JP3167812B2 - Photosensitive resin composition for sandblasting and laminated film using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to glass, ceramic,
On the surface of stone, wood, ceramics, plastic, etc., letters,
The present invention relates to a photosensitive resin composition for sandblasting and a laminated film using the same for efficiently engraving photographic images, patterns, and the like.

[0002]

2. Description of the Related Art Conventionally, as a method of forming an image on the surface of glass, ceramic, stone, or the like by sandblasting, a rubber plate, paper, or the like is attached to the surface of a base material, cut out with a cutter or the like, patterned, and then sandblasted. There is known a method in which a resist ink is pattern-printed and dried by screen printing, followed by sandblasting.

JP-A-60-10242 discloses a screen-printable photo-curable resin for sandblasting containing a urethane prepolymer having a terminal ethylenically unsaturated group and a monofunctional ethylenically unsaturated compound. Compounds are disclosed. Further, JP-A-60-104938 and JP-A-6-104938
Japanese Patent Application No. 0-104939 also discloses a transfer material for sandblasting, which also contains an unsaturated polyurethane having an ethylenically unsaturated group at a terminal and an ethylenically unsaturated compound.

In addition to the above, Japanese Patent Application Laid-Open No. 2-69754 discloses a photosensitive laminated film (dry film) for a sculpture mask in which a photosensitive resin composition and a photosensitive adhesive composition which are both water-developable are laminated. Has been proposed.

[0005]

However, the above rubber,
The method of cutting out paper or the like with a cutter has a problem that it is complicated and takes a long time, and the working efficiency is not improved. Also, when transferring an image mask made of a photosensitive resin using a polyurethane resin and a monofunctional ethylenically unsaturated compound, since the photosensitive composition is in a liquid state, it is difficult to control its handling and film thickness control, and furthermore, the resolution and There is a drawback that the degree of adhesion to the sculptured material is not sufficient, and furthermore, the photosensitive laminated film for the sculptured mask is safe in operation because the developing solution is water, When deep blast etching is performed, abrasion of the resist is severe. Therefore, when trying to thicken the resist film, especially 100 μm
In the above case, it is difficult to prepare the film due to thermal decomposition of the diazo resin or the like during drying, and the formed photosensitive film mask is of a low grade. Further, the transfer using an adhesive is not suitable when precision of an electronic component or the like is required.

[0006]

In order to solve the above-mentioned problems, the present invention provides a urethane oligomer having an ethylenically unsaturated double bond at a terminal and a cellulose derivative or a compound having an ethylenically unsaturated double bond. By using 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a photopolymerization initiator for the contained photosensitive resin composition, the workability is good, the resolution and the degree of adhesion with the engraved material are sufficient. Another object of the present invention is to provide a photosensitive resin composition having a wide allowable range of exposure and having excellent abrasion resistance during sandblasting.

[0007] Further, a water-soluble resin layer, a photosensitive resin composition layer and a release film are laminated in this order on a flexible film using the above-mentioned photosensitive resin composition layer for sand blast containing a cellulose derivative. The present invention also provides a photosensitive laminated film for sandblasting, which is excellent in workability.

The photopolymerization initiator according to the present invention,
4,6-Trimethylbenzoyldiphenylphosphine oxide is, for example, sold under the trade name “Lucirin TPO” by BASF, and is a photosensitive resin composition 1
0.05 to 20 parts by weight, and more preferably 0.
It is preferable to add 5 to 10 parts by weight. It is not clear why the above-mentioned remarkable effect can be obtained only when this photopolymerization initiator is used, but it absorbs a wavelength in an ultraviolet region and causes photocrosslinking of a compound having an ethylenically unsaturated double bond. It is presumed to be efficient.

The urethane oligomer having an ethylenically unsaturated double bond at the terminal according to the present invention is prepared by reacting a polyol component and an isocyanate component in an isocyanate group-excess state to form a prepolymer having a terminal NCO, and a hydroxyl-containing prepolymer. It can be formed by reacting a compound having an ethylenically unsaturated double bond to form an oligomer having a molecular weight of 30,000 or less.

