance, fluorescence, etc. can be improved.
From the viewpoint of suppressing the b value of the white layer after heating, the surface treatment of the titanium oxide is preferably an alumina treatment or a zirconia treatment, and an alumina / zirconia combined treatment is particularly preferred.

The content of the white inorganic pigment with respect to the total solid content of the white layer is 20 to 75% by mass, and the brightness and whiteness (L It is possible to form a decorating material having a high value and a low a value and a low b value) and satisfying other required characteristics at the same time.
The content of the white inorganic pigment with respect to the total solid content of the white layer is more preferably 25 to 60% by mass, and further preferably 30 to 50% by mass.
As used herein, the total solid content of the white layer means the total mass of nonvolatile components excluding the solvent and the like from the white layer.

The white inorganic pigment (which is the same for other pigments used in the light shielding layer described later) is desirably used as a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the white inorganic pigment and the pigment dispersant in an organic solvent (or vehicle). The vehicle refers to a portion of a medium in which a pigment is dispersed when the paint is in a liquid state, and is a liquid component that binds to the pigment to form a coating film (binder) and dissolves and dilutes it. Component (organic solvent).

The dispersing machine used for dispersing the white inorganic pigment is not particularly limited, and is described in, for example, Asakura Kunizo, “Encyclopedia of Pigments”, first edition, Asakura Shoten, 2000, item 438. Known dispersing machines such as a kneader, a roll mill, an atrider, a super mill, a dissolver, a homomixer, and a sand mill can be used. Further, fine grinding may be performed using frictional force by mechanical grinding described on page 310 of the document.

From the viewpoint of dispersion stability and hiding power, the white inorganic pigment as the white inorganic pigment (coloring material for the white layer) preferably has an average primary particle diameter of 0.16 μm to 0.3 μm, and more preferably 0. A thickness of 18 μm to 0.27 μm is preferable. Further, those with 0.19 μm to 0.25 μm are particularly preferable. When the average particle size of the primary particles is 0.16 μm or more, the hiding power is high, the base of the light shielding layer becomes difficult to see, and the viscosity is hardly increased. On the other hand, when the thickness is 0.3 μm or less, the whiteness is sufficiently high, the hiding power is high at the same time, and the surface shape when applied is good.
The “average particle size of primary particles” as used herein refers to the diameter when the electron micrograph image of the particles is a circle of the same area, and the “number average particle size” refers to the above-mentioned particle size for a large number of particles. The diameter is obtained and the average value of the arbitrary 100 is referred to.
On the other hand, when measuring the average particle size in the dispersion and coating solution, laser scattering HORIBA H (manufactured by Horiba Advanced Techno Co., Ltd.) can be used.

-Other materials-
An antioxidant may be added to the base color layer. In particular, when the base color layer is a white layer, it is preferable to add an antioxidant. As the antioxidant, a hindered phenol, semi-hindered phenol, phosphoric acid, or a hybrid antioxidant having phosphoric acid / hindered phenol in the molecule can be used.
The antioxidant that can be used in the present invention is preferably a phosphoric acid antioxidant, for example, IRGAFOS168 (manufactured by BASF) from the viewpoint of suppressing coloring.

In addition, as a solvent for producing the base color layer by coating, the solvents described in paragraphs [0043] to [0044] of JP 2011-95716 A can be used.
Solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, lactic acid Ethyl, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-oxypropionate and ethyl 3-oxypropionate 3-oxypropionic acid alkyl esters (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), and 2-oxypropionic acid 2-oxypropionic acid alkyl esters such as til, ethyl 2-oxypropionate, and propyl 2-oxypropionate (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy -Ethyl 2-methylpropionate), and methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, propylene glycol propyl ether acetate, etc .;

Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like;

Aromatic hydrocarbons such as toluene and xylene;

Of these, methyl ethyl ketone, methyl isobutyl ketone, xylene, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like are preferable.
A solvent may be used independently and may be used in combination of 2 or more type.

Further, other additives may be used for the base color layer. Examples of the other additives include surfactants described in paragraph [0017] of Japanese Patent No. 4502784, paragraphs [0060] to [0071] of JP-A-2009-237362, and Japanese Patent No. 4502784. Examples include the thermal polymerization inhibitor described in paragraph [0018], and other additives described in paragraphs [0058] to [0071] of JP-A No. 2000-310706. As the surfactant, commercially available ones may be used. For example, MegaFuck F553, MegaFuck F554, MegaFuck F556, MegaFuck F557, MegaFuck F559, MegaFuck F561, MegaFuck F-780F (DIC stock) Etc.) can be used.

-Thickness of ground color layer-
In the substrate with a decorating material pattern of the present invention, when the base color layer is a white layer, the thickness of the base color layer is 10 μm to 40 μm. Therefore, it is preferable. When the base color layer is a white layer, the thickness of the base color layer is more preferably 15 to 40 μm, and particularly preferably 20 to 38 μm.
In the substrate with a decorating material pattern of the present invention, when the base color layer is a metallic luster layer, the thickness of the base color layer is preferably in the range of 100 to 2000 mm, more preferably in the range of 200 to 800 mm, and still more preferably. Is in the range of 300-600 cm.
In the substrate with a decorative material pattern of the present invention, when the background color layer is a color other than the white layer and the metallic luster layer, the thickness of the background color layer is preferably 1 to 10 μm.

(Light shielding layer)
The manufacturing method of the board | substrate with a decorating material pattern of this invention has a light-shielding layer between the said support body and the said base color layer from a viewpoint of avoiding that a back side is transparent. In particular, when the color of the photosensitive resin layer or the base color layer is not black or gray, it is preferable to provide a light shielding layer.
Specifically, when using a decorative material-forming laminated material having a base color layer and a photosensitive resin layer in this order on a support, the support and the base color layer of the decorative material-forming laminated material are used. It is preferable to have a light shielding layer in between.
In the case of using a decorative material pattern-containing decorative material forming laminate material having a decorative material pattern in this order, which is obtained by exposing and developing a base color layer and a photosensitive resin layer on a support, the decorative material pattern-containing additive is used. It is preferable to have a light shielding layer between the said support body of the laminated material for decorating material formation, and the said base color layer.
When using another decorative material forming laminate material having a base color layer on the support, it may have a light shielding layer between the support and the base color layer of the other decorative material forming laminate material. preferable.

-Color material for light shielding layer-
As the color material for the light shielding layer, a pigment is preferable, and a black pigment is more preferable. Examples of the black pigment include carbon black, titanium black, titanium carbon, iron oxide, titanium oxide, and graphite. In the substrate with a decorative material pattern of the present invention, the light shielding layer is made of titanium oxide and carbon black. It is preferable to include at least one, and carbon black is more preferable.

-Resin with siloxane bond in the main chain-
The light shielding layer preferably contains a resin having a siloxane bond in the main chain. However, as long as it is not contrary to the gist of the present invention, the light shielding layer may contain other binder resin.
Components other than the resin having the siloxane bond in the main chain and the pigment that can be used for the light shielding layer are the same as those that can be used for the base color layer.
From the viewpoint of obtaining the effects of the present invention, the ratio of the resin having a siloxane bond in the main chain with respect to components other than the pigment contained in the light shielding layer is preferably 60% by mass or more, and 70% by mass or more. More preferred.
Furthermore, the ratio of the resin having the siloxane bond in the main chain with respect to components other than the pigment contained in the base color layer is 90% by mass or more, and with respect to components other than the pigment contained in the light shielding layer The ratio of the resin having a siloxane bond in the main chain is preferably 70% by mass or more. The more preferable range in this case is the same as the more particularly preferable range in the ground color layer or the light shielding layer, and the still more preferable range.

-Other materials-
Examples of other materials that can be used for the light-shielding layer include materials that can be used for the base color layer. Preferred ranges of other materials are also preferable ranges of materials that can be used for the base color layer. It is the same.

-Thickness of light shielding layer-
The thickness of the light shielding layer is preferably 1.0 μm to 5.0 μm from the viewpoint of enhancing the hiding power of the light shielding layer.
The thickness of the light shielding layer is more preferably from 1.0 to 4.0 μm, particularly preferably from 1.5 to 3.0 μm.

(Transparent adhesive layer)
In the production method of the present invention, it is preferable that the base color layer is a metallic gloss layer, and has a transparent adhesive layer on the surface adjacent to the metallic gloss layer and opposite to the support.
The transparent adhesive layer is not particularly limited, but the transparent adhesive layer preferably has high transparency, and preferably has high adhesiveness with the metallic gloss layer, the photosensitive resin layer, and the white photosensitive resin layer, It is preferable that heat resistance is high.

