JP6860186B2 - Certification system, certification method, coating for certification, and manufacturing method for coating for certification - Google Patents

Description

The present invention relates to an authentication system, an authentication method, a film for authentication, and a method for manufacturing a film for authentication. More specifically, an authentication system using an artificial metric element, an authentication method using an artificial metric element, and an artificial method. The present invention relates to a film having a physical metric element and a method for producing a film having an artificial metric element.

In recent years, individual authentication applying artificial metric technology has been proposed. The artificial object metric technology is a technology that analyzes the unique physical characteristics (artificial object metric elements) of the object to be authenticated and collates the data based on the analysis result with the pre-registered authentication data. That is, the artificial metric technology is a technology for authenticating by reading a unique physical feature corresponding to a human fingerprint, voiceprint, or iris from an object to be authenticated.

Patent Document 1 describes an example of artificial metric technology. Patent Document 1 describes that a label containing a hologram which is an authenticity discriminating element and fine particles as a taggant (tracking additive) is provided on one side of a base material. That is, in Patent Document 1, fine particles, which are artificial metric elements, are added to the label, and this label is provided on the base material.

Japanese Unexamined Patent Publication No. 2008-261967

However, when an artificial metric element is additionally provided in the object to be certified as in Patent Document 1, a step for that is required.

An object of the present invention is to provide a certification system, a certification method, a coating film for certification, and a method for producing a coating film for certification, which can reduce the trouble of providing an artificial metric element on the object to be certified.

The authentication system according to one aspect of the present invention is
A reader that reads the artificial metric elements of the film of the object to be certified,
A determination device for determining whether or not the authenticated object can be authenticated based on the result of reading the artificial object metric element is provided.
The film contains a cured product of a coating film of a curable resin composition.
The film comprises a wrinkled surface, which constitutes the artificial metric element.

The authentication method according to one aspect of the present invention is
A reading process that reads the artificial metric elements of the film of the object to be certified,
Including a determination step of determining whether or not the authenticated object can be authenticated based on the result of reading the artificial object metric element.
The film contains a cured product of a coating film of a curable resin composition.
The film comprises a wrinkled surface, which constitutes the artificial metric element.

The certification film according to one aspect of the present invention is
Containing a cured product of the coating film of the curable resin composition,
It has a wrinkled surface, which constitutes an artificial metric element.

The method for producing a coating film for certification according to one aspect of the present invention is as follows.
A method for producing a coating film having a wrinkled surface and the wrinkles constituting an artificial metric element.
This includes forming the coating film by curing the coating film after forming the coating film of the curable resin composition.
When the coating film is cured, the degree of curing of the surface layer of the coating film is higher than that of the deep part of the coating film, and then the entire coating film is cured to form the wrinkles.

According to one aspect of the present invention, it is possible to provide an authentication system, an authentication method, a film for authentication, and a method for producing a film for authentication, which can reduce the trouble of providing an artificial metric element on the object to be authenticated.

FIG. 1 is a schematic diagram showing an example of the configuration of an authentication system according to an embodiment of the present invention. 2A and 2B are enlarged photographs of the film provided on the object to be certified in the same certification system. FIG. 3 is a block diagram showing an example of the configuration of the determination device included in the authentication system of the same. 4A to 4C are schematic cross-sectional views showing an example of a method of forming a film provided on the object to be authenticated in the same authentication system. 5A-5E are schematic cross-sectional views showing an example of a method of forming a film provided on an object to be authenticated in the same authentication system. 6A to 6E are schematic cross-sectional views showing an example of a method of forming a film provided on an object to be authenticated in the same authentication system. 7A-7E are schematic cross-sectional views showing an example of a method of forming a film provided on an object to be authenticated in the same authentication system.

Hereinafter, an embodiment of the present invention will be described with reference to FIG.

The authentication system 1 according to the present embodiment authenticates the authenticated object 2 based on the reading device 3 that reads the artificial metric element 21 included in the film 20 included in the object 2 and the result of reading the artificial metric element 21. A determination device 4 for determining whether or not the above is possible is provided. The film 20 is a cured product of the curable resin composition. The film 20 comprises a surface with wrinkles 210, which wrinkles make up the artificial metric element 21.

In the present embodiment, by using the wrinkles 210 on the surface of the film 20 as the artificial metric element, it is possible to reduce the trouble of providing the artificial metric element on the object 2 to be authenticated. When the object 2 to be authenticated has the film 20 as a component thereof, the number of steps for providing the artificial metric element 21 on the object 2 to be authenticated can be reduced.

Further, since the artificial metric element 21 is composed of wrinkles 210 on the surface of the film 20, it is difficult to duplicate the artificial metric element 21. Therefore, the object to be certified 2 of the present embodiment is unlikely to be forged.

The authentication system 1 of the present embodiment will be described in more detail. The authentication system 1 is not limited to the following configuration.

As shown in FIG. 1, the authentication system 1 includes, for example, a reading device 3, a determination device 4, and a database 5. Although the authentication system 1 shown in FIG. 1 does not include the object to be authenticated 2, the authentication system 1 may include the object to be authenticated 2.

Examples of the object 2 to be authenticated include printed wiring boards, electronic devices, banknotes, securities, passports, certificates, personal authentication media, brand-name products, credit cards, cards such as electronic money cards, tags, and the like. .. In this case, the film 20 included in the object to be certified 2 may be a protective film for protecting the product, or may be a label for displaying product information. It is also preferable that the object to be certified 2 is a printed wiring board. The film 20 in this case is, for example, a solder resist layer. In this case, the printed wiring board can be authenticated by the solder resist layer provided on the printed wiring board.

The film 20 has an artificial metric element 21. The artificial metric element 21 is composed of wrinkles 210 on the surface of the film 20. The wrinkles 210 are non-uniform. Therefore, the artificial metric element 21 is a pattern composed of wrinkles 210.

The entire surface of the film 20 may have the artificial metric element 21, or a part of the surface of the film 20 may have the artificial metric element 21. In the present embodiment, the film 20 preferably includes a first region 22 having an artificial metric element 21 and a second region 23 having no artificial metric element 21. In this case, the authentication can be performed by using the artificial metric element 21 existing in a part of the film 20. The second region 23 may not have wrinkles and may have wrinkles that are different in degree from the wrinkles 210 that make up the artificial metric element 21.

Further, the anti-counterfeiting performance of the object 2 to be authenticated may be improved by combining the first region 22 and the second region 23. For example, authentication may be performed based on the position of the first region 22 or the second region 23 on the film 20. In this case, two-step verification consisting of authentication based on the arrangement position of the first region 22 or the second region 23 and authentication using the artificial metric element 21 can be performed.

2A and 2B are enlarged photographs of the film 20 having the artificial metric element 21. As shown in FIGS. 2A and 2B, the artificial metric element 21 is composed of wrinkles 210. In FIG. 2A, the right side of the XX line shows the first area 22, and the left side of the XX line shows the second area 23. The film 20 shown in FIG. 2B covers the insulating layer and the conductor wiring provided on the insulating layer. On the left side of the YY line in FIG. 2B, wrinkles 210 are formed in the portion directly in contact with the insulating layer of the film 20, and no wrinkles 210 are formed in the portion in direct contact with the conductor wiring of the film 20. Therefore, the portion directly in contact with the insulating layer of the film 20 is the first region 22, and the portion directly in contact with the conductor wiring of the film 20 is the second region 23. As shown in FIGS. 2A and 2B, the first region 22 has an artificial metric element 21 composed of wrinkles 210, and the second region 23 does not have an artificial metric element 22.

The reading device 3 is a device for reading the artificial metric element 21. The reading device 3 is not particularly limited as long as it can read the artificial metric element 21. The reading device 3 outputs the result of reading the artificial object metric element 21 to the determining device 4. When the film 20 has a first region 22 and a second region 23, the reading device 3 may read the position of the film 20 where the first region 22 or the second region 23 is arranged. ..

The reading device 3 may be, for example, an optical imaging device capable of imaging the artificial metric element 21. By reading the image of the artificial metric element 21 captured by the imaging device, the shape of the wrinkles 210 constituting the artificial metric element 21 can be grasped. Examples of imaging devices include cameras, scanners, electron microscopes, and laser microscopes. When the reading device 3 is an imaging device, the result of reading the artificial object metric element 21 may be an image of the artificial object metric element 21.

The reading device 3 may be, for example, a surface roughness meter. Examples of surface roughness meters include contact type surface roughness meters and non-contact type surface roughness meters. The surface roughness meter can measure the fine shape of the wrinkles 210 constituting the artificial metric element 21. When the reading device 3 is a surface roughness meter, the result of reading the artificial metric element 21 may be the roughness curve of the artificial metric element 21.

FIG. 3 is a block diagram showing an example of the configuration (hardware configuration) of the determination device 4. The determination device 4 shown in FIG. 3 includes a control device 41, a storage device 42, an input device 43, a display device 44, a media input / output device 45, a communication interface 46, and a peripheral device interface 47. Each device is connected by a bus 49. The determination device 4 is, for example, a computer.

The control device 41 includes, for example, a CPU (Central Processing Unit), a ROM (Read Only Memory), and a RAM (Random Access Memory).

The CPU can call the program stored in the storage device 42, ROM, recording medium, or the like into a work area on the RAM and execute the program. The CPU can drive and control each device connected by the bus 49. The ROM can permanently hold a boot program, a program such as a BIOS, data, and the like. The RAM can temporarily hold programs, data, and the like. The control device 41 may include a work area for performing various processes.

Examples of the storage device 42 include an HDD (hard disk drive) and an SSD (solid state disk). The storage device 42 can store a program executed by the control device 41, data necessary for executing the program, an OS (operating system), and the like. The control device 41 reads these programs as needed, transfers them to RAM, reads them to the CPU, and executes them.

Examples of the input device 43 include a keyboard, a mouse, a touch panel, a pointing device such as a tablet terminal, and a numeric keypad. The information input to the input device 43 is sent to the control device 41.

The display device 44 is composed of, for example, a display device such as a liquid crystal panel or a CRT monitor, and a logic circuit (video adapter or the like) for executing display processing in cooperation with the display device. The information sent from the control device 41 to the display device 44 is displayed on the display device.

Examples of the media input / output device 45 include a floppy (registered trademark) disk drive, a PD drive, a CD drive, a DVD drive, a Blu-ray disk drive, and an MO drive. The media input / output device 45 inputs and outputs data.

The communication interface 46 includes, for example, a communication control device, a communication port, and the like. The communication interface 46 can mediate communication between the determination device 4 and the external device via the network. The communication interface 46 can control communication. The communication interface 46 can mediate communication between the determination device 4, the database 5, the reading device 3, and the like, for example. Therefore, the database 5 and the reading device 3 can be connected to the determination device 4 via the communication interface 46.

The peripheral device interface 47 is, for example, a port for connecting a peripheral device to the determination device 4. The determination device 4 transmits / receives data to / from the peripheral device via the peripheral device interface 47. The peripheral device interface 47 may be composed of a USB terminal, an IEEE1394 terminal, an RS-232C terminal, or the like. The determination device 4 may have a plurality of peripheral device interfaces 47. The peripheral device interface 47 may be a terminal for a wired connection or a terminal for a wireless connection. When the peripheral device interface 47 is a terminal for wireless connection, the determination device 4 and the peripheral device may be wirelessly connected.

The bus 49 is a route for mediating the transfer of control signals, data signals, and the like between the devices.

In the determination device 4 having the above configuration, for example, a process of registering the data (registration data) of the result of reading the artificial object metric element 21 in the database 5 (registration process), and the result of reading the artificial object metric element 21. A process (authentication process) for determining whether or not the authenticated object 2 can be authenticated is performed by collating the data (verification data) with the registration data. The registration process and the authentication process can be executed by the control device 41 according to a program stored in the storage device 42 or the like.

Hereinafter, the registration process performed by the determination device 4 will be described in detail. In the registration process, for example, the following steps S101 to S104 are performed.

(Step S101)
In step S101, the reading device 3 reads the artificial metric element 21 in the authenticated object 2 disclosed for registration. As a result, the result of reading the artificial metric element 21 is obtained.

(Step S102)
In step S102, the result of reading the artificial metric element 21 is sent from the reading device 3 to the determining device 4 via the communication interface 46. As a result, the determination device 4 acquires the result of reading the artificial metric element 21. Further, the result of reading the artificial metric element 21 created by the reading device 3 is stored in the media by the media input / output device 45, and the reading result of the artificial metric element 21 is taken out from this media by the media input / output device 45. May be sent to the determination device 4.

