JPH0575740B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel etherified product of methylol acrylamide and a photocurable resin composition containing this etherified product as a monomer component. The resin composition of the present invention has particularly excellent suitability as a water-developable photosensitive resin plate-making material or as an ink for printed wiring boards. [Prior Art] In general, photocurable and water-soluble neutral liquid monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxy-3-propyl (meth)acrylate, and triethylene glycol. Methyl ether (meth)acrylate, methoxymethyl acrylamide, ethoxyethylacrylamide, dimethyl acrylamide, acryloylmorpholine, vinylpyrrolidone, and the like are known. However, these are all monofunctional monomers, and even if they are polymerized, it is not possible to obtain a polymer that is insoluble or dissolvable in water. [Problems to be Solved by the Invention] The present invention is directed to a water-soluble polyfunctional monomer that provides a cured product that is insoluble or sparingly soluble in water through a polymerization reaction such as photocuring, and a water-soluble polyfunctional monomer that produces a cured product that is insoluble or poorly soluble in water through a polymerization reaction such as photocuring. Provided is a photocurable resin composition containing: [Means for Solving the Problems] The water-soluble and photocurable polyfunctional monomer according to the present invention is an ether of N-methylolacrylamide and an alkylene oxide adduct of a dihydric or higher polyhydric alcohol. It is a compound, and a photocurable resin composition is made by disposing a photopolymerization initiator in this monomer. The monomer of the present invention is

[Formula] (wherein R ₁ represents a divalent to hexavalent chain, branched or cyclic hydrocarbon group or monosaccharide residue,
R ₂ represents hydrogen or an alkyl group, and n represents an integer of 2 to 6. ). It can be expressed as Specific examples of the hydrocarbon group for R ₁ include -(CH ₂ ) _l -,

