JPH0431406A - Production of photocurable resin - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) This invention relates to a method for producing a resin that is cured by light to form a transparent film.

(Prior Art) A resin that is cured by light to form a transparent film is known as a photocurable resin.

JP-A-58-199342 describes the use of a copolymer of a hydroxyl group-containing monomer and a nitrogen-containing monomer as a photocurable resin. The copolymer is produced by dissolving a nitrogen-containing monomer represented by the general formula as a hydroxyl group-containing monomer in an aqueous solvent, adding acetic acid, and copolymerizing with a water-soluble polymerization initiator. , a method for producing a photocurable resin. However, R, N R2, and R3 are all R,
OR.

It includes a compound represented by the general formula /R-5 R,0 or as a nitrogen-containing monomer. Here, horse represents HXCH8 or C2H5, and n is 1-3
represents an integer of , R3 represents H or cHs, and X represents 0
or NH, R4 represents an alkylene group having 2 or 3 carbon atoms, and R5, R6, 几 represent H or 1 carbon number.
- represents four alkyl groups, and Y represents an acid group.

JP-A-58-199342 discloses that the above copolymer contains a hydroxyl group-containing monomer in a proportion of 20-70% by weight and a nitrogen-containing monomer in a proportion of 5-80% by weight. It stipulates that there must be. Additionally, the above publication states that in order to use the above copolymer as a photocurable resin, the copolymer should first be prepared and then used by dissolving it in water or other solvent. There is. Moreover, the above-mentioned publication merely teaches that copolymerization is carried out using an organic solvent such as cellosolve, amide, or ether to produce a copolymer.

However, the teaching of this publication had a drawback.

Its biggest drawback is that an organic solvent must be used during copolymerization. Organic solvents such as cellosolve are harmful to the human body, so when performing copolymerization,
Special care was required to ensure that the health of workers was not compromised, and production equipment also required special measures to recover solvents and treat waste liquids. This has made implementation according to this teaching costly. Furthermore, this teaching was cumbersome in that an organic solvent was used during copolymerization, and it had to be redissolved in water or other solvent during coating.

The reason why organic solvents have traditionally been used exclusively in copolymerization is that the resulting copolymers are poorly soluble in water, so copolymerization in an aqueous solvent can generate turbidity and insoluble matter. ,
This is because, in extreme cases, precipitation and phase separation occur, making it impossible to obtain a uniform copolymer. This is because if the copolymer is not uniform, the photocurability will be uneven and the photocurable resin will not be of good quality.

(Problems to be Solved by the Invention) This invention does not use an organic solvent as the main solvent when making a resin, but instead uses a non-toxic aqueous solvent, and the resulting aqueous solution of the copolymer is This was done in an attempt to make it usable as a photocurable resin as it is.

(Means for Solving the Problem) The inventor decided to select and copolymerize a specific hydroxyl group-containing monomer and nitrogen-containing monomer taught in JP-A-58-199342, Furthermore, we have found that by using an aqueous solvent to which acetic acid has been added, copolymerization can be carried out to the end while the obtained copolymer remains dissolved, and therefore, a uniform copolymer can be obtained using an aqueous solvent. Moreover, this inventor has discovered that by doing the above,
It has been found that the copolymerization ratio is not limited to the blending ratio of monomers as specified in Japanese Patent No. 199.342, but can be set to a wider range of copolymerization ratios. This invention was made based on such knowledge.

(Summary of the Invention) This invention involves dissolving a hydroxyl group-containing monomer represented by the formula % in an aqueous solvent and a smaller amount of a nitrogen-containing monomer represented by the general formula or The gist of the present invention is a method for producing a photocurable resin, which is characterized by adding sulfuric acid and copolymerizing it with a water-soluble polymerization initiator.

Here, R1, H and R8 all represent H or CH, Melon represents (& or O, &, and X represents halogen.

(Explanation for each requirement) All hydroxyl group-containing monomers represented by [Formula 1] are water-soluble. Therefore, this monomer can be dissolved in water for polymerization. Specific examples of this monomer are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

The nitrogen-containing monomers represented by [Formula 2] and [Formula 3] also
All are water soluble. Therefore, this monomer can also be polymerized by being dissolved in water. Among these, specific examples of monomers belonging to [Formula 2] include dimethylaminopropylacrylamide and dimethylaminopropylmethacrylamide. Further, specific examples of the monomer belonging to [Formula 3] include acrylamidepropyltrimethylammonium chloride and methacrylamidepropyltrimethylammonium chloride, which correspond to the monomer chloride of [Formula 2] above.

In this invention, the monomer of [Formula 1] and [Formula 2] or [Formula 3]
] In copolymerizing with the monomer of [Formula 1], the monomer of [Formula 1] is used in a larger amount than the monomer of [Formula 2] or [Formula 3]. This is because the monomer of [Formula 1] needs to be present in a larger amount than the monomer of [Formula 2] or [Formula 3] in the resulting copolymer. These two types of monomers are copolymerized in coexisting proportions to produce a copolymer. That is, when the monomer of [Formula 1] is mixed in a proportion of 60% by weight and the monomer of [Formula 2] is copolymerized in a proportion of 40% by weight, they are copolymerized at the same proportion. A polymerized copolymer is obtained.

