JPH0743902A - (meth)acrylamide group introduced phenol-containing oligomer - Google Patents

Abstract

PURPOSE:To obtain a phenol-contg. polymerizable oligomer useful as starting material for a resin curable with active energy beams by introducing a specified functional group into each arom. ring of phenol in phenolic resin. CONSTITUTION:A functional group represented by the formula (where R is H or methyl) is introduced into each arom. ring of phenol in a polymer having phenol by bringing the arom. ring into an electro-philic substitution reaction with N-methylol (meth)acrylamide or its alkyl-etherified product to obtain the objective (meth)acrylamide group introduced phenol-contg. oligomer. The above- mentioned polymer having phenol is phenolic resin or a vinylphenol (co)polymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a novel polymerizable oligomer useful as a raw material for active energy ray-curable resins such as paints, printing inks, printing plates, adhesives, resists, etc.
It relates to a (meth) acrylamide group-introduced phenol-containing oligomer.

[0002]

2. Description of the Related Art In recent years, active energy ray curable resins have low pollution due to not requiring a solvent, high productivity due to short curing time, and curing in comparison with thermosetting resins. Since it does not require heat in particular, it can be used at low temperature, and it has been used in a wide range of fields such as paints, printing inks, printing materials, adhesives, and resists by taking advantage of various advantages such as energy saving. Came. With the expansion of such fields of application, adaptation to active energy rays used such as UV, EB, and laser, and further diversification of curing systems by combination with other curing methods such as heat curing, active energy ray curability Various performances are required for resins. Since the physical properties of the active energy ray-curable resin are greatly influenced by the polymerizable oligomer contained therein, development of the polymerizable oligomer is important.

Phenolic resin, vinylphenol (co)
Polymers with phenols such as polymers are electrically insulating,
Due to its excellent physical properties such as mechanical strength and dimensional stability, it is used in various fields such as molding materials for electrical parts and machine parts, laminate materials such as laminates, binders for shell molds, adhesives, paints, etc. It is used in.

As described above, various oligomers in which an unsaturated bond is introduced into a polymer having a useful phenol to impart a polymerizing property have been studied. The unsaturated bond introduction method can be classified into a phenolic hydroxyl group reaction type and a phenol aromatic ring substitution type.

The following oligomers are known for the phenolic hydroxyl group reaction type. That is, starting with so-called epoxy (meth) acrylate obtained from the reaction of glycidyl etherified phenol resin and (meth) acrylic acid, isocyanate ethyl methacrylate or hydroxyethyl (meth) acrylate and tolylene-2,
Carbamic acid ester of a compound having an isocyanate and a (meth) acrylic group, such as an adduct with 4-diisocyanate, and a phenol resin (DE 3,630,
954 A1), carbamic acid ester of isocyanate ethyl methacrylate and polyvinyl phenol (Japanese Patent Laid-Open No. 63-269,147), and methacrylic acid ester of brominated polyvinyl phenol (Nagai, Takahashi, Katagiri, Mukai, Ohki, The Printed Circuit Society of Japan) The 5th Scientific Lecture Meeting Proceedings, 157 (1990)), allyl etherified phenolic resin (Japanese Patent Publication No. 43-25,994, Morinaga, Murayama, Nakatsuka, Kogaku Kagaku, 22,615 (1965)) and the like. By the way, a polymer having phenol is characterized by having reactivity with a phenolic hydroxyl group and electrophilic substitution reactivity of an aromatic ring activated by the hydroxyl group.For example, the former is used as a curing agent for an epoxy resin, and the latter is When used in combination with hexamethylenetetramine, it is itself used as a thermosetting resin without introducing an unsaturated bond. Further, a polymer having a phenol is utilized as an alkali developing type photoresist for semiconductors by utilizing its solubility. However, the above-mentioned polymerizable oligomer is impaired in the characteristics such as reactivity and solubility of the polymer having phenol because the phenolic hydroxyl group is etherified, esterified or carbamate esterified.

As the other phenol-aromatic ring-substituted type, an oligomer in which an allyl group (Morinaga, Murayama, Nakatsuka, Kogaku Kagaku, 22,615 (1965)) or a propenyl group is introduced into a phenol resin is known. However, these functional groups have lower polymerization reactivity than acrylic groups.

[0007]

An object of the present invention is to provide a novel phenol-containing polymerizable oligomer useful as a raw material for active energy ray-curable resin.

[0008]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies on a novel phenol-containing polymerizable oligomer useful as a raw material for an active energy ray-curable resin. As a result, the aromatic ring of phenol in a polymer having phenol is The present invention has been completed by newly finding an oligomer in which the functional group represented by the structural formula (1) is introduced, that is, a (meth) acrylamide group-introduced phenol-containing oligomer.

[0009]

[Chemical 2] (In the formula, R represents hydrogen or a methyl group.)

The (meth) acrylamide group-introduced phenol-containing oligomer of the present invention is N-methylol (meth) to the aromatic ring of phenol in a polymer having phenol.
It can be obtained by an electrophilic substitution reaction of acrylamide or its alkyl ether compound.