-Resin with siloxane bond in the main chain-
The transparent adhesive layer preferably contains a binder resin. More preferably, the binder resin includes a resin having a siloxane bond in the main chain. However, other binder resins may be included in the transparent adhesive layer as long as not departing from the spirit of the present invention.
Examples and preferred ranges of the resin having a siloxane bond in the main chain that can be used in the transparent adhesive layer are the same as those of the resin having a siloxane bond in the main chain used in the base color layer. As the resin having a siloxane bond in the main chain, a commercially available resin may be used, and KR251, X40-9246 (manufactured by Shin-Etsu Silicone Co., Ltd.) is preferable from the viewpoint of adhesion and processability. KR251 and X40 Two types of mixture of −9246 (manufactured by Shin-Etsu Silicone Co., Ltd.) are more preferable.
The ratio of the resin having a siloxane bond in the main chain to the transparent adhesive layer is preferably 60% by mass or more from the viewpoint of obtaining transparency, adhesion to the metallic luster layer, and heat resistance, and is 70% by mass or more. It is more preferable that it is 80 mass% or more, and it is especially preferable that it is 90 mass% or more.

-Other materials-
The transparent adhesive layer may contain other additives. Examples and preferred ranges of other additives are the same as examples and preferred ranges of other additives used for the base color layer. Among them, the transparent adhesive layer preferably contains a surfactant. As the surfactant, a commercially available one may be used. For example, Megafac F-559 (manufactured by DIC Corporation) can be used.

-Thickness of transparent adhesive layer-
The thickness of the transparent adhesive layer is not particularly limited, but is preferably 1.0 μm to 40 μm, more preferably 5 to 30 μm, and particularly preferably 10 to 20 μm.

(Thermoplastic resin layer)
In the production method of the present invention, in the case where the condition (N) is satisfied, the other decorative material-forming laminated material having a base color layer on the support may have at least one thermoplastic resin layer. . The thermoplastic resin layer is preferably provided between the support and the base color layer. That is, it is preferable that the said other laminated material for decorating material formation contains the said support body, the said thermoplastic resin layer, and the said base color layer in this order.
The component used for the thermoplastic resin layer is preferably an organic polymer substance described in JP-A-5-72724, which is determined by the Vicat method (specifically, the polymer softening point measurement method based on the American Material Test Method ASTM D1235). It is particularly preferable that the softening point is selected from organic polymer materials having a temperature of about 80 ° C. or lower.

Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate and saponified products thereof. Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer Combined nylon, copolymer nylon, N-alkoxy Chill nylon, and organic polymeric polyamide resins such as N- dimethylamino nylon.

The thickness of the thermoplastic resin layer is preferably 6 to 100 μm, more preferably 6 to 50 μm. When the thickness of the thermoplastic resin layer is in the range of 6 to 100 μm, the unevenness can be completely absorbed even when the substrate has unevenness.

(Middle layer)
The other decorative material forming laminated material having a base color layer on the support in the case of satisfying the condition (N) used in the production method of the present invention is stored at the time of applying a plurality of coating liquids and after coating. For the purpose of preventing mixing of components at the time, at least one intermediate layer may be provided. The intermediate layer is preferably provided between the support and the base color layer (in the case of having the thermoplastic resin layer, between the thermoplastic resin layer and the base color layer). That is, it is preferable that the other decorative material-forming laminated material includes the support, the thermoplastic resin layer, the intermediate layer, and the base color layer in this order.
As the intermediate layer, it is preferable to use an oxygen-blocking film having an oxygen-blocking function described as “separation layer” in JP-A-5-72724. This reduces the time load and improves productivity.
The oxygen barrier film is preferably formed using a compound that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution, and can be appropriately selected from known compounds. Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.

The thickness of the intermediate layer is preferably from 0.1 to 5.0 μm, more preferably from 0.5 to 2.0 μm. In the range of 0.1 to 5.0 μm, the oxygen blocking ability does not decrease, and it does not take too much time during development or removal of the intermediate layer.

(Protective release layer)
The decorative material forming laminate material or the decorative material pattern-containing decorative material forming laminate material includes the base color layer, the photosensitive resin layer, and the decoration to protect against contamination and damage during storage. A protective release layer (also referred to as a cover film) is preferably provided so as to cover the material pattern. The protective release layer may be made of the same or similar material as the support, but should be easily separated from the base color layer, the photosensitive resin layer, and the decorating material pattern. Suitable materials for the protective release layer include, for example, silicone paper, polyolefin, or polytetrafluoroethylene sheet.

The maximum value of the haze degree of the protective release layer is preferably 3.0% or less, and from the viewpoint of more effectively suppressing the occurrence of white spots after development of the white layer, 2.5% or less is preferable. 2.0% or less is more preferable, and 1.0% or less is particularly preferable.

The thickness of the protective release layer is preferably 1 to 100 μm, more preferably 5 to 50 μm, and particularly preferably 10 to 30 μm. If the thickness is 1 μm or more, the strength of the protective release layer is sufficient, so that the protective release layer is not easily broken when a cover film is bonded to the base color layer or the photosensitive resin layer. When the thickness is 100 μm or less, the price of the protective release layer does not increase, and wrinkles are unlikely to occur when the protective release layer is laminated.

Such protective release layers are commercially available, for example, polypropylene films such as Alfane MA-410, E-200C, E-501, Shin-Etsu Film Co., Ltd. manufactured by Oji Paper Co., Ltd., manufactured by Teijin Limited. A polyethylene terephthalate film such as PS series such as PS-25 is exemplified, but not limited thereto. Moreover, it can be easily manufactured by sandblasting a commercially available film.

A polyolefin film such as a polyethylene film can be used as the protective release layer. The polyolefin film usually used as the protective release layer is produced by heat-melting raw materials, kneading, extrusion, biaxial stretching, casting or inflation.

As mentioned above, although the laminated material for decorating material formation or the laminated material for decorating material pattern containing decorating material formation which can be used for this invention was demonstrated, the said laminated material for decorating material forming or decorating material pattern containing decorating The material-forming laminated material may be a negative material or a positive material as necessary.

-Manufacturing method of decorative material forming laminate material or decorative material pattern-containing decorative material forming laminate material-
The method for producing the decorative material-forming laminated material or the decorative material pattern-containing decorative material-forming laminated material described above is not particularly limited, but for example, paragraph [0064] of JP-A-2005-3861 To [0066]. Further, the decorative material-forming laminated material or the decorative material pattern-containing decorative material-forming laminated material can also be prepared by the method described in, for example, JP-A-2009-116072.
As an example of a method for producing a decorative material-forming laminated material or a decorative material pattern-containing decorative material-forming laminated material, a step of applying a resin composition on a support and drying to form a base color layer; And a step of covering the formed colored layer with the protective release layer.
In the laminated material for forming a decorative material or the laminated material for forming a decorative material pattern-containing decorative material that can be used in the present invention, other layers may be formed as long as it does not contradict the gist of the present invention. Further, before forming the base color layer, the thermoplastic resin layer and / or the intermediate layer (oxygen barrier layer) is formed by applying a coating solution for forming the thermoplastic resin layer and / or a coating solution for forming the intermediate layer. May be.
As a method of applying the photosensitive resin layer forming composition, the base color layer forming composition, the thermoplastic resin layer forming coating solution, and the intermediate layer forming coating solution on a support. A known coating method can be used. For example, it can be formed by applying and drying these coating liquids using a coating machine such as a spinner, a wheeler, a roller coater, a curtain coater, a knife coater, a wire bar coater, or an extruder.

The method for covering the photosensitive resin layer, the base color layer or the decorating material pattern with the protective release layer is not particularly limited, but the protection is applied to the photosensitive resin layer, the base color layer or the decorating material pattern on the support. A method in which the release layers are stacked and pressure-bonded can be used.
For the pressure bonding, a known laminator such as a laminator, a vacuum laminator, or an auto-cut laminator capable of further improving productivity can be used.
The pressure bonding conditions are preferably an atmospheric temperature of 20 to 45 ° C. and a linear pressure of 1000 to 10000 N / m.

<Board>
Various substrates can be used as the substrate used in the method for producing a substrate with a decorating material pattern of the present invention, but the substrate is preferably a glass substrate or a film substrate, and has no optical distortion. It is more preferable to use one having high transparency. In the method for manufacturing a substrate with a decorating material pattern of the present invention, the substrate preferably has a total light transmittance of 80% or more.

When the substrate is made of glass, specifically, tempered glass obtained by chemical strengthening treatment in which some or all of ions having an ion radius smaller than potassium ions in the glass are replaced with potassium ions is preferable.
The glass used in the present invention is not particularly limited, but the strain point temperature obtained by a method according to JIS R3103-2 (2001) is preferably 500 ° C. to 520 ° C. Further, it is preferable that the temperature near the temperature at which glass is likely to be deformed, that is, the temperature of the molten salt is 490 to 530 ° C. For example, the surface of SiO ₂ —Na ₂ O—K ₂ O—CaO—MgO—Al ₂ O ₃ glass called soda lime glass manufactured by the float process is formed by a chemical strengthening treatment. preferable.

As the chemical strengthening treatment for forming the compression layer, the compression layer is formed by immersing glass in a molten salt and exchanging sodium ions in the glass and potassium ions in the molten salt. The compressive layer has a compressive stress value of 200 to 650 MPa, and when the glass is chemically strengthened so as to have the value, the temperature of the molten salt to be immersed is 450 to 550 ° C. and the immersion time. Is preferably 1 hour to 3 hours.

