JPH0710795B2 - Acrylic acid or methacrylic acid ester of 2,2-dimethylolcarboxylic acid - Google Patents

Description

FIELD OF THE INVENTION This invention relates to compounds useful as crosslinkers for UV resists.

2. Description of the Related Art In recent years, in the field of UV resists, a developing method that does not use organic solvents, that is, a developing method using alkaline water as water is desired in order to improve workability and working environment. Neopentyl glycol diacrylate, trimethylol propane triacrylate, pentaerythritol tri- or tetra-acrylate and the like are used as a UV resist cross-linking agent which can be developed with water or alkaline water.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention All of the conventionally used compounds have high hydrophobicity, and when used as a mixture with a base resin which is a main component of UV resist, they are ubiquitously distributed in the hydrophobic portion of the base resin, The effective crosslinking reaction may not occur. Further, since these compounds have poor water solubility, they are not necessarily preferable for the water phenomenon and alkaline water development.

The present invention can exhibit uniform dispersibility in the base resin
The present invention provides a compound useful as a crosslinking agent for UV resist.

Means for Solving the Problems The present invention relates to the formula (I) used as a crosslinking agent for UV resists. (In the formula, R is alkyl having 1 to 3 carbons and Y is acryloyl or methacryloyl) [hereinafter referred to as compound (I). The same applies to compounds of other formula numbers].

Compound (I) can be obtained by various methods as described below. That is, the formula (II) (Wherein R has the same meaning as defined above),
If necessary, in an inert solvent, 1) reacting with acrylic acid or methacrylic acid in the presence of an esterification catalyst if necessary, 2) reacting with acryloyl chloride or methacryloyl chloride in the presence of a base if necessary Method 3) A method of reacting an acrylic acid ester or a methacrylic acid ester in the presence of a suitable catalyst (transesterification reaction).

Inert solvents include benzene-based solvents such as benzene, toluene and xylene, halogenated lower alkanes such as methylene chloride, chloroform and carbon tetrachloride, lower alkyl esters of lower alkanoic acids such as ethyl acetate, acid amides such as dimethylformamide, Common solvents such as ethers such as ethyl ether and tetrahydrofuran are included, but benzene solvents, dimethylformamide, ethyl acetate and the like are particularly preferable.

Acrylic acid or methacrylic acid can be used as the solvent in the method 1), and an acrylic ester or methacrylic acid ester can be used as the solvent in the method 3) and a base as the method 2).

Next, the method 1) will be described in more detail. The esterification catalyst includes a mineral acid such as sulfuric acid, hydrochloric acid and phosphoric acid, and a sulfonic acid such as paratoluenesulfonic acid. It is preferable to use acrylic acid or methacrylic acid in an amount of 1 to 20 equivalents, particularly 2 to 5 equivalents, relative to compound (II). However, this is not the case when the latter is also used as a solvent.

The catalyst concentration in the reaction solution is preferably 0.1 to 10% by weight, more preferably 0.1 to 2% by weight. The reaction is usually carried out at 50-100 ° C,
Finish in 5 to 24 hours.

After completion of the reaction, the catalyst is neutralized, unreacted acrylic acid or methacrylic acid is distilled off, and then the compound (I) is obtained by recrystallization or column chromatography.

In more detail about method 2), the base includes pyridine, triethylamine and the like. The base is a compound (I
It is preferable to use 1 to 30 equivalents, particularly 1 to 5 equivalents, and an excess of the acid chloride with respect to I). However, this does not apply when a solvent such as pyridine is used as the solvent. Acryloyl chloride or methacryloyl chloride is a compound (I
It is preferable to use 1 to 5 equivalents, especially 1 to 1.5 equivalents, relative to I). The reaction is usually performed at 0 to 20 ° C for 3 to 24 hours.

After completion of the reaction, the solvent is distilled off, the compound (I) is released from the base addition salt of the compound (I) by acid treatment, extracted with diethyl ether or the like, concentrated and crystallized to obtain the compound (I).

The method 3) will be described in more detail. The transesterification catalyst includes a mineral acid such as sulfuric acid, a sulfonic acid such as paratoluenesulfonic acid, a metal alkoxide such as tetra-n-butoxytin and tetra-n-butoxytitanium. The catalyst concentration in the reaction solution is preferably 0.5 to 5% by weight. Acrylic acid esters and methacrylic acid esters include lower alkyl esters such as methyl ester, ethyl ester, n-butyl ester and the like. The use of methyl ester is particularly preferable because the equilibrium can be shifted by distilling off the produced methanol. The amount of these esters used is appropriately 1 to 10 equivalents relative to compound (II).
The reaction is usually carried out at 70 to 120 ° C. for 5 to 24 hours.

In the case of an acid catalyst, after neutralization or in the case of a metal alkoxide, it is decomposed by adding water, extracted with diethyl ether or the like, concentrated, and then recrystallized or subjected to column chromatography to obtain a compound (I).

In any of the above methods, it is desirable to add a polymerization inhibitor to the system in order to prevent the compound (I) from polymerizing during the reaction or purification. Such polymerization inhibitors include general polymerization inhibitors such as hydroquinone, cidroquinone monomethyl ether and phenothiazine, and are present in the reaction solution and / or the purified solution in an amount of 100 ppm to 5% by weight.

The compound (I) can be used as a crosslinking agent for a negative type UV resist. As the base resin, a homopolymer or copolymer prepolymer such as acrylic acid ester, methacrylic acid ester, polyester, epoxy resin or polyurethane having a reactive double bond, which is commonly used for UV resists, is used. When compound (I) is mixed with such a base resin and irradiated with ultraviolet rays, the cross-linking agent connects the prepolymers with each other by the bonds between the double bonds to make them prepolymerized and insolubilized.