When trying to obtain a copolymer containing a particularly large amount of the monomer of [Formula 1], it is preferable not to add the monomer of [Formula 1] all at once, but to add it later. . Also,
The same applies when the concentration of the polymerization initiator is low. The reason is that in such a case, the viscosity increases during the polymerization process, and the entire aqueous solution tends to gel, so this is to be prevented.

In this invention, in addition to the monomers of [Formula 1] to [Formula 3], other monomers may be added to form a ternary or higher copolymer. Other monomers include dimethylacrylamide, N-
Vinylpyrrolidone, diacetone acrylamide, N-methylolacrylamide, methoxymethylacrylamide, ethoxymethylacrylamide, acrylic acid, methacrylic acid, acrylamide, methacrylamide, methoxymethylacrylamide, ethoxymethylacrylamide, acryloylmorpholine, glycerin monoacrylate, diethylene glycol mono(meth) ) acrylate, triethylene glycol mono(meth)acrylate, etc. can be used. Since these monomers are also water-soluble, they can be polymerized as an aqueous solution. The content of these other monomers in the copolymer should be 20% by weight or less.

In this invention, the above monomer mixture is dissolved in an aqueous solvent and copolymerized. An aqueous solvent is a solvent containing water as a main component. Accordingly, the aqueous solvent may consist of water alone, such as deionized water, or may contain a small amount of a water-soluble liquid.

The main feature of this invention is that acetic acid is added to the aqueous solvent. The entire amount of acetic acid may be added to the aqueous solvent from the beginning of the polymerization, or it may be added as the copolymerization progresses. Regarding the amount of acetic acid to be added, firstly, if the monomer of C formula 3] is large, the amount of acetic acid should be increased, and secondly, the amount of acetic acid should be increased to obtain a copolymer with a large amount of monomer of C formula 1]. Thirdly, when trying to obtain a copolymer with a high degree of polymerization, the amount of acetic acid is increased. The amount of acetic acid in the aqueous solvent is suitably 5 to 25% by weight.

Various types of water-soluble polymerization initiators can be used. For example, 2.21-azobis(N,N'
-dimethyleneisobutyramidine) dihydrochloride, 2.2
'-Azobis(2-amidinopropane) diconicate, 4
．． 4'-azobis(4-cyanopentanoic acid), 2.2'
-Azobis(2-methyl-N-[1,1-bis(hydroxymethyl)2-hydroxyethyl]propionamide, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide, 2 .2'-Azobis (
Inbutyramide) dihydrate, ammonium persulfate, etc. can be used. The amount of polymerization initiator is preferably 0.1 to 2% by weight based on the monomer.

In this invention, the monomer, acetic acid, and polymerization initiator may be added in any order. By heating the aqueous solvent to which these substances are added, copolymerization is promoted to obtain a copolymer. The appropriate heating temperature is 50 to 90°C, especially 6
0 to 80°C is preferred.

It is suitable that the heating time is several hours.

The copolymer is obtained dissolved in an aqueous solvent. Therefore, the product obtained in this invention is a viscous liquid. This liquid is usually clear, although it may be slightly colored. The coloring is, for example, pale yellow-red. This product has only a small amount of residual monomer. The amount of residual monomer is usually less than 1% by weight.

This product can be used as it is as a photocurable resin. When used as a photocurable resin, a diazo compound or an azide compound is added to the product, as taught in JP-A-58-199342. The solution thus obtained may be applied to the surface of a desired article, dried, covered with a masking material, and exposed to light. Then, the remaining single plate and acetic acid etc. will evaporate from the solution, and the copolymer will remain behind.The part that was irradiated with light will harden, and the part that was not irradiated with light will remain as it is. It is possible to treat it with a suitable solvent and leave only the hardened part. Therefore, this product can be used as it is as a photocurable resin.

The product obtained by this invention contains a copolymer consisting of a hydroxyl group-containing monomer and a nitrogen-containing monomer, so when a film is formed from it, the film is tough and easily colored by dyes. Become something. In particular, it is easily dyed with acid dyes. Therefore, this film can be colored and used as a photographic filter, a printing filter, an imaging element for a video camera, a color filter for a liquid crystal display element, and the like.

(Effect of the invention) According to the present invention, the water-edge group-containing monomer represented by [Formula 1] and a smaller amount of the nitrogen-containing monomer represented by [Formula 2] or C formula 3] are combined. By dissolving in an aqueous solvent, adding acetic acid to the aqueous solvent, and copolymerizing with a water-soluble polymerization initiator, the copolymerization can proceed without making the resulting copolymer N-soluble. Therefore, a copolymer solution with a uniform composition can be prepared. Since no organic solvent is used, there is no risk of harming the health of workers, and there is no need to pay particular attention to solvent recovery or solvent disposal, making it possible to produce copolymers with an advantage in safety. .

