JP2000297082A - Unsaturated epoxy compound, its production and (co) polymer of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound having a photocationically polymerizable epoxy group, capable of providing a (co)polymer useful as a radiation-sensitive resin capable of forming films by binding a side chain having an epoxy group to an aromatic vinyl compound. SOLUTION: This compound is a compound of formula I (n is 1 to 5; R is hydrogen or methyl; Q is hydrogen or methyl), e.g. vinylphenethyloxirane. The compound of formula I is produced, for example, by reacting (A) a Grignard reagent of formula III (X is chlorine or bromine) with (B) epichlorohydrin or methylepichlorohydrin, at -30 to 50 deg.C, pref. -10 to 10 deg.C, for 0.1 to 10h. The component A is produced by reacting (i) an ω-haloalkylstyrene or ω-haloalkyl-α- methylstyrene with (ii) metallic magnesium in (iii) an anhydrous solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel unsaturated epoxy compound and a (co) polymer thereof. More specifically, the present invention relates to an aromatic monomer having an epoxy group in a side chain, a method for producing the same, and a (co) polymer having an epoxy group in a side chain obtained by polymerizing the aromatic monomer.

[0002]

2. Description of the Related Art Polymers obtained by polymerizing unsaturated monomers having a carbon-carbon double bond using radicals (hereinafter referred to as "polymers").
It is called "radical polymer". Is widely used for various uses, but if this polymer can be cross-linked by light or heat, it can be used as a functional polymer. It is known that a polymer having an epoxy group undergoes a cross-linking reaction by opening the ring of an epoxy group by a cation generated by ultraviolet irradiation in the presence of an onium salt-based photoacid generator. This material that is crosslinked by ultraviolet irradiation is widely used as a resist for manufacturing semiconductor integrated circuits and as a material for forming insulating films and protective films of electronic components. There is a need for a polymer having an epoxy group having the formula:

A radical polymer having an epoxy group can be easily produced by copolymerizing an epoxy compound having a radical polymerizable group, ie, an unsaturated epoxy compound, with a radical polymerizable monomer. As the unsaturated epoxy compound, vinylbenzyl glycidyl ether, allyl glycidyl ether, glycidyl methacrylate and the like are known. However, since these unsaturated epoxy compounds have an ether bond, their copolymers have a problem that although their thermosetting properties are fast, their photocuring properties are slow, and their use is limited. Therefore, a radical polymerizable epoxy compound having no ether bond is expected. As such a compound, 4-vinylbenzyloxirane has been reported (Makromol. Chem. 191, 1931-1939).
However, this compound had poor stability and was difficult to store or use for a long time.

[0004]

An object of the present invention is to provide a novel unsaturated epoxy compound in which a side chain having an epoxy group is bonded to an aromatic vinyl compound, and a method for producing the same. A further object of the present invention is to obtain homopolymers and copolymers of the obtained novel monomers (collectively,
It is referred to as "(co) polymer". ). Since the (co) polymer obtained here has an epoxy group in the side chain, it has photocurability and thermosetting properties.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have conducted a Grignard reaction using an aromatic vinyl compound having an alkyl halide group bonded to a benzene ring and a halogenated alkyl compound having an epoxy group as raw materials. It has been found that a novel unsaturated epoxy compound in which both are bonded by dehalogenation can be obtained by applying, and the present invention has been completed.

That is, the present invention provides an unsaturated epoxy compound represented by the general formula (1) (hereinafter referred to as "unsaturated epoxy compound (A)") and a method for producing the same.

[0007]

Embedded image

(Wherein, n represents an integer of 1 to 5, R represents a hydrogen atom or a methyl group, and Q represents a hydrogen atom or a methyl group.) The present invention also relates to the unsaturated epoxy compound of the present invention. It is intended to provide a homopolymer of the compound (A) and a copolymer with another unsaturated monomer.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The unsaturated epoxy compound (A) of the present invention has the chemical structure of the general formula (1). General formula (1)
In the formula, n is an integer of 1 to 5, preferably 1 to 3, and particularly preferably 1. R in the general formula (1) is a hydrogen atom or a methyl group. Q in the general formula (1) is a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
The unsaturated epoxy compound (A) of the present invention is obtained by reacting a Grignard reagent represented by the following general formula (2) (hereinafter, referred to as “compound (B)”) with epichlorohydrin or methylepichlorohydrin. Manufactured.