(Step S103)
In step S103, the determination device 4 creates registration data indicating a pattern composed of wrinkles 210 from the result of reading the artificial metric element 21. The data as a result of reading the artificial metric element 21 may be used as the registration data as it is.

(Step S104)
In step S104, the determination device 4 sends registration data to the database 5 via the communication interface 46. As a result, the registration data is registered in the database 5. The registration data may be associated with unique information of the object to be authenticated 2 such as a serial number. This unique information may be input by the input device 43 or displayed on the display device 44. Further, a plurality of registration data of the plurality of objects 2 to be authenticated may be registered in the database 5.

Hereinafter, the authentication process performed by the determination device 4 will be described in detail. In the authentication process, for example, the following steps S201 to S204 are performed.

(Step S201)
In step S201, the reading device 3 reads the artificial metric element 21 in the authenticated object 2 to be authenticated. As a result, the result of reading the artificial metric element 21 is created. Therefore, the authentication method according to the present embodiment includes a reading step of reading the artificial metric element 21 included in the film 20 included in the object 2 to be authenticated.

(Step S202)
In step S202, the result of reading the artificial metric element 21 is sent from the reading device 3 to the determining device 4 via the communication interface 46. As a result, the determination device 4 acquires the result of reading the artificial metric element 21. Therefore, the authentication method according to the present embodiment may include a reading result acquisition step of acquiring the result of reading the artificial metric element 21.

(Step S203)
In step S203, the determination device 4 creates collation data indicating a pattern composed of wrinkles 210 from the image of the artificial metric element 21. The data as a result of reading the artificial metric element 21 may be used as the collation data as it is. Therefore, the authentication method according to the present embodiment may include a collation data creation step of creating collation data from the result of reading the artificial metric element 21.

(Step S204)
In step S204, the determination device 4 searches the database 5 for registration data that matches the collation data by collating the registration data with the collation data. Therefore, the authentication method of the present embodiment may include a collation step of collating the registration data and the collation data.

(Step S205)
In step S205, when the registration data matching the collation data is found, the determination device 4 determines that the authentication is OK (authentication is “OK”). Further, in step S205, when the registration data matching the collation data is not found, the determination device 4 determines that the authentication is NG (authentication is "No"). In other words, in step S205, the determination device 4 determines whether or not the authenticated object 2 can be authenticated. Therefore, the authentication method according to the present embodiment includes a determination step of determining whether or not the authenticated object 2 can be authenticated based on the image of the artificial object metric element 21. In step S205, the determination device 4 may further collate the unique information of the authenticated object 2 such as the serial number with the unique information of the authenticated object 2 associated with the registration data. In this case, erroneous determination can be suppressed. The determination result by the determination device 4 in step S205 may be displayed on the display device 44, for example.

The configuration of the authentication system 1 is not limited to the above example.

For example, the authentication process may be performed by the determination device 4, and the registration process may be performed by a computer different from the determination device 4.

For example, each device included in the authentication system 1 may be connected via a network such as the Internet. For example, the determination device 4 and the reading device 3, or the determination device 4 and the database 5 may be connected via a network such as the Internet without going through the communication interface 46.

Hereinafter, the certification film 20 will be described in more detail.

As described above, the film 20 contains a cured product of the curable resin composition and has wrinkles 210 on the surface. The height difference of the wrinkles 210 is, for example, in the range of 1 to 1000 μm. The width between the peaks in the wrinkle 210 is, for example, in the range of 5 to 5000 μm. The wrinkles 210 constitute the artificial metric element 21.

The film 20 can be produced by the following production method.

The method for producing the film 20 of the present embodiment includes forming the coating film 24 of the curable resin composition and then curing the coating film 24 to form the film 20. In the present embodiment, when the coating film 24 is cured, the degree of curing of the surface layer of the coating film 24 is higher than that of the deep part of the coating film 24, and then the entire coating film 24 is cured. Wrinkles 210 are formed. When the entire coating film 24 is cured after passing through this state, curing shrinkage occurs in the deep part, but since the surface layer has already been cured, curing shrinkage does not easily occur in the surface layer. Therefore, the surface layer of the coating film 24 is deformed following the curing shrinkage of the deep portion, so that wrinkles 210 are generated on the surface of the coating film 24. As a result, a film 20 having an artificial metric element 21 composed of wrinkles 210 is obtained.

In the first method for producing the film 20, the curable resin composition is one kind of composition having thermosetting property and photocurability, and the coating film 24 is formed from the curable resin composition. It is a single-layer film to be formed. When the coating film 24 is cured, the wrinkles 210 are formed by exposing the coating film 24 so that the degree of curing of the surface layer of the coating film 24 is higher than that of the deep portion, and then heating the coating film 24. Form. In the first method, the curable resin composition for forming the coating film 24 includes a photopolymerization initiator (A), a thermosetting resin (B), and at least one ethylenically unsaturated molecule in one molecule. It preferably contains an unsaturated compound (C) containing a bond. In this case, the coating film 24 formed from the curable resin composition can be imparted with photocurability and thermosetting property. As a result, the coating film 24 can be cured by exposing the coating film 24 and heating the coating film 24.

By adjusting at least one of the thickness of the coating film 24 and the amount of exposure to the coating film 24, the degree of curing of the surface layer of the coating film 24 after exposure can be made higher than that of the deep portion. For example, by increasing the thickness of the coating film 24 or reducing the amount of exposure to the coating film 24, the amount of light reaching the deep part of the coating film 24 can be reduced, and the surface layer of the coating film 24 after exposure can be reduced. The degree of curing can be higher than that in the deep part. The thickness of the coating film 24 and the amount of exposure to the coating film 24 are such that the degree of curing of the surface layer of the coating film 24 is higher than that of the deep portion, depending on the composition of the curable resin composition for forming the coating film 24. Adjust accordingly. However, if the coating film 24 is too thin or the amount of exposure to the coating film 24 is too large, the coating film 24 is sufficiently cured from the surface layer to the deep part after exposure, and wrinkles 210 are less likely to occur. Therefore, when the thickness of the coating film 24 is in the range of 10 to 100 μm, the exposure amount to the coating film 24 is preferably in the range of ^{20 to 2000 mJ / cm 2.}

In the second method for producing the film 20, the curable resin composition contains a first composition having thermosetting and photocurability and a second composition having photocurability, and the coating film 24 includes a first coating film 240 formed from the first composition and a second coating film 241 on the first coating film 240 and formed from the second composition. When the coating film 24 is cured, by exposing the coating film 24, the photocuring reaction between the first coating film 240 and the second coating film 241 is performed, and the degree of curing of the second coating film 241 is the first coating. After advancing so as to be higher than the degree of curing of the film 240, the coating film 24 is heated to cure the entire coating film 24.

In the second method, the degree of curing of the second coating film 241 after exposure is determined by making the photocuring reaction of the first coating film 240 less likely to proceed than that of the second coating film 241. Can be higher than. When the coating film 24 is heated, the first coating film 240 undergoes curing shrinkage, but since the second coating film 241 has already been cured, the second coating film 241 is unlikely to undergo curing shrinkage. Therefore, the second coating film 241 is deformed following the curing shrinkage of the first coating film 240, so that wrinkles 210 can be generated on the surface of the second coating film 241. As a result, a film 20 including a film 201 which is a cured product of the first coating film 240 and a film 202 which is a cured product of the second coating film 241 and has wrinkles 210 is obtained. The thickness of the first coating film 240 and the second coating film 241 and the exposure amount to the coating film 24 are such that the degree of curing of the second coating film 241 is higher than that of the first coating film 240. It is appropriately prepared according to the composition of the second composition. However, if the thickness of the first coating film 240 and the second coating film 241 is too thin, or if the exposure amount to the coating film 24 is too large, the first coating film 240 is excessively cured and wrinkles 210 are formed on the surface of the coating film 20. May not be formed. Therefore, when the thickness of the first coating film 240 is in the range of 10 to 100 μm and the thickness of the second coating film 241 is in the range of 10 to 100 μm, the exposure amount is in the range of ^{20 to 2000 mJ / cm 2.} It is preferable to have.

The second composition does not have to have thermosetting property, but preferably has thermosetting property. When the second composition is thermosetting, the second composition contains a photopolymerization initiator (A), a thermosetting resin (B), and at least one ethylenically unsaturated bond in one molecule. It preferably contains an unsaturated compound (C). Thereby, the second coating film 241 formed from the second composition can be imparted with photocurability and thermosetting property. The first composition is not particularly limited as long as it has thermosetting and photocuring properties and has a lower photocuring property than the second composition.

In the second method, the second composition is preferably prepared so that the photocurability of the second coating film 241 is higher than that of the first coating film 240. For that purpose, for example, the concentration of the photopolymerization initiator (A) blended in the second composition may be higher than the concentration of the photopolymerization initiator (A) blended in the first composition. For example, the second composition contains a photopolymerization initiator (A) that easily absorbs light in a specific wavelength range, and the first composition contains a photopolymerization initiator (A) that does not easily absorb light in this wavelength range. May be blended. For example, the concentration of the unsaturated compound (C) blended in the second composition may be higher than the concentration of the unsaturated compound (C) blended in the first composition. For example, the second composition may contain an unsaturated compound (C) having a small steric hindrance, and the first composition may contain an unsaturated compound (C) having a large steric hindrance. For example, the photopolymerization initiator (A) having a high radical generation rate may be blended in the second composition, and the photopolymerization initiator (A) having a slow radical generation rate may be blended in the first composition. For example, the type, amount, and the like of the colorant (E) blended in the first composition and the second composition may be adjusted to lower the UV transparency of the first composition. The light reflectance of the light may be increased.

In the second method, it is also preferable to form the second coating film 241 with a second composition containing a white pigment. In this case, the light applied to the coating film 24 can be reflected on the surface of the second coating film 241, making it difficult for the light to reach the first coating film 240. Thereby, the degree of curing of the second coating film 241 after exposure can be made higher than that of the first coating film 240. Examples of white pigments may include titanium oxide. The components other than the white pigment contained in the second composition may be the same as the composition of the second composition described above.

In the second method, it is also preferable to form the first coating film 240 with the first composition containing a black pigment. In this case, since the black pigment has low light transmission, it is possible to prevent the photocuring reaction from occurring in the first coating film 240, and the degree of photocuring of the first coating film 240 is lower than that of the second coating film 241. can do. Examples of black pigments may include carbon black, perylene black, titanium black, aniline black. The black pigment preferably contains carbon black, which has low light transmission.

In the third method for producing the film 20, the curable resin composition comprises a first composition having thermosetting property and not photocuring property and a second composition having photocuring property. Including, the coating film 24 includes a first coating film 240 formed from the first composition and a second coating film 241 on the first coating film 240 and formed from the second composition. When the coating film 24 is cured, the coating film 24 is exposed to cure the second coating film 241 and then the coating film 24 is heated to cure the entire coating film 24. By exposing the coating film 24, a photocuring reaction occurs in the second coating film 241 having photocurability, but the photocuring reaction does not occur in the first coating film 240 having no photocuring property. Therefore, when the coating film 24 after exposure is heated, the first coating film 240 undergoes curing shrinkage, but since the second coating film 241 has already been cured, the second coating film 241 is unlikely to undergo curing shrinkage. Therefore, the second coating film 241 is deformed following the curing shrinkage of the first coating film 240, so that wrinkles 210 are generated on the surface of the second coating film 241. As a result, a film 20 including a film 201 which is a cured product of the first coating film 240 and a film 202 which is a cured product of the second coating film 241 and has wrinkles 210 is obtained. The thickness of the first coating film 240 and the second coating film 241 and the amount of exposure to the coating film 24 are appropriately adjusted according to the compositions of the first composition and the second composition.

In the third method, the second composition does not have to be thermosetting, but is preferably thermosetting. When the second composition is thermosetting, the second composition contains a photopolymerization initiator (A), a thermosetting resin (B), and at least one ethylenically unsaturated bond in one molecule. It preferably contains an unsaturated compound (C). Thereby, the second coating film 241 formed from the second composition can be imparted with photocurability and thermosetting property. The first composition is not particularly limited as long as it has thermosetting property and does not have photocuring property.