Examples of the above-mentioned polyol components include polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, and reaction of diols such as ethylene glycol and diethylene glycol with dibasic acids such as adipic acid and phthalic anhydride. And polyester polyols obtained by the above method. Examples of the isocyanate component include 2,4-
Toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, and the like.

Examples of the compound having a hydroxyl group-containing ethylenically unsaturated double bond include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxyethyl methacrylate.
Examples thereof include hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and the like, or those obtained by reacting these with ε-caprolactone, and esterified products of acrylic acid and methacrylic acid with the above polyols.

The cellulose derivative according to the present invention is contained in a photosensitive resin composition suitable for forming the above-mentioned laminated film, and has good compatibility with the urethane oligomer. It satisfies the requirements such as good adhesion to the flexible film, good releasability from the flexible film, and easy removal by a developer. As such a cellulose derivative, those having a carboxyl group are preferable, and cellulose acetate phthalate is particularly preferable. This cellulose derivative is
10 to 1 with respect to 100 parts by weight of the urethane oligomer
It is preferable to add 00 parts by weight.

Further, the compound having an ethylenically unsaturated double bond according to the present invention is one which is photopolymerized by an active light source in the presence of a photopolymerization initiator and becomes insoluble in a developing solution. Examples of the compound include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxy acrylate, phenoxy methacrylate, isobornyl acrylate, isobornyl methacrylate Rate, and the like. The compound having an ethylenically unsaturated double bond is preferably added in an amount of 10 to 200 parts by weight based on 100 parts by weight of the urethane oligomer. In the photosensitive resin composition, as other components, a polymerization inhibitor, a plasticizer,
Conventionally known dyes and pigments such as dyes and pigments can be used as needed.

The photosensitive resin composition for sandblasting of the present invention may be applied in a liquid state to a material to be carved and etched to form a photosensitive resin layer according to the application as described above, by a screen printing method. It can be used for both the forming method and the method in which a photosensitive resin layer is formed on a flexible film in advance and dried, and then the film is attached to a material to be carved and etched (dry film method). it can. If these methods are used, when precise alignment of electronic components or the like is required, it is not necessary to transfer a resin pattern formed in advance, so that a resin pattern can be formed at an accurate position and high precision can be obtained. Engraving can be realized.

FIG. 1 shows an example of a dry film. A water-soluble resin layer 2 is applied on a flexible film 1, and a photosensitive resin composition layer 3 of the present invention is formed thereon. Further, the release film 4 is further mounted thereon and integrated therewith.

The film 1 supports the photosensitive resin composition layer 3 of the present invention and needs to have appropriate flexibility. Therefore, a polyethylene terephthalate (PET) film having a thickness of 16 to 125 μm is preferable. In addition, synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyvinyl chloride can be used.

The water-soluble resin layer 2 serves to prevent the photosensitive resin from desensitizing to oxygen and to prevent the mask pattern from sticking during exposure, and must be water-soluble so that it can be removed by a developer. . Suitable examples of such a material include polyvinyl alcohol and partially saponified polyvinyl acetate. For the purpose of improving the releasability from the flexible film, 100 parts by weight of the material of the water-soluble resin layer 2 is further mixed with ethylene glycol, propylene glycol, or a condensate or derivative thereof.
It is also preferable to add 0.001 to 10 parts by weight of a seed or more. By doing so, the water-soluble resin layer 2 can be easily peeled from the flexible film.

The water-soluble resin layer 2 is obtained by applying a 5 to 20% by weight aqueous solution using a bar coater, a roll coater, a curtain flow coater or the like so as to have a dry thickness of 1 to 10 μm. If the thickness is less than 1 μm, poor adhesion may occur, and if it exceeds 10 μm, the resolution tends to be poor. In preparing the aqueous solution, a solvent such as methanol, methyl cellosolve, acetone or the like may be added in consideration of the viscosity of the liquid, defoaming, and the like.

The photosensitive resin composition layer 3 is prepared by mixing the above-mentioned components and adding a solvent, if desired, to an applicator,
It is applied by a bar coater, a roll coater, a curtain flow coater or the like so as to have a dry thickness of 10 to 100 μm.