[0010]

Embedded image

(Wherein, n represents an integer of 1 to 5, X represents a chlorine atom or a bromine atom, and Q represents a hydrogen atom or a methyl group.) The compound (B) is ω-haloalkyl-styrene or ω-
It can be produced by reacting haloalkyl-α-methylstyrene (hereinafter, referred to as “compound (C)”) with metallic magnesium in a dried solvent. Here, the alkyl of the haloalkyl is — (CH ₂ ) _n — (n is an integer of 1 to 5), and halo is chlorine or bromine, preferably chlorine.

The bonding position of the halomagnesium alkyl group of the compound (B) can be at the ortho, meta or para position with respect to the vinyl group or α-methylvinyl group. The bonding positions of the epoxyalkylene groups in the unsaturated epoxy compound (A) and the (co) polymer obtained by polymerizing the same are the same as those in the compound (B). Compound (B)
(Usually a reaction solution obtained by reacting compound (C) with metallic magnesium) is used to react epichlorohydrin or methylepichlorohydrin to obtain an unsaturated epoxy compound ( A) is manufactured.

The production of compound (B) is carried out by reacting compound (C) with metallic magnesium, usually at a 1: 1 molar ratio. Examples of the reaction solvent include diethyl ether and tetrahydrofuran. These solvents are sufficiently dehydrated and dried. The compound (C)
Is dissolved in a solvent at a concentration of 10 to 80% by weight and reacted with metallic magnesium. The reaction temperature is generally -30 to 50C, preferably -10 to 10C, and the reaction time is 0.1 to 10 hours.

Subsequently, epichlorohydrin or methyl epichlorohydrin is added to the reaction solution containing the compound (B) and reacted to produce an unsaturated epoxy compound (A). The reaction temperature is usually -30 to 50C, preferably -1.
At 0-10 ° C, the reaction time is 0.1-10 hours. After the reaction, a concentrated alkaline aqueous solution is added to the reaction solution to remove the magnesium halide, followed by washing, extraction, dehydration, and drying, and then the solvent is removed by distillation under reduced pressure, and the remaining crude unsaturated epoxy compound ( A) is purified by distillation under reduced pressure. The yield is usually 30-80%.

The unsaturated epoxy compound (A) can be subjected to radical polymerization alone. Further, the unsaturated epoxy compound (A)
Can be copolymerized with other radically polymerizable monomers. This (co) polymer is represented by the general formula (4).

[0016]

Embedded image

(Wherein, n represents an integer of 1 to 5, R represents a hydrogen atom or a methyl group, Q represents a hydrogen atom or a methyl group. In the formula, Y represents another copolymerizable repeating unit. And h and i are numbers representing the molar ratio of each repeating unit, and h> 0, i ≧ 0, h + i = 1, and i = 0
At this time, it becomes a homopolymer. The molecular weight of the (co) polymer is 1,000 to 1,000, as a weight average molecular weight in terms of polystyrene measured by the GPC method.
000, preferably 3,000 to 200,000. The molar ratio between h and i is preferably such that h is 0.20
I is 0.80 to 0, more preferably h
Is 0.40 to 1 and i is 0.60 to 0.

The repeating unit Y has a structure in which the polymerizable carbon-carbon double bond of the vinyl monomer is cleaved. Examples of vinyl monomers include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene,
p-methylstyrene, p-methoxystyrene, p-methoxymethylstyrene, pt-butoxystyrene, p-
Styrenes such as chloromethylstyrene; dienes such as butadiene, isoprene and 2,3-dimethylbutadiene;
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate,
I-butyl (meth) acrylate, s (meth) acrylate
ec-butyl, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2- (meth) acrylate
Ethylhexyl, lauryl (meth) acrylate, n-dodecyl (meth) acrylate, benzyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, cyclopentyl (meth) acrylate, (meth) ) Cyclohexyl acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 4-methylcyclohexyl (meth) acrylate, phenyl (meth) acrylate, cresyl (meth) acrylate (Meth) acrylic acid esters, acrylic acid, methacrylic acid, maleic acid, itaconic acid and the like can be mentioned.