Further, two or more kinds selected from the group consisting of the above-mentioned first method, second method, and third method may be combined. For example, the first method and the second method may be combined. In this case, the coating film 24 composed of the first coating film 240 having photocurability and thermosetting property and the second coating film 241 having higher photocurability than the first coating film 240 is formed, and the first coating film 24 is formed. The film thicknesses of the one coating film 240 and the second coating film 241 may be adjusted.

Further, as described above, the film 20 may have a first region 22 having the artificial metric element 21 and a second region 23 having no artificial metric element 21. The second region 23 may not have wrinkles and may have wrinkles that are different in degree from the wrinkles 210 that constitute the artificial metric element 21. The wrinkles contained in the second region 23 may be wrinkles having a height difference different from that of the wrinkles 210, or wrinkles having different widths between peaks in the wrinkles 210.

The method of forming the second region 23 is not particularly limited.

For example, in the first method, when exposing the coating film 24, the exposure amount for the second region 23 may be larger than the exposure amount for the first region 22. In this case, when the coating film 24 is exposed, the photocuring reaction can be sufficiently advanced from the surface layer to the deep part of the second region 23. As a result, when the coating film 24 after exposure is heated, curing shrinkage of the surface layer of the second region 23 can be made less likely to occur, and wrinkles 210 can be less likely to occur on the surface of the second region 23. it can.

For example, in the first method and the second method, the film thickness of the second region 23 may be smaller than the film thickness of the first region 22. In this case, when the coating film 24 is exposed, the deep portion of the second region 23 can be sufficiently cured. As a result, when the coating film 24 after exposure is heated, it is possible to prevent curing shrinkage of the deep portion of the second region 23 from occurring, and it is possible to prevent wrinkles 210 from occurring on the surface of the second region 23. it can.

For example, in the second method and the third method, the first region 22 is composed of the first coating film 240 and the second coating film 241 and the second region 23 is composed of only the first coating film 240. You may. In this case, when the coating film 24 is exposed, the deep portion of the second region 23 can be sufficiently cured. As a result, when the coating film 24 after exposure is heated, the curing shrinkage of the first coating film 240 in the second region 23 can be prevented from occurring, and wrinkles 210 are generated on the surface of the second region 23. It can be made difficult.

Hereinafter, each component contained in the curable resin composition used for forming the coating film 24 will be described in more detail.

As described above, the curable resin composition comprises a photopolymerization initiator (A), a thermosetting resin (B), and an unsaturated compound (C) containing at least one ethylenically unsaturated bond in one molecule. including. The curable resin composition may further contain a carboxyl group-containing resin (D2), a colorant (E), an organic solvent (F), and other components (G).

[Photopolymerization Initiator (A)]
The photopolymerization initiator (A) is a compound that generates radicals, cations, anions and the like when irradiated with ultraviolet rays or electron beams, and triggers a polymerization reaction. The photopolymerization initiator (A) is preferably a compound that generates radicals when irradiated with ultraviolet rays. The photopolymerization initiator (A) is, for example, benzoyl and its alkyl ethers; acetophenones such as acetophenone and benzyl dimethyl ketal; anthraquinones such as 2-methylanthraquinone; 2,4-dimethylthioxanthone and 2,4-diethylthioxanthone. , 2-Isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diisopropylthioxanthone and other thioxanthones; benzophenone, 4-benzoyl-4'-methyldiphenylsulfide and other benzophenones; Nitrogen-containing initiators such as 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one; 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1- Phenyl-propane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hirodoxy-1- {4- [4] -(2-Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, α-hydroxyalkylphenones such as phenylglycolic acid methyl ester; 2-methyl-1- (4-Methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[ Α-Aminoalkylphenones such as (4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2, Monoacylphosphine oxide-based photopolymerization initiators such as 4,6-trimethylbenzoyl-ethyl-phenyl-phosphinate; and bis- (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis- (2,6-- Dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2, 6-Dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxy) Benzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, (2,5,6-trimethylbenzoyl) -2,4,4 Acylphosphine-based photopolymerization initiators such as -trimethylpentylphosphine oxide, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9-ethyl Contains at least one compound selected from the group consisting of oxime ester-based photopolymerization initiators such as -6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime). it can. The photopolymerization initiator (A) is more preferably a nitrogen-containing initiator such as 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, and an acylphosphine oxide-based photopolymerization. Contains at least one selected from the group consisting of initiators.

The ratio of the photopolymerization initiator (A) to the solid content of the curable resin composition is preferably in the range of 0.01% by mass to 50% by mass. It is more preferably in the range of 0.05% by mass to 25% by mass, and further preferably in the range of 0.1% by mass to 15% by mass.

[Thermosetting resin (B)]
The thermosetting component (B) can impart thermosetting property to the curable resin composition. The thermosetting component (B) preferably contains a compound having a cyclic ether skeleton. The compound having a cyclic ether skeleton preferably contains an epoxy compound and an oxetane compound, and more preferably contains an epoxy compound.

The epoxy compound preferably has at least two epoxy groups in one molecule. The epoxy compound may be a solvent-insoluble epoxy compound or a general-purpose solvent-soluble epoxy compound. The type of epoxy compound is not particularly limited. The epoxy compounds include phenol novolac type epoxy resin (specific example, product number EPICLON N-775 manufactured by DIC Co., Ltd.), cresol novolac type epoxy resin (specific example, product number EPICLON N-695 manufactured by DIC Co., Ltd.), and bisphenol A type epoxy. Resin (part number jER1001 manufactured by Mitsubishi Chemical Co., Ltd. as a specific example), bisphenol A-novolac type epoxy resin (part number EPICLON N-865 manufactured by DIC Co., Ltd. as a specific example), bisphenol F type epoxy resin (specific example, Mitsubishi Chemical Co., Ltd.) Company product number jER4004P), bisphenol S type epoxy resin (specific example, product number EPICLON EXA-1514 manufactured by DIC Co., Ltd.), bisphenol AD type epoxy resin, biphenyl type epoxy resin (specific example, product number YX4000 manufactured by Mitsubishi Chemical Co., Ltd.) ), Biphenyl novolac type epoxy resin (specific example, product number NC-3000 manufactured by Nippon Kayaku Co., Ltd.), hydrogenated bisphenol A type epoxy resin (specific example, product number ST-4000D manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), naphthalene type. Epoxy resin (specific example, product number EPICLON HP-4032, EPICLON HP-4700, EPICLON HP-4770 manufactured by DIC Co., Ltd.), tertiary butyl catechol type epoxy resin (specific example, product number EPICLON HP-820 manufactured by DIC Co., Ltd.) , Dicyclopentadiene type epoxy resin (specific example, product number EPICLON HP-7200 manufactured by DIC), Adamantane type epoxy resin (specific example, product number ADAMANTATE X-E-201 manufactured by Idemitsu Kosan Co., Ltd.), biphenyl ether type epoxy resin (specific example) As a specific example, product number YSLV-80DE manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., special bifunctional epoxy resin (as a specific example, product number YL7175-500 and YL7175-1000 manufactured by Mitsubishi Chemical Co., Ltd .; -960, EPICLON TER-601, EPICLON TSR-250-80BX, EPICLON 1650-75MPX, EPICLON EXA-4850, EPICLON EXA-4816, EPICLON EXA-4822, and EPICLON EXA-9726; Nippon Steel & Sumitomo Metal Corporation -120TE), 1,3,5-Tris (2, Contains at least one compound selected from the group consisting of 3-epoxypropyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, and other bisphenol epoxy resins. it can.

The ratio of the thermosetting resin (B) to the solid content of the curable resin composition is preferably in the range of 3% by mass to 90% by mass, and more preferably in the range of 5% by mass to 70% by mass. More preferably, it is in the range of 10% by mass to 50% by mass.

[Unsaturated compound (C)]
The unsaturated compound (C) is a compound having an ethylenically unsaturated double bond. The unsaturated compound (C) can impart photocurability to the curable resin composition. The unsaturated compound (C) is a monofunctional (meth) acrylate such as 2-hydroxyethyl (meth) acrylate; as well as a diethylene glycol di (meth) acrylate, a trimethylol propandi (meth) acrylate, and a trimethyl propanthry (meth). Polyfunctional (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ε-caprolactone-modified pentaeristol hexaacrylate, etc. It can contain at least one compound selected from the group consisting of meta) acrylates.

The unsaturated compound (C) may contain a trifunctional compound, that is, a compound having three unsaturated bonds in one molecule. In this case, the resolution when the film formed from the resin composition is exposed and developed is improved, and the developability of the resin composition with an alkaline aqueous solution is particularly improved. Trifunctional compounds include, for example, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, pentaeristoltri (meth) acrylate, ethoxylated isocyanurate tri (meth) acrylate and ε-caprolactone-modified. It can contain at least one compound selected from the group consisting of tris- (2-acryloxyethyl) isocyanurate and ethoxylated glycerin tri (meth) acrylate.

The unsaturated compound (C) may contain a phosphorus-containing compound (phosphorus-containing unsaturated compound). In this case, the flame retardancy of the cured product of the resin composition is improved. The phosphorus-containing unsaturated compounds include, for example, 2-methacryloyloxyethyl acid phosphate (specific examples, part numbers Light Ester P-1M and Light Ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.) and 2-acryloyloxyethyl acid phosphate. (Specific example, product number Light Acrylate P-1A manufactured by Kyoeisha Chemical Co., Ltd.), Diphenyl-2-methacryloyloxyethyl phosphate (Product number MR-260 manufactured by Daihachi Kogyo Co., Ltd. as a specific example), and Showa High Polymer Co., Ltd. HFA series (for example, product number HFA-6003, which is an addition reaction product of dipentaeryristol hexaacrylate and HCA (9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide), and It can contain at least one compound selected from the group consisting of HFA-6007, caprolactone-modified dipentaeryristol hexaacrylate and HCA, product number HFA-3003, HFA-6127, etc.).

The unsaturated compound (C) may contain a prepolymer. The prepolymer is selected from the group consisting of, for example, a prepolymer obtained by polymerizing a monomer having an ethylenically unsaturated bond and then adding an ethylenically unsaturated group, and oligo (meth) acrylate prepolymers. Can contain one type. Oligo (meth) acrylate prepolymers include, for example, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spirane resin (meth) acrylate. It can contain at least one selected from the group consisting of.

The ratio of the unsaturated compound (C) to the solid content of the curable resin composition is preferably in the range of 5% by mass to 90% by mass, more preferably in the range of 10% by mass to 70% by mass. More preferably, it is in the range of 20% by mass to 60% by mass.

The unsaturated compound (C) may contain an unsaturated compound having a carboxyl group (hereinafter, also referred to as a carboxyl group-containing resin (D1)). When the curable resin composition contains the carboxyl group-containing resin (D1), the film 20 formed from the curable resin composition can be imparted with developability by an alkaline solution, that is, alkali developability.

The carboxyl group-containing resin (D1) includes, for example, at least one of the epoxy groups in the epoxy compound (d1) having two or more epoxy groups in one molecule, and an ethylenically unsaturated compound (d2) having a carboxyl group. Can contain a resin having a structure (hereinafter referred to as the first resin (d)) to which a compound (d3), which is at least one selected from the group consisting of a polyvalent carboxylic acid and an anhydride thereof, is added. ..

The epoxy compound (d1) includes, for example, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A-novolac type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, and the like. At least one compound selected from the group consisting of a polymer of an ethylenically unsaturated compound including a biphenyl aralkyl type epoxy resin, a bisphenol fluorene type epoxy resin, triglycidyl isocyanurate, an alicyclic epoxy resin, and a compound having an epoxy group. Can be contained.

The epoxy compound (d1) may contain a polymer of an ethylenically unsaturated compound (p) containing a compound (p1) having an epoxy group. The ethylenically unsaturated compound (p) may contain only the compound having an epoxy group (p1), or may contain a compound having an epoxy group (p1) and a compound having no epoxy group (p2). Good.

The compound (p1) having an epoxy group can contain at least one selected from the group consisting of appropriate polymers and prepolymers. Specifically, the compound having an epoxy group (p1) includes epoxycyclohexyl derivatives of acrylic acid, epoxycyclohexyl derivatives of methacrylic acid, alicyclic epoxy derivatives of acrylate, alicyclic epoxy derivatives of methacrylate, and β-methylglycidyl acrylate. , And at least one component selected from the group consisting of β-methylglycidyl methacrylate. In particular, the compound (p1) having an epoxy group preferably contains a glycidyl (meth) acrylate that is widely used and easily available.