The release film 4 is for stably protecting the photosensitive resin composition layer 3 when not in use.
It is stripped off when used. Therefore, it is necessary to have an appropriate mold releasability that does not peel off when not used and can be easily peeled off when used. As the release film 4 that satisfies such conditions, a PET film, a polypropylene film, a polyethylene film, or the like, having a thickness of 16 to 125 μm, coated or baked with silicone is suitable.

FIG. 2 shows a method of engraving using the dry film prepared as described above. In FIG. 2A, the release film 4 of the dry film shown in FIG. 1 is peeled off, and is brought into close contact with the engraved material 5 to be turned upside down. Since the urethane oligomer is added to the photosensitive resin composition layer 3, the adhesion is very good.

Next, in FIG. 1B, the mask pattern 6 is brought into close contact with the water-soluble resin layer 2 and exposed to ultraviolet rays 7 using a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an arc lamp, a xenon lamp, or the like. Excimer laser, X-ray, electron beam and the like can also be irradiated in addition to ultraviolet rays. When 2,4,6-trimethylbenzoyldiphenylphosphine oxide, which is a photopolymerization initiator according to the present invention, is used, the allowable range of the exposure amount is wide (that is, the dimensional accuracy is large or small even if the exposure amount is large or small). And the blast resistance is not significantly different), so that the resolution is high and the workability is good. After this exposure, the mask pattern 6 is removed and development is performed.

FIG. 3C shows the state after development. By the development, the ultraviolet-ray non-exposed portion of the water-soluble resin layer 2 and the photosensitive resin composition layer 3 is removed, and only the exposed portion of the resin layer 8 remains. As a developer used for this development, a general-purpose alkali developer can be used. Examples of the alkali component used in the developer include lithium, sodium, hydroxide of an alkali metal such as potassium,
Primary amines such as carbonate, bicarbonate, phosphate, pyrophosphate, benzylamine and butylamine, secondary amines such as dimethylamine, dibenzylamine and diethanolamine, trimethylamine, triethylamine and triethanolamine Cyclic amines such as tertiary amines, morpholine, piperazine, piperidine and pyridine; polyamines such as ethylenediamine and hexamethylenediamine; tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylbenzylammonium hydroxide and the like Ammonium hydroxides,
Sulfonium hydroxides such as trimethylsulfonium hydroxide, diethylmethylsulfonium hydroxide, and dimethylbenzylsulfonium hydroxide; and choline and silicate-containing buffers.

When the photosensitive resin composition of the present invention is used, the pattern profile of the resin layer 8 formed after exposure and development is improved (without trailing). Further, the resin layer 8
And the engraving material 5 are high in adhesion, so that even a fine pattern does not peel off, and the engraving accuracy during sandblasting is increased.

FIG. 3D shows the state after sandblasting. Since the resin layer 8 has higher abrasion resistance than a conventional dry film, it does not wear out before the sculpture of a desired depth is completed. Finally, the resin layer 8
Is peeled off with an alkaline aqueous solution to complete a carved product shown in FIG.

[0026]

By using the photosensitive resin composition of the present invention or the photosensitive laminated film for sandblasting, the resolution of the pattern and the degree of adhesion to the engraved material are improved, the allowable range of the exposure amount is expanded, and Abrasion resistance during sandblasting increases.

[0027]

Embodiments of the present invention will be described below. Examples 1 to 8 UV-3000B K8 which is a urethane acrylate having a urethane bond in the molecule and having an acrylic group at the terminal
0 (manufactured by Nippon Gosei Kagaku; contains 20% by weight of methyl ethyl ketone), 43.8 parts by weight of cellulose phthalate acetate (manufactured by Wako Pure Chemical Industries; trade name: KC-71), and 60 parts by weight of a 25% by weight solution of methyl ethyl ketone. , 4,
6 parts by weight of 6-trimethylbenzoyldiphenylphosphine oxide, 0.005 parts by weight of aluminum salt of N-nitrosophenylhydroxylamine, oil blue 613
0.1 part by weight (manufactured by Orient Chemical) was added and dissolved to prepare a photosensitive resin composition of the present invention.