Specific materials when the substrate is a film substrate include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate (PC), triacetyl cellulose (TAC), and cycloolefin polymer (COP).
The substrate is preferably selected from glass, TAC, PET, PC or COP, more preferably made of glass or a cycloolefin polymer, and particularly preferably glass.

Various functions may be added to the substrate surface. Specifically, an antireflection layer, an antiglare layer, a retardation layer, a viewing angle improving layer, a scratch resistant layer, a self-healing layer, an antistatic layer, an antifouling layer, an antimagnetic wave layer, and a conductive layer can be exemplified.
As the conductive layer, those described in JP-T-2009-505358 can be preferably used.

The thickness of the substrate is preferably 40 to 200 μm, more preferably 40 to 150 μm, and particularly preferably 50 to 120 μm.

In addition, in order to improve the adhesion of the photosensitive resin layer or the decorative material pattern by lamination in the lamination process, the non-contact surface of the substrate (input of a finger or the like out of the surface of the substrate constituting the capacitive input device) is performed in advance. Surface treatment can be performed on the surface opposite to the surface with which the means is brought into contact. As the surface treatment, it is preferable to perform a surface treatment (silane coupling treatment) using a silane compound. As the silane coupling agent, those having a functional group that interacts with the photosensitive resin are preferable. For example, a silane coupling solution (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3% by mass aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) is sprayed for 20 seconds with a shower, and pure water shower washing To do. Thereafter, the reaction is carried out by heating. A heating tank may be used, and the reaction can be promoted by preheating the substrate with a laminator.

<Lamination (Lamination method)>
Lamination (bonding) of the photosensitive resin layer, the base color layer or the decorating material pattern to the substrate surface is performed by pressing the photosensitive resin layer, the base color layer or the decorating material pattern on the substrate surface, and applying pressure and heating. Is done. For laminating, a known laminator such as a laminator, a vacuum laminator, and an auto-cut laminator that can further improve productivity can be used.
As the laminating method, a method in which bubbles do not enter between the decorative material forming laminated material or the decorative material pattern-containing decorative material forming laminated material and the substrate is preferable from the viewpoint of increasing the yield.
Specifically, the use of a vacuum laminator can be preferably mentioned.

Examples of the apparatus used for laminating (continuous type / single-wafer type) include V-SE340aaH manufactured by Climb Products Co., Ltd.
Examples of the vacuum laminator device include those manufactured by Takano Seiki Co., Ltd., Taisei Laminator Co., Ltd., FVJ-540R, FV700, and the like.

Before sticking the decorative material forming laminate material or the decorative material pattern-containing decorative material forming laminate material to the substrate, the photosensitive resin layer, the base color layer or the decorative material pattern of the support Including the step of further laminating another support on the opposite side can sometimes provide a preferable effect of preventing bubbles during lamination. Although there is no restriction | limiting in particular as a support body used at this time, For example, a polyethylene terephthalate, a polycarbonate, a triacetyl cellulose, a cycloolefin polymer is mentioned.
The film thickness can be selected in the range of 50 to 200 μm.

<Step of removing the support>
The production method of the present invention may include a step of removing the support from the decorative material forming laminate material or the decorative material pattern-containing decorative material forming laminate material attached to the substrate. It does not have to be. If the exposure process is not affected and the base material is glass, the decorative material formed on the substrate is formed from the viewpoint of preventing scattering of glass fragments when damaged due to external impact. It is preferable not to include the step of removing the support from the laminated material for decoration or the laminated material for decorating material-containing decorative material formation. On the other hand, when performing the exposure step, the step of removing the support from the decorative material forming laminate material or the decorative material pattern-containing decorative material forming laminate material attached to the substrate as necessary is performed. Also good.

<Exposure process>
The said exposure process is a process of exposing the photosensitive resin layer of the laminated material for decorating material formation, or the said photosensitive resin layer laminated | stacked on the board | substrate. Moreover, when the laminated material for decorating material pattern containing decoration material formation has the said base color layer or the said light shielding layer, it is laminated | stacked on the board | substrate of the laminated material for decorating material pattern containing decoration material formation as needed. And a step of exposing the base color layer and the light shielding layer.
Specifically, a mask for forming a predetermined decorating material pattern is arranged above the photosensitive resin layer formed on the substrate, and then the mask, if necessary, a thermoplastic resin layer and a necessary Accordingly, there is a method of exposing the photosensitive resin layer from above the mask through an intermediate layer. In the production method of the present invention, the base color layer, the light shielding layer, and the like may be cured by exposure. In that case, the photocurable resin is passed through a thermoplastic resin layer and an intermediate layer without using a mask. A method of exposing the entire surface of the layer can be mentioned.
Here, the light source for the exposure can be appropriately selected and used as long as it can irradiate light in a wavelength region capable of curing the photosensitive resin layer (for example, 365 nm, 405 nm, etc.). Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned. The exposure dose is usually about 5 to 200 mJ / cm ² , preferably about 10 to 100 mJ / cm ² . However, when the photosensitive resin layer contains a colorant that absorbs light in the wavelength range (for example, when a white photosensitive resin layer containing titanium oxide as a white pigment is used), the exposure amount is increased to 100 to 2000 mJ. / Cm ² , preferably about 300 to 1200 mJ / cm ² .

<Development process>
The developing step is a step of developing the exposed photosensitive resin layer (the base color layer and the light shielding layer as necessary).
In the present invention, the developing step is not a developing step in a narrow sense in which the pattern-exposed photosensitive resin layer is pattern-developed with a developer, but a thermoplastic resin after the entire surface of the base color layer and the light-shielding layer is exposed. This is a development process including a case of a development process in a broad sense in which the base color layer itself and the light shielding layer itself do not form a pattern simply by removing a layer or an intermediate layer.
The development can be performed using a developer. The developer is not particularly limited, and known developers such as those described in JP-A-5-72724 can be used. The developer preferably has a development behavior in which the photosensitive resin layer has a dissolution type. For example, a developer containing a compound with pKa = 7 to 13 at a concentration of 0.05 to 5 mol / L is preferable. On the other hand, the developer in the case where the base color layer itself or the light shielding layer itself does not form a pattern preferably has a development behavior that does not dissolve the non-alkaline development type composition layer. For example, pKa = 7 to Those containing 13 compounds at a concentration of 0.05 to 5 mol / L are preferred. A small amount of an organic solvent miscible with water may be added to the developer. Examples of organic solvents miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzyl alcohol And acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like. The concentration of the organic solvent is preferably 0.1% by mass to 30% by mass. Further, a known surfactant can be added to the developer. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.

The development method may be any of paddle development, shower development, shower & spin development, dip development and the like. Here, the shower development will be described. The uncured portion can be removed by spraying a developer onto the photosensitive resin layer after exposure. When a thermoplastic resin layer or an intermediate layer is provided, an alkaline solution having a low solubility of the photosensitive resin layer is sprayed by a shower before development, and the thermoplastic resin layer, the intermediate layer, etc. are removed. It is preferable to keep it. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like. The liquid temperature of the developer is preferably 20 ° C. to 40 ° C., and the pH of the developer is preferably 8 to 13.

The production method of the present invention may have other steps such as a post-exposure step and a post-bake step. When the photosensitive resin layer, the base color layer, and the light shielding layer are also thermosetting transparent resin layers, it is preferable to perform a post-bake process.

The patterning exposure and the entire surface exposure may be performed after the support in the decorative material-forming laminated material or the decorative material pattern-containing decorative material-forming laminated material is peeled off. You may expose before peeling, and may peel the said support body after that. In the above, exposure through a desired mask has been described as an example for forming a decorative material pattern, but the patterning exposure may be exposure through a mask or digital exposure using a laser or the like.

<The process of removing a thermoplastic resin layer, the process of removing an intermediate | middle layer>
Furthermore, when the said laminated material for decorating material formation or the laminated material for decorating material pattern containing decorating material formation contains a thermoplastic resin layer and an intermediate | middle layer, it has a process of removing a thermoplastic resin layer and an intermediate | middle layer. Is preferred.
The step of removing the thermoplastic resin layer and the intermediate layer can be performed using an alkaline developer generally used in a photolithography method. As the alkaline developer, a developer used in the step of developing the exposed photosensitive resin layer can be used in the same manner.

The method for removing the thermoplastic resin layer and the intermediate layer may be any method such as paddle, shower, shower & spin, and dip. Here, the shower will be described. The thermoplastic resin layer and the intermediate layer can be removed by spraying a developer with a shower. Further, after the development, it is preferable to remove the residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like. The liquid temperature is preferably 20 ° C. to 40 ° C., and the pH is preferably 8 to 13.

