JPH01163166A - Novel polyfunctional monomer and photo-setting type resin composition containing said monomer - Google Patents

Abstract

NEW MATERIAL:A polyfunctional monomer which is an etherified substance of an alkylene oxide adduct of a bi- or polyhydric alcohol with N- methylolacrylamide. EXAMPLE:An etherified substance of an adduct of 3mol ethylene oxide with trimethylolpropane with N-methyolacrylamide. USE:A principal component of a photo-setting type resin composition, such as photosensitive resin plate making material developable wuth water or ink for printed circuit board. PREPARATION:An N-methylolated substance of acrylamide and an alkylene oxide adduct of a bi- or polyhydric alcohol are subjected to ether type condensation to afford the aimed polufJcntional monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] 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,
Even if polymerized, a polymer that is insoluble or poorly soluble in water cannot be obtained.

[Problems to be Solved by the Invention] The present invention includes a water-soluble polyfunctional monomer that provides a cured product that is insoluble or poorly soluble in water through a polymerization reaction such as photocuring, and a monomer that contains this monomer as a main component. A photocurable resin composition is provided.

[Means for solving the problems] The water-soluble and photocurable polyfunctional monomer according to the present invention is
It is an etherified product of N-methylol acrylamide and an alkylene oxide adduct of a dihydric or higher polyhydric alcohol, and the photocurable resin composition is made by disposing a photopolymerization initiator to this monomer.

The monomer of the present invention can be easily obtained by ether-type condensation of an N-methylolated product of 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 is carried out in the presence of an acid catalyst such as phosphoric acid, oxalic acid, maleic anhydride, or phthalic anhydride or a cation exchange resin in an azeotropic solvent such as benzene or toluene, and
The reaction can be carried out at a temperature of 120°C. 1. After neutralizing the reaction product, remove the catalyst by washing with water, etc., and then remove the solvent by means such as vacuum distillation or azeotropic distillation to obtain the desired monomer. Obtainable.

The polyfunctional monomer produced by such dehydration etherification is a colorless, odorless, and low-volatility liquid that can be used in water, acetone,
Soluble in ethyl acetate, toluene, etc. In addition, a photopolymerization initiator can be added to this and applied to the surface of glass, iron plates, etc., but in this state the viscosity is generally high, so
It may be applied by dissolving it in an appropriate solvent.

If solvent-free is desired, acryloylmorpholine, which is a water-soluble monofunctional monomer with low viscosity,
Methoxymethylacrylamide, 2-hydroxyethyl acrylate, triethylene glycol monomethyl ether acrylate, etc., preferably by adding tetrahydrofurfuroxymethylacryamide to adjust the viscosity, are applied to glass, copper-clad laminates, iron plates, etc. and exposed to light. When cured, it hardens quickly and forms a hard and strong coating. This coating film remains unchanged even after being immersed 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. The viscosity is also extremely high.

The photocurable resin composition according to the present invention contains a photopolymerization initiator in addition to the above-mentioned polyfunctional monomer. As a photopolymerization initiator, benzoin, benzoin ethyl ether, benzyl, benzophenone, benzyl dimethyl ketal, hydroxycyclohexylphenyl ketone, jetoxyacetophenone, 2-hydroxy-2-methylpropiophenone, Michler's ketone, glolothioxanthone, 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 dibutylamine, triethylamine, diethylaminoethyl methacrylate, etc., if necessary, and is blended into the composition in a range of 0.01 to 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, the resin composition of the present invention preferably has 5
It is possible to add other types of monomers as a third component in an amount not exceeding 0% by weight. In this case, monomers include 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, methoxymethyl Acrylamide, ethoxyethylacrylamide, (meth)acrylamidopropyltrimethylammonium chloride, tert-butylacrylamide sulfonic acid, sodium styrene sulfonate, dimethylacrylamide.

