JPS61271312A - Production of copolymer of hydroxystyrene with maleimide - Google Patents

Abstract

PURPOSE:To obtain the title linear copolymer excellent in heat resistance, adhesiveness and film formability and good in hue, by copolymerizing a hydroxystyrene with a maleimide in the presence of a polymerization initiator and water. CONSTITUTION:The title copolymer composed of linearly bonded structural units of formulas III-IV (wherein R6O is meta or para to the main chian) is obtained by copolymerizing a hydroxystyrene of formula I (wherein R1-3 are each a 1-4C alkyl, R6 is H, aralkyl or acetyl, Z is a 1-4C alkyl, m is 0-3 and R6O is meta or para to the vinyl group) with a maleimide of formula II (wherein R4-5 are each one of R1-3, and R7 is H, a 1-10C alkyl, phenyl, aralkyl or acetoxy) at a molar ratio of 10-90:90-10 at 120-350 deg.C when 1-80% water is used) or at 0-50 deg.C when 80% or more water is used) in the presence of a polymerization initiator selected from among a radical initiator, an acid, a base, light, heat and radiations.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for producing a novel copolymer consisting of hydroxystyrenes and maleimides. A method for producing a novel copolymer having a phenol group and an imide group in the side chain of the polymer by carrying out a copolymerization reaction with a radical initiator, and at least one of acids, bases, light, heat, and radiation. In particular, it is appropriate to copolymerize hydroxystyrenes and maleimides in a state containing 1% or more of water. We have discovered that the presence of water makes it easier to remove the copolymerization heat during the process, and furthermore, the hydroxystyrenes are hydrated, making it easier to control the copolymerization.

(Prior art) Conventionally, hydroxystyrene was polymerized with acetic acid, succinic acid, acrylic acid, levulinic acid, benzoic acid, ascorbic acid, carbon dioxide gas, etc.
In addition, polymerization with formic acid, oxalic acid, glycolic acid, salicylic acid, etc. was introduced in 1986-44608, and as a molecular weight regulator, water, alcohol, phenol, acetone, dimethyl sulfone, dimethyl sulfoxide, nitromethane, tetrahydrofuran, formamide, Or asel
-2) Polymerize hydroxystyrene with an organic carboxylic acid in the presence of IJ. Japanese Unexamined Patent Publication No. 57-
No. 44609.

In addition, homopolymerization of maleimides is R, C, P.

Cubbon, Po1yrr+er, 6.419
(1966) Yani-Kojrma et al., J. Pol.
ymer Sci, s A-1゜4.1121 (196
6) and Masamori Yamada et al., Kouka.

6, 393 (1969).

Furthermore, the copolymerization reaction of parahydroxystyrene or metahydroxystyrene with methyl methacrylate or styrene is M, Ka t o .

J-Polymer Sci, A-1, 7, 21
75 (1969) VC, copolymerization reaction of paraacetoxystyrene and styrene, F. Danusso et al.

Chim, Ind. (Milan) 47.585
(1965). On the other hand, the copolymerization reaction of maleimide with vinylidene chloride, methyl methacrylate, or styrene is described by G-Van Paesschen et al.

Makromol, Chem, 78, 11.2 (196
4) The copolymerization reaction of N-methylmaleimide or N-ethylmaleimide with vinyl chloride is described by Michio Inuzuka et al.
Koka, 72, 2505 (1969) describes the copolymerization reaction of N-phenylmaleimide and vinyl monide as described by Michio Inuzuka et al., Koka, 73. 1.062 (1970), N-
The copolymerization reaction of phenylmaleimide with methyl methacrylate or styrene has been reported by Masamori Yamada et al.
6 (1967).

(Problems to be Solved) The present inventors have conducted various studies on the production of functional polymers synthesized from hydroxystyrene, and as part of their research, they have also developed a hydroxystyrene-based polymer with excellent heat resistance. I conducted research to find out. It is known that the heat resistance of some polymers can be improved by including an imide group in the polymer chain or by mixing an imide group-containing compound with the polymer. Attempted copolymerization with similar tomaleimides,
We have successfully synthesized a new copolymer of hydroxystyrenes and maleimides. The copolymer of hydroxystyrene and 71/imide obtained by the method of the present invention has heat resistance,
It has excellent adhesion, film-forming properties, etc., and has a good hue, and according to the method of the present invention, a high-molecular-weight copolymer can also be easily obtained.