【formula】

【formula】

【formula】

[Formula] Pentose, hexose residue (l is an integer from 2 to ₆ , CH ₂
-) Shows ₃ units. ). It can be easily obtained by ether-type condensation of an N-methylolated acrylamide and an alkylene oxide adduct of a dihydric or higher polyhydric alcohol. Here, the alkylene oxide adducts of dihydric or higher polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hexanediol, cyclohexanediol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, It refers to an alcohol obtained by adding 1 mole or more, preferably 1 to 3 moles, of an alkylene oxide, typically ethylene oxide or propylene oxide, to a dihydric or higher polyhydric alcohol such as dipentaerythritol, pentose, hexose, etc. The above dehydration etherification can proceed at a temperature of 80 to 120°C in an azeotropic solvent such as benzene or toluene in the presence of an acid catalyst such as phosphoric acid, oxalic acid, maleic anhydride, or phthalic anhydride or a cation exchange resin. The desired monomer can be obtained by neutralizing the reaction product, removing the catalyst by washing with water, etc., and then removing the solvent by means such as vacuum distillation or azeotropic distillation. The polyfunctional monomer produced by such dehydration etherification is a colorless, odorless, and low volatility liquid.
Soluble in water, acetone, ethyl acetate, toluene, etc. In addition, a photopolymerization initiator can be added to this and applied to the surface of glass, iron plates, etc.
In this state, the viscosity is generally high, so it may be applied by dissolving it in a suitable solvent. If solvent-free is desired, water-soluble polyfunctional monomers with low viscosity such as acryloylmorpholine, methoxymethyl acrylamide, 2-hydroxyethyl acrylate, triethylene glycol monomethyl ether acrylate, etc., are preferably used in tetrahydrocarbons. If you add furfuroxymethylacrylamide to adjust the viscosity and apply it to glass, copper-clad laminates, iron plates, etc. and photocure it,
Cures quickly and forms a hard and tough coating film. This coating film remains unchanged even after being soaked in running water for about 10 minutes, and does not become sticky due to moisture absorption. The monomers of the present invention can also be thermally polymerized using radical initiators such as benzoyl peroxide and azobisisobutyronitrile instead of using photoinitiators. Just to be sure, the product obtained by directly reacting N-methylol acrylamide with a dihydric or higher polyhydric alcohol to which no alkylene oxide has been added and performing dehydration etherification is difficult to dissolve in water and has a low viscosity. Extremely high. The photocurable resin composition according to the present invention contains a photopolymerization initiator in addition to the above-mentioned polyfunctional monomer.
Examples of photopolymerization initiators include benzoin, benzoin ethyl ether, benzyl, benzophenone, benzyl dimethyl ketal, hydroxycyclohexyl phenyl ketone, diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, Michler's ketone, chlorothioxanthone, and benzoyl. Benzyltrimethylammonium chloride and the like can be used. From the viewpoint of surface hardening, benzophenone and benzoylbenzyltrimethylammonium chloride are preferably used. The photopolymerization initiator is used in combination with a sensitizer such as dibruamine, triethylamine, diethylaminoethyl methacrylate, etc. as necessary, and the
It is blended into the composition in a range of 10% by weight. The photocurable resin composition of the present invention is basically composed of the above-described polyfunctional monomer and a photopolymerization initiator, but this composition also contains a prepolymer of the monomer of the present invention. Can be blended. Furthermore, other types of monomers can be added as a third component to the resin composition of the present invention, preferably in an amount not exceeding 50% by weight. In this case, the monomer is 2-
Hydroxyethyl (meth)acrylate, 2-hydroxy-3-propyl (meth)acrylate,
(meth)acrylic acid, (meth)acrylamide, triethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, dimethylaminoethyl (meth)acrylate, methoxymethylacrylamide, ethoxyethyl acrylamide, (meth)acrylamide Included are propyltrimethylammonium chloride, tert-butylacrylamide sulfonic acid, sodium styrene sulfonate, dimethylacrylamide, acryloylmorpholine, vinylpyrrolidone, vinyl acetate, and the like. However, if the amount of the monomer added as the third component is increased too much, the water resistance of the photocured coating film will decrease. The photocurable resin composition of the present invention contains polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, methyl Various synthetic resins such as cellulose, sodium polyacrylate, polyethylene oxide, and polyacrylamide, as well as starch, etc., can be mixed, and, like ordinary photocurable resin compositions, pigments, stabilizers, antioxidants, and interfaces can be mixed. An activator, a wetting agent, a viscosity modifier, etc. can be mixed as necessary. When applying the photocurable resin composition of the present invention to an object, it can be diluted with an appropriate solvent such as water, methyl ethyl ketone, ethyl acetate, toluene, etc. as necessary, and then applied using a roll coater, brush coating, screen printing, etc. Any coating method can be employed. The resin composition of the present invention adheres well to glass, copper-clad laminates, steel plates, etc., and has high hardness when cured, so it can be used as a photosensitive resin plate-making material or as a resist ink for printed wiring boards, etc. by water development. It is suitable as a photocurable resin in the field. [Example] Example 1 (Monomer synthesis) 82 g of 3 moles of ethylene oxide adduct of trimethylolpropane, 156 g of toluene, 80 mg of hydroquinone monomethyl ether, maleic anhydride
A solution containing 1.2 g was heated and stirred, and while blowing air, a 70% aqueous solution containing 112 g of N-methylolacrylamide was added dropwise over 2 hours, and heating under reflux was continued while azeotropically dehydrating. The reaction time was 6 hours and the final reaction temperature was 95°C. Dehydration amount is 63.7
g and contained 2.5% formaldehyde.
This corresponds to 96.5% of the theoretical amount of etherification dehydration. Next, when a caustic soda aqueous solution containing 20% of Glauber's salt was added to neutralize at 60°C, the mixture was separated into an upper layer mainly consisting of toluene, a middle layer containing the product, and a lower layer consisting of an alkaline aqueous solution, and the middle layer was separated. Add 100 g of methyl ethyl ketone to this middle layer, wash with 20% sodium sulfate water, distill off toluene, methyl ethyl ketone, and water contained in the oil under reduced pressure, and filter the remaining oil to add 3 moles of ethylene oxide to trimethylolpropane. 159 g of a dehydrated ether of N-methylolacrylamide and N-methylolacrylamide was obtained. This product was colorless, had a viscosity of 1600 poise, and was soluble in toluene, ethyl acetate, and water. The molecular formula is as follows. (CH ₂ = CHCONHCH ₂ OCH ₂ CH ₂ OCH ₂ )― ₃ C
-C ₂ H ₅ Also, the results of elemental analysis and IR analysis of this product are shown below. (a) Elemental analysis C H O N Measured value 55.7% 8.2% 28.5% 7.6% Theoretical value 55.9% 8.0% 28.1% 8.0% (b) IR analysis (KBr overcoat film) 3420cm N-H expansion and contraction of ^-1 acid amide Vibration 1670cm ^-1 C=O stretching vibration of acid amide 1640cm ^-1 Vinyl group CH ₂ =CH- stretching vibration 1540cm ^-1 N-H bending vibration of -1 acid amide 1400cm ^-1 Vinyl group CH ₂ =CH- in-plane bending Vibration 1085cm ^-1 Ether C-O-C stretching vibration Example 2 (monomer synthesis) N
- 70% containing 166.5g of methylol acrylamide
An aqueous solution was added, heated and stirred while blowing air to perform azeotropic dehydration, and reflux heating was performed until the dehydration was completed. The reaction time was 6 hours, and the final reaction temperature was 108
It was warm at ℃. The amount of dehydrated water was 98g and contained 2.5% formaldehyde. This corresponds to 97% of the theoretical amount of etherification dehydration. Next, when a caustic soda aqueous solution containing 20% of Glauber's salt was added to neutralize at 60°C, the mixture was separated into an upper layer mainly consisting of toluene, a middle layer containing the product, and a lower layer consisting of an alkaline aqueous solution, and the middle layer was separated. 200 g of methyl ethyl ketone was added to this middle layer, washed with 20% sodium sulfate water, toluene, methyl ethyl ketone, and water contained in the oil were distilled off under reduced pressure, and the residual oil was filtered to remove N-methylol acrylamide from propoxyglycerin. Dehydrated etherified product 254g
I got it. This product was colorless, had a viscosity of 410 poise, and was soluble in toluene, ethyl acetate, and water. The molecular formula is as follows.

