JP3285606B2 - Method for improving adhesion of photosensitive resin structure - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface modification of a resin used for various structures, particularly a resin used for a structure made of a photosensitive resin.

[0002]

2. Description of the Related Art In general, an injection molding method is mainly used for manufacturing a structure made of resin from the viewpoint of productivity. As a specific example, in the field of a structure having a fine shape, a manufacturing method using a photosensitive resin has been known. The photosensitive resin used in the structure was a solvent development type resin having water resistance and chemical resistance.

[0003]

However, the prior art has the following problems.

[0004] In the production of a structure using the solvent-developable photosensitive resin, a chlorine-based solvent or a flammable solvent must be used as a solvent in the development step, which poses environmental problems and safety problems in handling. Therefore, replacement with a photosensitive resin other than the solvent development, that is, a photosensitive resin of an alkali development type has been studied. However, the alkali developing type photosensitive resin has a problem in water resistance and chemical resistance because a carboxyl group is added to a resin structure that can be developed with an alkaline aqueous solution, for example, a resin serving as a base.
It is generally said that a photosensitive resin increases the degree of polymerization by ultraviolet light and heat treatment, thereby improving water resistance and chemical resistance, but is insufficient in the durability performance of the structure. As a result, there is a problem that it cannot be used particularly in applications of a structure made of a photosensitive resin that requires water resistance or chemical resistance.

[0005] Further, an alkali developing type photosensitive resin is
In general, since it is assumed that the support substrate is peeled off after use, when manufacturing a structure made of a photosensitive resin that requires adhesion with the support substrate, the support substrate is evaluated during the water resistance and chemical resistance during or after manufacture. Peeling occurred between the resins. Even if the coupling agent is applied to the interface between the support substrate and the resin to improve the adhesion, the coupling agent may be subjected to a chemical resistance test and a water resistance test due to the chemical resistance of the coupling agent and the stress of the resin. Peeled from the interface of the agent.

The present invention solves the above-mentioned problems, and an object of the present invention is to send an activating gas to a structure made of a solvent-type or alkali-development-type photosensitive resin having poor water resistance and chemical resistance. An object of the present invention is to provide a method for modifying the surface of a photosensitive resin structure capable of improving water resistance and chemical resistance by treating in a contact or active gas atmosphere.

[0007]

According to the surface modification method for a resin structure of the present invention, after forming an arbitrary shape by exposure and development, a reactive gas generated by an activation treatment in advance is brought into contact with a predetermined condition, By promoting the polymerization reaction of the photosensitive resin, the water resistance and the chemical resistance of the resin structure are improved.

[0008] The reactive gas is one of oxygen, nitrogen, carbon dioxide, carbon monoxide or a gas activated from carbon tetrafluoride gas.

[0009] It is characterized in that the activation treatment method is any one of a corona discharge method, a plasma excitation method and an ultraviolet irradiation excitation method.

[0010] The photosensitive resin structure of the present invention is manufactured by a method using a photosensitive resin. Particularly, as for the photosensitive resin, the photosensitive resin was laminated on a supporting substrate such as glass or stainless steel by thermocompression bonding, and an arbitrary structure was formed by exposure and development.

The mechanism relating to the surface modification of the photosensitive resin structure of the present invention is considered to be that the reactive gas promotes the polymerization reaction of the photosensitive resin to improve water resistance or chemical resistance. Especially when ozone is used as the reactive gas, in the case of photosensitive resin,

[0012]

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Or

[0014]

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Or

[0016]

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It is considered that the polymerization reaction proceeds as described above.

The method of activating the gas includes corona discharge, plasma excitation or ultraviolet irradiation excitation, and the types of gas include not only oxygen but also nitrogen, carbon dioxide, carbon monoxide, carbon tetrafluoride, and the like. The object of the present invention can be achieved by any gas and the method of exciting the gas. In particular, the activation of oxygen by irradiation with ultraviolet rays utilizes a mechanism in which oxygen is decomposed into atoms at a wavelength of about 250 nm or less to change into ozone having strong oxidizing power.

If necessary, ultraviolet irradiation and heat treatment may be added.

[0020]

The effects of the present invention will be described in detail with reference to the following examples.