It is therefore an object of the present invention to provide a process for the production of copolymers of meta- or parahydroxystyrenes and maleimides. A second object of the present invention is to provide a method for producing a novel copolymer of hydroxystyrenes and maleimides, which is a material with excellent heat resistance, adhesiveness, and film-forming properties, and a good hue. Yet another object is to provide a method for producing linear copolymers of hydroxystyrenes and tomaleimides that are soluble in various organic solvents.

(Means for Solving the Problems) That is, the gist of the present invention is as follows: General formula (1) (wherein R1, R2 and R3 are hydrogen or have 1 carbon number
-4 alkyl group, R6 represents hydrogen, aralkyl group or acetyl group, Z represents an alkyl group having 1 to 4 carbon atoms, m is 0.1.2 or 3, R
60 groups are at the meta or para position relative to the vinyl group. ) and the general formula (I[
) (However, R4 and R5 are hydrogen or have 1 to 4 carbon atoms.)
represents an alkyl group, and R7 is hydrogen, an alkyl group having 1 to 10 carbon atoms, a phenyl group, an aralkyl group, or an acetoxy group. ) when the molar ratio of the hydroxystyrene and the maleimide is 1.
In the range of 0:90 to 90:10, radical initiator, acid,
At least one of base, light, heat and radiation is used to contain 1% or more of water as a copolymerization solvent, and the water content is 1 to 80%.
If it contains water, it copolymerizes in a temperature range of 120 to 350°C, and if it contains 80% or more water, it copolymerizes in a temperature range of 0 to 50°C. (
1) and general formula (IY) (However, R1, R2, R3, R4, R5, R6, R7
, m and Z are the same as above, and the R60 group is at the meta or para position with respect to the main chain). It consists in a method for producing a copolymer.

The hydroxystyrene used as a raw material for the copolymerization reaction in the present invention may be a pure product, or may be a crude hydroxystyrene that is usually obtained industrially. Generally, apart from the purity, only parahydroxystyrene is used, but depending on the requirements, for example, a mixture of parahydroxystyrene and metahydroxystyrene, or a mixture of parahydroxystyrene and parahydroxy-α-methylstyrene may be used. A mixture of two or more types of hydroxystyrenes such as metals can also be used. Preferred specific examples of hydroxystyrenes include parahydroxystyrene, metahydroxystyrene, parahydroxy-α-
These include methylstyrene, metahydroxy-α-methylstyrene, parahydroxy-α-ethylstyrene, paraacetoxystyrene, and parahydroxystyrene is more preferred. Thus, the phenolic hydroxyl group of hydroxystyrenes is located at the meta or rose position relative to the alkenyl group such as vinyl group. Z is generally a methyl group, and m is usually 1 or 0.

These hydroxystyrenes and their production methods are well known; for example, a method for producing and synthesizing para-hydroxystyrene is described in 脣显显57-4407. Metahydroxystyrene may also be produced or synthesized in the same manner as parahydroxystyrene. Valisopropenylphenol (also known as halahydroxy-α-methylstyrene) can be synthesized in a similar manner. Acetoxystyrene can be synthesized, for example, by reacting hydroxystyrene with acetic anhydride.

The maleimide which is the other raw material for the copolymer of the present invention may of course be a pure product, but it may also be a crude maleimide which is usually obtained industrially. Generally, apart from purity, only maleimide is used for maleimide, and only N-7 enylmaleimide is used for N-phenylmaleimide, but if desired, for example, a mixture of maleimide and N-phenylmaleimide, etc.
It is also possible to use mixtures of m or more.

Preferred specific examples of maleimides include maleimide, N-methylmaleimide, N-ethylmaleimide, and N-phenylmaleimide. Maleimides and their production methods are known. For example, in the case of maleimide, maleimide is produced by oxidizing virol with a chromic acid mixture, by heating maleamide with zinc chloride, or by reacting maleic anhydride with urea. Dehydrate the acid and N-
It is obtained by further thermally decomposing carbamyl maleimide. In the case of N-alkylmaleimide,
L., E., Coleman.

Jr. et al., J-Org-Chem, 24,135 (1
959), maleic anhydride is reacted with a primary amine to synthesize N-alkylmaleamic acid, which is then cyclodehydrated with acetic anhydride and sodium acetate. N-phenylmaleimide can be produced in the same manner as N-alkylmaleimide by using aniline as the primary amine. In the case of N-acetoxymaleimide, Masamori Yamada et al.

