JPS5825304A - Light-insolubilizable resin and its production - Google Patents

Abstract

PURPOSE:To produce a light-insolubilizable resin which shows a high sensitivity at a low level of photosensitive groups introduced and is soluble in any organic solvent, by reacting specified photosensitive PVA or partially saponified PVAc with a carboxylic acid halide or an aldehyde. CONSTITUTION:PVA or partially saponified PVAc having a photosensitive residue of the formula, wherein m is an integer of 1-6, n is 0 or 1, R is H, methoxy or ethoxy and A is an aromatic, quaternized nitrogen-containing heterocyclic residue, is reacted with a carboxylic acid halide or an aldehyde. Thus, at least about 30mol% of the OH groups of the PVA or partially saponified PVAc are replaced with acyl or acetal groups. The photosensitive resin thus produced shows a high sensitivity at a markedly low level of photosensitive groups introduced and is light-insolubilizable.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photoinsoluble photosensitive resin in which the photosensitive group exhibits extremely high sensitivity to raw eel, and a method for producing the same.

Photosensitive resin is printing plate manufacturing material, 7# etching, 7t
It is used as a 7# resist for Tomilling, etc., and as a photosensitive vehicle for paints and printing inks. Until now, photosensitive resins have been used with Y' photosensitive groups such as azide groups, cinnamoyl groups, acryloyl groups,
i: m C->h-c "6"・In order to obtain sensitivity without any practical problems, these photosensitive groups should be introduced into the base polymer in as large a quantity as possible; Mixing sensitizers is practiced.

Looking at the most representative photosensitive resin, cinnamo vinyl, we find that in order for this resin to be put to practical use, it is essential that a large amount of the photosensitive group cinnamoyl be introduced ( M., J., Poly.

Sai, A, 2, 290) (1964)), and about 1% of sensitizer must be mixed. This fact brings to light the following two problems. First, the proportion of photosensitive groups is extremely high, and the price of the resulting resin is largely controlled by the raw material for the photosensitive groups, so the selection of photosensitive groups is limited from economic considerations.

2nd Ks Various physical properties of the photosensitive resin obtained, for example,
Inspectability of the substrate, developability, chemical resistance, printability, etc.
In order to reflect the properties of the material used, photosensitive resins must be selected and manufactured by trial and error each time depending on the purpose. Now that photosensitive resins are being used in large quantities in many different fields, it is easy to predict the properties of photosensitive Im resins from the physical properties of the basic polymer, and to create PM resins that suit the purpose through so-called molecular design. Needless to say, it would be extremely useful if it could be manufactured. In order to solve the above-mentioned problems, the ratio of photosensitive groups in the backbone polymer can be significantly reduced to such an extent that the effect on the physical properties of the backbone polymer can be completely ignored. However, in reality, even if the rate of introduction of some of the above-mentioned photosensitive groups is significantly reduced by 1, the sensitivity will be drastically reduced, or even the photosensitivity will not be exhibited at all.

According to JP-A-56-5761, JP-A-56-5762, and JP-A-56-11906, when polyvinyl alcohol is introduced with a photosensitive group having a styryl quaternary salt beak, the introduction rate is It has been reported that it exhibits high sensitivity at an unprecedentedly low value. It is inferred that this is because these photosensitive groups have an associative property (Fukuzai, Watanabe, J.
Poly, Rai.

(See Poly, L.tt., 1B, 613 (1980)). However, the photosensitivity thus obtained was 4! ! Fats are highly hydrophilic, and developing solutions are limited to water, solvents, and water-containing organic solvents.

The present inventor believes that if styryl quaternary residues, which are woody residues, are inherently easy to associate with, the basic zt' IJ mom-
It is not hydrophilic like polyvinyl alcohol′,
It was concluded that a highly sensitive and photosensitive molecule with a significantly reduced photosensitive group introduction rate could be obtained even if it was hydrophobic. In this case, K14WC basically controls the solubility of the hydrophilic residue and the hydrophobic backbone polymer that binds it.
The ratio is a very important factor. As a result of conducting extensive research from this viewpoint, the present inventors have come to produce a photosensitive resin that is soluble in any organic solvent and can be developed using the same.

That is, the present invention provides general formula (T) represents an aromatic quaternized 1! elemental residue.
Moru no Mizut! ! The present invention provides a photosensitive resin characterized in that it is composed of a polyvinyl alcohol S zero whose group is substituted with an acyl group or an acetal group.

In this general formula (T), A in 8 is an aromatic heterocycle or a heterocyclic ring containing a quaternized nitrogen atom as a constituent unit, but is not limited thereto. These rings may be substituted with a methyl group, an acyloxy group or a water group. Further, the 1-substituent in these quaternized atom rings can include, in addition to a hydrogen atom, a γ-alkyl group or an aralkyl group.