(Embodiment 1) FIGS. 1 and 2 show Embodiment 1 of the present invention.
It is a perspective view according to a manufacturing process of the structure of FIG. Description will be made with reference to this figure.

First, as shown in FIG. 1, an alkali developing type acrylic epoxy photosensitive resin layer 2 having a bond of -C = C- having an infrared absorption characteristic as shown in FIG. 3 was laminated on a glass substrate 1.

Next, as shown in FIG. 2, exposure and development are performed to produce an arbitrary three-dimensional shape, and ultraviolet light of about 350 nm is irradiated with 2 J / cm 2.
Irradiation and heat treatment at 150 degrees Celsius.

Finally, this arbitrary three-dimensional shape was irradiated with an activating gas under the conditions shown in Table 1 to perform surface modification.

[0025]

[Table 1]

Samples 1 to 10 were treated using an ozone treatment apparatus manufactured by Samco International Laboratories Co., Ltd. to perform surface modification.

As a comparative experiment, comparative samples shown in Table 2 were produced.

[0028]

[Table 2]

A sample subjected to the above surface modification and an untreated sample as a comparison were immersed in 10% sulfuric acid and 3% sodium hydroxide for 1 day and in pure water for 15 days, and tested for chemical resistance and water resistance. Was performed. Table 3 shows “○” when no deformation of the photosensitive resin structure or peeling from the support substrate was observed, “△” when deformation of the photosensitive resin structure or peeling from the support substrate was partially observed, When the deformation of the conductive resin structure or the separation of the support substrate was observed, the result was evaluated as “x”.

[0030]

[Table 3]

As shown in Table 3, all the modified samples showed good results without peeling from the glass and deformation of the resin under all the test conditions.

On the other hand, in the comparative sample, the resin was deformed under each test condition, and peeled off from the supporting substrate. Clearly, the surface modification by the activating gas showed an effect on water resistance and chemical resistance.

In the surface modification in which oxygen was activated as a gas, the surface-modified resin surface layer contained more oxygen than the inside of the resin.

Example 2 A photosensitive resin having an arbitrary shape was produced in the same manner as in Example 1 except that the photosensitive resin of Example 1 was changed to a solvent developing type photosensitive resin having a -C = C- bond. A structure of a conductive resin was manufactured.

Next, the surface was modified by irradiation with an activating gas under the conditions shown in Table 4.

[0036]

[Table 4]

A sample was manufactured as a comparative sample under the conditions shown in Table 5.

[0038]

[Table 5]

The above samples were immersed in 10% sulfuric acid and 3% sodium hydroxide for 1 day and in pure water for 15 days, and tested for chemical resistance and water resistance. Table 4 shows “○” when no deformation of the photosensitive resin structure or peeling from the support substrate is observed, “△” when deformation of the photosensitive resin structure or peeling from the support substrate is partially observed, If the deformation of the conductive resin structure or peeling of the support substrate is seen as "x",
It is an evaluation result.

[0040]

[Table 6]

As shown in Table 6, the samples showed good results without any deformation of the resin under each test condition.

On the other hand, in the comparative sample, the resin was deformed under each test condition, and peeled off from the supporting substrate. Clearly, the surface modification by the activating gas showed an effect on water resistance and chemical resistance.

(Embodiment 3) FIGS. 4 to 5 are perspective views of the structure of this embodiment in different manufacturing steps. Description will be made with reference to this figure.

First, as shown in FIG. 4, a coupling agent 4 such as “KB” manufactured by Shin-Etsu Chemical Co., Ltd.
P-43 ″ was applied, and an alkali developing type epoxy photosensitive resin layer 5 was laminated.

Next, as shown in FIG. 5, exposure and development were carried out to produce grooves 6 of a structure made of a photosensitive resin having an arbitrary shape through which fluid flows.

The surface was modified by irradiating it with an activating gas under the conditions shown in Table 7.

[0047]

[Table 7]

A sample was manufactured as a comparative sample under the conditions shown in Table 8.

[0049]

[Table 8]

The surface-modified sample was immersed in 10% nitric acid and 3% sodium hydroxide for 1 day and in pure water for 15 days, and subjected to chemical resistance and water resistance tests. Table 5 shows
When the deformation of the photosensitive resin structure or peeling from the support substrate is not seen, “○”, when the deformation of the photosensitive resin structure or peeling from the support substrate is partially seen, “△”, the photosensitive resin structure The results are evaluated as "x" when deformation of the support substrate or peeling of the support substrate is observed.