<Post-bake process>
It is preferable to include a post-baking step after the laminating step, and it is more preferable to include a step of performing post-baking after the step of removing the thermoplastic resin layer and the intermediate layer.
The manufacturing method of the said board | substrate with a decorating material pattern makes 0.08 the said base color layer (the light shielding layer as needed) of the said laminated material for decorating material formation or the laminated material for decorating material pattern containing decorating material formation. Forming by heating to 180 to 300 ° C. in an environment of up to 1.2 atm is preferable from the viewpoint of achieving both productivity and reliability when incorporated in an electronic device or the like.
The post-baking is more preferably performed in an environment of 0.5 atm or more. On the other hand, it is more preferable to carry out in an environment of 1.1 atm or less, and it is particularly preferred to carry out in an environment of 1.0 atm or less. Furthermore, it is more preferable to carry out in an environment of about 1 atm (atmospheric pressure) from the viewpoint of reducing the manufacturing cost without using a special decompression device. Here, conventionally, when the base color layer and the light shielding layer are cured by heating, the whiteness and the light shielding layer after baking are reduced by heating in a reduced pressure environment of a very low pressure to lower the oxygen concentration. Although the color tone of the substrate side is maintained, by using the decorative material-forming laminated material or the decorative material pattern-containing decorative material-forming laminated material, the present material is baked in the above pressure range. The board | substrate side color of the said white layer of the board | substrate with a decorating material pattern of invention and the light shielding layer can be improved (b value is made small), and the whiteness and the color of the board | substrate side of a light shielding layer can be improved. .
The post-baking temperature is more preferably 200 to 280 ° C., and particularly preferably 220 to 260 ° C.
The post-baking time is more preferably 20 to 150 minutes, and particularly preferably 30 to 100 minutes.
The post-baking may be performed in an air environment or a nitrogen substitution environment, but it is particularly preferable to perform the post-bake from the viewpoint of reducing the manufacturing cost without using a special decompression device.

<Other processes>
The manufacturing method of this invention may have other processes, such as a post-exposure process.
When the base color layer and the light shielding layer have a photocurable resin, the base color layer and the light shield layer preferably include a post-exposure step. The post-exposure step may be performed only from the surface of the base color layer and the light-shielding layer that is in contact with the substrate, from only the surface that is not in contact with the transparent substrate, or from both surfaces. Good.

Examples of the exposure step, the development step, the step of removing the thermoplastic resin layer and the intermediate layer, and other steps are described in paragraph numbers [0035] to [0051] of JP-A-2006-23696. This method can also be suitably used in the present invention.

[Substrate with decorative material pattern]
The board | substrate with a decorating material pattern of this invention was manufactured by the manufacturing method of the board | substrate with a decorating material pattern of this invention, It is characterized by the above-mentioned.
Hereinafter, the preferable aspect of the board | substrate with a decorating material pattern of this invention is demonstrated.

<Layer structure>
It is preferable that the board | substrate with a decorating material pattern of this invention has a decorating material pattern and a base color layer in this order on a board | substrate. The decorating material pattern and the base color layer may be laminated in direct contact with each other, or may be laminated through other layers, but when forming the decorating material pattern, a photosensitivity other than white is used. In the case of using a conductive resin layer, it is preferable that the layers are laminated in direct contact. On the other hand, when a white photosensitive resin layer is used when forming the decorating material pattern, the base color layer is a metallic luster layer, and the decorating material pattern and the base color layer (that is, the metallic luster layer) are It is preferable that the layers are laminated via the transparent adhesive layer.
When only a decorating material pattern and a base color layer that is a white layer are laminated on a substrate to form a decorating material, the optical density may be low. In the board | substrate with a decorating material pattern of this invention, light leakage etc. are suppressed by setting it as the structure containing the decorating material pattern, the base color layer which is a white layer, and the light shielding layer in this order from the board | substrate (film or glass) side. I can do it.

<Characteristics of substrate with decorative material pattern>
The board | substrate with a decorating material pattern of this invention has a highly accurate decorating material pattern. When the decorative material pattern is linear, the pattern line width is preferably 150 μm or less, more preferably 100 μm or less, particularly preferably 50 μm or less, and particularly preferably 20 μm or less. Even more preferably, it is 15 μm or less.

<Touch panel>
The substrate with a decorative material pattern of the present invention is preferably used for the back exterior of electronic devices such as mobile phones and smartphones and information display devices, and particularly for electronic devices such as mobile phones and smartphones and information display devices having a touch panel. More preferably, it is used for the back exterior. As the touch panel, a capacitive input device is preferable.
The capacitance type input device and the image display device including the capacitance type input device as a component are “latest touch panel technology” (Techno Times, issued on July 6, 2009), supervised by Yuji Mitani. The configurations disclosed in “Technology and Development of Touch Panels”, CMC Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, and the like can be applied.

The information display device that can use the touch panel is preferably a mobile device, and examples thereof include the following information display devices.
iPhone4, iPad (above made by Apple Inc., USA), Xperia (SO-01B) (produced by Sony Ericsson Mobile Communications), Galaxy S (SC-02B), Galaxy Tab (SC-01C) (above, Samsung Electronics Korea) BlackBerry 8707h (manufactured by Kankoku Research in Motion), Kindle (manufactured by Amazon, USA), Kobo Touch (manufactured by Rakuten, Inc.).

Hereinafter, the present invention will be described more specifically with reference to examples. The materials, reagents, ratios, instruments, operations, and the like shown in the following examples can be appropriately changed without departing from the scope of the present invention, and therefore the present invention is not limited to the examples shown below. In the following examples, unless otherwise specified, both “%” and “part” are based on mass, and the molecular weight represents a weight average molecular weight.

[Production Example 1]
<Preparation of black colored liquid 1 and white colored liquid 1>
A black colored liquid 1 and a white colored liquid 1 described in Table 1 below were prepared using the following materials. In the table, the numerical values described in the columns of the black colored liquid 1 and the white colored liquid 1 represent “parts by mass”.

Black dispersion 1 (GB4016, manufactured by Sanyo Pigment Co., Ltd., the following composition)
Black pigment (carbon black) 25.0 mass%
Dispersing aid 9.5% by mass
Dispersing solvent (propylene glycol monomethyl ether acetate) 65.5% by mass

・ White dispersion (FP White B422, manufactured by Sanyo Dye Co., Ltd., the following composition)
White pigment (titanium dioxide) 70.0 mass%
Dispersing aid 3.5% by mass
Dispersing solvent (methyl ethyl ketone) 26.5% by mass

-Silicone resin solution 1 (KR300, manufactured by Shin-Etsu Silicone Co., Ltd., the following composition)
Xylene solution of silicone resin (solid content 50% by mass)

・ Silicone resin solution 2 (KR311, manufactured by Shin-Etsu Silicone Co., Ltd., the following composition)
Xylene solution of silicone resin (solid content 60% by mass)

・ Coating aid (Megafac F-780F, manufactured by DIC Corporation, composition shown below)
30% by weight of surfactant
Methyl ethyl ketone 70% by mass

・ Acrylic resin solution (the following composition)
Benzyl methacrylate / methacrylic acid random copolymer (molar ratio 78/22, weight average molecular weight 38,000) 27% by mass
Propylene glycol monomethyl ether acetate 73% by mass

・ Acrylic monomer solution (Nippon Kayaku Co., Ltd., following composition)
Dipentaerythritol hexaacrylate 76% by mass
Propylene glycol monomethyl ether acetate 24% by mass

Photopolymerization initiator (IRGACURE 379EG, manufactured by BASF, the following compound)

・ Polymerization inhibitor (phenothiazine, the following compounds)

・ Organic solvent 1 (methyl ethyl ketone)

<Preparation of white coloring liquid 2>
White coloring liquid 2 was prepared using the following materials.
(White colored liquid 2: prescription)
White pigment dispersion (FP WHITE B422, Sanyo Dye Co., Ltd., the following composition) 16.7 parts by mass-White pigment (titanium dioxide) 70.0% by mass
-Dispersing aid 3.5% by weight
-Dispersion solvent (methyl ethyl ketone) 26.5% by weight
・ Methyl ethyl ketone 2.06 parts by mass ・ Silicone resin solution 3 (KR251, Shin-Etsu Silicone Co., Ltd., solid resin 20 mass% toluene solution) 78.8 parts by mass ・ Silicone resin solution 4 (X40-9246 Shin-Etsu Silicone ( Co., Ltd., silicone oligomer) 1.75 parts by mass D-15 Shin-Etsu Silicone Co., Ltd. (silicone resin catalyst, zinc-containing catalyst xylene solution (solid content 50 mass%))
0.700 parts by mass, MegaFuck F559 0.120 parts by mass, manufactured by Dainippon Ink & Chemicals, Inc.

[Production Example 2]
<Preparation of coating liquid CG-1 for forming a green (G) photosensitive resin layer>
A dispersion for green (G) (G-1) was prepared according to the following formulation.
Pigment Green 36 (average particle size 47 nm in SEM observation) 11 parts Pigment Yellow 150 (average particle size 39 nm in SEM observation) 7 parts Solution 5 parts of the following dispersion resin A-3 Dispersant (trade name: Disperbyk-161 3 parts, alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (= 85/15 [mol ratio] copolymer, molecular weight 30,000, propylene glycol monomethyl ether acetate solution (solid content) : 50 mass%)) 11 parts ・ Solvent: 70 parts of propylene glycol monomethyl ether acetate

The above components were stirred for 1 hour using a homogenizer under the condition of 3000 rpm. The obtained mixed solution was finely dispersed for 8 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads, and a green (G) dispersion (G-1 ) When the dispersed particles in the obtained green (G) dispersion liquid (G-1) were observed with an SEM, the average particle diameter was 32 nm.