The phenol-containing polymer mentioned here is a phenol resin or a vinylphenol (co) polymer. To explain in more detail, phenolic resin is
It is a polymer having a molecular weight of 300 to 10,000 obtained by condensing phenols and aldehydes, and examples of the phenols include phenol, methylphenol, dimethylphenol, dihydrobenzene, bisphenol A,
As bisphenol F and the like, as aldehydes, formaldehyde, paraformaldehyde, acetaldehyde, furfural and the like can be used. The vinylphenol (co) polymer has a molecular weight of 300 to 50,
It is a homopolymer or copolymer of 000 vinylphenols. As comonomers, for example, diene derivatives such as butadiene and isoprene, styrene, styrene derivatives such as α-methylstyrene, vinyl ester derivatives such as vinyl acetate, (meth) acrylic acid and its esters, (meth) acrylamide and its N- Substitutes, (meth) acrylonitrile, maleic acid including maleic anhydride and maleimide, maleimide derivatives,
Examples include N-vinylpyrrolidone and vinyl ether.

Low molecular weight compounds with phenols, eg 4
-Hydroxybenzophenone (JP-B-59-29,56)
2), bisphenol A (USP 3,839,447
(1974)) and other electrophilic substitution reactions of N-methylolacrylamide have already been studied.
The acrylamide group-introduced phenol-containing oligomer of the present invention can also be synthesized using these methods. That is, a polymer having phenol and N-methylol (meth)
An acrylamide group-introduced phenol-containing oligomer is obtained by reacting acrylamide or its alkyl ether compound in a solvent in the presence of an acid catalyst. The solvent is acetone, methyl ethyl ketone or acetone.
Water mixed solvent, methanol, ethanol, propanol,
Dimethylformamide, 2-pyrrolidone, etc. can be used. As the catalyst, an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid or an organic acid such as p-toluenesulfonic acid can be used. The reaction is 0 to 150 ° C, preferably room temperature to 80 ° C
The reaction time is 30 minutes to several days.

The position and number of the functional group represented by the structural formula (1) that can be introduced into the aromatic ring of phenol in the polymer having phenol is determined by the number of substituents and the number of substituents on the aromatic ring of phenol in the polymer to be reacted. It is impossible to say unconditionally because it is affected by various effects such as the position of, the steric hindrance of the substituent, the inducing effect of the substituent, and the resonance effect of the substituent. For example, in the case of a phenol resin, ideally, up to one functional group represented by the structural formula (1) can be introduced per one phenol at the ortho or para position of the hydroxyl group. Further, in the case of a vinylphenol (co) polymer, ideally, up to about two functional groups represented by the structural formula (1) can be introduced per one phenol at the ortho and para positions of the hydroxyl group. On the other hand, when the number of introduced functional groups represented by the structural formula (1) is small, the active energy ray curability of the resulting oligomer is low. Therefore, the number of functional groups represented by the structural formula (1) introduced into a polymer having phenol is 0.1 to 1 per one aromatic ring of phenol in the case of phenol resin, and that of vinylphenol (co) polymer in the case of phenol resin. , 0.1 to 2 per one aromatic ring of phenol
Individuals are appropriate.

The acrylamide group-introduced phenol-containing oligomer of the present invention has various monofunctional and polyfunctional (meth).
An active energy ray-curable resin composition can be obtained by adding it to a composition comprising a part or all of acrylate or (meth) acrylamide, a photopolymerization initiator, a sensitizer, a binder polymer, a filler and the like. Examples of the monofunctional or polyfunctional (meth) acrylate or (meth) acrylamide include 2-ethylhexyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate and 2
-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone,
N-acryloylmorpholine, N, N-dimethyl (meth) acrylamide, diacetone (meth) acrylamide, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol (meth) acrylate, 1,4-butanediol Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate , Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate Rate, urethane (meth)
Acrylate, polybutadiene (meth) acrylate,
Silicone (meth) acrylate or the like can be used. As the photoinitiator, for example, 2-hydroxy-2-methyl-1
-Phenylpropan-1-one, 2-methyl-1- [4
Acetophenones such as-(methylthio) phenyl] -2-morpholinopropan-1-one, benzoins such as benzoin isopropyl ether, benzophenones, thioxanthones, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and camphorquinone can be used. . As the sensitizer, various amines can be used.
Examples of the binder polymer include polyvinyl alcohol, polyethylene glycol, polypropylene glycol, polyacrylamide, polyvinylpyrrolidone, polyvinyl ether, phenoxy resin, styrene-maleic anhydride copolymer, polybutadiene and polyurethane. As the filler, barium sulfate, barium titanate, silica, talc, calcium carbonate, aluminum hydroxide or the like can be used.

The above-mentioned active energy ray-curable resin composition containing the acrylamide group-introduced phenol-containing oligomer of the present invention can be used in paints, printing inks, printing plate materials, adhesives, resists and the like. The present invention will be described below with reference to examples.