The compound having no epoxy group (p2) can be, for example, a compound copolymerizable with the compound having an epoxy group (p1). Compounds (p2) that do not have an epoxy group include, for example, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, and 2- (meth) acryloyloxypropyl phthalate. , Benzyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, EO-modified cresol (meth) acrylate, ethoxylated phenyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate (Degree of polymerization n = 2 to 17), ECH-modified phenoxy (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, Tribromophenyl (meth) acrylate, EO-modified tribromophenyl (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di (meth) acrylate, modified bisphenol A di (meth) acrylate, EO-modified bisphenol F di (meth) acrylate, ECH modified phthalic acid di (meth) acrylate, trimethylpropanbenzoate (meth) acrylate, EO modified phthalic acid (meth) acrylate, EO, PO modified phthalic acid (meth) acrylate, vinyl carbazole, styrene , N-phenylmaleimide, N-benzylmaleimide, N-succinimidyl 3-maleimide benzoate, aliphatic or alicyclic group having linear or branched (however, it may have a partially unsaturated bond in the ring. ) (Meta) acrylic acid ester, hydroxyalkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, and at least one compound selected from the group consisting of N-substituted maleimides (eg, N-cyclohexyl maleimide). ..

The compound having no epoxy group (p2) may further contain a compound having two or more ethylenically unsaturated groups in one molecule. By using this compound and adjusting the blending amount thereof, the hardness and oiliness of the film can be easily adjusted. Compounds having two or more ethylenically unsaturated groups in one molecule include, for example, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth). It can contain at least one compound selected from the group consisting of acrylates.

For example, a polymer can be obtained by polymerizing the ethylenically unsaturated compound (p) by a known polymerization method such as a solution polymerization method or an emulsion polymerization method. For example, the solution polymerization method is a method of heating and stirring an ethylenically unsaturated compound (p), an appropriate organic solvent, and a polymerization initiator in a nitrogen atmosphere, or an azeotropic polymerization method.

The organic solvents used for the polymerization of the ethylenically unsaturated compound (p) include ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, and ethyl acetate, butyl acetate and cellosolve acetate. , Butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate and other acetate esters, and dialkyl glycol ethers can contain at least one compound selected from the group.

The polymerization initiator used for the polymerization of the ethylenically unsaturated compound (p) is hydroperoxides such as diisopropylbenzene hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-di. -(T-Butylperoxy) -Dialkyl peroxides such as hexane, diacyl peroxides such as isobutyryl peroxide, ketone peroxides such as methyl ethyl ketone peroxide, alkyl peroxides such as t-butyl peroxyvivarate. , Peroxydicarbonates such as diisopropylperoxydicarbonate, azo compounds such as azobisisobutyronitrile, and at least one compound selected from the group consisting of redox-based initiators.

The ethylenically unsaturated compound (d2) having a carboxyl group can contain at least one component selected from the group consisting of appropriate polymers and prepolymers. The ethylenically unsaturated compound (d2) can contain a compound having only one ethylenically unsaturated group. Compounds having only one ethylenically unsaturated group include, for example, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2 − Methacryloyloxyethyl phthalic acid, β-carboxyethyl acrylate, acryloyloxyethyl succinate, methacryloyloxyethyl succinate, 2-propenoic acid, 3- (2-carboxyethoxy) -3-oxypropyl ester, 2-acryloyl It can contain at least one compound selected from the group consisting of oxyethyl tetrahydrophthalic acid, 2-methacryloyl oxyethyl tetrahydrophthalic acid, 2-acryloyl oxyethyl hexahydrophthalic acid, and 2-methacryloyl oxyethyl hexahydrophthalic acid. Further, the ethylenically unsaturated compound (d2) can contain a compound having a plurality of ethylenically unsaturated groups. Compounds having a plurality of ethylenically unsaturated groups include, for example, hydroxylates such as pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. It can contain at least one compound selected from the group consisting of a polyfunctional acrylate having a group and a compound obtained by reacting a polyfunctional methacrylate with a dibasic acid anhydride.

In particular, it is preferable that the ethylenically unsaturated compound (d2) having a carboxyl group contains at least one component selected from the group consisting of acrylic acid and methacrylic acid. Since the ethylenically unsaturated group derived from acrylic acid and methacrylic acid is particularly excellent in photoreactivity, the photoreactivity of the first resin (a) can be improved.

The amount of the carboxyl group of the carboxyl group-containing resin (D1) with respect to 1 mol of the epoxy group of the epoxy compound (d1) is preferably in the range of 0.4 to 1.2 mol, more preferably 0.5 to 1. It is within the range of 1 mol.

The compound (d3) composed of a polyvalent carboxylic acid or an anhydride thereof (hereinafter, also referred to as compound (d3)) is, for example, phthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylnadic acid, hexahydrophthalic acid, methylhexa. Dicarboxylic acids such as hydrophthalic acid, succinic acid, methylsuccinic acid, maleic acid, citraconic acid, glutaric acid, itaconic acid; cyclohexane-1,2,4-tricarboxylic acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, It can contain at least one compound selected from the group consisting of tribasic acids or more polyvalent carboxylic acids such as methylcyclohexenetetracarboxylic acid and biphenyltetracarboxylic acid; and anhydrides of these polyvalent carboxylic acids.

The main purpose of use of the compound (d3) is to impart acidity to the first resin (d) to impart redispersion and resolubility to the resin composition with a dilute alkaline aqueous solution. The amount of the compound (d3) used is preferably adjusted so that the acid value of the first resin (d) is 30 mgKOH / g or more, and more preferably the acid value of the first resin (d) is 60 mgKOH / g. The amount of the compound (d3) used is preferably adjusted so that the acid value of the first resin (d) is 160 mgKOH / g or less, and more preferably 130 mgKOH / g or less. Is adjusted to be.

In the synthesis of the first resin (d), an addition reaction between an epoxy compound (d1) and an ethylenically unsaturated compound (d2) having a carboxyl group, and an addition reaction product (addition reaction product) and a compound ( The addition reaction with d3) is carried out by a known method. For example, in the addition reaction between the epoxy compound (d1) and the ethylenically unsaturated compound (d2), the ethylenically unsaturated compound (d2) is added to the solvent solution containing the epoxy compound (d1), and further thermally polymerized as necessary. A reactive solution is obtained by adding a banning agent and a catalyst and stirring and mixing. The addition reaction product is obtained by reacting this reactive solution by a conventional method, preferably at 60 to 150 ° C., more preferably at 80 to 120 ° C. The thermal polymerization inhibitor is, for example, hydroquinone or hydroquinone monomethyl ether. The catalyst is, for example, tertiary amines such as benzyldimethylamine and triethylamine, quaternary ammonium salts such as trimethylbenzylammonium chloride and methyltriethylammonium chloride, triphenylphosphine and triphenylstibine.

In the addition reaction between the addition reaction product and the compound (d3), the compound (d3) is added to the solvent solution containing the addition reaction product, and if necessary, a thermal polymerization inhibitor and a catalyst are added and mixed by stirring. Then, a reactive solution is obtained. The first resin (d) is obtained by reacting this reactive solution by a conventional method. The reaction conditions may be the same as the reaction conditions for the addition reaction of the epoxy compound (d1) and the ethylenically unsaturated compound (d2) having a carboxyl group. As the thermal polymerization inhibitor and catalyst, the same thermal polymerization inhibitor and catalyst used in the addition reaction between the epoxy compound (d1) and the ethylenically unsaturated compound (d2) having a carboxyl group can be used.

The carboxyl group-containing resin (D1) comprises a part of a carboxyl group in a polymer of an ethylenically unsaturated monomer containing an ethylenically unsaturated compound having a carboxyl group and an ethylenically unsaturated compound having an epoxy group. A resin obtained by reacting (referred to as a second resin (e)) may be contained. The ethylenically unsaturated monomer may contain an ethylenically unsaturated compound having no carboxyl group, if necessary.

The ethylenically unsaturated compound having a carboxyl group for obtaining the second resin (e) can contain an appropriate polymer and prepolymer. For example, an ethylenically unsaturated compound having a carboxyl group can contain a compound having only one ethylenically unsaturated group. More specifically, the ethylenically unsaturated compounds having a carboxyl group include, for example, acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n≈2) monoacrylate, crotonic acid, cinnamic acid, 2-acryloyloxyethyl succinic acid. Acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl phthalic acid, β-carboxyethyl acrylate, acryloyloxyethyl succinate, methacryloyloxyethyl succinate, 2-propenoic acid , 3- (2-carboxyethoxy) -3-oxypropyl ester, 2-acryloyloxyethyl tetrahydrophthalic acid, 2-methacryloyloxyethyl tetrahydrophthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, and 2-methacryloyloxyethyl It can contain at least one compound selected from the group consisting of hexahydrophthalic acid. The ethylenically unsaturated compound having a carboxyl group can contain a compound having a plurality of ethylenically unsaturated groups. More specifically, for example, the ethylenically unsaturated compounds having a carboxyl group include pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol. It can contain a compound obtained by the reaction of a polyfunctional (meth) acrylate having a hydroxyl group selected from the group consisting of pentamethacrylate and a dibasic acid anhydride. These compounds may be used alone or in combination of two or more.

The ethylenically unsaturated compound having no carboxyl group for obtaining the second resin (e) can be, for example, a compound copolymerizable with the ethylenically unsaturated compound having a carboxyl group. The ethylenically unsaturated compound having no carboxyl group can contain a compound having an aromatic ring and a compound having no aromatic ring.

Compounds having an aromatic ring include, for example, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, and benzyl (meth). Acrylate, neopentyl glycol benzoate (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, EO-modified cresol (meth) acrylate, ethoxylated phenyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate (n = 2- 17), ECH-modified phenoxy (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, tribromophenyl (meth) acrylate. , EO-modified tribromophenyl (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di (meth) acrylate, modified bisphenol A di (meth) acrylate, EO-modified bisphenol F di (meth) acrylate, ECH-modified di (meth) phthalate, trimetyl propanebenzoate (meth) acrylate, EO-modified phthalic acid (meth) acrylate, EO, PO-modified phthalic acid (meth) acrylate, vinylcarbazole, styrene, vinylnaphthalene, and vinylbiphenyl. It can contain at least one compound selected from the group consisting of.

Compounds that do not have an aromatic ring include, for example, linear or branched aliphatic or alicyclic (but may have a partially unsaturated bond in the ring) (meth) acrylic acid ester, hydroxyalkyl. It can contain at least one compound selected from the group consisting of (meth) acrylates, alkoxyalkyl (meth) acrylates and the like; and N-substituted maleimides such as N-cyclohexylmaleimides. Compounds that do not have an aromatic ring include ethylene in one molecule, such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate. It may contain a compound having two or more sex unsaturated groups. These compounds may be used alone or in combination of two or more. By using these compounds, the hardness and oiliness of the film can be easily adjusted.

The ethylenically unsaturated compound having an epoxy group for obtaining the second resin (e) is an appropriate polymer or prepolymer. The ethylenically unsaturated compound having an epoxy group is selected from the group consisting of, for example, epoxycyclohexyl derivatives of acrylic acid or methacrylate; alicyclic epoxy derivatives of acrylate or methacrylate; β-methylglycidyl acrylate and β-methylglycidyl methacrylate. At least one compound. These compounds may be used alone or in combination of two or more. The ethylenically unsaturated compound is preferably a glycidyl (meth) acrylate that is widely used and readily available.

The carboxyl group-containing resin (D1) has a part or all of the hydroxyl groups in the polymer of the ethylenically unsaturated compound having a carboxyl group and the ethylenically unsaturated compound having a hydroxyl group. , A resin obtained by adding a compound having an ethylenically unsaturated group and an isocyanate group (hereinafter referred to as a third resin (f)) may be contained. The ethylenically unsaturated monomer may contain an ethylenically unsaturated compound having no carboxyl group and a hydroxyl group, if necessary.

The example of the ethylenically unsaturated compound having a carboxyl group for obtaining the third resin (f) is the same as the ethylenically unsaturated compound having a carboxyl group for obtaining the second resin (e) described above. You may.