Using the obtained green (G) dispersion liquid (G-1), a green (G) photosensitive resin layer forming coating liquid CG-1 was prepared according to the following formulation.
-Green (G) dispersion (G-1) 100 parts-Epoxy resin: 2 parts (trade name EHPE3150 manufactured by Daicel Chemical Industries)-Polymerizable compound: Dipentaerythritol penta-hexaacrylate 8 parts-Polymerizable compound: Tetra (ethoxy acrylate) 2 parts of pentaerythritol, polymerization initiator: 1,3-bistrihalomethyl-5-benzooxolantolyazine 2 parts, polymerization initiator: 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1 1 part ・ Polymerization initiator: diethylthioxanthone 0.5 part ・ Polymerization inhibitor: 0.001 part of p-methoxyphenol ・ Fluorosurfactant (trade name: Megafac R08 Dainippon Ink and Chemicals, Inc. Kogyo Co., Ltd.) 0.02 part, nonionic Surfactant (trade name: Emulgen A-60, manufactured by Kao Corporation) 0.5 parts, solvent: 120 parts of propylene glycol monomethyl ether acetate, solvent: 30 parts of propylene glycol n-propyl ether acetate G) A coating solution CG-1 for forming a photosensitive resin layer was obtained.

-Synthesis of Dispersing Resin A-3-
(1. Synthesis of chain transfer agent A3)
Dipentaerythritol hexakis (3-mercaptopropionate) [DPMP; manufactured by Sakai Chemical Industry Co., Ltd.] (the following compound (33)) 7.83 parts, and having an adsorption site and a carbon-carbon double bond The following compound (m-6) (4.55 parts) having the following formula was dissolved in 28.90 parts of propylene glycol monomethyl ether and heated to 70 ° C. under a nitrogen stream. To this was added 0.04 part of 2,2′-azobis (2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.] and heated for 3 hours. Further, 0.04 part of V-65 was added and reacted at 70 ° C. for 3 hours under a nitrogen stream. By cooling the obtained reaction liquid to room temperature, a 30% solution of a mercaptan compound (chain transfer agent A3) shown below was obtained.

(2. Synthesis of dispersion resin A-3)
A mixed solution of 4.99 parts of a 30% solution of chain transfer agent A3 obtained as described above, 19.0 parts of methyl methacrylate, 1.0 part of methacrylic acid, and 4.66 parts of propylene glycol monomethyl ether was added to nitrogen. It heated to 90 degreeC under airflow. While stirring this mixed solution, 0.139 part of dimethyl 2,2′-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.], 5.36 parts of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate 9 40 parts of the mixed solution was added dropwise over 2.5 hours. After completion of the dropwise addition, the resulting solution was reacted at 90 ° C. for 2.5 hours, and then a mixed solution of 0.046 part of dimethyl 2,2′-azobisisobutyrate and 4.00 part of propylene glycol monomethyl ether acetate. The reaction was continued for another 2 hours. To the obtained reaction liquid, 1.52 parts of propylene glycol monomethyl ether and 21.7 parts of propylene glycol monomethyl ether acetate were added and cooled to room temperature, whereby a solution of dispersion resin A-3 (polystyrene equivalent weight average molecular weight 24000) ( Dispersion resin 30 mass%, propylene glycol monomethyl ether 21 mass%, propylene glycol monomethyl ether acetate 49 mass%) was obtained.
The acid value of this dispersion resin A-3 was 48 mg / g. The structure of Dispersing Resin A-3 is shown below.

[Production Example 3]
A coating solution for a thermoplastic resin layer was prepared.
(Coating solution for thermoplastic resin layer: Formulation H1)
Methanol: 11.1 parts by mass Propylene glycol monomethyl ether acetate: 6.36 parts by mass Methyl ethyl ketone: 52.4 parts by mass Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio) (Molar ratio) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg≈70 ° C.): 5.83 parts by mass. Styrene / acrylic acid copolymer (copolymerization composition ratio (mol) Ratio) = 63/37, weight average molecular weight = 10,000, Tg≈100 ° C.): 13.6 parts by mass Monomer 1 (trade name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.): 9.1 mass Part / coating aid: 0.54 parts by mass In addition, 120 ° C. after removing the solvent from the coating liquid H1 for the thermoplastic resin layer The viscosity was 1500Pa · sec.

[Production Example 4]
An intermediate layer coating solution was prepared.
(Coating liquid for intermediate layer: prescription P1)
Polyvinyl alcohol: 32.2 parts by mass (trade name: PVA205, manufactured by Kuraray Co., Ltd., saponification degree = 88%, polymerization degree 550)
・ Polyvinylpyrrolidone: 14.9 parts by mass (trade name: K-30, manufactured by IS Japan Co., Ltd.)
-Distilled water: 524 parts by mass-Methanol: 429 parts by mass

[Production Example 5]
A coating solution for a transparent adhesive layer was prepared.
(Coating solution for transparent adhesive layer: prescription)
Silicone resin solution 3 (KR251, Shin-Etsu Silicone Co., Ltd., silicone resin solid content 20% by weight toluene solution) 90.0 parts by mass Silicone resin solution 4 (X40-9246, Shin-Etsu Silicone Co., Ltd., silicone oligomer) 9.90 parts by mass / Mega-Fak F559 0.100 parts by mass made by Dainippon Ink & Chemicals, Inc.

[Production Example 6]
A coating liquid for white photosensitive resin layer was prepared.
(Coating liquid for white photosensitive resin layer: prescription)
-White pigment dispersion (FP WHITE B422, Sanyo dye Co., Ltd., the following composition) 11.2 parts by mass-White pigment (titanium dioxide) 70.0% by mass
-Dispersing aid 3.5% by weight
-Dispersion solvent (methyl ethyl ketone) 26.5% by weight
・ Methyl ethyl ketone 46.6 mass parts ・ Alkali soluble acrylic resin (Alloset CF100, Nippon Shokubai Co., Ltd.)
31.4 parts by mass dipentaerythritol hexaacrylate (DPHA) (solid content 76% by mass, propylene glycol monomethyl ether acetate solution)
10.0 parts by mass-Irgacure 907 (manufactured by BASF) 0.640 parts by mass-Megafac F559 (manufactured by Dainippon Ink and Chemicals) 0.100 parts by mass

[Example 1]
<Preparation of laminated material (A-1) for decorating material formation>
On the support B (75 μm PET base), a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer were laminated in this order.
The thermoplastic resin layer is coated with the coating solution for the thermoplastic resin layer prepared above using a die coater so that the film thickness after drying is 15.0 μm, and then at 120 ° C. for 3 minutes. Formed by drying.
The intermediate layer is prepared by applying the intermediate layer coating solution prepared above using a die coater so that the film thickness after drying is 1.8 μm, and then drying it at 120 ° C. for 2 minutes. Formed.
The photosensitive resin layer was coated with the green (G) photosensitive resin layer forming coating solution CG-1 prepared above using a die coater so that the film thickness after drying was 2.0 μm. Subsequently, it formed by making it dry on 120 degreeC conditions for 2 minutes.
A polypropylene cover film having a thickness of 12 μm was pressure-bonded onto the prepared photosensitive resin layer to obtain a laminated material (A-1) for decorating material formation.

<Production of decorative material-forming laminated material (B) (other decorative material-forming laminated materials)>
A light-shielding layer and a base color layer (white layer) were laminated in this order on the release layer of Support A (Unitika Ltd. PET film with release layer Unipeel TR-6 75 μm).
The light-shielding layer is formed by applying the black colored liquid 1 prepared above using a die coater so that the film thickness after drying is 2.0 μm, and then drying it at 120 ° C. for 2 minutes. did.
For the base color layer (white layer), the white colored liquid 1 prepared above is applied using a die coater so that the film thickness after drying is 20 μm, and then dried under conditions of 120 ° C. for 4 minutes. Was formed.
A polypropylene cover film having a thickness of 12 μm was pressure-bonded onto the produced base color layer (white layer) to obtain a decorative material-forming laminate material (B).

<Preparation of substrate with decorative material pattern of Example 1>
The support B, the thermoplastic resin layer, the intermediate layer and the photosensitive layer are formed on a glass substrate (tempered glass, 300 mm × 400 mm × 0.7 mm) using the decorative material-forming laminate material (A-1) from which the cover film is peeled off. The resin layer is laminated with the surface of the photosensitive resin layer facing the surface of the glass substrate, under conditions of a substrate temperature of 100 ° C., an upper roll temperature of 100 ° C., a lower roll temperature of 100 ° C., and a conveyance speed of 0.6 m / min. And laminated together.
After the lamination, the support B of the decorative material-forming laminated material (A-1) was removed.
Then, with respect to the glass substrate which transferred the thermoplastic resin layer, the intermediate | middle layer, and the photosensitive resin layer, with the intensity | strength of 50 mJ / cm < ² > through a photomask (Quartz exposure mask which has a pattern for decorating materials with a line | wire width of 10 micrometers). Exposure was performed by irradiating ultraviolet rays having a wavelength of 365 nm.

