JPH0420178B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a mask transfer material for solid surface processing, and more specifically, to a mask transfer material for solid surface processing that has a sandblasting mask pattern layer with a delicate design that can be transferred to a substrate to be processed. be. When sandblasting is used to engrave the surface of glass, stone, ceramics, wood, synthetic resin, metal, leather, etc., a mask is usually used to protect the non-engraved surface. Conventionally, when using this sandblasting mask, a mask with a pattern was obtained from rubber or paper by hand, and it was attached to the substrate to be processed using adhesive, but this method was time-consuming. It was not possible to obtain a mask with delicate designs on the top. Therefore, in order to improve these drawbacks, various methods have recently been proposed using sandblasting masks made of photosensitive resin. For example, a method has been proposed (Japanese Patent Publication No. 46-35681) in which a photosensitive resin layer is directly provided on a substrate to be processed, imagewise exposed and developed to create a mask having a pattern. However, in this method,
In addition to being difficult to process curved surfaces, it also requires a great deal of labor when the substrate to be processed is large. Furthermore, a method of transferring a mask pattern layer formed of a photosensitive resin onto a support film by attaching it to a substrate to be processed (Japanese Unexamined Patent Publication No. 53
-99258) has been proposed. However, in this method, although the drawbacks of the above-mentioned methods are improved to some extent, since no adhesive layer is provided on the support film, dots and lines may be formed during the development process in creating the mask pattern layer. There is a problem in that the fine cured resin layer falls off from the support film, and furthermore, when the support film is peeled off after the transfer material has been attached to the substrate to be processed, the support film may fall off. Due to the adhesive force between the mask pattern layer and the cured product, there is a problem that the mask pattern layer with a fine design detaches from the substrate to be processed, making it impossible to use it for processing delicate designs. Furthermore, in a mask transfer material having a mask pattern layer formed of a photosensitive resin on a support film, there is a space between the support film and the mask pattern layer that is removable from the film and that allows the substrate to be processed to be A method of providing an intermediate film such as methacrylic acid ester that adheres closely to the material and can be destroyed by sandblasting (Utility Model Publication No. 55-89555)
No. 2) has been proposed. However, in this proposal, although the detachment of the mask pattern layer is improved when the support film is peeled off after the transfer material is attached to the substrate to be processed, the intermediate coating layer and the support film are separated. If it is easily peeled off, the adhesive force with the photosensitive resin cured product becomes weaker, causing the mask pattern layer to fall off in the development process for forming the mask pattern layer, and conversely, the adhesive strength between the photosensitive resin cured product and the photosensitive resin cured product becomes weaker. If the adhesive force is sufficient, the peeling resistance from the support film will increase, and the peeling of the support film, especially the mask pattern layer, will occur. Therefore, balance the adhesive force in the intermediate coating layer. The problem is that it is difficult to The present inventors have solved these problems and created a mask for solid surface processing that has a mask pattern layer with a delicate design and that can be transferred to a processed substrate without damaging the mask pattern layer at all. As a result of extensive research in order to provide a transfer material, we discovered that this objective could be achieved by interposing a retaining layer made of a water-insoluble cellulose derivative between the supporting base material and the mask pattern layer. Based on this knowledge, we have completed the present invention. That is, the present invention provides a mask for solid surface processing, which comprises a holding layer made of a water-insoluble cellulose derivative on the surface of a supporting base material, and a mask pattern layer formed by curing a photosensitive resin composition thereon. It provides a transfer material. Examples of the supporting base material used in the mask transfer material of the present invention include synthetic resin films such as polypropylene, polyester, polyvinyl chloride, polycarbonate, polystyrene, and polyethylene;
Examples include metal sheets such as steel and aluminum. The thickness of these supporting base materials is 50μ ~
A range of 1 mm is preferred. If the thickness is less than 50 μm, the supporting base material loses its so-called stiffness, making it difficult to function as a supporting base material, and if it is thicker than 1 mm, handling efficiency becomes undesirable. In the mask transfer material of the present invention, a supporting base material;
