JPS63284202A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which is easy of processing, capable of providing commercially available photosensitive resins with extensive physical properties and usable as a general-purpose resin for diverse applications, by mixing a specified methoxymethylated polyamide resin with a photosensitive vinyl compd. CONSTITUTION:The title photosensitive resin composition is obtained by mixing a methoxymethylated polyamide resin, which is obtained by methoxymethylating 10-50% of the amide bonds in a polyamide resin, with a photosensitive vinyl compd. (e.g. hydroxyethyl methacrylate, N-methylacrylamide, etc.). This photosensitive resin can provide commercially available general photosensitive resins with extensive physical properties, and can be used as a general-purpose resin for diverse applications. Since its viscosity changes with temp., it is easy of processing, and the resin of a low viscosity, mixed with a pigment, can be bonded to a resin in another color. Since the present product can be sliced or cut easily, it is made possible to tint specially designed articles. Moreover, a plastic surface, coated with the present product, can be improved in printing characteristics, solvent resistance and heat resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Industrial Application Field The present invention relates to a novel photosensitive resin composition.

(b) Prior Art Many photosensitive resin compositions have been known in the past, and their uses are wide-ranging.

The photosensitive resin composition refers to a composition that is polymerized and cured by irradiation with light, and includes azo compounds, azide compounds, acrylic compounds, and the like. These compounds do not require dispersion of a solvent or heating during curing, have adhesive properties with light, and can be used for optical image production and photomolding.

Due to the above-mentioned performance, photosensitive resin compositions have recently been used in adhesives, paints, electronic parts, printing plates, and the like.

(e) Problems to be Solved by the Invention In order to improve the processability of the above-mentioned photosensitive resins, special monomers or oligomers are used and adapted to a suitable system.

These monomers are generally expensive. Therefore, there are few products that can be used for multiple purposes like the current general-purpose resins.
Many of these are specialized resins with limited uses. This can be said to be limiting the expansion of applications for photosensitive resins.

Therefore, in the resin industry, there has been a desire to use photosensitive resins having such excellent properties for multiple purposes like general-purpose resins.

fdl Means to Solve the Problems In view of the above-mentioned current situation, as a result of intensive research, the present inventors have completed the composition of the present invention, which is characterized by the amide bond of the polyamide resin. The point is that one or more photosensitive vinyl compounds are mixed with a methoxymethylated polyamide resin in which 10 to 50% of the polyamide resin is methoxymethylated.

Here, the polyamide resin is so-called nylon, and includes not only the most common 6,6-nylon and 6-nylon, but also all polymers having an amide bond, such as 10-nylon and 8-nylon. , or one having a benzene ring as a part of the carbon molecular chain.

The degree of polymerization of this polyamide is not particularly limited and may be a general value.

Methylmethoxylation of an amide bond refers to replacing a hydrogen atom bonded to a nitrogen atom with a methylmethoxy group. An example in which 6-nylon is substituted is shown in formula [1].

+ (CH2) s N-Chr ...... [
1] CH20CH3 This method is simple, in which formaldehyde and methanol are added to polyamide resin and heated. However, the method of methoxymethylation is not limited to this method.

The degree of methoxymethylation is preferably about 10 to 50%, preferably about 15 to 40%. If it is less than 10%, the methoxymethylation rate often becomes uneven and the solubility becomes uneven. Methoxymethylation of more than 50% is generally difficult. The efficiency was highest at around 30%, and the compound itself was also excellent.

The photosensitive vinyl compound refers to a compound having an unsaturated double bond that has the property of polymerizing upon irradiation with light, and a hexamer having an acryloyl group or an allyl group as an active group is preferable. - by way of example, acrylic acid, methacrylic acid, acrylamide, methacrylamide or derivatives thereof, including 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate,
-Hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1.6 hexanediol di(meth)acrylate,
Methyl (meth)acrylamide, ethyl (meth)acrylamide, dimethyl (meth)acrylamide, methylol (meth)acrylamide, etc. can be used.

These 7-mers do not necessarily need to be directly soluble in the methoxymethylated polyamide, as long as they can be dissolved, dispersed, or kneaded in a mixed system. In other words, one type of 7-mers does not dissolve. Even if it is a monomer, it only needs to be dissolved as a whole when mixed with other monomers.

The invention originates from the discovery that methoxymethylated polyamide dissolves in these vinyl compounds.

Among them, hydroxyethyl methacrylate and N-
Methylacrylamide, N-(di)methylolacrylamide, etc. are suitable.

Furthermore, the photosensitive vinyl compound is used as a concept that includes not only monomers as described above but also oligomers and prepolymers. Moreover, not only one type of photosensitive resin but also a plurality of types may be mixed.