The photosensitive resin of the present invention has polyvinyl alcohol as its main structure, and contains the structural unit represented by the general formula (1) and other structural units 1, that is, vinyl alcohol units, vinyl acetate units, and acyloxy groups or acetal units. The ratio to the sum is 0 to α3:9a'y to 51o:s and (K
LO: 9 & O ~ 3i0: 9'7.0 range long - or
Or, if the insolubilized state does not have enough practical strength and the proportion of a certain structural unit exceeds the above, the viscosity of the resin will increase significantly or the gel ratio will increase. Mainly 1. "・Width 119.゛Difficult to use" [1] In the ratio of the constituent units other than the constituent units represented by the general formula ((), the proportion of vinyl alcohol units is particularly high in the present invention. The solubility of the resin greatly affects the sound, so it is l1kv.If the ratio is less than about 60 arcs, it becomes insoluble in water and dissolves in various organic solvents.As the content decreases, the amount of organic solvent that dissolves - For example, if the acetal unit has butyral, as the molar capacity decreases by 1 vinyl alcohol, the most suitable solvents are alcohol, acetone, 60 form, It can be changed like dioxane.

Acetal or acyloxy units are photosensitive in the present invention!
M is a part that plays a role in controlling the solubility and sieving properties of fat, but if the ratio is 20 moles or more, it becomes insoluble in water and becomes soluble in organic solvents alone. It is known that acetalization to polyvinyl alcohol does not proceed quantitatively and that there is a theoretical upper limit, but even in the resin of the present invention, all vinyl alcohol units cannot be converted to acetal units. However, it is not necessary.

As described later, the vinyl acetate unit is present in the case where the starting material of the photosensitive resin of the present invention is water-soluble polyvinyl alcohol or partially saponified polyvinyl acetate, and the proportion thereof is 0 to 30 mol. within attack range.

The photosensitive polymer of the present invention is disclosed in JP-A-36-5761, JP-A-55-57'62, and JP-A-56-11906.
Acylation and acetalization of a photosensitive polyvinyl alcohol derivative represented by the general formula (1) (in the formula, m, m, a, and R have the same meanings as above) obtained by the method described in No. It can be produced by reaction. The manufacturing method will be explained below.

The acylation reaction of the photosensitive vinyl alcohol derivative of general formula (1) can be carried out in the same manner as in the case of polyvinyl alcohol. In other words, the photosensitivity achieved by one general formula (setting)! It is pyridine, dimethylformamide 1
It can also be dissolved in polar solvents such as dimethyl hydroxide.
II Make it cloudy, and carboxylic acid is good for garlic. The reaction temperature is preferably from room temperature to about 100°C, and the reaction time is preferably 1 to 40 hours.

The acylating agents used include esteryl chloride, monochloride,
Examples include, but are not limited to, chlorides such as pionyl and benzoyl chloride, and acid anhydrides such as acetic anhydride and benzoyl anhydride.

Alternatively, a mixture of these may be reacted.

The amount of the acylating agent (1) is desirably in a molar range equivalent to about 5 times the calculated amount per vinyl alcohol unit of the photosensitive vinyl alcohol island conductor represented by the general formula (It).

The acetalization reaction of the photosensitive gelvinyl alcohol derivative of general formula (0) can be carried out in the same manner as in the case of polyvinyl alcohol. In other words, a photosensitive resin prepared by the general formula (■) is made into an aqueous solution, and m as a catalyst is added to this solution.
is added to react the aldehyde. The reaction product will precipitate - this can be separated and washed. In this case, following the reaction for producing the photosensitive vinyl alcohol derivative of general formula (1), the photosensitive resin of general formula (11) is produced using the photosensitive vinyl alcohol in a homogeneous system. death,
There is no problem even if it is subsequently acetalized. Alternatively, a product dissolved in the organic solvent can be obtained by suspending the photosensitive resin represented by the general formula (11) in an organic solvent and adding a catalytic acid and an aldehyde thereto for reaction. The organic solvents used at this time include ^rogenated carbons such as methylene chloride and dichloroethane, benzene,
Aromatic hydrocarbons such as toluene are used. reaction temperature t
Range 1 from room temperature to 100℃! #Preferably, the reaction time is about 1 to 40 hours.