The monomer is not limited to these, but one or more monomers are appropriately selected depending on the purpose of the polymer. Of these other monomers, styrene,
α-Methylstyrene, pt-butoxystyrene, butadiene, isoprene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and the like are preferred.

Homopolymerization of the unsaturated epoxy compound (A),
Alternatively, the copolymerization reaction of this with another monomer is carried out in a polymerization solvent in the presence of a radical polymerization initiator, preferably 40
The reaction is carried out under a temperature condition of -100 ° C, more preferably 50-90 ° C, and the reaction time is usually 1-48 hours.

Examples of the polymerization solvent include alcohols such as methanol, ethanol, n-propanol and n-butanol; cyclic ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; , N-dimethylformamide, N-
Amide-based protic polar solvents such as methyl-2-pyrrolidone; esters such as ethyl acetate, n-butyl acetate, i-amyl acetate, and ethyl lactate; methyl 3-methoxypropionate, methyl 2-methoxypropionate, 3- Alkoxy esters such as ethyl methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, and ethyl 2-ethoxypropionate; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl Ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether,
Alkyl ethers of polyhydric alcohols such as ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether; ethyl cellosolve Examples include alkyl ether acetates of polyhydric alcohols such as acetate, carbitol acetate, and 3-methoxypropyl acetate; and ketones such as cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone.

Of these, cyclic ethers, polyhydric alcohol alkyl ethers, polyhydric alcohol alkyl ether acetates and esters are preferred. These polymerization solvents can be used alone or in combination of two or more. The ratio of the monomer and the polymerization solvent used is
Although not particularly limited, the polymerization solvent is usually 20 to 1,000 parts by weight based on 100 parts by weight of the monomer.

The radical polymerization initiator includes:
For example, 2,2′-azobisisobutyronitrile,
2'-azobis- (2,4-methylvaleronitrile),
Azo compounds such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1-bis- (t-butyl Peroxy)
Organic peroxides such as cyclohexane; and hydrogen peroxide. These radical polymerization initiators can be used alone or in combination of two or more.

When an organic peroxide or hydrogen peroxide is used as a radical polymerization initiator, these may be used as a redox polymerization initiator in combination with a reducing agent. After completion of the reaction, the (co) polymer solution thus obtained can be precipitated and recovered by pouring the reaction solution into a large amount of an aqueous acetic acid solution or isopropanol.

The (co) polymer of the present invention may be used alone or, if necessary, with a known photoradical polymerization initiator, photocationic polymerization initiator, photoacid generator, crosslinkable compound, filler,
As a radiation-sensitive resin composition containing a viscosity modifier, a dye, a pigment, a plasticizer, a solvent, etc., it can be cured by irradiation with ultraviolet rays, electron beams, or radiation or by heating, for lithography, and for coating. Can be used.

[0026]

EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples. The percentages and parts in the examples are on a weight basis unless otherwise specified.

Example 1 A 500 ml four-necked flask was equipped with a stirrer, and 4.5 g of magnesium for Grignard reaction (0.5 g) was added under a nitrogen stream.
19 mol) and 70 ml of dry diethyl ether, and the mixture was stirred for 30 minutes in an ice bath while maintaining the temperature at 0 ° C. Subsequently, chloromethylstyrene (meta-form: para-form = 70: 3) was added in an ice bath.
0, CMS-P manufactured by Seimi Chemical Co., Ltd.) 26.1 g
(0.17 mol) and a solution consisting of 40 ml of dry diethyl ether were added dropwise over 2 hours, and after completion of the addition, the mixture was reacted with stirring in an ice bath for 1 hour and further at room temperature for 3 hours.