23.166 (1965) by the reaction of maleic anhydride with an alkanolamine,
Oxyalkylmaleamic acid is obtained by dehydrating and esterifying it with acetic anhydride and sodium acetate.

The copolymer of hydroxystyrene and maleimide of the present invention can be produced as follows. That is, 10 hydroxystyrenes and maleimides
: coexisting at a molar ratio in the range of 90 to 90:10, containing 1% or more of water as a copolymerization solvent by at least one of a radical initiator, an acid, a base, light, heat, and radiation;
When containing 1 to 80% water, the temperature range is 120 to 350 °C, preferably 130 to 250 °C,
When the water content is 80% or more, the polymerization can be carried out in a temperature range of 0 to 50°C, preferably in a temperature range of 5 to 40°C, using methods such as bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, etc. I can do it.

When a radical initiator is used, for example, hydroperoxides such as methyl hydroperoxide and cumene hydroperoxide, dialkyl peroxides such as di-tert-butyl peroxide, peracetic acid, perbenzoic acid, tert-butyl perbenzoate, tertiary-butyl peroxide, etc. Peracids and their esters such as butyl peroxytriphenyl acetate, di-tert-butyl monoperoxyoxalate, diacyl and sialoyl peroxides such as acetyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,2-azobisisobutyl Initiators such as azo compounds such as lonitrile, disulfides such as tetramethylthiuram disulfide, persulfates such as potassium persulfate and ammonium persulfate can be used.

The amount of radical initiator used is 0.01 to 10% relative to the reaction system.
Weight % is appropriate.

In the case of initiation by light, copolymerization can be initiated by irradiation with ultraviolet rays from an ultra-high pressure mercury lamp.

For example, when a 250 W ultra-high pressure mercury lamp is used, the appropriate amount of light is irradiation for 1 minute to 1 hour at a distance of 45 c1rL.

In the case of initiation by radiation, copolymerization can be initiated by irradiation with gamma rays from Kobal 60. For example, a dose rate of 10 to 10 rad/sec is suitable.

When using an acid as an initiator, for example, oxalic acid, sulfuric acid,
Protic acids such as perchloric acid and trifluoroacetic acid, Lewis acids such as borohydride, aluminum chloride, titanium tetrachloride, ferric chloride, and ferric chloride can be used as initiators.

When a base is used as an initiator, for example, a hydroxide such as sodium hydroxide or a Lewis base such as an amine can be used as the initiator. The appropriate amount of acid or base to be used is 0.001 to 5% by weight based on the reaction system.

In order to obtain the copolymer of the present invention, the molar composition ratio of hydroxystyrenes and maleimides is not particularly limited, and the molar composition ratio is from 10:90 to 90:10. However, in order to carry out the copolymerization reaction more efficiently, the molar composition ratio is preferably about 30:0 to 70:30.

In carrying out the method of the present invention, it is usually preferable to carry out solution polymerization, but it is also possible to carry out bulk polymerization using the amphomer as a self-solvent. It is also possible to carry out emulsion polymerization or suspension polymerization.

In the case of emulsion polymerization, emulsifiers include anionic surfactants such as oleic sodium, alkali metals of fatty acids such as alkylsulfonic acids, cationic surfactants such as amine salts, quaternary ammoniums, and ethylene oxide of alkylphenols. Nonionic surfactants such as adducts can be used.

In the case of suspension polymerization, starch,
Water-soluble polymers such as pectin, alginates, gelatin, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, polyvinyl alcohol, polyacrylic acid, and polyvinylpyrrolidone or fine inorganic substances such as barium sulfate and magnesium phosphate can be added. I can do it.

During copolymerization, water becomes a very important factor as a solvent. This is because hydroxystyrenes are hydrophilic monomers. In addition to this, alcohol, phenol, ethylphenol, acetone,
Dimethyl sulfone, dimethyl sulfoxide, nitromethane, tetrahydrofuran, dioxane, formamide,
Acetonitrile, ethyl acetate, glopyrene carbonate, chloroform, pyridine, acetic acid, methylene chloride and toluene, or a mixed solvent thereof, or a mixed solvent of these and water can be used.