Acryloylmorpholine, vinylpyrrolidone, vinyl acetate and the like are included. 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 may be diluted with an appropriate solvent such as water, methyl ethyl ketone, ethyl acetate, toluene, etc. as necessary, and then applied by brushing with a roll coater or by screen printing. Any coating method can be used. 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) A solution containing 82 g of 3 moles of ethylene oxide adduct of trimethylolpropane, 156 g of toluene, 80 mg of hydroquinone monomethyl ether, and 1.2 g of maleic anhydride was heated and stirred, and air was removed. While blowing, a 70% aqueous solution containing 112 g of N-methylolacrylamide was added dropwise over 2 hours, and reflux heating was continued while azeotropically dehydrating. The reaction time was 6 hours, and the final reaction temperature was 95°C. The amount of dehydrated water was 63.7 g, which contained 2.5% formaldehyde. This is 96.5 of the etherification dehydration theory
Corresponds to %.

Next, a caustic soda aqueous solution containing 20% of Glauber's salt was added to
When neutralized at °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 aqueous alkali solution, so the middle layer was separated.

Add 100g of methyl ethyl ketone to this middle layer to make a 20%
The toluene, methyl ethyl ketone, and water contained in the oil were distilled off under reduced pressure, and the residual oil was filtered to obtain a dehydrated ether of 3 moles of ethylene oxide adduct of trimethylolpropane and N-methylol acrylamide. 159 g of compound was obtained. This substance is colorless and has a viscosity of 1
600 voids and was soluble in toluene, ethyl acetate, and water. The molecular formula is as follows.

(C11□=CIC0NICI1.OCH,CH,0
CH2), c-c2H5 The results of elemental analysis and IR analysis of this product are shown below.

(a) Elemental analysis (b) IR analysis (KBr top coat) 3420■-1 N-)1 stretching vibration of acid amide 1670
C=O stretching vibration of cm-1 acid amide 1640 cm-”
Vinyl group C112=CH-Stretching vibration 1540 an-1
N-[1 bending vibration of acid amide 1400 an-1 vinyl group CI+2=C1+- in-plane bending vibration 1085 ■-1 ether C-0-C stretching vibration Example 2 (monomer synthesis) Propylene oxide of glycerin 3 molar adduct 152
A 70% aqueous solution containing 166.5 g of N-methylolacrylamide was added to a solution containing 136 g of toluene, 120 mg of hydroquinone monomethyl ether, and 1.5 g of phosphoric acid, and azeotropic dehydration was carried out by heating and stirring while blowing air, and the dehydration was completed. The mixture was heated to reflux. Reaction time is 6
The final reaction temperature was 108°C. The amount of dehydration is 9
8g and contained 2.5% formaldehyde. This corresponds to 97% of the theoretical amount of etherification dehydration.

Next, a caustic soda aqueous solution containing 20% of Glauber's salt was added to
When neutralized at °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 aqueous alkali solution, so the middle layer was separated.

Add 200g of methyl ethyl ketone to this middle layer to make a 20%
The toluene, methyl ethyl ketone, and water contained in the oil were distilled off under reduced pressure, and the residual oil was filtered to obtain 254 g of a dehydrated ether of N-methylolacrylamide of propoxyglycerin. This product was colorless, had a viscosity of 410 boids, and was soluble in toluene, ethyl acetate, and water. The molecular formula is as follows.

CH2=ClIC0NHC! (,OCH(CH,)CH
,-octt.

C112=CHCONHCH,OCH(CH,)CH,
−0CRCI+, =ClIC0Nl(CH□QC)l
(CH,)CH2-OCH.

Further, the results of elemental analysis and IR analysis of this product are shown below.

(b) Elemental analysis (b) IR analysis (KBr topcoat film) It exhibited characteristic absorption at the same wave number as in Example 1.

Example 3 (monomer synthesis) 178 g of N-methylol acrylamide was added to a solution containing 130.5 g of 4 moles of ethylene oxide adduct of pentaerythritol, 182 g of toluene, 120 mg of hydroquinone monomethyl ether, and 1.3 g of phosphoric acid, and air was blown into the solution. The mixture was heated and stirred for azeotropic dehydration, and heated under reflux until the dehydration was completed. The reaction time was 6 hours, and the final reaction temperature was 92°C. The amount of dehydration is 28.5g,
It contained 2.8% formaldehyde. This corresponds to 95.5% of the theoretical amount of etherification dehydration.