The ethylenically unsaturated compound having a hydroxyl group for obtaining the third resin (f) is, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate. , Cyclohexanedimethanol mono (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalate, caprolactone (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, trimethyl propanedi It can be hydroxyalkyl (meth) acrylates such as (meth) acrylates, pentaerythritol tri (meth) acrylates, dipentaerythritol penta (meth) acrylates, hydroxybutyl vinyl ethers, hydroxyethyl vinyl ethers, and N-hydroxyethyl (meth) acrylamides. ..

Examples of the compound having an ethylenically unsaturated group and an isocyanate group for obtaining the third resin (f) include 2-acryloyloxyethyl isocyanate (specific example, Showa Denko Co., Ltd .; product number "Karenzu AOI"), 2-. Methacryloyloxyethyl isocyanate (specific example, Showa Denko Co., Ltd .; product number "Karen's MOI"), methacryloyloxyethoxyethyl isocyanate (specific example, Showa Denko Co., Ltd .; product number "Karen's MOI-EG"), Karen's MOI isocyanate block (specific example) As a specific example, Showa Denko Co., Ltd .; product number "Karenzu MOI-BM"), an isocyanate block body of Karenz MOI (as a specific example, Showa Denko Co., Ltd .; product number "Karenzu MOI-BP"), and 1,1- (bisacryloyloxy). Methyl) ethyl isocyanate) (specific example, Showa Denko Co., Ltd .; product number "Karenzu BEI").

The weight average molecular weight of the entire carboxyl group-containing resin (D1) is preferably in the range of 800 to 100,000. In this case, the curable resin composition is imparted with particularly excellent photosensitivity and resolvability.

The acid value of the entire carboxyl group-containing resin (D1) is preferably 30 mgKOH / g or more. In this case, good developability is imparted to the curable resin composition. The acid value of the entire carboxyl group-containing resin (D1) is more preferably 60 mgKOH / g or more. The acid value of the entire carboxyl group-containing resin (D1) is preferably 160 mgKOH / g or less. In this case, the amount of carboxyl groups remaining in the film formed of the curable resin composition is reduced. Therefore, good electrical characteristics, electrolytic corrosion resistance, water resistance, and the like of the film can be maintained. The acid value of the entire carboxyl group-containing resin (D1) is more preferably 130 mgKOH / g or less. [Carboxyl group-containing resin (D2)]
The curable resin composition may contain a carboxyl group-containing resin (D2) having no ethylenically unsaturated bond in one molecule.

The carboxyl group-containing resin (D2) contains, for example, a polymer of an ethylenically unsaturated monomer containing an ethylenically unsaturated compound having a carboxyl group. The ethylenically unsaturated monomer may contain an ethylenically unsaturated compound having no carboxyl group.

The ethylenically unsaturated compound having a carboxyl group can contain an appropriate polymer and prepolymer, and can contain, for example, a compound having only one ethylenically unsaturated group. More specifically, the ethylenically unsaturated compounds having a carboxyl group include, for example, acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n≈2) monoacrylate, crotonic acid, cinnamic acid, 2-acryloyloxyethyl succinic acid. Acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl phthalic acid, β-carboxyethyl acrylate, acryloyloxyethyl succinate, methacryloyloxyethyl succinate, 2-propenoic acid , 3- (2-carboxyethoxy) -3-oxypropyl ester, 2-acryloyloxyethyl tetrahydrophthalic acid, 2-methacryloyloxyethyl tetrahydrophthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, and 2-methacryloyloxyethyl It can contain at least one compound selected from the group consisting of hexahydrophthalic acid. The ethylenically unsaturated compound having a carboxyl group can also contain a compound having a plurality of ethylenically unsaturated groups. More specifically, the ethylenically unsaturated compounds having a carboxyl group include pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol penta. It may contain a compound obtained by reacting a polyfunctional (meth) acrylate having any hydroxyl group of methacrylate with a dibasic acid anhydride. These compounds may be used alone or in combination of two or more.

The ethylenically unsaturated compound having no carboxyl group may be a compound copolymerizable with the ethylenically unsaturated compound having a carboxyl group. The ethylenically unsaturated compound having no carboxyl group may contain both a compound having an aromatic ring and a compound having no aromatic ring.

Compounds having an aromatic ring include, for example, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, and benzyl (meth). ) Acrylate, neopentyl glycol benzoate (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, EO-modified cresol (meth) acrylate, ethoxylated phenyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate (n = 2) ~ 17), ECH-modified phenoxy (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, tribromophenyl (meth) Acrylate, EO-modified tribromophenyl (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di (meth) acrylate, modified bisphenol A di (meth) acrylate, EO-modified bisphenol F di (meth) acrylate , ECH-modified phthalic acid di (meth) acrylate, trimethylpropanbenzoate (meth) acrylate, EO-modified phthalic acid (meth) acrylate, EO, PO-modified phthalic acid (meth) acrylate, vinylcarbazole, styrene, vinylnaphthalene, and vinyl. It can contain at least one compound selected from the group consisting of biphenyl.

Compounds that do not have an aromatic ring include, for example, linear or branched aliphatic or alicyclic (but may have an unsaturated bond in the ring) (meth) acrylic acid ester, hydroxyalkyl (meth). It can contain at least one compound selected from the group consisting of acrylates, alkoxyalkyl (meth) acrylates and the like; and N-substituted maleimides such as N-cyclohexylmaleimide. Compounds that do not have an aromatic ring include ethylene in one molecule, such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate. It may contain a compound having two or more sex unsaturated groups. These compounds may be used alone or in combination of two or more. By using these compounds, the hardness and oiliness of the film can be easily adjusted.

From the viewpoint of alkali developability of the film 20 formed from the curable resin composition, the total ratio of the carboxyl group-containing resin (D1) and the carboxyl group-containing resin (D2) to the solid content of the curable resin composition is preferable. Is in the range of 5% by mass to 85% by mass, more preferably in the range of 10% by mass to 75% by mass, and further preferably in the range of 30% by mass to 60% by mass. In this case, the alkali developability of the film 20 can be sufficiently ensured.

[Colorant (E)]
The colorant (E) can color the curable resin composition and the film 20. The colorant (E) includes, for example, at least one material selected from the group consisting of pigments, dyes, and pigments. Colorants can include both pigments and dyes. However, although the colorant (E) is colored, a substance that becomes colorless by heating in the process of forming a film from the curable resin composition is not included in the colorant (E) because it does not color the film 20.

The colorant (E) is, for example, a black colorant, a white colorant, a blue colorant, a yellow colorant, a green colorant, a red colorant, a purple colorant, an orange colorant, a brown colorant, and a color other than the above. Can contain at least one material selected from the group consisting of colorants of.

When the colorant (E) contains a black colorant, the film 20 is colored black. Examples of black colorants may include carbon black. When the colorant (E) contains a white colorant, the film 20 is colored white. Examples of the white colorant may include titanium oxide. When the colorant (E) contains both a blue colorant and a yellow colorant, the film 20 is colored green. Examples of blue colorants include phthalocyanine blue colorants (phthalocyanine blue), anthraquinone blue colorants, Pigment Blue 15; Pigment Blue 15: 1; Pigment Blue 15: 2; Pigment Blue 15: 3; Pigment Blue 15: 4; Pigment Blue 15: 6; Pigment Blue 16; and Pigment Blue 60 are included. Examples of yellow colorants include monoazo yellow colorants, disazo yellow colorants, condensed azo yellow colorants, benzimidazolone yellow colorants, isoindolinone yellow colorants, anthraquinone yellow colorants, Pigment. Yellow 24; Pigment Yellow 108; Pigment Yellow 193; Pigment Yellow 147; Pigment Yellow 150; Pigment Yellow 199; Pigment Yellow 202; Pigment Yellow 110; Pigment Yellow 109; Pigment Yellow 139; Pigment Yellow 179; Pigment Yellow 185; Pigment Yellow 93 Pigment Yellow 94; Pigment Yellow 95; Pigment Yellow 128; Pigment Yellow 155; Pigment Yellow 166; Pigment Yellow 180; Pigment Yellow 120; Pigment Yellow 151; Pigment Yellow 154; Pigment Yellow 156; Pigment Yellow 175; and Pigment Yellow 181, 1,1'-[(6-phenyl-1,3,5-triazine-2,4-diyl) bis (imino)] bis (9,10-anthracendione) is included. When the colorant (E) contains a green colorant, the film 20 is colored green. Examples of green colorants include phthalocyanine-based green colorants, anthraquinone-based green colorants, perylene-based green colorants, metal-substituted or unsubstituted phthalocyanine compounds, Pigment Green 7, and Pigment Green 36.

When the coating film 24 includes the first coating film 240 and the second coating film 241, the first composition for forming the first coating film 240 and the second coating film 241 for forming the second coating film 241 are formed. The composition may contain different colorants (E). As a result, the first coating film 240 and the second coating film 241 can be colored in different colors. When increasing the light reflectivity of the second coating film 241, the second composition preferably contains a white pigment, and more preferably titanium oxide.

When the curable resin composition contains the organic component colorant (E), the ratio of the organic component colorant (E) to the solid content of the curable resin composition is preferably 0.01% by mass to 20% by mass. It is in the range of%, more preferably in the range of 0.05% by mass to 10% by mass, and further preferably in the range of 0.1% by mass to 5% by mass. When the curable resin composition contains the inorganic component colorant (E), the proportion of the inorganic component colorant (E) is preferably in the range of 1% by mass to 80% by mass, more preferably. Is in the range of 3% by mass to 70% by mass, more preferably in the range of 5% by mass to 60% by mass.

[Organic solvent (F)]
The organic solvent (F) is used for the purpose of liquefaction or varnishing of the curable resin composition, adjusting the viscosity, adjusting the coatability, adjusting the film-forming property, and the like.

The organic solvent (F) is, for example, linear, branched, secondary or polyhydric alcohols such as ethanol, propyl alcohol, isopropyl alcohol, hexanol and ethylene glycol; ketones such as methyl ethyl ketone and cyclohexanone; aromatics such as toluene and xylene. Group hydrocarbons; Petroleum-based aromatic mixed solvents such as Swazole series (manufactured by Maruzen Petrochemical Co., Ltd.) and Solbesso series (manufactured by Exxon Chemical Co., Ltd.); Carbitols such as; propylene glycol alkyl ethers such as propylene glycol methyl ether; polypropylene glycol alkyl ethers such as dipropylene glycol methyl ether; acetates such as ethyl acetate, butyl acetate, cellosolve acetate, carbitol acetate; and It can contain at least one compound selected from the group consisting of dialkyl glycol ethers.

When the curable resin composition contains an organic solvent (F), the ratio of the organic solvent (F) to the entire curable resin composition is the organic solvent (F) when the coating film of the curable resin composition is dried. In other words, the organic solvent (F) is adjusted so as not to remain in the dry coating film. The ratio of the organic solvent (F) to the entire curable resin composition is preferably in the range of 5 to 99.5% by mass. In this case, good coatability of the curable resin composition can be obtained. The preferred proportion of the organic solvent (F) varies depending on the coating method and the like.

[Other ingredients (G)]
The curable resin composition includes known curing agents, photopolymerization accelerators, sensitizers, sensitizers for laser exposure methods, and the like.
It may contain a filler or the like. The curable resin composition may contain an appropriate additive. The curable resin composition is, for example, a copolymer such as silicone or acrylate; a leveling agent; an adhesion imparting agent such as a silane coupling agent; a thixotropy agent; a polymerization inhibitor; an antihalation agent; a flame retardant; an antifoaming agent; It may contain at least one selected from the group consisting of antioxidants; surfactants; and polymer dispersants.

A curable resin composition can be prepared by blending the raw materials of the curable resin composition and kneading the curable resin composition by a known kneading method using a three-roll, ball mill, sand mill or the like. When the raw material of the curable resin composition contains a liquid component, a low-viscosity component, etc., the curable resin composition is prepared by kneading the other components and then adding the liquid or low-viscosity component. obtain.

From the viewpoint of storage stability and the like, the first agent may be prepared by mixing a part of the raw materials, and the second agent may be prepared by mixing the rest of the raw materials. That is, the curable resin composition may include a first agent and a second agent. For example, a first agent is prepared by mixing a thermosetting resin (B), an unsaturated compound (C), an organic solvent (F), etc. among the raw materials of the curable resin composition, and the curable resin composition is prepared. The second agent may be prepared by mixing the rest of the raw materials. In this case, a cured product of the curable resin composition can be formed by curing the mixed solution of the first agent and the second agent.