The time required for the copolymerization reaction varies depending on the conditions used, but is generally about several minutes to 48 hours, preferably 0.
．． The copolymer of hydroxystyrene and maleimide, which is the product of the process of the present invention, has various types of phenolic nuclei in the copolymer by a polymer reaction known per se. Substituents can be easily introduced. For example, by the method disclosed in the case of polyvarahydroxystyrene,
No. 762), no-romethyl group (JP-A No. 59-43006)
), methylol group (% Publication No. 44-7350), sulfonic acid group (% Publication No. 55-24444), sulfomethyl group (Japanese Unexamined Patent Publication No. 49-66581), phosphoric acid group (Japanese Unexamined Patent Application Publication No. 1973)
No. 3-47489), alkyl phosphoric acid group (%
No. 47489), alkylaminomethyl group (Japanese Patent Publication No. 1983)
-25202).

'Alkylammonium methyl group (% Kōsho 55-252
No. 02], nitroso group (1% 1988-148892), nitro group (Journal of the Fist Chemical Society, Journal of the Che
mical 5ociety, I 964°26
19-2620).

The copolymer of hydroxystyrenes and maleimides obtained by the present invention has excellent chemical, physical, and biological properties, and can be used as an ultra-heat-resistant resin, a photosensitive resin, a chelate resin, and a heat-resistant adhesive. It is a functional polymer material that has a wide range of uses, including agents, paints, liquid crystal alignment agents, polymer matrix agents for composite materials, metal surface treatment agents, coating agents for glass and wires, and various separation membranes. In particular, this new copolymer has excellent processability and color, and can be used to produce colorless and transparent or white films, tapes, fibers, laminates, etc.
You can easily manufacture festivals and molded products.

Next, this new copolymer of hydroxystyrenes and tomaleimides can be applied as a photosensitive resist for microfabrication to various MFI exposures such as ultraviolet rays, deep ultraviolet rays, electron beams, and X-rays, and has a good effect on substrates. Excellent adhesion, heat resistance, dry etching resistance, and resolution. Furthermore, this novel copolymer is useful as a thermosetting resin composition when blended with an epoxy resin.

EXAMPLES The present invention will be illustrated in more detail by way of Examples below, but these are merely given for the purpose of illustration and are not intended to limit the scope of the present invention. In this example, GC is an abbreviation for gas chromatography, and GPC is an abbreviation for gel permeation chromatography.

Example 1 A predetermined amount of recrystallized purified rose hydroxystyrene, a predetermined amount of distilled purified rose ethylphenol (purity 99.3% by GC' analysis), and a predetermined amount of distilled water were placed in a polymerization tube of rs 500 rrtl that had been previously purged with nitrogen. was added and quickly dissolved almost uniformly. Separately, a solution prepared by dissolving a predetermined amount of recrystallized purified N-phenylmaleimide in a predetermined amount of distilled purified paraethylphenol or an organic solvent was quickly added to a 500 ml polymerization tube that had been purged with nitrogen at room temperature. Transfer to a polymerization tube containing the above-mentioned bulk hydroxystyrene, mixer (manufactured by Taiyo Kagaku Kogyo ■, A
The mixture was stirred using a UTOMATIC MIXER, S-5N). When using a predetermined amount of initiator, a solution containing N-phenylmaleimide was quickly added and stirred to dissolve.

Thereafter, a copolymerization reaction was carried out for a predetermined time in a solution containing parahydroxystyrene and N-phenylmaleimide in a thermostatic polymerization tank at a predetermined temperature. After the copolymerization reaction, the copolymer solution was poured into approximately 20 times the amount of n-hebutane solvent to precipitate the copolymer, and after passing through the mouth, the solution was thoroughly washed with n-hebutane. It was further separated by further rinsing. This copolymer was vacuum dried at 30° C. until it reached a constant weight, and the yield was determined. All of the produced copolymers were white.

In addition, GPC analysis of the produced copolymer was performed to measure the molecular weight and molecular weight distribution, and the microstructure of the produced copolymer was determined by TR
Analysis, determined by NMR analysis, %K, C-NMR
By analysis, the composition of the copolymer of parahydroxystyrene and N-phenylmaleimide was determined. Furthermore, the softening point (Ts, 'C) of the resulting copolymer was measured. These results are summarized in Table 1.