Next, a caustic soda aqueous solution containing 20% of Glauber's salt was added to
When neutralized at °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 aqueous alkali solution, so the middle layer was separated.

Add 220g of methyl ethyl ketone to this middle layer to make a 20%
The toluene, methyl ethyl ketone, and water contained in the oil were distilled off under reduced pressure, and the residual oil was filtered to obtain a dehydrated ether of pentaerythritol with 4 moles of ethylene oxide and N-methylolacrylamide. 245g was obtained. This substance is colorless and has a viscosity of 45
It had zero voids and was soluble in toluene, ethyl acetate, and water. The molecular formula is as follows.

(CH2=CI(CONHCII□OCH, CH20C
H□+4C Further, the results of elemental analysis and IR analysis of this product are shown below.

(b) Elemental analysis (b) IR analysis (KBr topcoat film) It exhibited characteristic absorption at the same wave number as in Example 1.

Example 4 (monomer synthesis) 192 g of tripropylene glycol, 339 g of toluene
, hydroquinone monomethyl ether 170170mg
, N-methylolacrylamide 222g, phosphoric acid 1g
The mixed solution containing was heated and stirred while blowing air to perform azeotropic dehydration, 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 37 g, which contained 3.5% formaldehyde. Subsequently, the same post-treatment as in Example 3 was carried out to obtain 333 g of a dehydrated etherified product of tripropylene glycol and N-methylolacrylamide.

This product was colorless, had a viscosity of 52 poise, and was soluble in toluene, ethyl acetate, and water. The molecular formula is as follows.

CH.

Y-0-% CH-C1120+, Y However, Y: CH,=CHC0N)ICl3-Also,
The results of elemental analysis and IR analysis of this product are shown below.

(b) Elemental analysis (b) IR analysis (KBr topcoat film) It exhibited characteristic absorption at the same wave number as in Example 1.

Example 5 60 g of tetrahydrofurfuroxymethylacrylamide was added to 40 g of the dehydrated etherified product of 3 moles of ethylene oxide of trimethylolpropane and N-methylol acrylamide obtained in Example 1, and 2 g of benzophenone, a photopolymerization initiator, was dissolved. It dissolves easily in water, but it was applied to a glass plate to a thickness of 30 μm.
4m/min at 15cm below the 80W/■ UV lamp
When placed on a belt conveyor running at high speed and exposed once, the coated surface immediately lost its fluidity and tackiness, and after a total of 4 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 To 90 g of the dehydrated etherified product of propoxyglycerin and N-methylol acrylamide obtained in Example 2, 10 g of water was added.
A film obtained by applying a solution containing 2 g of benzoylbenzyltrimethylammonium chloride to a thickness of 30 μm on a glass plate can be easily wiped off with water, but after evaporating the water by air drying, By similarly irradiating with a UV lamp, a smooth coating film with a pencil hardness of 5H could be obtained. This coating film did not change even when immersed in running water.

Example 7 40 g of tetrahydrofurfuroxymethylacrylamide was added to 60 g of the dehydrated etherified product of 4 moles of ethylene oxide of pentaerythritol obtained in Example 3 and N-methylolacrylamide, and 2 g of benzophenone was further dissolved. Easily soluble in water.

This material was applied to a glass plate to a thickness of 30μ, and Example 5
By irradiating with a UV lamp, the pencil hardness is 3H.
A smooth coating film was obtained. This coating film remained unchanged even after being immersed in running water for 10 minutes.

Patent applicant: Soken Chemical Co., Ltd.

Claims (1)

[Scope of Claims] A polyfunctional monomer which is an etherified product of an alkylene oxide adduct of a mono-, di- or higher-hydric alcohol and N-methylolacrylamide. A photocurable resin composition containing a photopolymerization initiator and a polyfunctional monomer that is an etherified product of an alkylene oxide adduct of a dihydric or higher polyhydric alcohol and N-methylol acrylamide.