Next, triethanolamine developer (containing 30% by mass of triethanolamine, trade name: T-PD2 (manufactured by FUJIFILM Corporation) 12 times with pure water (1 part of T-PD2 and 11 parts of pure water) The glass substrate after exposure was shower-developed at 30 ° C. for 20 seconds at a flat nozzle pressure of 0.1 MPa to remove the thermoplastic resin layer and the intermediate layer. Subsequently, after air was blown off on the upper surface of the glass substrate, pure water was sprayed for 10 seconds by a shower, pure water shower cleaning was performed, and air was blown to reduce a liquid pool on the substrate.

Thereafter, a sodium carbonate / sodium hydrogen carbonate developer (trade name: T-CD1 (manufactured by FUJIFILM Corporation) is diluted 5 times with pure water (mixed with 1 part of T-CD1 and 4 parts of pure water). The shower pressure was set to 0.1 MPa at 30 ° C. using the diluted solution), and the washed glass substrate was developed for 30 seconds. Subsequently, the glass substrate after development was washed with pure water, and the photosensitive resin layer was removed, thereby forming a decorative material pattern on the glass substrate by exposing and developing the photosensitive resin layer.

On the decorative material pattern surface of the glass substrate having the decorative material pattern thus formed, the decorative material-forming laminated material (B) (other decorative material-forming laminated material) with the cover film peeled off The surface temperature of the base color layer side (white layer side) and the surface of the decorative material pattern surface side are made to face each other, and the light shielding layer, base color layer (white layer), and support A are collectively measured at the substrate temperature. Laminated at 100 ° C., upper roll temperature of 100 ° C., lower roll temperature of 100 ° C., and conveyance speed of 0.6 m / min, decorative material pattern, ground color layer (white layer), light shielding layer and support on glass substrate A was laminated in this order. Next, the base color layer (white layer) was cured by heating the glass substrate on which the decorating material pattern and the like were formed at 150 ° C. for 30 minutes, and the substrate with the decorating material pattern of Example 1 was produced. At that time, the support A was left without peeling.

[Example 2]
<Preparation of laminated material for decorating material formation (A-2)>
A photosensitive resin layer was formed on the release layer of the support A.
The photosensitive resin layer was coated with the green (G) photosensitive resin layer forming coating solution CG-1 prepared above using a die coater so that the film thickness after drying was 2.0 μm. Subsequently, it formed by making it dry on 120 degreeC conditions for 2 minutes.
A 12 μm-thick polypropylene cover film was pressure-bonded onto the produced photosensitive resin layer to obtain a decorative material-forming laminate material (A-2).

<Preparation of substrate with decorative material pattern of Example 2>
50 mJ / cm is applied to the photosensitive resin layer of the decorative material forming laminate material (A-2) from which the cover film has been peeled off, through a photomask (quartz exposure mask having a decorative material pattern with a line width of 10 μm). Exposure was performed by irradiating with an ultraviolet ray having a wavelength of 365 nm at an intensity of ² .
A sodium carbonate / sodium hydrogen carbonate developer (trade name: T-CD1 (manufactured by FUJIFILM Corporation) was diluted 5 times with pure water (mixed in a ratio of 1 part of T-CD1 and 4 parts of pure water). The shower pressure was set to 0.1 MPa at 30 ° C. using the liquid, and the decorative material-forming laminated material (A-2) after exposure was developed for 30 seconds. Next, the decorative material-forming laminated material (A-2) after development is washed with pure water, and the photosensitive resin layer is exposed and developed on the decorative material-forming laminated material (A-2). A decorative material pattern was formed.
After that, the surface of the decorative material pattern side of the decorative material forming laminated material (A-2) on which the decorative material pattern is formed is opposed to the surface of the glass substrate (tempered glass, 300 mm × 400 mm × 0.7 mm). The substrate temperature was 100 ° C., the upper roll temperature was 100 ° C., the lower roll temperature was 100 ° C., and the conveyance speed was 0.6 m / min, and the decorative material pattern and the support A were laminated on the glass substrate. After the lamination, the support A was peeled off.

Using the decorative material forming laminated material (B) (other decorative material forming laminated material) obtained by peeling the cover film on the decorative material pattern surface thus formed, a base color layer (white layer) ) The surface on the side faces the surface of the decorative material pattern, and the substrate layer temperature is 100 ° C., the upper roll temperature is 100 ° C., and the lower roll temperature is 100 ° C. for the light shielding layer, the base color layer (white layer) and the support A. The laminate was laminated under the condition of a conveyance speed of 0.6 m / min, and a decorative material pattern, a base color layer (white layer), a light shielding layer and a support A were laminated in this order on a glass substrate. Next, the base color layer (white layer) was cured by heating the glass substrate on which the decorating material pattern and the like were formed at 150 ° C. for 30 minutes, thereby producing the substrate with the decorating material pattern of Example 2. At that time, the support A was left without peeling.

[Example 3]
<Production of decorative material-forming laminated material (i) -1 of Example 3>
On the release layer of the support A, a base color layer (white layer) and a photosensitive resin layer were laminated in this order.
For the base color layer (white layer), the white colored liquid 1 prepared above is applied using a die coater so that the film thickness after drying is 20 μm, and then dried under conditions of 120 ° C. for 4 minutes. Was formed.
The photosensitive resin layer was coated with the green (G) photosensitive resin layer forming coating solution CG-1 prepared above using a die coater so that the film thickness after drying was 2.0 μm. Subsequently, it formed by making it dry on 120 degreeC conditions for 2 minutes.
A polypropylene cover film having a thickness of 12 μm was pressure-bonded onto the prepared photosensitive resin layer to obtain a laminated material (i) -1 for decorating material formation of Example 3.

<Production of decorative material pattern-containing decorative material forming laminate material of Example 3>
With respect to the photosensitive resin layer of the decorative material-forming laminate material (i) -1 from which the cover film has been peeled off, 50 mJ / cm ² through a photomask (quartz exposure mask having a decorative material pattern with a line width of 10 μm). Exposure was carried out by irradiating with ultraviolet light having a wavelength of 365 nm at an intensity of.
Then, sodium carbonate / sodium bicarbonate developer (trade name: T-CD1 (manufactured by FUJIFILM Corporation) is diluted five times with pure water (mixed in a ratio of 1 part of T-CD1 and 4 parts of pure water). The shower pressure was set to 0.1 MPa at 30 ° C. using the diluted liquid), and the exposed decorative material-forming laminate material (i) -1 was developed for 30 seconds. Next, the decorative material-forming laminated material (i) -1 after development is washed with pure water, and the photosensitive resin layer is exposed and developed on the decorative material-forming laminated material (i) -1. A decorative material pattern was formed to obtain a decorative material pattern-containing decorative material-forming laminate material of Example 3.

<Production of substrate with decorative material pattern of Example 3>
Thereafter, the decorative material forming laminate material (i) -1 of Example 3 in which a decorative material pattern formed by exposing and developing the photosensitive resin layer was formed (that is, the decorative material pattern-containing additive of Example 3). The surface of the decorative material pattern side of the laminated material for decorating material) is opposed to the surface of the glass substrate (tempered glass, 300 mm × 400 mm × 0.7 mm), the substrate temperature is 100 ° C., the upper roll temperature is 100 ° C., and the lower roll is used. By laminating under conditions of a temperature of 100 ° C. and a conveyance speed of 0.6 m / min, a decorative material pattern, a base color layer (white layer) and a support A were laminated in this order on the glass substrate. Subsequently, the base color layer (white layer) was cured by heating the glass substrate on which the decorative material pattern and the like were formed at 150 ° C. for 30 minutes, and the substrate with the decorative material pattern of Example 3 was produced. At that time, the support A was left without peeling.

[Example 4]
<Preparation of decorative material-forming laminate material (i) -2 of Example 4>
On the release layer of the support A, a light shielding layer, a base color layer (white layer), and a photosensitive resin layer were laminated in this order.
The light-shielding layer is formed by applying the black colored liquid 1 prepared above using a die coater so that the film thickness after drying is 2.0 μm, and then drying it at 120 ° C. for 2 minutes. did.
For the base color layer (white layer), the white colored liquid 1 prepared above is applied using a die coater so that the film thickness after drying is 20 μm, and then dried under conditions of 120 ° C. for 4 minutes. Was formed.
The photosensitive resin layer was coated with a green (G) photosensitive resin layer forming coating solution CG-1 using a die coater so that the film thickness after drying was 2.0 μm, and then at 120 ° C. for 2 minutes. It was formed by drying under the conditions of
A polypropylene cover film having a thickness of 12 μm was pressure-bonded onto the prepared photosensitive resin layer to obtain a laminate material (i) -2 for decorating material formation of Example 4.