Hereinafter, specific examples 1 to 4 of the method for forming the film 20 from the curable resin composition will be described, but the method for forming the film 20 is not limited to these specific examples.

(Specific example 1)
Specific examples of the first method for producing the film 20 will be described with reference to FIGS. 4A to 4C.

First, the base material 200 and the curable resin composition are prepared. When the object 2 to be certified is a printed wiring board, the base material 200 is, for example, a core base material including an insulating layer and conductor wiring. The curable resin composition has photocurability and thermosetting property.

Next, as shown in FIG. 4A, the coating film 24 is formed on the base material 200. The coating film 24 is formed by applying a curable resin composition on the base material 200 and drying it. Examples of methods for applying the curable resin composition include a dipping method, a spray method, a spin coating method, a roll coating method, a curtain coating method, and a screen printing method. The coating film 24 may be formed by a dry film method.

Next, as shown in FIG. 4B, the mask 25 is directly or indirectly applied to the coating film 24, and the coating film 24 is irradiated with ultraviolet rays. In other words, the coating film 24 is exposed through the mask 25. Examples of ultraviolet light sources include chemical lamps, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, LEDs, g-line (436 nm), h-line (405 nm), and i-line (365 nm). , And a combination of two or more of the g-line, h-line and i-line.

The mask 25 includes a region 250 having high light transmission and a region 251 having no light transmission. When the coating film 24 is irradiated with ultraviolet rays through the mask 25, the region of the coating film 24 corresponding to the region 250 (first region 22) is irradiated with ultraviolet rays, and the region of the coating film 24 corresponding to the region 251 is irradiated. (Second region 23) is not irradiated with ultraviolet rays. By adjusting the film thickness of the coating film 24 and the amount of exposure to the coating film 24, the degree of curing of the surface layer of the first region 22 irradiated with ultraviolet rays can be made higher than that of the deep portion. In addition, the second region 23 of the coating film 24 that is not irradiated with ultraviolet rays can be made uncured.

Next, the coating film 24 is heated. As a result, a thermosetting reaction of the thermosetting resin (B) occurs, and the entire coating film 24 is cured to form the film 20. The heating temperature of the coating film 24 is preferably in the range of 90 to 300 ° C. The heating of the coating film 24 causes curing shrinkage in the deep part of the first region 22, but since the surface layer has already been cured, curing shrinkage is unlikely to occur in the surface layer of the first region 22. Therefore, the surface layer of the first region 22 is deformed following the curing shrinkage of the deep portion, so that wrinkles 210 can be generated on the surface of the first region 22 of the film 20. Further, in the second region 23, since curing shrinkage occurs in the surface layer and the deep portion due to the heating of the coating film 24, wrinkles 210 are less likely to occur or are prevented from occurring on the surface of the second region 23 of the film 20. be able to.

By the above method, as shown in FIG. 4C, a film containing a first region 22 having an artificial metric element 21 composed of wrinkles 210 and a second region 23 having no artificial metric element 21. 20 can be formed.

The mask 25 may not be used as long as the amount of ultraviolet rays irradiated to each region of the coating film 24 can be controlled. For example, as a method of controlling the amount of ultraviolet rays radiated to each region of the coating film 24 without using the mask 25, a direct drawing method of irradiating only the portion to be exposed on the coating film 24 with the ultraviolet rays emitted from the light source is used. The coating film may be exposed. The light source of the direct drawing method may be the same as that described above.

(Specific example 2)
Specific examples of the first method for producing the film 20 will be described with reference to FIGS. 5A to 5E.

First, the base material 200 and the curable resin composition are prepared. When the object 2 to be certified is a printed wiring board, the base material 200 is, for example, a core base material including an insulating layer and conductor wiring. The curable resin composition has photocurability and thermosetting property.

Next, as shown in FIG. 5A, the first coating film 240 is formed on the base material 200. The first coating film 240 is formed by applying a curable resin composition on the base material 200 and drying it. As a method for applying the curable resin composition, the same method as in Specific Example 1 can be applied. The first coating film 240 may be formed by a dry film method.

Next, as shown in FIG. 5B, a second coating film 241 is formed on the first coating film 240. The second coating film 241 is formed by applying a curable resin composition to a part of the first coating film 240 and drying it. As a method for applying the curable resin composition, the same method as in Specific Example 1 can be applied. The second coating film 241 may be formed by a dry film method.

By the above steps, a coating film 24 composed of a first coating film 240 and a second coating film 241 is formed. That is, by partially overlapping the first coating film 240 and the second coating film 241 formed from the same curable resin composition, the film thickness is smaller than that of the first region 22 and the first region 22. A coating film 24 having a second region 23 can be formed.

Next, as shown in FIG. 5C, the mask 25 is directly or indirectly applied to the coating film 24, and the coating film 24 is irradiated with ultraviolet rays. In other words, the coating film 24 is exposed through the mask 25. As the ultraviolet light source, the same light source as in Specific Example 1 can be applied.

The mask 25 includes a region 250 having high light transmission and a region 251 having no light transmission. When the coating film 24 is irradiated with ultraviolet rays through the mask 25, the region corresponding to the region 250 of the coating film 24 (exposed area) is irradiated with ultraviolet rays, and the region corresponding to the region 251 of the coating film 24 (non-exposed). The area) is not irradiated with ultraviolet rays. This exposure region includes a first region 22 and a second region 23 of the coating film 24. By making the film thickness of the first region 22 larger than that of the second region 23 and adjusting the exposure amount to the coating film 24, the degree of curing of the surface layer of the first region 22 can be made higher than that of the deep portion. Further, by making the film thickness of the second region 23 smaller than that of the first region 22, it is possible to sufficiently cure the second region 23 from the surface layer to the deep portion. In addition, the unexposed region of the coating film 24 that is not irradiated with ultraviolet rays can be made uncured.

Next, as shown in FIG. 5D, the unexposed area is removed by the developing process. As a result, the first region 22 and the second region 23 of the coating film 24 remain on the base material 200. When the first composition contains at least one selected from the group consisting of the carboxyl group-containing resin (D1) and the carboxyl group-containing resin (D2), it is in an uncured state by development treatment with an alkaline solution (alkali development). The non-exposed area of the coating film 24 can be removed.

Next, the coating film 24 is heated. As a result, a thermosetting reaction of the thermosetting resin (B) occurs, and the entire coating film 24 is cured to form the film 20. The heating temperature of the coating film 24 is preferably in the range of 90 to 300 ° C. The heating of the coating film 24 causes curing shrinkage in the deep part of the first region 22, but since the surface layer has already been cured, the surface layer of the first region 22 is deformed following the curing shrinkage in the deep part. , Wrinkles 210 can be generated on the surface of the first region 22 of the film 20. Further, since the surface layer and the deep portion of the second region 23 have already been cured, curing shrinkage is less likely to occur in the surface layer and the deep portion of the second region 23 when the coating film 24 is heated, and the second film 20 Wrinkles 210 are less likely to occur on the surface of the region 23, or can be prevented from occurring.

By the above method, as shown in FIG. 5E, a film containing a first region 22 having an artificial metric element 21 composed of wrinkles 210 and a second region 23 having no artificial metric element 21. 20 can be formed.

The mask 25 may not be used as long as the amount of ultraviolet rays irradiated to each region of the coating film 24 can be controlled. For example, as a method of controlling the amount of ultraviolet rays radiated to each region of the coating film 24 without using the mask 25, a direct drawing method of irradiating only the portion to be exposed on the coating film 24 with the ultraviolet rays emitted from the light source is used. The coating film may be exposed. The light source of the direct drawing method may be the same as that described above.

(Specific example 3)
Specific examples of the second method for producing the film 20 will be described with reference to FIGS. 6A to 6D.

First, the base material 200, the first composition, and the second composition are prepared. When the object 2 to be certified is a printed wiring board, the base material 200 is, for example, a core base material including an insulating layer and conductor wiring. The first composition has photocurability and thermosetting property. The second composition is photocurable and contains a white pigment.

Next, as shown in FIG. 6A, the first coating film 240 is formed on the base material 200. The first coating film 240 is formed by applying the first composition on the base material 200 and drying it. The first coating film 240 is provided on the entire surface of the base material 200. As the coating method of the first composition, the same method as the coating method of the curable resin composition of Specific Example 1 can be applied. The first coating film 240 may be formed by a dry film method.

Next, as shown in FIG. 6B, the second coating film 241 is formed on the first coating film 240. The second coating film 241 is formed by applying the second composition on the first coating film 240 and drying it. The second coating film 241 is provided on the entire surface of the first coating film 240. As the method for applying the second composition, the same method as the method for applying the curable resin composition of Specific Example 1 can be applied. The second coating film 241 may be formed by a dry film method.

By the above steps, a coating film 24 including the first coating film 240 and the second coating film 241 is formed.

Next, as shown in FIG. 6C, the mask 25 is directly or indirectly applied to the coating film 24, and the coating film 24 is irradiated with ultraviolet rays. In other words, the coating film 24 is exposed through the mask 25. As the ultraviolet light source, the same light source as in Specific Example 1 can be applied.

The mask 25 includes a region 250 having high light transmission and a region 251 having no light transmission. When the coating film 24 is irradiated with ultraviolet rays through the mask 25, the region corresponding to the region 250 of the coating film 24 (exposed area) is irradiated with ultraviolet rays, and the region corresponding to the region 251 of the coating film 24 (non-exposed). The area) is not irradiated with ultraviolet rays. In this exposure region, since ultraviolet rays are reflected on the surface of the second coating film 241 containing the white pigment, it is difficult for the ultraviolet rays to reach the first coating film 240. Therefore, the degree of curing of the second coating film 241 can be made higher than that of the first coating film 240. In addition, the unexposed region of the coating film 24 that is not irradiated with ultraviolet rays can be made uncured.

Next, as shown in FIG. 6D, the unexposed area is removed by the development process. As a result, only the exposed region of the coating film 24 remains on the base material 200. When the first composition and the second composition contain at least one selected from the group consisting of the carboxyl group-containing resin (D1) and the carboxyl group-containing resin (D2), the development treatment with an alkaline solution (alkali development) is performed. The unexposed region of the coating film 24, which is in an uncured state, can be removed.

Next, the coating film 24 is heated. As a result, a curing reaction of the thermosetting resin (B) occurs, and the entire coating film 24 is cured to form the film 20. Specifically, a film 201 which is a cured product of the first coating film 240 and a film 202 which is a cured product of the second coating film 241 are formed. Therefore, the film 20 is composed of the film 201 and the film 202. The heating temperature of the coating film 24 is preferably in the range of 90 to 300 ° C. The heating of the coating film 24 causes the first coating film 240 to undergo curing shrinkage, but since the second coating film 241 has already been cured, the second coating film 241 is unlikely to undergo curing shrinkage. Therefore, the second coating film 241 is deformed following the curing shrinkage of the first coating film 240, so that wrinkles 210 can be generated on the surface of the coating film 202.

By the above method, as shown in FIG. 6E, a film 20 having an artificial metric element 21 composed of wrinkles 210 can be formed.

(Specific example 4)
Specific examples of the second method for producing the film 20 will be described with reference to FIGS. 7A to 7E.

First, the base material 200, the first composition, and the second composition are prepared. The base material 200 has a recess 300 and a flat portion 301. When the object 2 to be certified is a printed wiring board, the recess 300 and the flat portion 301 can be manufactured by etching a laminated board composed of an insulating layer and a conductor layer. In this case, the recess 300 is a portion where the conductor layer has been removed by etching, and the flat portion 301 is a portion where the conductor layer remains after etching. The first composition has photocurability and thermosetting property. The second composition is photocurable.

Next, as shown in FIG. 7A, the first coating film 240 is formed on the base material 200. The first coating film 240 is formed by applying the first composition on the base material 200 and drying it. The first coating film 240 is provided on the entire surface of the base material 200. As the coating method of the first composition, the same method as the coating method of the curable resin composition of Specific Example 1 can be applied. The recess 300 and the flat portion 301 can form a first coating film 240 having regions having different film thicknesses. Specifically, the film thickness of the portion of the first coating film 240 in contact with the recess 300 can be made larger than that of the portion in contact with the flat portion 301.