Separately, 0.5 part by weight of polyethylene glycol (average molecular weight: 400) was added to 10 parts of a 10% solution of polyvinyl alcohol (manufactured by Kuraray; trade name: PVA-405; saponification degree: 80 mol%, polymerization degree: 500). The stirred and mixed water-soluble resin solution was dried on a 75 μm-thick PET film using a bar coater so as to have a thickness of 5 μm to form a water-soluble resin layer.

Further, the photosensitive resin composition was applied thereon by using an applicator so that the film thickness after drying was 50 μm to form a photosensitive resin composition layer. The polyethylene film was laminated with a rubber roller so that no air bubbles remained, thereby completing a film-shaped photosensitive resin according to the present invention. Similarly, a film having a thickness of 100 μm after drying was prepared.

The polyethylene film layer of the resulting film-shaped photosensitive resin was peeled off, and the exposed photosensitive resin composition layer was laminated on a glass surface heated to 80 ° C. using a rubber roller, and the PET film was removed. Thus, the water-soluble resin layer was exposed. 200, 150, 1
A test pattern mask having a line width of 25, 100, 80, 70, 60, 50, and 40 μm is brought into close contact with the mask, and 50, 100, 150, and 200 mJ / c is applied by an ultra-high pressure mercury lamp.
UV exposure was performed at an irradiation dose of m ² . Then the liquid temperature is 25
1.2 kg / c with 0.2% Na ₂ CO ₃ aqueous solution
At an injection pressure of m ² , spray development was carried out for a film thickness of 50 μm for 70 seconds and for a film thickness of 100 μm for 120 seconds.

Adhesion / resolution (line / spa) at each film thickness
ce) is shown in (Table 1). Here, “adhesion” means the above 20
0, 150, 125, 100, 80, 70, 60, 50
And among the resin layers formed to have a line width of 40 μm, the values of the thinnest line widths having a peel resistance value of 300 g / cm ² or more at 20 ° C. are shown. The smaller the numerical value, the better the adhesion. Express. “Resolution” indicates the value of the thinnest line width that does not make contact with an adjacent line. The smaller the numerical value, the higher the resolution.

[0032]

[Table 1]

Comparative Examples 1 to 8 In the same manner as in Examples 1 to 8, except that 2 parts by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide in Examples 1 to 8 was changed to 4 parts by weight of dimethylbenzyl ketal. The adhesion / resolution was examined. The results are also shown in (Table 1).

From the results shown in Table 1, the resin layer of the example according to the present invention has an exposure amount of 50 to 200 mJ / cm ^2.
It is clear that both the adhesion and the resolution are excellent over a wide range. On the other hand, for the resin layer of the comparative example using another photopolymerization initiator, when the resin layer thickness is 100 μm,
Although only the adhesiveness was almost the same as that of the example, the values of the adhesiveness in other ranges and the resolutions in all the ranges were significantly lower than those of the examples.

Examples 9 and 10 and Comparative Examples 9 and 10 Films of 50 μm thickness and 100 μm thickness formed in the same manner as in Example 1 and Comparative Example 1 were laminated on a glass surface heated to 80 ° C. using a rubber roller. Then, the PET film was removed to expose the water-soluble resin layer. And 50μ
m The thickness of the things 100 mJ / cm ^2, and 100μm solid exposure at 200 mJ / cm ² for one thickness (overall exposure), using abrasive SiC # 600 this, nozzle distance 100 mm, blasting pressure 5 kg / cm The time until the resin layer was worn out and disappeared by sandblasting with fixing the nozzle position in ² was measured. The results are shown in (Table 2).

[0036]

[Table 2]

As is clear from Table 2, the resin layer according to the present invention had about 2-3 times the abrasion resistance of the comparative example. In addition, when the resin layer wear time by sandblasting is plotted against the resin layer thickness in Examples 9 and 10, a curve as shown in FIG. 3 is drawn. If a curve as shown in the figure is prepared, when a necessary blast resistance time is determined according to a desired etching depth, it is possible to determine a film thickness to be formed in accordance with the blast resistance time. It is convenient.