The support layer interposed between the mask pattern layer formed by curing the photosensitive resin composition is made of a water-insoluble cellulose derivative, and does not have adhesive properties itself, but is sufficiently strong with respect to the mask pattern layer. It has adhesive strength, can be easily peeled from the supporting base material, and has the property of being destroyed by sandblasting. This holding layer made of a water-insoluble cellulose derivative is a water-based washing solution such as water, an aqueous alkali solution, or an aqueous surfactant solution used in the step of washing out an unexposed photosensitive resin composition when forming a mask pattern layer on a supporting substrate. It is insoluble in the material and has the role of preventing the fine dots and lines of the cured resin material from detaching from the supporting base material in the process, and furthermore, after the transfer material is affixed to the processed base material, It has the role of preventing the mask pattern layer from detaching from the substrate to be processed when the supporting substrate is peeled off. The peel resistance between the holding layer and the supporting base material is desirably 10 g/cm or less from the viewpoint of workability when the supporting base material is peeled off. Among the water-insoluble cellulose derivatives used in the former retention layer, alkyl celluloses such as ethyl cellulose and methyl cellulose, and ester compounds of cellulose and monocarboxylic acids such as cellulose acetate butyrate are particularly effective in their insolubility in aqueous washouts. preferable. This retaining layer is preferably used in a thickness of 0.5 to 20 microns. If the thickness is less than 0.5μ, the function as a retaining layer will be poor, and if it exceeds 20μ, it will be difficult and uneconomical to manufacture a supporting base material provided with such a retainer layer. The photosensitive resin composition used to form the mask pattern layer in the mask transfer material of the present invention is
The cured product has sufficient sandblasting resistance and has a peel resistance value of 300°C at a temperature of 20°C.
It is necessary to have a surface tackiness of at least g/cm, and to be able to wash out unexposed areas with an aqueous washing solution such as water, an aqueous alkali solution, or an aqueous surfactant solution. Suitable examples of such photosensitive resin compositions include (a) General formula B(XA) _o XB ... () [In the formula, X is a urethane residue, A is a polyether,
Polyester, polyether polyester block copolymer, polydiene, polyene and mixtures thereof, B is the general formula

[Formula] (Z is a hydrogen atom or a methyl group, Y is -(CH ₂ -)
m ₁ o−, −(CH ₂ CH ₂ O−) m ₂ or −(CH ₂ CH ₂ O−)
m ₃ and m ₁ are 1 to 6, m ₂ and m ₃ are each 1 to 15
A photosensitive resin containing as main components an unsaturated polyurethane represented by (b) an ethylenically insoluble compound and (c) a photopolymerization initiator, where n is 1 to 10. Examples include, but are not limited to, compositions. Examples of the ethylenically unsaturated compound used in the photosensitive resin composition include acrylic acid, methacrylic acid, or esters thereof, such as alkyl,
Cycloalkyl, tetrahydrofurfuryl, allyl, glycidyl, hydroxyalkyl acrylates and their methacrylates, alkylene glycol, polyalkylene glycol mono- and diacrylates and their methacrylates, pentaerythritol tetraacrylate and their methacrylates, etc.; acrylamide, methacrylamide, or these derivatives such as N-methylolacrylamide and its methacrylamide, N,N'-alkylenebisacrylamide and its methacrylamide, diacetone acrylamide and its methacrylamide; addition-polymerizable unsaturated monomers such as styrene, vinyltoluene , divinylbenzene, diallyl phthalate, triallyl cyanurate, vinyl acetate, acrylonitrile, etc.;
Unsaturated polyesters; alkyd resins; unsaturated polyurethanes such as polyurethanes modified with addition-polymerizable monomers having active hydrogen, such as hydroxyacrylates and their methacrylates. In addition, examples of the photopolymerization initiator used in the photosensitive resin composition include benzoin, benzoin alkyl ester, α-methylbenzoin and its alkyl ether, α-phenylbenzoin,
α-allylbenzoin, anthraquinone, chloroanthraquinone, methylanthraquinone, ethylanthraquinone, benzyl, diacetyl, acetophenone, ω-bromoacetophenone, 2,2-
Examples include dimethoxyphenylacetophenone, α-naphthalenesulfonyl chloride, diphenyl disulfide, and dyes such as eosin and thionin. Next, an example of the method for manufacturing the mask transfer material of the present invention will be described. First, a coating is formed on the surface of the protective film that is easily peeled from the film and is soluble in the washing solution of the unexposed photosensitive resin composition. A protective film is formed on a transparent image carrier in such a manner that the protective film is exposed. Examples of the protective film include transparent synthetic resin films such as polypropylene, polyester, polyethylene, polystyrene, polyvinyl chloride, polyamide, cellulose acetate, and polycarbonate.