The mixing ratio of the methoxymethylated polyamide and the photosensitive vinyl compound varies depending on the ft and molecular weight of the photosensitive vinyl compound, but is usually 1:9 to 1:2. Preferably, the ratio is around 1:4.

It is of course possible to add additives that are mixed into ordinary photosensitive resin compositions, such as a polymerization initiator and a coloring agent, to the composition of the present invention.

Furthermore, resins other than methoxymethylated polyamide may be mixed with the composition of the present invention. Of course, it is a prerequisite that the above photosensitive vinyl compound is dissolved, dispersed or kneaded in the composition. These resins include acrylic resin,
Examples include vinyl acetate resin and polyamide resin.

It is also useful to add alcohols to the composition of the invention. For example, methanol, ethanol, propyl alcohol, benzyl alcohol, ethylene glycol,
These include glycerin and sorbitol. These improve the compatibility of the above compounds and with other substances, such as water,
Improve or express compatibility with proteins and others.

The first feature of the composition of the present invention is that its viscosity changes with temperature. The viscosity at room temperature increases as the molecular weight of the photosensitive vinyl compound itself increases, and when a low molecular weight photosensitive vinyl compound is used, it decreases as the mixing ratio of the photosensitive vinyl compound increases.

When the photosensitive vinyl compound is hydroxyethyl methacrylate and the mixing ratio is about 70%, high temperature (70~
At around 80℃), the viscosity is low and the viscosity is lower than that of starch syrup.
At room temperature or low temperature (-10 to +30°C), it has a very high viscosity and is agar-like.

This has the effect that it is easy to pour into a mold etc. at high temperature, and easy to mold at room temperature etc.

By this, when the viscosity is low, it can be roughly molded (such as by putting it into a mold), and when the viscosity is high, it can be molded more finely (easily cut, etc.).
(can be carved and sliced) and then cured after the shape is determined.

Furthermore, it is easy to mix in colorants when the viscosity is low, and by combining resins made separately from materials of different colors before curing, it is possible to create a one
It is possible to color different parts of two resin plates. Of course,
It may be colorless and transparent without using any colorant.

After the composition of the present invention is cured by ultraviolet rays, it can be further crosslinked by heat treatment. The heat treatment method involves adding an organic acid catalyst (citric acid, itaconic acid, etc.) in advance and preheating at about 70 to 80°C.
This can be easily carried out by processing at 120 to 150°C for about 10 to 20 minutes.

The composition of the present invention can be used to make conventional celluloid-like materials and denko-like materials because of the ease of coloring described above.

In addition, since it has a certain degree of shape retention before it is completely cured, it is possible to examine and confirm the shape before it is completely cured. This application can also be applied to printing plates and the like.

Furthermore, since it can be cured only with light and there is no need to evaporate solvents, it is also useful as an adhesive. It can be used to bond various things such as bases, wooden products, and metals. When used as an adhesive, the composition can be simply applied to the surface to be adhered and irradiated with light or the like, so it has the advantage of being very simple and requiring a short curing time.

The resin composition of the present invention can be applied to the surface of plates and foams, which are processed products of general-purpose thermoplastics that are sensitive to heat and solvents, or paper and cloth, to create surface smoothness, drawing and printing. For example, it is usually not possible to draw on the surface of items made of Styrofoam, nor can the Styrofoam itself be glued. because,
This is because styrene dissolves in ink solvents, adhesive solvents, etc., and because it melts due to heat. After coating and curing the resin composition, drawing is possible because it does not dissolve in a solvent, and it can also be easily bonded by simply applying water.

Furthermore, since Styrofoam and the like are made of bead foam, they have a structure in which many independent foam bodies are fixed together. Therefore, the surface smoothness is inherently poor.

However, after the composition of the present invention is applied and cured, it becomes very smooth.

Styrofoam is normally difficult to adhere to, but by using the composition of the present invention, plastic sheets, etc. can be easily adhered to, and Styrofoam can be used in fields where it could not be used conventionally due to its low surface hardness. For example, insulation containers that require hardness, simple structures, simple buildings, etc.

In addition, in the case of conventional photosensitive resins, their viscosity is low before curing, making it difficult to mold them into three-dimensional shapes, but with the composition of the present invention, the viscosity at low temperatures can be made extremely high, resulting in three-dimensional molding. It also has a very remarkable feature in that it is easy to mold.

Furthermore, in the composition of the present invention, since the photosensitive resin itself can be appropriately blended with a commercially available 7-mer, it is easy to adjust the viscosity, improve processability, and improve various other physical properties. It can be used as a general-purpose resin.

The composition of the present invention is cured in the same manner as ordinary photosensitive resins, and is easily cured by irradiation with light, ultraviolet rays, electron beams, etc.