Examples of aldehydes that can be used include, but are not limited to, aliphatic aldehydes such as 1-inch acetaldehyde, 10-butyraldehyde, 1-butyraldehyde, hexylaldehyde, and nonylaldehyde. Examples of the aromatic aldehyde include, but are not limited to, benzaldehyde, various substituted benzaldehydes, 7-enyl acetate [%-dehyde], and the like. Moreover, it is also possible to react as a mixture of these. These aldehydes are photosensitive polyvinyl γ represented by the formula -1 The photosensitive polymer of the present invention is soluble in a wide range of organic solvents, and the content of 1 and 1 in the photosensitive screen is small and 1 [4] It shows high sensitivity. In order to exhibit sensitivity comparable to that of the other materials, it is sufficient to introduce only about 1 mol % of photosensitive IE.

As described above, the photosensitive polymer of the present invention exhibits sufficiently high photosensitivity with an extremely low photosensitive group introduction rate and without using any sensitizer, and is thus excellent in economical efficiency. Furthermore, since the inner group other than the photosensitive group unit and its beak formation ratio can be arbitrarily changed, it has the advantage that a photosensitive polymer having desired physical properties can be produced.

Therefore, the uninvented photosensitive 4 molecules can be used as a printing plate material, 7r
Photo-curing of image-forming materials such as photoresists, inks, paints, and other photosensitive vehicles! It is useful in a wide range of fields such as 9-grain cutting.

Next, the non-invention will be further explained to KIN using examples. , this V
c314"F'1i-', i °1.-Methyl-4-(2,2-dimethoxyethoxy)
After that, 1 NO of 85% phosphoric acid was added to this solution, and the mixture was stirred at 90° C. for 24 hours. When 5d of butyraldehyde was added to the thus obtained water-soluble photosensitive resin solution eoosw and stirred at 40-50°C for several hours, precipitation occurred. By washing this with water and drying it, a photosensitive resin 5 soluble in methyl alcohol and methyl cellosolve 1DMa is prepared.
Got to 3 towns. This resin was dissolved in methyl alcohol and coated on an aluminum plate, exposed for 5 seconds with a canon lamp, and developed with methyl 74 soap. The resin was insolubilized to 7 to 8 stages with Kodak Step Food Predet. This corresponded to about 8 times the sensitivity of a commercially available polycinnamon-vinyl photosensitive resin (TPR).

Example 2 Polyvinyl alcohol containing styrylquinolinium and 8 moles of LI groups obtained in the same manner as in Example 1 was reprecipitated into 177 tons and purified and dried. This resin 50011P was suspended in 1 ocd of L2-dichloroethane, and 60
2F of benzaldehyde and 221 of concentrated salt solution were added and stirred at room temperature for 24 hours. The reaction mixture was reprecipitated in ethanol, and the reaction product was separated, thoroughly washed with ethanol, and dried. This was dissolved in PLz-dichloroethane, placed on an aluminum plate with KIk cloth, and exposed to a xenon lamp.
It became insolubilized up to 6+9 in seconds.

Example 3 Polyvinyl alcohol containing L4υ moles of 1-methyl to styrylpyridinium groups (Ik degree 1700)
Whole goat LooI was suspended in pyridine and dried in vacuo to obtain a resin soluble in chloroform. The product thus obtained was about 5 times more sensitive than TePRK.

Example No. Example 344 - In place of anhydrous vinegar, 2I benzoyl chloride was used and the mixture was stirred for 24 hours. The reaction product was reprecipitated in ethanol, redissolved in chloroform, and then reprecipitated in ethanol. A photosensitive f#I fat was obtained by vacuum drying.

It was dissolved in L8-dichloroethane and coated on an aluminum plate, and the sensitivity was determined to 111I. As a result, it showed a sensitivity that was almost the same as that of TPR.

Claims (1)

[Claims] (1) General formula (S in the formula represents an integer from 1 to 6 and represents n#'io or 1. RFi represents a hydrogen atom - methoxy, ethoxy group, Aromatic quaternized nitrogen-containing unit represented by 111 is a photosensitive unit, and at least 30 moles of water is replaced by an acyl or acetal region from a yQ vinyl alcohol conductor. (2) The photosensitive tltMO according to claim 1, wherein the photosensitive unit has α3 to 5 molar groups (8) Aromatic quaternized nitrogen-containing nitrogen II4 is the general formula (in the formula, R represents a hydrogen atom, an alkyl group, or an aralkyl group, z; i is an atomic group forming aromatic TI4, and all benzene may be condensed <, xh strong The photosensitive resin according to claim 1, which is an IIU group which is anion of f!!
The photosensitive resin according to claim 1, which has a molecular weight of 0 to 3,000. (5) Kiribinyl alcohol or partially saponified polyvinyl acetate, which has a chemical residue represented by the general formula (Illll, R, A#i has the same meaning as above), is converted into a carbide halide or aldehyde. A method for producing a photosensitive 4!1 fat according to claim 1, which is characterized by reacting with ◎