Its thickness is usually 5 to 50 μm. If the film is thicker than this, the reproducibility of images will be lowered due to light scattering within the film, and if it is thinner than this, handling will be poor. Preferably the thickness is 9 to 25 microns. Furthermore, if the film has low oxygen permeability,
Since it tends to reduce the surface tackiness of the formed sandblasting mask pattern layer, the oxygen permeation rate is 30×10 ^-6 g/24hr/m ² /mm thickness/cmHg (21
℃) or higher is preferable. From this point of view, polypropylene film, cellulose ester film, polycarbonate film, polyethylene film, polystyrene film, etc. are suitable. Furthermore, considering ease of handling, polypropylene film is most suitable. The coating provided on the surface of the protective film needs to be easily peelable from the film and soluble in the washing solution of the unexposed photosensitive resin composition. Further, the peel resistance value from the film is preferably 10 g/cm or less. Therefore, for this coating, for example, cellulose derivatives such as hydroxyl group-containing cellulose ethers or esters, carboxyl group-containing cellulose ethers or esters, partially saponified polyvinyl acetate, etc. can be used. Examples of hydroxyl group-containing cellulose derivatives include hydroxyethylcellulose, hydroxypropylcellulose, and cellulose hydroxyacetate, and examples of carboxyl group-containing cellulose ethers include carboxymethylcellulose and carboxyethylcellulose. In addition, the carboxyl group-containing cellulose ester may be a combination of cellulose and polycarboxylic acids such as di- or tricarboxylic acids, such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, or the like. Examples include esterification products in which a portion of the above is replaced with a monocarboxylic acid such as acetic acid, propionic acid, butyric acid, or benzoic acid.
Further, these carboxylic acids may be in the form of salts. Materials other than those mentioned above can also be used as long as they are soluble in the washing liquid and have film properties. In addition, if the oxygen permeability of these coating materials is low, the surface will harden rapidly during the exposure process and the adhesiveness of the formed sandblasting mask pattern layer will decrease, which is undesirable.From this point of view, cellulose with high oxygen permeability is Derivatives are preferred. Among these cellulose derivatives, carboxyl group-containing cellulose derivatives that have low hygroscopicity and are soluble in weak alkali aqueous solutions and surfactant aqueous solutions are preferred, and esters of cellulose and polycarboxylic acids and monocarboxylic acids are more preferred, especially esters of cellulose and polycarboxylic acids and monocarboxylic acids. Cellulose acetate phthalate is most suitable because of its easy availability. The thickness of this coating typically ranges from 0.1 to 10 microns. If it is thicker than this, the image reproducibility will deteriorate, and if it is thinner than this, it will be difficult to control the thickness in manufacturing, and pinholes will be more likely to occur. Preferred coating thicknesses range from 0.2 to 5 microns. Next, a photosensitive resin composition layer is provided on the protective film coating, and a supporting base material with a retaining layer provided thereon is placed so that the retaining layer is in contact with the photosensitive resin composition layer. Laminate on. Next, the transfer material of the present invention is obtained by performing imagewise exposure to actinic light through the transparent image carrier, removing the transparent image carrier, peeling off the protective film, washing out the unexposed areas, and drying. At this time, the thickness of the photosensitive resin composition layer provided on the protective film is usually in the range of 0.05 to 3 mm. If it is thinner than this, sufficient sandblasting resistance cannot be obtained, and if it is thicker than this, the resolution becomes poor, which is not preferable. In addition, examples of the active light source used for image exposure include arc lamps, mercury lamps, xenon lamps, fluorescent lamps, ultraviolet generators, and sunlight. The wavelength of the active light is in the range of 200 to 800 mμ, preferably 300 to 500 mμ. Furthermore, as a washing liquid for the unexposed area, for example, water, sodium hydroxide, sodium carbonate,
Alkaline aqueous solutions such as sodium carbonate oxide, sodium borate, sodium phosphate, sodium silicate, and triethanolamine; Examples include aqueous solutions of surfactants such as oxyalkylene glycol alkyl esters, sorbitan fatty acid esters, and polyoxyalkylene glycol sorbitan fatty acid esters. Further, drying is performed by blowing warm air or hot air, or by leaving it at room temperature. The mask transfer material for solid surface processing of the present invention has a mask pattern layer with a delicate design. No detachment occurs, and the mask pattern layer can be transferred to the substrate to be processed without any damage. EXAMPLES Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples in any way. Example 1 Cellulose acetate phthalate was dissolved in methyl ethyl ketone/cellosolve acetate mixed solvent (weight ratio 6/
1) and coated it on a 22μ thick polypropylene film using a bar coater to obtain a polypropylene film having a 2μ thick cellulose acetate phthalate film. This is called film A. In addition, ethyl cellulose was dissolved in methyl ethyl ketone, and this was coated on a 75μ thick polyester film using a bar coater.