[0051]

[Table 9]

As shown in Table 9, all the samples showed good results without peeling from the stainless steel and deformation of the resin under all the test conditions.

On the other hand, in the comparative sample, the resin was deformed under each test condition, and peeled off from the supporting substrate. Clearly, the surface modification by the activating gas showed an effect on water resistance and chemical resistance.

The above embodiment is a part of the present invention.
Regardless of the type of the resin, the shape of the resin, the type of the coupling agent, and the presence or absence of post-treatment of the resin, the effect of the present invention is not affected at all.

[0055]

As described above, according to the present invention, an arbitrary shape is formed by exposure and development on a resin structure made of a water-soluble development type photosensitive resin formed on a substrate, and then an activation treatment is performed. By contacting the reactive gas generated by the under certain conditions, to promote the polymerization reaction of the photosensitive resin,
Water resistance and chemical resistance of the resin structure can be improved. In particular, even without using a solvent developing type photosensitive resin, the above-mentioned activating gas is brought into contact with the exposed and developed photosensitive resin to improve the water resistance and chemical resistance of the alkali developing type photosensitive resin structure. In addition, the adhesion to the support substrate was improved, and it became possible to use an alkali developing type photosensitive resin. As a result, a structure made of a photosensitive resin can be safely manufactured without using a chlorine-based solvent or a flammable solvent in the developing process.

[Brief description of the drawings]

FIG. 1 is a perspective view of a structure of Example 1 for each manufacturing process.

FIG. 2 is a perspective view of the structure of Example 1 for each manufacturing process.

FIG. 3 is an infrared absorption characteristic diagram of the photosensitive resin of Example 1.

FIG. 4 is a perspective view of a structure according to a third embodiment in each manufacturing process.

FIG. 5 is a perspective view of the structure according to the third embodiment in each manufacturing process.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Alkali development type acrylic epoxy photosensitive resin layer 3 Stainless steel substrate 4 Coupling agent 5 Alkali development type epoxy photosensitive resin layer 6 Groove

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yuji Suzuki 3-3-5 Yamato, Suwa-shi, Nagano Seiko Epson Corporation (72) Inventor Rinjiro Ichikawa 1-4-16 Nihombashi Bakurocho, Chuo-ku, Tokyo Fujimori Inside the Industrial Co., Ltd. (72) Inventor Haruyasu Tsuboi 1-4-16, Nihonbashi Bakurocho, Chuo-ku, Tokyo Inside Fujimori Industrial Co., Ltd. (72) Inventor Kobayashi Tetsunosuke 1-4-16, Nihonbashi Bakurocho, Chuo-ku, Tokyo Fujimori (56) References JP-A-63-298242 (JP, A) JP-A-63-228616 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F 7 / 40

Claims (4)

(57) [Claims] 1. After forming an arbitrary shape by exposure and development on a resin structure made of a water-soluble development type photosensitive resin formed on a substrate, a reactive gas generated in advance by activation treatment is applied for 5 minutes. A surface modification of the resin structure, wherein the water resistance and the chemical resistance of the resin structure are improved by contacting the resin structure at a temperature of 50 ° C. or higher to promote the polymerization reaction of the photosensitive resin. Method. 2. After forming an arbitrary shape by exposure and development on a resin structure made of a water-soluble developing type photosensitive resin formed on a substrate, a reactive gas generated in advance by an activation process is applied for 10 minutes. And contact at 25 ° C or higher,
A method for modifying the surface of a resin structure, wherein the polymerization reaction of the photosensitive resin proceeds to improve the water resistance and chemical resistance of the resin structure. 3. The method according to claim 1, wherein the reactive gas is any one of oxygen, nitrogen, carbon dioxide, carbon monoxide, or a gas activated by carbon tetrafluoride gas. Surface modification method for a resin structure. 4. The method for modifying a surface of a resin structure according to claim 1, wherein the activation treatment method is any one of a corona discharge method, a plasma excitation method, and an ultraviolet irradiation excitation method.