[Formula] Also, the results of elemental analysis and IR analysis of this product are shown below. (a) Elemental analysis C H O N Measured value 56.0% 8.6% 27.9% 7.5% Theoretical value 55.9% 8.0% 28.1% 8.0% (b) IR analysis (KBr overcoat film) Characteristic absorption at the same wave number as in Example 1 Indicated. Example 3 (Monomer synthesis) Ethylene oxide of pentaerythritol 4
Add 178 g of N-methylolacrylamide to a solution containing 130.5 g of the molar adduct, 182 g of toluene, 120 mg of hydroquinone monomethyl ether, and 1.3 g of phosphoric acid, heat and stir while blowing air for azeotropic dehydration, and heat under reflux until the dehydration is complete. Summer. The reaction time was 6 hours and the final reaction temperature was 92°C.
The amount of dehydrated water was 28.5g, which contained 2.8% formaldehyde. This is 95.5 of the theoretical amount of etherification dehydration.
Corresponds to %. Next, a caustic soda aqueous solution containing 20% of Glauber's salt was added to neutralize at 60°C, and the mixture was separated into an upper layer mainly consisting of toluene, a middle layer containing the product, and a lower layer consisting of an alkaline aqueous solution, and the middle layer was separated. 220 g of methyl ethyl ketone was added to this middle layer, washed with 20% sodium sulfate water, toluene, methyl ethyl ketone, and water contained in the oil were distilled off under reduced pressure, and the residual oil was filtered to form a 4-mol ethylene oxide adduct of pentaerythritol. 245 g of a dehydrated etherified product of and N-methylolacrylamide was obtained. This product was colorless, had a viscosity of 450 poise, and was soluble in toluene, ethyl acetate, and water. The molecular formula is as follows. (CH ₂ = CHCONHCH ₂ OCH ₂ CH ₂ OCH ₂ ) - ₄ C Moreover, the results of elemental analysis and IR analysis of this product are shown below. (a) Elemental analysis C H O N Measured value 54.4% 7.9% 29.6% 8.1% Theoretical value 54.0% 7.5% 29.8% 8.7% (b) IR analysis (KBr overcoat film) Characteristic absorption at the same wave number as Example 1 Indicated. Example 4 (Monomer synthesis) A mixed solution containing 192 g of 2 moles of ethylene oxide adduct of tripropylene glycol, 339 g of toluene, 170 mg of hydroquinone monomethyl ether, 222 g of N-methylolacrylamide, and 1 g of phosphoric acid was heated and stirred while blowing air. The mixture was azeotropically dehydrated and heated under reflux until the dehydration was completed. The reaction time was 7 hours and the final reaction temperature was 97°C.
The amount of dehydrated water was 37g, which contained 3.5% formaldehyde. Next, when the same post-treatment as in Example 3 was carried out, tripropylene glycol and N
- 333 g of a dehydrated etherified product with methylol acrylamide was obtained. This product was colorless, had a clay content of 52 poise, and was soluble in toluene, ethyl acetate, and water. The molecular formula is as follows.