Thereafter, the solution was returned to the ice bath again, and a solution comprising 23.0 g (0.25 mol) of epichlorohydrin and 70 ml of dry diethyl ether was added dropwise in about 2 hours, and the reaction was carried out in the ice bath for 2 hours. And 1 liter with 500 ml of water
Poured into a beaker and separated the diethyl ether phase. 0.85 mol g of a 50% aqueous NaOH solution was added dropwise to this diethyl ether phase over 30 minutes in an ice bath, and the mixture was further stirred at room temperature for 2 hours. After completion of the reaction, the reaction solution is poured into 1 liter of ice water, the product is extracted with toluene, washed with water, dried over anhydrous MgSO ₄ overnight, and the solvent is removed under reduced pressure. Obtained at 41%. Boiling point 53-55 ° C (0.8Tor
r). The obtained vinylphenethyloxirane C ₁₂ H ₁₄ O
Was consistent with the calculated value from the chemical formula. The molecular weight was measured from the parent peak of the mass spectrum and was calculated as 1
And 74. The IR absorption curve is shown in FIG. NMR
The data is shown below. From these data, it was confirmed that the product was vinylphenethyloxirane. The chemical structural formula of vinylphenethyloxirane is shown in the following formula (5).

[0029]

Embedded image

H ¹ -NMR; CDCl ₃ , 270 MH δ ppm; 1.72-1.96 (m, 2H), 2.42-
2.50 (m, 1H), 2.70-2.90 (m, 3H),
2.90-3.00 (m, 1H), 5.14-5.28
(Dd, 1H), 5.64-5.78 (dd, 1H), 6.62
-6.78 (dd, 1H), 7.10-7.40 (m, 4H)

Example 2 An experiment was carried out in the same manner as in Example 1 except that 27.0 g of methyl epichlorohydrin was used instead of epichlorohydrin, and vinylphenethyl-2-methyloxirane was obtained at a yield of 43%. Obtained. The boiling point is 47-50 ° C (0.4 Torr). The obtained vinylphenethyl-2-methyloxirane C ₁₃ H ₁₆
The elemental analysis value of O was consistent with the calculated value from the chemical formula. The molecular weight was measured from the parent peak of the mass spectrum and was consistent with the calculated value of 188. The IR absorption curve is shown in FIG. NM
The R data is shown below. From these data, it was confirmed that the compound was vinylphenethyl-2-methyloxirane.

H ¹ -NMR; CDCl ₃ , 270 MHz δ ppm; 1.38 (s, 3H), 1.78-2.00
(M, 2H), 2.54-2.76 (m, 4H), 5.20
(Dd, 1H), 5.72 (dd, 1H), 6.68 (dd, 1H)
H), 7.00-7.44 (m, 4H)

Example 3 In a 100 ml three-necked flask equipped with a reflux tube, 8.7 g of the vinylphenethyloxirane obtained in Example 1 (0.
05 mol), benzene 25 ml, and azoisobutyronitrile 0.042 g, and stirred at room temperature for 30 minutes under a nitrogen stream.
Thereafter, the reaction was performed at 60 ° C. for 24 hours. After completion of the reaction, the reaction solution was poured into 500 ml of hexane, reprecipitated twice with a benzene / hexane mixed solvent, and lyophilized to isolate a polymer. The yield was 86%, the weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 79,900, the number average molecular weight Mn was 40,800, and the glass transition temperature Tg measured by the DSC (differential calorimeter) method was 36 ° C. Met. The IR absorption curve is shown in FIG. The NMR data is shown below.

H ₁ -NMR; CDCl ₃ , 270 MHz δ ppm; 1.02-2.20 (b, 5H), 2.30-
3.00 (b, 5H) 6.20-7.40 (b, 4H)

Example 4 8.7 g (0.05 mol) of vinylphenethyloxirane
The experiment was conducted in the same manner as in Example 3 except that 4.35 g (0.025 mol) and 2.6 g (0.025 mol) of styrene were used instead of the above, and the copolymer of vinylphenethyloxirane and styrene was used. The polymer was obtained with a yield of 92%. GP
The polystyrene equivalent weight average molecular weight Mw measured by the method C was 35,400, the number average molecular weight Mn was 19,600, and the glass transition temperature Tg measured by the DSC method was 55 ° C.