Next, as shown in FIG. 7B, a second coating film 241 is formed on the first coating film 240. The second coating film 241 is formed by applying the second composition on the first coating film 240 and drying it. The second coating film 241 is provided on the entire surface of the first coating film 241. As the method for applying the second composition, the same method as the method for applying the curable resin composition of Specific Example 1 can be applied. The recess 300 and the flat portion 301 can form a second coating film 241 having regions having different film thicknesses. Specifically, the film thickness of the portion of the second coating film 241 provided on the recess 300 can be made larger than that of the portion provided on the flat portion 301.

By the above steps, a coating film 24 including the first coating film 240 and the second coating film 241 is formed. In the coating film 24, the portion in contact with the recess 300 is the first region 22, and the portion in contact with the flat portion 301 is the second region 23. That is, the coating film 24 having the first region 22 and the second region 23 having a film thickness smaller than that of the first region 22 can be formed by the recess 300 and the flat portion 301 of the base material 200. ..

Next, as shown in FIG. 7C, the mask 25 is directly or indirectly applied to the coating film 24, and the coating film 24 is irradiated with ultraviolet rays. In other words, the coating film 24 is exposed through the mask 25. As the light source of ultraviolet rays, the same light source as in Specific Example 1 can be used.

The mask 25 includes a region 250 having high light transmission and a region 251 having no light transmission. When the coating film 24 is irradiated with ultraviolet rays through the mask 25, the region corresponding to the region 250 of the coating film 24 (exposed area) is irradiated with ultraviolet rays, and the region corresponding to the region 251 of the coating film 24 (non-exposed). The area) is not irradiated with ultraviolet rays. This exposure region includes a first region 22 and a second region 23 of the coating film 24. By making the film thickness of the first region 22 larger than that of the second region 23 and adjusting the exposure amount to the coating film 24, in the first region 22, the degree of curing of the second coating film 241 can be determined. It can be higher than one coating film 240. Further, by making the film thickness of the second region 23 of the coating film 24 smaller than that of the first region 22, the first coating film 240 and the second coating film 241 are sufficiently cured in the second region 23. be able to. In addition, the unexposed region of the coating film 24 that is not irradiated with ultraviolet rays can be made uncured.

Next, as shown in FIG. 7D, the unexposed area is removed by the developing process. As a result, the first region 22 and the second region 23 remain on the base material 200. When the first composition contains at least one selected from the group consisting of the carboxyl group-containing resin (D1) and the carboxyl group-containing resin (D2), it is in an uncured state by development treatment with an alkaline solution (alkali development). The non-exposed area of the coating film 24 can be removed.

Next, the coating film 24 is heated. As a result, a curing reaction of the thermosetting resin (B) occurs, and the entire coating film 24 is cured to form the film 20. Specifically, a film 201 which is a cured product of the first coating film 240 and a film 202 which is a cured product of the second coating film 241 are formed. Therefore, the film 20 includes the film 201 and the film 202. The heating temperature of the coating film 24 is preferably in the range of 90 to 300 ° C. In the first region 22, the curing shrinkage of the first coating film 240 occurs due to the heating of the coating film 24, but since the second coating film 241 has already been cured, the curing shrinkage of the second coating film 241 is unlikely to occur. .. Therefore, in the first region 22, the second coating film 241 deforms following the curing shrinkage of the first coating film 240 to generate wrinkles 210 on the surface of the first region 22 of the coating film 202. Can be done. Further, in the second region 23, since the first coating film 240 and the second coating film 241 have already been cured, the curing shrinkage of the first coating film 240 and the second coating film 241 when the coating film 24 is heated. Wrinkles 210 are less likely to occur on the surface of the second region 23 of the film 202, or can be prevented from occurring.

By the above method, as shown in FIG. 7E, a first region 22 having an artificial metric element 21 composed of wrinkles 210 and a second region 23 having no artificial metric element 21 are included. The film 20 is obtained.

In the above specific example 4, the coating film 24 including the first coating film 240 and the second coating film 241 is formed on the substrate 200 having the recess 300 and the flat portion 301, but the coating film 24 is formed on the substrate 200. The coating film 24, which is a single-layer film, may be formed on the surface. In this case, the film thickness of the portion of the coating film 24 in contact with the recess 300 (first region 22) is larger than that of the portion in contact with the flat portion 301 (second region 23). By adjusting the exposure amount to the coating film 24, the degree of curing of the surface layer of the coating film 24 can be made higher than that in the deep portion in the first region 22, and in the second region 23, the coating film 24 can be cured. Can be sufficiently cured from the surface layer to the deep part of. When the coating film 24 after exposure is heated, curing shrinkage occurs in the deep part of the coating film 24 in the first region 22, but since the surface layer has already been cured, curing shrinkage does not easily occur on the surface layer. Therefore, in the first region 22, the surface layer of the coating film 24 is deformed following the curing shrinkage of the deep portion, so that wrinkles 210 can be generated on the surface of the first region 22 of the coating film 24. .. Further, in the second region 23, since the deep portion and the surface layer of the coating film 24 have already been cured, the curing shrinkage of the surface layer and the deep portion is less likely to occur when the coating film 24 is heated, and the second coating film 24 has a second coating film 24. Wrinkles 210 are less likely to occur on the surface of the region 23, or can be prevented from occurring.

Hereinafter, the present invention will be specifically described with reference to Examples.

(Synthesis Example A-1)
48 parts of methacrylic acid, 50 parts of ω-carboxy-polycaprolactone (n≈2) monoacrylate (Aronix M-5300 manufactured by Toa Synthetic Co., Ltd.), 92 parts of methyl methacrylate, 10 parts of styrene, 430 parts of dipropylene glycol monomethyl ether, And 3.5 parts of azobisisobutyronitrile were mixed in a four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for a nitrogen substituent and a stirrer. Further, the mixture was heated at 75 ° C. for 5 hours in a four-necked flask under a nitrogen stream to allow the polymerization reaction to proceed. As a result, a copolymer solution having a concentration of 32% was obtained.

Subsequently, 0.1 part of hydroquinone, 64 parts of glycidyl methacrylate and 0.8 part of dimethylbenzylamine were added to the copolymer solution, and the copolymer solution was placed in a four-necked flask at 80 ° C. for 24 hours. Heated.

As a result, a 38% by mass solution of the carboxyl group-containing resin of Synthesis Example A-1 (hereinafter, also referred to as carboxyl group-containing resin A-1) was obtained.

(Synthesis Example A-2)
120 parts by mass of glycidyl methacrylate, 25 parts by mass of methyl methacrylate, 20 parts by mass of t-butyl acrylate, 35 parts by mass of t-butyl methacrylate, 200 parts by mass of diethylene glycol monoethyl ether acetate, 18.4 parts by mass of azobisisobutyronitrile. Mixing was performed in a four-necked flask equipped with a reflux cooler, a thermometer, a glass tube for nitrogen replacement and a stirrer. Further, the mixture was heated in a four-necked flask under a nitrogen stream at 95 ° C. for 8 hours to allow the polymerization reaction to proceed. As a result, a copolymer solution having a concentration of 50% by mass was obtained.

To this copolymer solution, 0.2 parts by mass of hydroquinone, 73.9 parts by mass of acrylic acid, and 2.0 parts by mass of dimethylbenzylamine were added, and this copolymer solution was placed in a four-necked flask at 110 ° C. It was heated for 10 hours.

Subsequently, 60.8 parts by mass of tetrahydrophthalic anhydride and 16.5 parts by mass of diethylene glycol monoethyl ether acetate were added to the copolymer solution, and the copolymer solution was heated at 81 ° C. for 3 hours.

As a result, a 60% by mass solution of the carboxyl group-containing resin of Synthesis Example A-2 (hereinafter, also referred to as carboxyl group-containing resin A-2) was obtained.

(Synthesis Example A-3)
Cresol novolac type epoxy resin with epoxy equivalent 203 (manufactured by Nippon Steel & Sumitomo Metal Corporation, product number YDC-700-5) 203 parts by mass, diethylene glycol monoethyl ether acetate 160.1 parts by mass, methylhydroquinone 0.2 parts by mass, acrylic acid 72 .7 parts by mass and 0.6 parts by mass of dimethylbenzylamine were mixed in a four-necked flask equipped with a reflux cooler, a thermometer, an air blow tube and a stirrer. The mixture was heated in a flask at 110 ° C. for 10 hours.

Subsequently, 60.8 parts by mass of tetrahydrophthalic anhydride and 78.9 parts by mass of diethylene glycol monoethyl ether acetate were added to the copolymer solution, and the copolymer solution was added to the copolymer solution in a four-mouth flask at 90 parts. It was heated at ° C. for 3 hours.

As a result, a 65% by mass solution of the carboxyl group-containing resin of Synthesis Example A-3 (hereinafter, also referred to as carboxyl group-containing resin A-3) was obtained.

The resin compositions of Composition Examples 1 to 4 were prepared by mixing the above-mentioned carboxyl group-containing resins A-1 to A-3 and the following raw material components at the ratios shown in Table 1 below.
(Ingredients)
-Epoxy resin A: Biphenyl type epoxy resin, manufactured by Mitsubishi Chemical Corporation, product number YX-4000.
Epoxy resin B: 1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (high melting point type).
-70% by mass solution of epoxy resin C; a solution of cresol novolac type epoxy resin, product name EPICLON N-695 manufactured by DIC Corporation, in diethylene glycol monoethyl ether acetate with a solid content of 70%.
-Photopolymerizable compound A: ε-caprolactone-modified dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd., product number KAYARAD DPCA-120.
-Photopolymerizable compound B: Dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd., product number KAYARAD DPHA.
-Photopolymerization initiator A: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, trade name IRGACURE TPO manufactured by BASF.
-Photopolymerization initiator B: 1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by BASF, product number IRGACURE 184.
-Photopolymerization initiator C: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, manufactured by BASF, product number IRGACURE 907.
-Photopolymerization initiator D: 2,4-diethylthioxanthene-9-one, manufactured by Nippon Kayaku Co., Ltd., product number KAYACURE-DETX-S.
-White pigment: rutile type titanium oxide, manufactured by Ishihara Sangyo Co., Ltd., product number CR-80.
-Black pigment: carbon black, manufactured by Mitsubishi Chemical Corporation, MA-7.
-Blue pigment: Phthalocyanine blue.
-Yellow pigment: 1,1'-[(6-phenyl-1,3,5-triazine-2,4-diyl) bis (imino)] bis (9,10-anthracene dione).
-Melamine: Fine powder melamine manufactured by Nissan Chemical Industries, Ltd.
-Barium sulfate: Made by Sakai Chemical Industry Co., Ltd., product number Variace B30.
-Differential silica: Made by Tokuyama Corporation, product number MT-10.
-Bentonite: Organic bentonite, manufactured by Leox, product number Benton SD-2.
-Defoamer: manufactured by Shin-Etsu Silicone Co., Ltd., product number KS-66.
-Organic solvent: diethylene glycol monoethyl ether acetate.

(Example 1)
First, a wet coating film was formed on the surface of the substrate by applying the resin composition of Composition Example 2 by screen printing on the entire surface of a glass epoxy copper-clad laminate having a copper foil having a thickness of 35 μm. By heating this wet coating film at 80 ° C. for 20 minutes and pre-drying it, a dry coating film having a film thickness of 60 μm was formed on the copper foil.

The dry coating film was selectively exposed by applying a negative mask directly on the surface of the dry coating film and irradiating with ultraviolet rays of ^{150 mJ / cm 2.} The dry coating film after exposure was heated at 150 ° C. for 60 minutes and thermoset to form a film. On the surface of this film, wrinkles were generated in the region irradiated with ultraviolet rays, but no wrinkles were generated in the region not irradiated with ultraviolet rays.

In the region irradiated with ultraviolet rays, the degree of curing of the surface layer of the coating film is higher than that in the deep part, and by further heating this coating film, curing shrinkage occurs in the deep part of the coating film, but the surface is already cured. Therefore, it is considered that wrinkles were generated because the surface followed the hardening shrinkage in the deep part.

On the other hand, in the region not irradiated with ultraviolet rays, the photocuring reaction did not proceed on the surface and the deep part of the coating film, and further heating the coating film caused curing shrinkage on the surface and the deep part of the coating film. , It is probable that no wrinkles occurred.

From these facts, it was possible to form a film having a wrinkled region and a wrinkle-free region by changing the irradiation amount of ultraviolet rays.