(e) Actual example [Example 1] 20 parts by weight of a polyamide resin in which 30% of the amide groups were methoxymethylated was dissolved with stirring in 80 parts by weight of hydroxyethyl methacrylate at a temperature of 75°C, and 1 part by weight of benzoinethyl was dissolved. Ether was added to obtain a colorless and transparent resin liquid.

This material was poured into a pool-like liquid reservoir formed on a glass plate, and cooled at room temperature of 20° C. to obtain a solidified agar-like transparent solid. This solid was cut into an arbitrary shape, sandwiched between two polyester films, and exposed to a 370 nm ultraviolet fluorescent lamp at a distance of 3C11 for 3 minutes to produce a cured resin.

[Example 2] 20 parts by weight of a polyamide resin in which 25% of the amide groups were methoxymethylated, 60 parts by weight of hydroxyethyl methacrylate and 20 parts by weight of methylolacrylamide,
8 in a solvent mixed with 20 parts by weight of N-methylacrylamide.
The mixture was stirred and dissolved at a temperature of 0° C., and 1 part by weight of 2·-hydroxy-2-methyl-1-phenylpropane was added to prepare a colorless and transparent resin composition. This material was sandwiched between polyester resin films, spread, and exposed in the same manner as in the above example to obtain a colorless and transparent rechargeable film.

[Example 3] Commercially available polymethacrylic acid resin 5f was added to the resin composition of the above example! A certain amount was added, melted at a temperature of 80°C, poured into a reservoir frame made of a glass frame on a glass plate to a depth of 10 cm, and exposed for 30 minutes in the same manner as in the above example.
A hard and transparent resin block with a thickness of 10 m++ was obtained.

[Example 4] 10 parts by weight of methyl alcohol was added to the resin composition of Example 1 above, and the mixture was sandwiched between two polyester films.
The resin sheet was spread to a thickness of 1 mm and exposed in the same manner as in the above example to obtain a soft transparent resin sheet with a thickness of 1 mm.

[Example 5] A citric acid ester of polyethylene glycol having an average molecular weight of 400 was obtained by stirring and dissolving 20 parts by weight of 28% of the amide groups of a polyamide resin in 80 parts by weight of hydroxyethyl methacrylate at a temperature of 80°C. 20ft of diacrylate! ) part was added, sandwiched between polyester films, and rolled out to obtain a resin composition having a thickness of 111 mm, with both front and back sides sandwiched between polyester films.

A photographic negative film for plate making was adhered to one side of this material, and a 40 second exposure was performed using a 400 W high pressure mercury lamp at a distance of 25 cm from the side on which the photographic negative film was not adhered, and for 2 minutes from the photographic negative film side. After exposure, the resin was taken out and washed with soapy water to obtain a resin relief plate that reproduced the image of the photographic negative film.

[Example 6] After methoxymethylating 33% of the amide groups of a polyamide resin, 25 parts by weight were dissolved in 75 parts by weight of N-methylacrylamide with stirring at a temperature of 75°C, and 1 part by weight of 2-hydroxy-2 -Methyl-1-phenylpropane was added to obtain a colorless and transparent resin liquid.

This material was applied to the surface of a styrofoam plate, and Example 1
It was exposed in the same way. When hydroxyethyl methacrylate is used instead of N-methylacrylamide, it is better to attach a polyester film or the like to the surface to block air since polymerization is inhibited by air.

This Styrofoam board has very good printing and drawing properties.

(f) Effect of the invention According to the present invention, there are the following major advantages.

(1) A wide range of physical properties can be imparted using a commercially available general photosensitive resin, and it can be used for many purposes as a general-purpose resin.

(2) Since the viscosity changes depending on the temperature, it is very easy to process.

(3) Pigment is mixed into resin with low viscosity, and it is easy to adhere to other colored resins and to slice, cut, etc.
This makes it possible to create special designs, instep patterns, and other special colors that cannot be achieved with conventional plastics.

(4) Printing properties, solvent resistance, and heat resistance can be improved by coating and curing the plastic surface.

(5) Since plastic sheets and the like can be easily adhered to polystyrene foam, the uses of polystyrene foam are greatly expanded.

(6) It possesses all other advantages that ordinary photosensitive resins have.

Claims (1)

[Claims] 1. A methoxymethylated polyamide resin in which 10% or more and less than 50% of the amide bonds of the polyamide resin are methoxymethylated, and one or more photosensitive vinyl compounds are mixed therein. Photosensitive resin composition. 2. The photosensitive resin composition according to claim 1, which contains a photoreaction initiator. 3. The photosensitive resin composition according to claim 1 or 2, which further contains another resin. 4. The photosensitive resin composition according to claim 1, 2 or 3, which further contains alcohol. 5. The photosensitive vinyl compound is hydroxyethyl (meth)
The photosensitive resin composition according to claim 1, which is acrylate, methyl (meth)acrylamide or methylol (meth)acrylamide.