Example 5 9.41 g (0.05 mol) of vinylphenethyl-2-methyloxirane obtained in Example 2, 25 ml of benzene, and azoisobutyronitrile were placed in a 100 ml three-necked flask equipped with a reflux tube. 0.042 g, put under nitrogen stream 30
After stirring at room temperature for 20 minutes, the reaction was carried out at 60 ° C. for 24 hours. After completion of the reaction, the reaction solution was poured into 500 ml of hexane, reprecipitated twice with a benzene / hexane mixed solvent, and the polymer was isolated by freeze-drying. 86% yield, G
Polystyrene-equivalent weight average molecular weight Mw measured by PC method
Was 81,000, the number average molecular weight Mn was 41,500, and the glass transition temperature Tg measured by the DSC method was 51 ° C. The IR absorption curve is shown in FIG. The NMR data is shown below.

H ¹ -NMR; CDCl ₃ , 270 MHz δ ppm; 1.00-2.10 (b, 8H), 2.20-
2.70 (b, 4H) 6.10-7.20 (b, 4H)

Example 6 A photoacid generator (trade name: SP-170; manufactured by Asahi Denka Kogyo KK) was added to the (co) polymers obtained in Examples 3 and 4 for each of the (co) polymers. On the other hand, two kinds of films containing 2% by weight were prepared by spin coating. The film having a thickness of 5 μm was irradiated with ultraviolet rays of 500 mJ / cm ² . The irradiated film was placed in tetrahydrofuran, the insoluble content was determined, and this was defined as the gel fraction of the film. As a result, the gel fraction was 88% for the polymer of Example 3 and 9% for the copolymer of Example 4.
It was found that these (co) polymers were easily crosslinked by ultraviolet irradiation. This property indicates that these (co) polymers are useful as radiation-sensitive resins.

[0039]

The unsaturated epoxy compound of the present invention provides a novel radically polymerizable monomer. The (co) polymer of this monomer has a photocationically polymerizable epoxy group, is capable of forming a film, and is useful as a radiation-sensitive resin.

[Brief description of the drawings]

FIG. 1 shows an IR absorption curve of the compound obtained in Example 1.

FIG. 2 shows an IR absorption curve of the compound obtained in Example 2.

FIG. 3 shows an IR absorption curve of the polymer obtained in Example 3.

FIG. 4 shows an IR absorption curve of the polymer obtained in Example 5.

Continuing on the front page F term (reference) 4C048 AA01 BB02 CC01 UU03 UU05 XX02 XX04 4J036 AJ24 AK04 BA01 JA01 JA09 4J100 AB02Q AB03Q AB04Q AB07P AB07Q AL03Q AL04Q AL05Q AL08Q AL11Q AS02Q AS03Q AS06Q BA04PCA38 BC03 BC04

Claims (4)

[Claims] 1. An unsaturated epoxy compound represented by the general formula (1). Embedded image (In the formula, n represents an integer of 1 to 5, R represents a hydrogen atom or a methyl group, and Q represents a hydrogen atom or a methyl group.) 2. n is 1, R is a hydrogen atom or a methyl group,
The unsaturated epoxy compound according to claim 1, wherein Q is a hydrogen atom. 3. The method for producing an unsaturated epoxy compound according to claim 1, comprising reacting a Grignard reagent represented by the general formula (2) with epichlorohydrin or methyl epichlorohydrin. Embedded image (In the formula, n represents an integer of 1 to 5, X represents a chlorine atom or a bromine atom, and Q represents a hydrogen atom or a methyl group.) 4. A weight average molecular weight having a repeating unit represented by the following general formula (3): 1,000 to 1,000,000.
00 (co) polymer. Embedded image (In the formula, n represents an integer of 1 to 5, R represents a hydrogen atom or a methyl group, and Q represents a hydrogen atom or a methyl group.)