[C] Also, the results of elemental analysis and IR analysis of this product are shown below. (a) Elemental analysis C H O N Measured value 60.3% 8.0% 26.3% 5.4% Theoretical value 60.2% 7.8% 26.2% 5.8% (b) IR analysis (KBr top coat) Characteristic absorption in the same ripples as in Example 1 Indicated. Example 5 To 40 g of the dehydrated etherified product of 3 moles of ethylene oxide adduct of trimethylolpropane obtained in Example 1 and N-methylol acrylamide, 60 g of tetrahydrofurfuroxymethyl acrylamide was added.
A solution of 2 g of photopolymerization initiator benzophenone and 2 g of benzophenone, which is a photopolymerization initiator, is easily dissolved in water.
When placed 15cm below the UV lamp on a belt conveyor running at a speed of 4m/min and exposed once,
The coated surface immediately lost its fluidity and tackiness, and after a total of four exposures, a smooth coating film with a pencil hardness of 2H was obtained. This coating film remained unchanged even after being immersed in running water for 8 minutes. Example 6 Dehydrated etherified product of propoxyglycerin obtained in Example 2 and N-methylolacrylamide 90
A film made by coating a glass plate with a solution of 10g of water, 2g of benzoylbenzyltrimethylammonium chloride, and 2g of benzoylbenzyltrimethylammonium chloride to a thickness of 30μ can be easily wiped off with water, but it can be easily wiped off with water after the water is evaporated by air drying. By irradiating with a UV lamp as in Example 5, a smooth coating film with a pencil hardness of 5H could be obtained. This coating did not change even when immersed in running water. Example 7 To 60 g of the dehydrated etherified product of 4 moles of ethylene oxide adduct of pentaerythritol obtained in Example 3 and N-methylol acrylamide, 40 g of tetrahydrofurfuroxymethyl acrylamide was added.
and 2 g of benzophenone are easily dissolved in water. By applying this material to a thickness of 30 μm on a glass plate and irradiating it with a UV lamp as in Example 5, a smooth coating film with a pencil hardness of 3H could be obtained. This coating film is submerged under running water.
There was no change even after soaking for 10 minutes.

Claims (1)

[Scope of Claims] 1. A polyfunctional monomer which is an ether compound of an alkylene oxide adduct of a dihydric or higher polyhydric alcohol represented by the following formula and N-methylolacrylamide [Formula] (wherein R ₁ represents a divalent to hexavalent chain, branched or cyclic hydrocarbon group or monosaccharide residue,
R ₂ represents hydrogen or an alkyl group, and n represents an integer of 2 to 6. ). 2 A polyfunctional monomer which is an ether compound of an alkylene oxide adduct of a dihydric or higher polyhydric alcohol represented by the following formula and N-methylolacrylamide [Formula] (wherein, R ₁ is a divalent to hexavalent Indicates a chain, branched or cyclic hydrocarbon group or monosaccharide residue,
R ₂ represents hydrogen or an alkyl group, and n represents an integer of 2 to 6. ). and a photocurable resin composition containing a photopolymerization initiator.