Since the compound (I) has a hydrophobic part and a hydrophilic part (carboxyl group) in the same molecule, it can generally maintain sufficiently good dispersibility in the base resin. In addition, the carboxyl group-free form is partially neutralized or fully neutralized with, for example, an organic amine (triethylamine, etc.) to improve the solubility in water, or by changing the type of organic amine, the dispersibility in the base resin is improved. Can be further improved.

Next, examples of the present invention will be described.

Example 1 Method for Producing 2,2-Diacryloyloxymethylpropionic Acid <Method Using Acid Chloride> 2,2-Dimethylolpropionic acid was added to 950 ml of N, N-dimethylformamide dehydrated in advance with molecular sieve 4A.
80.5 g (0.60 mol) is added and, after dissolution, cooled to 0-5 ° C. To this liquid, 194 g (1.92 mol) of triethylamine was added, and 119 g (1.32 mol) of acroyl chloride was added dropwise over about 2 hours while stirring and maintaining the temperature at 1 to 5 ° C. 10 mg of hydroquinone monomethyl ether was added to the obtained yellow suspension, N, N-dimethylformamide was distilled off under reduced pressure, 750 ml of cold water was added to the residue, and the pH was adjusted to 1 with concentrated hydrochloric acid, and 400 ml of diethyl ether was added. It was extracted twice with. The extracted oil layer was dried over anhydrous MgSO ₄ and then concentrated under reduced pressure to obtain 118.7 g of crude 2,2-diacryloyloxymethylpropionic acid (yield 82
%).

By recrystallizing and refining with n-hexane / chloroform, 74.8 g of white needles was obtained (yield 63%), and it was confirmed from NMR, IR and elemental analysis that it was 2,2-diacryloylmethylpropionic acid. .

Shape white crystals m.p61~62 solubility 1.18 g / 100 g to ° C. water, (20 ° C.) analysis _{^{IR 1720cm -1, 1690cm -1 ν C}} = O 1070cm -1, 1280cm -1 ν CO 1620cm -1, ν _{C = C} 2700 cm ^-1 , ν _OH NMR 1.38 ppm (3H, s) 4.40 ppm (4H, s) 5.7 to 6.8 ppm (6H, m) 11.47 ppm (1H, s) Elemental analysis C% H% O% Theoretical value 54.54 5.83 39.63 Actual value 54.18 5.90 39.92 Example 2 Method for producing 2,2-diacryloyloxymethylpropionic acid <Method by transesterification> 2,2-Dimethylolpropionic acid 13.4 g (0.10 mol), methyl acrylate 86.1 g ( 1.0 mol), concentrated sulfuric acid 0.40 g (4 mmol) and phenothiazine 20 mg were mixed and reacted under reflux for 8 hours. The reaction mixture was concentrated under reduced pressure, 500 ml of water was added to the residue, and the mixture was extracted twice with 500 ml of diethyl ether, and 18.2 g of a colorless oily substance was obtained by the same procedure as in Example 1. This 1.82 g was isolated and purified by silica gel chromatography to obtain 0.50 g of white crystals.

By NMR, IR, and elemental analysis, it was confirmed to be 2,2-diacryloyloxymethylpropionic acid shown in Example 1 (yield 20%).

Example 3 Method for producing 2-2-dimethacryloyloxymethylpropionic acid <Method using acid chloride> 2,2-Dimethylolpropionic acid was added to 470 ml of N, N-dimethylformamide which had been dehydrated with molecular sieve 4A in advance.
40.2 g (0.30 mol) is added and, after dissolution, cooled to 0-5 ° C. To this solution, 97 g (0.68 mol) of triethylamine was added, and 69 g (0.66 mol) of methacryloyl chloride was added dropwise over about 2 hours while stirring and maintaining the temperature at 0 to 5 ° C. After that, 50 mg of hydroquinone monomethyl ether was added to the yellow suspension obtained by aging at the same temperature for 1 hour, and N, N-dimethylformamide was distilled off under reduced pressure.
After adding ml, the mixture was adjusted to pH 1 with concentrated hydrochloric acid and extracted twice with 200 ml of diisopropyl ether. The extracted oil layer was dried over anhydrous MgSO ₄ and concentrated under reduced pressure to obtain 70 g of crude 2,2-dimethacryloyloxymethylpropionic acid. (Yield 86%) The above crude product was dissolved twice in 200 ml of n-hexane, extracted, and then n-hexane was concentrated and removed, followed by recrystallization and purification with toluene to obtain 42 g of white needles. (Yield 52%), NMR, I
From R and elemental analysis, it was confirmed to be 2,2-dimethacryloyloxypropionic acid.

Shape white crystals M.P92～94 ° C. analysis _{^{IR 1720,1690cm -1 ν C = O 1630cm}} -1 ν C = C 2700cm -1 ν OH NMR 1.38ppm (3H, s) 5.6~6.2ppm (4H, m) 1.98ppm (6H, s) 9.0ppm (1H, s) 4.18ppm (4H, s) Elemental analysis C% H% O% Theoretical value 57.77 6.71 35.52 Actual value 57.38 6.80 35.91 Effect of the invention Uniform dispersibility to base resin A compound useful as a cross-linking agent for a UV resist that can be provided is provided.

Claims (1)

[Claims] 1. A formula (In the formula, R is alkyl having 1 to 3 carbon atoms, and Y is acryloyl or methacryloyl).