[0016]

【Example】

[0017]

Example 1 Phenolic novolac resin (Showa High Polymer Co., Ltd., trade name BRG-559) 212 g (2.0 equivalents), N-methylol acrylamide 202 g (2.0
mol) and 400 ml of acetone while stirring, while adding 203 g of 36% hydrochloric acid to the reaction mixture at a temperature of 4
The solution was gradually added dropwise while keeping the temperature below 0 ° C. The reaction mixture was heated and stirred on a 50 ° C. oil bath for 6 hours. After cooling to room temperature, 2.5 l of methyl ethyl ketone and 1 l of distilled water were added to the reaction mixture and shaken to separate the organic layer. 5% of this organic layer
Neutralize with sodium hydrogen carbonate aqueous solution, and add distilled water 50
Wash 3 times with 0 ml. The solvent was distilled off, and the obtained solid substance was crushed and then dried under reduced pressure. 334 g of solid was obtained. A part thereof was dissolved in a small amount of tetrahydrofuran and poured into a large amount of dichloromethane. The precipitate obtained was filtered off, ground and dried. 1H NMR of this material
The spectrum is shown in FIG. 0.8 functional groups represented by the structural formula (1) (wherein R is hydrogen) were introduced per one phenol of the phenol novolac resin.

[0018]

[Example 2] Poly p-vinylphenol (manufactured by Maruzen Petrochemical Co., Ltd., trade name Marca Linker MS-2P) 24
0 g (2.0 equivalents), N-methylol acrylamide 2
While stirring a mixture of 02 g (2.0 mol) and 400 ml of acetone, 203 g of 36% hydrochloric acid was gradually added dropwise thereto while keeping the temperature of the reaction mixture at 40 ° C or lower. The reaction mixture was heated and stirred on a 50 ° C. oil bath for 6 hours. After allowing to cool to room temperature, 2.5 l of methyl ethyl ketone was added to the reaction mixture,
Distilled water (1.1 L) was added and the mixture was shaken to separate the organic layer.
This organic layer was neutralized with a 5% aqueous sodium hydrogen carbonate solution,
Further, it was washed twice with 500 ml of distilled water. Add 2 l of methyl ethyl ketone to the organic layer and add 500 ml of distilled water.
Washed with. The solvent was distilled off, and the obtained solid substance was crushed and then dried under reduced pressure. 360 g of solid was obtained. A part of it was dissolved in a small amount of acetone and poured into a large amount of dichloromethane. The precipitate obtained is filtered off and ground,
Dried. The 1H NMR spectrum of this material is shown in FIG. 0.9 functional groups represented by structural formula (1) (where R is hydrogen) were introduced per one phenol of poly-p-vinylphenol.

[0019]

Example 3 A mixture of 120 g (1.0 equivalent) of poly-p-vinylphenol, 202 g (2.0 mol) of N-methylolacrylamide and 250 ml of acetone, which was the same as in Example 2, was stirred, while 101 g of 36% hydrochloric acid was added thereto. The reaction mixture was gradually added dropwise while keeping the temperature at 40 ° C or lower.
The reaction mixture was heated with stirring on a 50 ° C. oil bath for 4 hours. After cooling to room temperature, methyl ethyl ketone 1.5 was added to the reaction mixture.
1, and 300 ml of distilled water were added and shaken to separate the organic layer. This organic layer was neutralized with a 5% aqueous sodium hydrogencarbonate solution. To this, 600 ml of methyl ethyl ketone and 300 ml of distilled water were added to separate the organic layer. This operation was repeated 3 times. The solvent was distilled off, and the obtained solid substance was crushed and then dried under reduced pressure. 218 g of solid was obtained. When its 1H NMR spectrum was measured, 1.9 functional groups represented by Structural Formula (1) (where R is hydrogen) were introduced per one phenol of poly-p-vinylphenol.

[0020]

EFFECT OF THE INVENTION A novel phenol-containing polymerizable oligomer useful as a raw material for an active energy ray-curable resin was obtained.

[Brief description of drawings]

FIG. 1 is an NMR spectrum of a phenol novolac resin into which N-methyl acrylamide has been introduced.

FIG. 2 shows poly-p having N-methyl acrylamide introduced.
-Vinylphenol resin.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location H01L 21/027

Claims (4)

[Claims] 1. 0.1 to 1 functional group represented by the following structural formula (1) is introduced per one aromatic ring of phenol of a phenol resin having a molecular weight of 300 to 10,000 (meta). ) An acrylamide group-introduced phenol-containing oligomer. [Chemical 1] (In the formula, R represents hydrogen or a methyl group.) 2. The functional group represented by the structural formula (1) is from 0.1 to 2 per aromatic ring of phenol of a vinylphenol (co) polymer having a molecular weight of 300 to 50,000.
An individually introduced (meth) acrylamide group-introduced phenol-containing oligomer. 3. An active energy ray curable resin composition comprising the oligomer shown in claim 1 and / or 2. 4. A cured product of the composition shown in claim 3.