A polyester film having an 8μ thick ethylcellulose layer was obtained. This is called film B. Furthermore, 39 parts by weight of polypropylene glycol adipate diol (number average molecular weight 2500), polypropylene glycol (with a total of 10 weight % of ethylene oxide added to both ends, number average molecular weight
2500) and 6 parts by weight of toluylene diisocyanate were reacted to obtain a polyurethane having isocyanate groups at both ends. This was reacted with 15 parts by weight of 2-hydroxypropyl methacrylate to obtain an unsaturated polyurethane having methacrylate groups at both ends. To this unsaturated polyurethane, 20 parts by weight of polypropylene glycol monomethacrylate (number average molecular weight 550), 3 parts by weight of diethylene glycol dimethacrylate, 2,2-
1.5 parts by weight of dimethoxyphenylacetopheenone,
0.1 part by weight of 2,6-di-t-butyl-p-cresol was added and mixed to obtain a liquid photosensitive resin composition. Next, a positive film was placed on a glass plate having a thickness of 10 mm, and the positive film was covered with the film A so that the cellulose acetate phthalate film was exposed. Furthermore, a Teflon spacer with a thickness of 0.3 mm was placed, and the liquid photosensitive resin composition prepared as described above was poured into the spacer. Next, the film B was laminated so that the ethyl cellulose membrane was in contact with the photosensitive resin composition layer, and a 10 mm thick glass plate was placed thereon and the four ends were fixed with clips to control the thickness. The structure obtained in this way was placed 50 cm from a 2KW high-pressure mercury lamp, and a positive film was passed through it.
Exposure was made for 80 seconds. Next, the glass plate was removed, and the film A that was in contact with the positive film was peeled off. At this time, there was almost no peeling resistance, and even a small portion of the cured resin did not come off. Next, a 2% by weight surfactant (Lipon F, manufactured by Lion Corporation) aqueous solution was added.
By spraying for 150 seconds at a pressure of 0.8Kg/ ^cm2 ,
The unexposed photosensitive resin composition was washed out. At this time, the cured resin did not come off. then 60
A sandblasting mask transfer material was obtained by drying at ℃ for 10 minutes. Next, this transfer material was adhered to a glass plate having a thickness of 7 mm, and the polyester film of film B was peeled off. At this time, there was almost no peeling resistance. Next, using a siphon-type sandblaster, we sprayed random #180 as an abrasive over the entire surface at an air pressure of 3.5 kg/cm ² for 30 seconds to engrave the mask.The mask did not separate from the glass and the desired pattern was achieved. was able to engrave. Example 2 As film B in Example 1, a 4μ thick cellulose acetate butyrate film was coated with a 120μ thick film.
A sandblasting mask transfer material was prepared in exactly the same manner as in Example 1, except that it was provided on a thick polyester film. Next, in the same manner as in Example 1, the transfer material was attached to a glass plate and sandblasted.
I was able to engrave the desired pattern. Comparative Example In place of the film B in Example 1, a 10μ thick polymethacrylic acid methyl ester coating was provided on a 75μ thick polyester film, and a 75μ thick polyester film without this retaining layer was used. An attempt was made to create a sandblasting mask transfer material in the same manner as in Example 1, but in both cases, during the uncured resin development process, the cured resin material in the form of small dots and lines forming the pattern was detached from the film. However, I was unable to obtain the desired pattern.

Claims (1)

[Scope of Claims] 1. A solid surface processing method comprising a holding layer made of a water-insoluble cellulose derivative on the surface of a supporting base material, and a mask pattern layer formed by curing a photosensitive resin composition on top of the holding layer. Mask transfer material. 2. The transfer material according to claim 1, wherein the water-insoluble cellulose derivative is an alkyl cellulose or an ester compound of cellulose and a monocarboxylic acid.