Examples 11 to 34 and Comparative Examples 11 to 34 A 50 μm thick film formed in the same manner as in Example 1 and Comparative Example 1 was laminated on a glass surface heated to 80 ° C. using a rubber roller, and PET was used. The film was removed to expose the water-soluble resin layer. And 40, 50, 100, 1
Solid exposure (overall exposure) at 50, 200 and 220 mJ / cm ² , using a polishing agent SiC # 600, fixing the nozzle position at a nozzle distance of 100 mm and a blast pressure of 5 kg / cm ² and sandblasting the resin layer The time to wear and disappear was measured. Further, a film having a thickness of 50 μm was subjected to post-exposure at 200 mJ / cm ² , and a film having a thickness of 100 μm was subjected to post-exposure at 400 mJ / cm ² .
The post-exposure and the post-baking at 150 ° C. for 20 minutes, and the post-baking only, were similarly subjected to a sand blast wear test. These results are shown in (Table 3), (Table 4), (Table 5) and (Table 6).
Shown in

[0039]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

FIG. 4 shows an example without post-exposure and post-bake (ie, Examples 11 to 16; line segment A), a comparative example (ie, comparative examples 11 to 16; line segment a), and post-exposure. Example (i.e., Examples 17 to 22; line segment B), Comparative Example (i.e., Comparative Examples 17 to 22; line segment b), and Example with both post-exposure and post-bake (i.e., Examples 23-2
8; line C), the comparative example (i.e., comparative examples 23 to 28; line c), and an example having only post-baking (i.e.,
The numerical values of Examples 29 to 34; line segment D) and the comparative example (that is, Comparative Examples 29 to 34; line segment d) were plotted.

In FIG. 4, the maximum value of the resin layer wear time of the line segment a of the comparative example was 40 seconds (exposure amount: 100 mJ / cm).
The ratio of the line segments A to D in each example with respect to ² ) is as follows: A / a is 2.6 times, B / a is 3.2 times, C / a is 2.8 times, and D / a is 4. It was 6 times. B / b is 1.8 times, C
The value of / c was 1.6 times and the value of D / d was 3.8 times, all of which were longer than the comparative examples. Also, from the figure, the resin layer of the example is different from the comparative example in that the exposure amount is 50 to 200 m.
It is also clear that it has high blast resistance in a wide range of J / cm ² .

[0042]

As described above, by using the photosensitive resin composition of the present invention, the pattern profile of the photocured resin layer is improved, so that highly accurate engraving can be performed. Further, since the allowable range of the exposure amount is widened, the resolution is high and the workability is improved. Further, since the blast resistance of the resin layer is greatly improved, the amount of the photosensitive resin composition used can be reduced, and highly accurate engraving can be performed.

Further, by using the dry film of the present invention, in addition to the various effects described above, the resolution is improved due to the good adhesion with the mask pattern, and the adhesion with the engraved material is also improved. Therefore, even if it is a fine pattern, it does not peel off, and the engraving accuracy at the time of sandblasting increases.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing an example of a dry film of the present invention.

FIG. 2 is a process diagram showing a method of engraving using the dry film of the present invention.

FIG. 3 is a resin layer thickness-resin layer wear time diagram.

FIG. 4 is a plot of exposure dose versus resin layer wear time.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... film, 2 ... water-soluble resin layer, 3 ... photosensitive resin composition layer, 4 ... release film, 5 ... engraving material, 8 ... resin layer.

Continuation of front page (51) Int.Cl. ⁷ identification code FI G03F 7/029 G03F 7/029 7/11 7/11 (56) References JP-A-55-36812 (JP, A) JP-A-4- 296315 (JP, A) JP-A-4-202412 (JP, A) JP-A-59-75245 (JP, A) JP-A-2-69754 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F 7/004

Claims (2)

(57) [Claims] 1. A photosensitive resin composition for sandblasting comprising a urethane oligomer having an ethylenically unsaturated double bond at a terminal, and a cellulose derivative or a compound containing an ethylenically unsaturated double bond, wherein as a photopolymerization initiator, A photosensitive resin composition comprising 4,6-trimethylbenzoyldiphenylphosphine oxide. 2. In a photosensitive laminated film for sandblasting wherein a water-soluble resin layer, a photosensitive resin composition layer, and a release film are laminated in this order on a flexible film, the photosensitive resin composition layer has a terminal. A laminated film comprising a urethane oligomer having an ethylenically unsaturated double bond, a cellulose derivative, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a photopolymerization initiator.