Furthermore, the obtained product is uniform and exhibits good photocurability, so it has a wide range of uses as a photocurable resin. In addition, the resin produced here contains a large amount of the hydroxyl group-containing monomer of [Formula 1] and a small amount of the nitrogen-containing monomer of [Formula 2] or [Formula 3], so it is strong as a film. It also has good stainability with dyes and is therefore suitable for making colored skin layers. Furthermore, since the product obtained by this invention contains only a small amount of residual monomer, acetic acid, and water in addition to the copolymer, the product can be directly applied to the surface of a desired article. Therefore, it is possible to form a film, and therefore it is convenient to use. This invention provides such benefits.

(Example) Examples and comparative examples will be given below to specifically clarify the advantages of this invention. In the following, parts simply mean parts by weight.

Example 1 2-Hydroxyethyl methacrylate dimethylaminopropyl methacrylamide methacrylamide 75 parts 2.2'-Azobis-(2-amidinopropane) dihydrochloride 0.8 acetic acid acid deionized water Four of the above mixtures were placed in a Lof flask. Place the mixture in a 75°C water bath, flush with nitrogen, and use a metering pump to cool the mixture for 40 minutes.
I was fed up with time. The mixture was further stirred for 4 hours. The liquid temperature was maintained at 72-73°C from the start of the addition until the end of the reaction.

The reaction product was a pale yellow-red transparent liquid.

When this was measured using a liquid chromatograph, the residual monomer concentration was 0.8% by weight of the charged amount. When the solid content of this reaction product was adjusted to 20% and the viscosity at 20"C was measured using a Brookfield viscometer, it was 280 cHp,
It was easy to apply.

A diazo resin was added as a sensitizer to this reaction product and used as a photocurable resist material as described below.

10 parts of the above reaction product were diluted with 15 parts of deionized water and filtered through a membrane filter with a pore size of 0.45 fim, followed by a membrane filter with a pore size of 0.20 μm. 0.2 parts of diazo resin was added to 20 parts of the solution thus filtered, and the mixture was uniformly dissolved using a shaker, and then passed through a filter with a pore size of 0.2 mm to obtain a photosensitive solution. Pour this photosensitive liquid onto a glass disk and apply 1500r
After spin footing at -p and m, prebaking was performed at 70°C for 8 minutes to obtain a photosensitive plate.

Layer a photomask on this photosensitive plate and use an ultra-high pressure mercury lamp to
It emitted light of mJ/cy1m. This was developed with water at 25° C. for 1 minute, dried, and then heat-treated at 130″C for 20 minutes.

After immersing this sample plate in a dyeing bath containing blue dye and having the composition shown below at 70°C for 3 minutes, washing it with warm water and drying it,
A clear blue image was obtained.

Composition of dyeing bath EIue5F (manufactured by Nippon Kayaku Co., Ltd.) 5 parts Deionized water (adjusted to pH 4 with acetic acid) 995 parts Comparative Example 1 In Example 1, Suimu was not used, and deionized water was added to 300 parts. The reaction was carried out in exactly the same manner as in Example 1 except for the following steps. Three hours after the monomer liquid was added, the reaction solution began to become cloudy, and after six hours, the solution became so viscous that it was difficult to stir, and became an opaque liquid.

Example 2 2-hydroxyethyl methacrylate) 6
5% 2-Hydroxypropyl methacrylate 10 Dimethylaminopropyl methacrylamide 15 Dimethylacrylamide 102.2'-Azobis-(2-amidinopropane) dihydrochloride
0.8 acetic acid
50 deionized water
250 The above mixture was added dropwise over 4 hours in the same manner as in Example 1, and stirred for an additional 4 hours to complete the reaction.

Although the reaction solution was slightly cloudy, no precipitate was observed even after it was left for one week.

Comparative Example 2 Example 2 was carried out in exactly the same manner as in Example 2, except that the vinegar sauce was replaced with water. It started to become cloudy 2 hours after starting to drop the monomer, and after 5 hours. became a suspension containing many lumps. When this was incubated overnight, it was separated into a sediment and a supernatant.

Example 3 2-hydroxyethyl methacrylate 88
Part methacrylamide propyltrimethylammonium chloride 10 Dimethylacrylamide 72.2 Hyazobis-(2-amidinopropane) dihydrochloride
0.8 acetic acid
5゜Deionized water
250 above - The mixture was treated and reacted exactly as in Example 1.

The reaction product is a slightly yellow transparent liquid with a solids content of 2
The viscosity at 20° C. at 0% was 315 cp.

Claims (1)

[Claims] General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼A hydroxyl group-containing monomer represented by [Formula 1] and a smaller amount of the general formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ Formula 2] or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [Formula 3] Dissolve the nitrogen-containing monomer represented by the following in an aqueous solvent, add acetic acid, and copolymerize with a water-soluble polymerization initiator. A method for producing a photocurable resin, characterized by: However, R_
1, R_2, and R_3 all represent H or CH_3, R_4 represents CH_3 or C_2H_5, and
represents halogen.