<Production of decorative material pattern-containing decorative material forming laminate material of Example 4>
50 mJ / cm is applied to the photosensitive resin layer of the decorative material forming laminate material (i) -2 from which the cover film has been peeled off, through a photomask (quartz exposure mask having a decorative material pattern with a line width of 10 μm). Exposure was performed by irradiating with an ultraviolet ray having a wavelength of 365 nm at an intensity of ² .
Thereafter, a sodium carbonate / sodium hydrogen carbonate developer (trade name: T-CD1 (manufactured by FUJIFILM Corporation) is diluted 5 times with pure water (mixed with 1 part of T-CD1 and 4 parts of pure water). The shower pressure was set to 0.1 MPa at 30 ° C. using the diluted solution), and the decorative material-forming laminate material (i) -2 after development was developed for 30 seconds. Next, the decorative material-forming laminated material (i) -2 after development is washed with pure water, and the photosensitive resin layer is exposed and developed on the decorative material-forming laminated material (i) -2. A decorative material pattern was formed, and a decorative material pattern-containing laminated material for forming a decorative material of Example 4 was obtained.

<Preparation of substrate with decorative material pattern of Example 4>
Thereafter, the decorative material forming laminate material (i) -2 of Example 4 in which the decorative material pattern formed by exposing and developing the photosensitive resin layer was formed (that is, the decorative material pattern-containing additive of Example 4). The surface of the decorative material pattern side of the laminated material for decorating material) is opposed to the surface of the glass substrate (tempered glass, 300 mm × 400 mm × 0.7 mm), the substrate temperature is 100 ° C., the upper roll temperature is 100 ° C., and the lower roll is used. By laminating under conditions of a temperature of 100 ° C. and a conveyance speed of 0.6 m / min, a decorative material pattern, a base color layer (white layer) light-shielding layer and a support A were laminated in this order on the glass substrate. . Subsequently, the base color layer (white layer) was cured by heating the glass substrate on which the decorating material pattern or the like was formed at 150 ° C. for 30 minutes, and the substrate with the decorating material pattern of Example 4 was produced. At that time, the support A was left without peeling.

[Example 5]
<Preparation of decorative material-forming laminate material (i) -3 of Example 5>
On the aluminum vapor deposition layer (underlying color layer) of the support C (25 μm PET base with an aluminum vapor deposition layer as a base color layer, aluminum vapor deposition layer 400 mm (0.04 μm), manufactured by Reiko Co., Ltd.), a transparent adhesive layer, And a white photosensitive resin layer were laminated in this order.
The transparent adhesive layer is prepared by applying the coating liquid for transparent adhesive layer prepared above using a die coater so that the film thickness after drying is 15 μm, and then drying it at 120 ° C. for 3 minutes. Formed.
For the white photosensitive resin layer, the white photosensitive resin layer coating solution prepared above was applied using a die coater so that the film thickness after drying was 4.5 μm, and then the temperature was 120 ° C. for 3 minutes. It was formed by drying under conditions.
A polypropylene cover film having a thickness of 12 μm was pressure-bonded onto the white photosensitive resin layer to obtain a decorative material-forming laminate material (i) -3 of Example 5.

<Production of (white) decorative material pattern-containing decorative material forming laminated material of Example 5>
The wavelength of the white photosensitive resin layer of the decorative material-forming laminated material (i) -3 with an intensity of 500 mJ / cm ² through a photomask (quartz exposure mask having a decorative material pattern with a line width of 10 μm) Exposure was performed by irradiating with 365 nm ultraviolet rays.
Thereafter, a sodium carbonate / sodium hydrogen carbonate developer (trade name: T-CD1 (manufactured by FUJIFILM Corporation) is diluted 5 times with pure water (mixed with 1 part of T-CD1 and 4 parts of pure water). The shower pressure was set to 0.1 MPa at 30 ° C. using the diluted solution), and the exposed decorative material-forming laminate material (i) -3 was developed at 29 ° C. for 180 seconds. Next, the laminated material for forming a decorative material (i) -3 after development is washed with pure water, and the (white) photosensitive resin layer is exposed and developed on the laminated material for forming a decorative material (i-3). The decorative material pattern formed was formed, and the (white) decorative material pattern-containing decorative material forming laminate material of Example 5 was obtained.

<Preparation of a substrate with a (white) decorative material pattern of Example 5>
Thereafter, the decorative material forming laminate material (i) -3 of Example 5 in which a decorative material pattern formed by exposing and developing the (white) photosensitive resin layer was formed (that is, the decorative material of Example 5) The surface of the decorative material pattern side of the laminate material for pattern-containing decorative material formation) is opposed to the surface of the glass substrate (tempered glass, 300 mm × 400 mm × 0.7 mm), the substrate temperature is 100 ° C., the upper roll temperature is 100 (White) decorative material pattern (layer formed by exposing and developing a white photosensitive resin layer) on a glass substrate by laminating under the conditions of ℃, lower roll temperature of 100 ℃, and conveyance speed of 0.6 m / min A transparent adhesive layer, a base color layer (aluminum vapor deposition layer), and a PET base (support C) were laminated in this order. Subsequently, the base color layer (white layer) was cured by heating the glass substrate on which the decorative material pattern and the like were formed at 150 ° C. for 30 minutes, and the substrate with the decorative material pattern of Example 5 was produced. At that time, the PET base of the support C was left without peeling.

[Examples 11 to 14]
The decoration of Examples 1 to 4 except that the white colored liquid 1 used for forming the base color layer (white layer) was changed to the white colored liquid 2 in the production of the decorative material forming laminated material of Examples 1 to 4. In the same manner as the production of the material forming laminated material, the decorative material forming laminated material of Examples 11 to 14 was produced, and using these, the decorative material pattern-containing decorative material of Examples 11 to 14 was formed. The laminated material and the substrate with the decorating material pattern of Examples 11 to 14 were manufactured.

[Comparative Example 1]
<Preparation of substrate with decorative material pattern of Comparative Example 1>
A decorative material pattern was formed on a glass substrate (tempered glass, 300 mm × 400 mm × 0.7 mm). The decorative material pattern is printed so that the film thickness after drying becomes 2.0 μm by using a screen printing machine using the green (G) photosensitive resin layer forming coating solution CG-1 prepared above as an ink. And then dried at 120 ° C. for 2 minutes.
Furthermore, on the decorative material pattern, the white coloring liquid 1 prepared above is applied using a screen printer so that the film thickness after drying is 20 μm, and then dried under the condition of 120 ° C. for 4 minutes. As a result, a base color layer (white layer) was formed.
Further, the black colored liquid 1 prepared above was applied onto the base color layer (white layer) using a screen printer so that the film thickness after drying was 2.0 μm, and then 120 ° C. 2 A light-shielding layer was formed by drying under conditions of minutes.
Thus, the board | substrate with the decorating material pattern of the comparative example 1 by which the decorating material pattern, the base color layer (white layer), and the light shielding layer were laminated | stacked in this order on the glass substrate was produced.

[Reference Example 1]
In Example 5, a laminated material G for decorating material formation was used in the same manner as in Example 5 except that instead of the support C, a support D (25 μm PET base having no aluminum vapor deposition layer (that is, a base color layer)) was used. Next, a substrate with a (white) decorative material pattern of Reference Example 1 was produced in the same manner as in Example 5.
Reference example 1 is a reference example for clarifying the hiding power of the white layer when the metallic gloss layer is combined.

[Evaluation]
<Evaluation of film thickness variation>
For the film thicknesses of the (white) photosensitive resin layer and the base color layer (white layer or metallic luster layer) of the substrates with decorative material patterns of the obtained Examples, Reference Examples and Comparative Examples, a stylus type film thickness meter Measurement was performed at n = 20 points in an area of 9 cm × 9 cm according to (trade name Surface Profiler P-10, manufactured by TENCOR).
The thickness of the white layer is obtained by removing a part of the white layer from the glass with a razor and measuring the level difference between the exposed glass surface and the surface of the adjacent white layer using the above P-10. It was.
The film thickness variation calculated by the following formula was calculated from the measured values at 20 points. The results are shown in Table 2 below.
(formula)
Film thickness variation = (maximum film thickness-minimum film thickness) / (average film thickness) x 100%

<Evaluation of patterning accuracy (decorative material pattern line width)>
The decorative material pattern line widths of the substrates with the decorative material patterns of the obtained Examples, Reference Examples and Comparative Examples were measured using an optical microscope and image analysis software (manufactured by Olympus Corporation, trade name: XM51, and Mikasa Co., Ltd., Cp-30). ) Was used to measure 20 arbitrary locations, and the average value was obtained to evaluate the patterning accuracy. The results are shown in Table 2 below.