(Example 2)
First, a wet coating film was formed on the surface of the substrate by applying the resin composition of Composition Example 2 by screen printing on the entire surface of a glass epoxy copper-clad laminate having a copper foil having a thickness of 35 μm. By heating this wet coating film at 80 ° C. for 15 minutes and pre-drying it, a dry coating film having a film thickness of 20 μm was formed on the copper foil.

A wet coating film was formed by applying the resin composition of Composition Example 2 to one surface of the dry coating film by screen printing. This wet coating film was preheated at 80 ° C. for 20 minutes and pre-dried to form a dry coating film having a film thickness of 30 μm.

Therefore, a region having a film thickness of 50 μm (first region) and a region having a film thickness of 20 μm (second region) were formed on the half surface of the copper foil. A dry coating film having a film thickness of 20 μm and a dry coating film having a film thickness of 30 μm are laminated and provided in the first region, and only a dry coating film having a film thickness of 20 μm is provided in the second region. It was.

The dry coating film was selectively exposed by applying a negative mask directly on the surface of the dry coating film and irradiating with ultraviolet rays of ^{100 mJ / cm 2.} By developing the dry coating film after exposure with an aqueous sodium carbonate solution, a portion of the dry coating film cured by exposure (cured film) remained on the substrate.

The cured film was formed by heating at 150 ° C. for 60 minutes and thermosetting the film. In this film, wrinkles were generated in the first region and no wrinkles were generated in the second region.

In the first region where the film thickness is large, the degree of curing of the surface layer of the coating film is higher than that in the deep part, and by further heating this coating film, curing shrinkage occurs in the deep part of the coating film, but the surface is already present. Since it is hardened, it is considered that wrinkles are generated because the surface follows the hardening shrinkage in the deep part.

On the other hand, in the second region where the film thickness is smaller than that of the first region, the photocuring reaction proceeds on the surface and the deep part of the coating film. It is probable that shrinkage was unlikely to occur and wrinkles did not occur.

From these facts, by making the film thickness of the coating film different, it was possible to form a film having a region having wrinkles and a region having no wrinkles.

(Example 3)
First, a wet coating film was formed on the surface of the substrate by applying the resin composition of Composition Example 3 by screen printing on the entire surface of a glass epoxy copper-clad laminate having a copper foil having a thickness of 35 μm. By heating this wet coating film at 80 ° C. for 15 minutes and pre-drying it, a dry coating film having a film thickness of 20 μm was formed on the copper foil.

A wet coating film was formed by applying the resin composition of Composition Example 1 to the entire surface of the dry coating film by screen printing. This wet coating film was preheated at 80 ° C. for 20 minutes and pre-dried to form a dry coating film having a film thickness of 40 μm.

The dry coating film was selectively exposed by applying a negative mask directly on the surface of the dry coating film and irradiating with ultraviolet rays of ^{400 mJ / cm 2.} By developing the dry coating film after exposure with an aqueous sodium carbonate solution, a portion of the dry coating film cured by exposure (cured film) remained on the substrate.

The cured film was formed by heating at 150 ° C. for 60 minutes and thermosetting the film. Wrinkles were generated on the surface of this film.

The coating film of Composition Example 1 provided on the coating film of Composition Example 3 is white and has high light reflectivity. Therefore, when the coating film is exposed, a photocuring reaction proceeds on the surface of the coating film, but since a large amount of ultraviolet rays are reflected on this surface, it is difficult for the ultraviolet rays to reach the deep part of the coating film, and light is emitted in the deep part. The curing reaction does not proceed easily. As a result, the degree of curing of the surface layer of the coating film is higher than that of the deep portion. By curing the coating film after exposure, curing shrinkage occurs in the deep part of the coating film, but since the surface has already been cured, it is considered that wrinkles were generated because the surface followed the curing shrinkage in the deep part. ..

From this, it was possible to form wrinkles on the surface of the coating film by increasing the light reflectivity of the surface layer of the coating film.

(Example 4)
First, a printed wiring board was obtained by etching and patterning a glass epoxy copper-clad laminate having a copper foil having a thickness of 35 μm. A wet coating film was formed on the surface of the substrate by applying the resin composition of Composition Example 2 to the entire surface of the printed wiring board by screen printing. By heating this wet coating film at 80 ° C. for 15 minutes and pre-drying it, a dry coating film having a film thickness of 15 μm was formed on the copper foil.

Subsequently, the resin composition of Composition Example 4 was applied to the entire surface of the dry coating film of the printed wiring board by screen printing to form a wet coating film on the surface of the substrate. By heating this wet coating film at 80 ° C. for 20 minutes and pre-drying it, a dry coating film having a film thickness of 35 μm was formed on the copper foil.

Therefore, the dry coating film has a region in contact with the glass epoxy (first region) and a region in contact with the copper foil (second region).

The dry coating film was selectively exposed by applying a negative mask directly on the surface of the dry coating film and irradiating with ultraviolet rays of ^{60 mJ / cm 2.} By developing the dry coating film after exposure with an aqueous sodium carbonate solution, a portion of the dry coating film cured by exposure (cured film) remained on the substrate.

The cured film was formed by heating at 150 ° C. for 60 minutes and thermosetting the film. In this film, wrinkles were generated in the first region and no wrinkles were generated in the second region.

Since the film thickness of the coating film is large in the first region in contact with the glass epoxy, the degree of curing of the surface layer of the coating film after exposure is higher than that in the deep portion. Further, since the coating film includes the coating film of Composition Example 2 containing a black pigment and the coating film of Composition Example 4 provided on the coating film, the degree of curing of the surface layer of the coating film after exposure. However, it is higher than the deep part. By heating this coating film, curing shrinkage occurs in the deep part of the coating film, but since the surface has already been cured, it is considered that wrinkles are generated because the surface follows the curing shrinkage in the deep part.

On the other hand, since the second region in contact with the copper foil has a smaller film thickness than the first region, the photocuring reaction proceeds on the surface and the deep part of the coating film. It is considered that even when this coating film was heated, curing shrinkage did not easily occur on the surface and the deep part, and wrinkles did not occur. From these facts, it was possible to form a film having wrinkles in the area where there is no wiring on the printed wiring board and having no wrinkles on the wiring.

(Comparative Example 1)
A film was formed by the same method as in Example 3 except that the dry coating film of Composition Example 3 was provided on the dry coating film of Composition Example 1. No wrinkles were formed on the surface of this film.

Since the coating film of Composition Example 2 having high light reflectivity is provided under the coating film of Composition Example 3, when these coating films are exposed, the photocuring reaction proceeds on the surface and the deep part of the coating film. Even if this coating film is heated, curing shrinkage does not easily occur on the surface and deep part of the coating film. Therefore, it is considered that no wrinkles were generated on the surface of the film.

(Comparative Example 2)
A film was formed by the same method as in Example 4 except that the exposure amount to the coating film was set to 500 mJ / cm ^2. No wrinkles were formed on the surface of this film.

In the first region in contact with the glass epoxy, the film thickness of the coating film is large, but if the exposure amount is too large, the photocuring reaction proceeds on the surface and the deep part of the coating film. It is considered that even when this coating film was heated, curing shrinkage did not easily occur on the surface and deep part of the coating film, and wrinkles did not occur.

1 Certification system 2 Certified object 20 Film 21 Artificial object Metrics element 210 Wrinkles 22 First area 23 Second area 24 Coating 240 First coating 241 Second coating 3 Reader

Claims (13)

An object to be certified with a film having an artificial metric element and
A reader that reads the object to be certified, and
A determination device for determining whether or not the authenticated object can be authenticated based on the result of reading the authenticated object is provided.
The film contains a cured product of a coating film of a curable resin composition.
The coating comprises a wrinkled surface, which constitutes the artificial metric element.
The object to be certified is a printed wiring board.
The film is a solder resist layer.
Authentication system. An object to be certified with a film having an artificial metric element and
A reader that reads the object to be certified, and
A determination device for determining whether or not the authenticated object can be authenticated based on the result of reading the authenticated object is provided.
The film contains a cured product of a coating film of a curable resin composition.
The coating comprises a wrinkled surface, which constitutes the artificial metric element.
The curable resin composition contains a photopolymerization initiator (A), a thermosetting resin (B), and an unsaturated compound (C) containing at least one ethylenically unsaturated bond in one molecule.
Authentication system. The thermosetting resin (B) has a cyclic ether structure.
The authentication system according to claim 2. The film has a first region having the artificial metric element and a second region having no artificial metric element.
The authentication system according to any one of claims 1 to 3. A reading process that reads the artificial metric elements of the film of the object to be certified,
Including a determination step of determining whether or not the authenticated object can be authenticated based on the result of reading the artificial object metric element.
The film contains a cured product of a coating film of a curable resin composition.
The coating comprises a wrinkled surface, which constitutes the artificial metric element .
The curable resin composition contains a photopolymerization initiator (A), a thermosetting resin (B), and an unsaturated compound (C) containing at least one ethylenically unsaturated bond in one molecule.
Authentication method. Containing a cured product of the coating film of the curable resin composition,
It has a wrinkled surface, the wrinkles that make up the artificial metric element,
The curable resin composition contains a photopolymerization initiator (A), a thermosetting resin (B), and an unsaturated compound (C) containing at least one ethylenically unsaturated bond in one molecule.
A film for certification. A first region having the artificial metric element and a second region not having the artificial metric element include.
The certification film according to claim 6. A method for producing a coating film having a wrinkled surface and the wrinkles constituting an artificial metric element.
This includes forming the coating film by curing the coating film after forming the coating film of the curable resin composition.
When the coating film is cured, the degree of curing of the surface layer of the coating film is higher than that of the deep part of the coating film, and then the entire coating film is cured to form the wrinkles.
The curable resin composition has thermosetting property and photocurability, and the coating film is a single-layer film formed from the curable resin composition.
When the coating film is cured, the coating film is exposed so that the degree of curing of the surface layer of the coating film is higher than that of the deep portion, and then the coating film is heated to cover the entire coating film. Cure,
Method for producing a film for authentication. A method for producing a coating film having a wrinkled surface and the wrinkles constituting an artificial metric element.
This includes forming the coating film by curing the coating film after forming the coating film of the curable resin composition.
When the coating film is cured, the degree of curing of the surface layer of the coating film is higher than that of the deep part of the coating film, and then the entire coating film is cured to form the wrinkles.
The curable resin composition contains a photopolymerization initiator (A), a thermosetting resin (B), and an unsaturated compound (C) containing at least one ethylenically unsaturated bond in one molecule.
Method for producing a film for authentication. The curable resin composition contains a photopolymerization initiator (A), a thermosetting resin (B), and an unsaturated compound (C) containing at least one ethylenically unsaturated bond in one molecule.
The method for producing a coating film for certification according to claim 8. A method for producing a coating film having a wrinkled surface and the wrinkles constituting an artificial metric element.
This includes forming the coating film by curing the coating film after forming the coating film of the curable resin composition.
When the coating film is cured, the degree of curing of the surface layer of the coating film is higher than that of the deep part of the coating film, and then the entire coating film is cured to form the wrinkles.
The curable resin composition contains a first composition having thermosetting and photocurability and a second composition having photocurability.
The coating film includes a first coating film formed from the first composition and a second coating film on the first coating film and formed from the second composition.
By exposing the coating film when the coating film is cured, the degree of curing of the second coating film is the degree of curing of the first coating film to the photocuring reaction between the first coating film and the second coating film. The entire coating film is cured by heating the coating film after advancing it so as to be higher than the degree of curing.
Method for producing a film for authentication. A method for producing a coating film having a wrinkled surface and the wrinkles constituting an artificial metric element.
This includes forming the coating film by curing the coating film after forming the coating film of the curable resin composition.
When the coating film is cured, the degree of curing of the surface layer of the coating film is higher than that of the deep part of the coating film, and then the entire coating film is cured to form the wrinkles.
The curable resin composition contains a first composition having thermosetting property and not photocuring property, and a second composition having photocuring property.
The coating film includes a first coating film formed from the first composition and a second coating film on the first coating film and formed from the second composition.
When the coating film is cured, the second coating film is cured by exposing the coating film, and then the entire coating film is cured by heating the coating film.
Method for producing a film for authentication. The second composition contains a photopolymerization initiator (A), a thermosetting resin (B), and an unsaturated compound (C) containing at least one ethylenically unsaturated bond in one molecule.
The method for producing a coating film for certification according to claim 11 or 12.

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