<Evaluation of hiding power of white decorative material pattern>
The hiding power of the white decorative material pattern of the substrate with the decorative material pattern obtained in Example 5 and Reference Example 1 was laid out by placing black paper and white paper under the decorative material pattern substrate without gaps. The degree to which the boundary portion between the black paper and the white paper was seen through the decorating material was sensory evaluated.
A: The border between black paper and white paper cannot be seen through.
B: The border between black paper and white paper can be seen through.

<Evaluation of white decorating material pattern whiteness>
The whiteness of the white decorative material pattern of the obtained substrate with a decorative material pattern of Example 5 and Reference Example 1 was laid with black paper under the substrate with the decorative material pattern, and the hue (L *, a *, b *) was measured and evaluated. Evaluation was performed from the substrate side with the decorating material pattern using a colorimeter (CM-700d, manufactured by Konica Minolta Sensing Co., Ltd., SCI mode, D65 light source, 10 ° measurement).

<Evaluation of glass scattering property (drop test)>
The obtained substrates with decorating material patterns of Examples, Reference Examples and Comparative Examples were freely dropped from a height of 5 m to a concrete floor at an initial speed of zero.
Evaluation was made according to the following evaluation criteria. The results are shown in Table 2 below.
A: Glass breaks but does not scatter B: Glass breaks and scatters

From the said Table 2, the board | substrate with a decorating material pattern of this invention manufactured with the manufacturing method of the board | substrate with a decorating material pattern of this invention exposes and develops a decorating material pattern (white photosensitive resin layer). It was found that there was little variation in the film thickness of the layer) and the base color layer, and a highly accurate decorative material pattern was provided.
More specifically, in the method for producing a substrate with a decorating material pattern of Examples 1 to 4 and 11 to 14, since it can be continuously and stably applied in a film state by a die coater, there is little variation in film thickness. A substrate with a decorative material pattern could be produced. In the manufacturing method of the substrate with a decorating material pattern of Example 5, since the ground color layer was an aluminum vapor deposition layer, it became a homogeneous film with little film thickness variation. On the other hand, in the manufacturing method of the board | substrate with a decorating material pattern of the comparative example 1, the variation in film thickness became large.
In the method for producing a substrate with a decorating material pattern of Examples 1 to 5 and 11 to 14, when a film-like coating material is produced, it can be continuously and stably applied by a die coater. The laminate material for decorating material formation was able to be produced in large quantities, and the board | substrate with a decorating material pattern was efficiently mass-produced by laminating | stacking the said laminate material for decorating material formation. On the other hand, in Comparative Example 1, since coating and drying were performed one by one, it took time for coating and drying, and it was not possible to efficiently produce a substrate with a decorating material pattern.

The substrates with decorating material patterns of Examples 1 to 5 and 11 to 14 use a tempered glass substrate as the substrate. In the substrates with decorating material patterns of Examples 1 to 5 and 11 to 14 using such a tempered glass substrate, PET that is a support (film) of the laminated material for decorating material formation is a substrate with a decorating material pattern. Therefore, even if the glass substrate breaks due to falling, the broken glass is not scattered and excellent in safety. On the other hand, the decorative material-patterned substrate using the tempered glass substrate of Comparative Example 1 was inferior in safety because the broken glass was scattered.

In addition, from the said Table 2, as for the board | substrate with a decorating material pattern of Example 5 which used together the metallic glossy layer (underlying color layer) and white photosensitive resin layer which are aluminum vapor deposition layers, the thickness of the white photosensitive resin layer is 4 It was found that the hiding power and whiteness were high even at .5 μm. High whiteness is determined by L * being high and a * and b * being low.
On the other hand, it was found that the decorative material-patterned substrate of Reference Example 1 provided with a 4.5 μm white photosensitive resin layer without a metallic luster layer (underlying color layer) has low hiding power and whiteness.

Claims

A step of exposing and developing the photosensitive resin layer of the decorative material-forming laminate material having a photosensitive resin layer on the support to form a decorative material pattern, and the formed decorative material pattern on the substrate Laminating step;
A step of laminating the photosensitive resin layer of a decorative material forming laminate material having a photosensitive resin layer on a support on a substrate, and exposing and developing the laminated photosensitive resin layer to form a decorative material pattern Forming; or
Any of the processes of laminating | stacking the said decorating material pattern of the decorating material pattern containing laminated material for decorating material formation which has a decorating material pattern in which the photosensitive resin layer is exposed and developed on a support body on a board | substrate. Including the steps of
The manufacturing method of the board | substrate with a decorating material pattern which satisfy | fills the following conditions (M) or conditions (N).
Condition (M): Between the support of the laminate material for decorating material formation and the photosensitive resin layer, or the support of the decorating material pattern-containing laminate material for decorating material and the decorating material. A base color layer is provided between the patterns.
Condition (N): including a step of laminating the base color layer of another decorating material forming laminated material having a base color layer on the support on the decorating material pattern.
Satisfying the condition (M),
Exposing the photosensitive resin layer of the laminated material for decorative material formation having the base color layer and the photosensitive resin layer in this order on the support;
Developing the exposed photosensitive resin layer to prepare a decorative material pattern-containing laminated material for forming a decorative material pattern in which a decorative material pattern is formed; and
The board | substrate with a decorating material pattern of Claim 1 including the process of laminating | stacking the said decorating material pattern containing laminated material for decorating material formation on the said board | substrate with the said decorating material pattern side facing the board | substrate. Manufacturing method.
Satisfying the condition (M),
The decorating material pattern-containing laminate material for forming a decorating material pattern having a decorating material pattern formed by exposing and developing the base color layer and the photosensitive resin layer in this order on the support, and the decorating material on a substrate. The manufacturing method of the board | substrate with a decorating material pattern of Claim 1 including the process laminated | stacked on the said board | substrate in the state which made the material pattern side oppose.
Satisfying the condition (N),
Exposing the photosensitive resin layer of the decorative material-forming laminate material having the photosensitive resin layer on the support;
Developing the exposed photosensitive resin layer to form a decorative material pattern; and
Laminating the decorative material pattern of the decorative material forming laminate material (A) on a substrate;
With the decorating material pattern of Claim 1 including the process of laminating | stacking the said base color layer of the said other laminated material for decorating material formation which has the said base color layer on the said support body on the said decorating material pattern. A method for manufacturing a substrate.
Satisfying the condition (N),
Laminating the photosensitive resin layer of the decorative material-forming laminate material having the photosensitive resin layer on the support, on the substrate;
Peeling the support from the photosensitive resin layer;
Exposing the photosensitive resin layer;
Developing the exposed photosensitive resin layer to form a decorative material pattern; and
With the decorating material pattern of Claim 1 including the process of laminating | stacking the said base color layer of the said other laminated material for decorating material formation which has the said base color layer on the said support body on the said decorating material pattern. A method for manufacturing a substrate.
The decoration according to any one of claims 1 to 5, further comprising a light-shielding layer between the support and the base color layer, wherein the base color layer and the light-shield layer are stacked on the substrate in a lump. A method for manufacturing a substrate with a material pattern.
The method for producing a substrate with a decorative material pattern according to any one of claims 1 to 6, wherein the base color layer is a white layer.
The method for producing a substrate with a decorating material pattern according to claim 2 or 3, wherein the base color layer is a metallic luster layer.
The manufacturing method of the board | substrate with a decorating material pattern of Claim 8 which has a transparent contact bonding layer on the surface on the opposite side to the said support body adjacent to the said metallic luster layer.
The method for producing a substrate with a decorating material pattern according to claim 8 or 9, wherein the metallic luster layer is a metal thin film layer.
The method for producing a substrate with a decorating material pattern according to any one of claims 1 to 10, wherein the photosensitive resin layer contains a photopolymerization initiator and an ethylenically unsaturated compound.
The method for producing a substrate with a decorating material pattern according to any one of claims 1 to 11, wherein the photosensitive resin layer contains a dye or a pigment.
A substrate with a decorative material pattern manufactured by the method for manufacturing a substrate with a decorative material pattern according to any one of claims 1 to 12.
Decorative material forming laminate material having a base color layer and a photosensitive resin layer in this order on a support.
The laminate material for decorating material formation according to claim 14, further comprising a light shielding layer between the support and the base color layer.
The laminated material for decorating material formation according to claim 14 or 15, wherein the base color layer is a white layer or a metallic luster layer.
The base color layer is a metallic luster layer;
The laminated material for decorating material formation of Claim 16 which has a transparent contact bonding layer on the surface on the opposite side to the said support body adjacent to the said metallic luster layer.
The laminated material for forming a decorating material according to claim 16 or 17, wherein the metallic luster layer is a metal thin film layer.
The decorative material-forming laminated material according to any one of claims 14 to 18, wherein the photosensitive resin layer contains a photopolymerization initiator and an ethylenically unsaturated compound.
The decorative material-forming laminated material according to any one of claims 14 to 19, wherein the photosensitive resin layer contains a dye or a pigment.
The decorative material pattern-containing laminate for decorative material formation, which has a decorative material pattern formed by exposing and developing the photosensitive resin layer of the decorative material forming laminate material according to any one of claims 14 to 20. material.