The IR spectrum of Exp-1 is shown in Figure 1, and its C
-NMR spectrum is shown as FIG.

Example 2 A copolymerization reaction between hydroxystyrenes and maleimides was carried out in the same manner as in Example 1. The reaction conditions and results are shown in Table 2.

Reference Example 1 Copolymer of parahydroxystyrene and N-phenylmaleimide obtained in Exp, 1 of Example 1 2.84. @(
Weight average molecular weight 30.250, parahydroxystyrene 58.3 mol % in the copolymer) and 0.88 g of orthonaphthoquinone diazide were mixed with ethyl cellosolve acetate 4.
0.9 and N,N-dimethylformamide 10. A resist solution was prepared by dissolving the resist solution in F and F, and the resist solution was applied onto an aluminum plate to form a resist layer with a thickness of 2.179/m. Then, this was prebaked at a temperature of 105°C for 40 minutes, and then ultraviolet light with a wavelength of 320 to 500 ss was applied. Exposure was carried out under the positive original.

Thereafter, the resist was developed at a temperature of 50 DEG C. with an aqueous solution of 4% by weight trisodium phosphate and 3% by weight sodium silicate, and rinsed with water to obtain a positive image.

Generally, one way to express the performance of a photoresist is to measure the number of sheets that can be printed without showing wear when printed with an offset printing machine after applying oil-based ink.The offset printing performance of this resist is 8. It was a very good product with over 10,000 copies. This performance was more than twice that of polyparavinylphenol and orthonaphthoquinone diazide.

Reference Example 2 Bisphenol-based epoxy resin Epicoat 828 (Epoxy equivalent: 1
90, molecular weight approximately 380) 19, mixed with O, F (phenolic hydroxyl group/epoxy group (OH/9) is 1.0) L,
This was heated and dissolved at 190 to 210°C. This melt was poured into a glass mold (cellophane was pasted on the inside) and heated at 180° C. for 1 hour and then at 250° C. for 3 hours to obtain a pale yellow transparent cast material.

The heat distortion temperature (°C) of the test piece cut out from this cast material (
HDT) was measured and found to be 207°C.

Reference Example 3 In Reference Example 2, parahydroxystyrene and N-phenylmaleimide copolymer 28.
A curing reaction was carried out in the same manner as in Reference Example 2, except that 4.9 and the bisphenol-based epoxy resin Epicoat 82819 manufactured by Shell Co., Ltd. and OII were quickly added to the heated melt. As a result, the heat distortion temperature (HDT) An extremely excellent cast product was obtained with a temperature of 248°C.

Reference Example 4 Rose hydroxystyrene and N-phenylmaleimide copolymer similar to that used in Reference Example 2 28.4. Bisphenol-based epoxy resin DER331-J manufactured by P and Dow
18.91! and para-aminobenzaldehyde o, sI
I and 4500.9 were dissolved in methyl ethyl ketone to form a festival. This face was poured onto a tin plate and a glass plate, dried at room temperature for 4 hours, then heat-treated at 180℃ for 1 hour, and then at 220℃ for 1 hour to achieve a film thickness of approximately 15μ.
A coating film was obtained. The coating film using glass as a support thus obtained was immersed in methyl ethyl ketone at room temperature for 48 hours or left under refluxing methyl ethyl ketone for 12 hours, and the extent of the coating film was examined. In both tests, the coating film was It is very stable and is not affected by methyl ethyl ketone.

Good curing was achieved. In addition, when a coating film using a tin plate as a support was subjected to a base grain test and a bending resistance test, the results were very good, and the ship registration hardness was 5H.

Reference Example 5 Rose hydroxystyrene and N-phenylmaleimide copolymer 28.4.9 similar to those used in Reference Example 2 and bisphenol-based epoxy resin DER331-J manufactured by Dow Corporation
18.9g and 0.5g of BF3/Pipe/Lysine for 40
01 was dissolved in acetone to make a festival. Glass cloth (satin weave made by Nippon Glass ■, micro glass E) will be featured at this festival.
S-21NH) and left at room temperature for 2 hours at 60°C.
It was dried at 90° C. for 10 minutes and at 90° C. for 30 minutes.

The thus obtained prepreg cloth had no tackiness at room temperature and had very good workability. In addition, the above heat treatment did not cause any curing reaction and had excellent storage stability. Next, 36 sheets of this prepreg cloth were stacked one on top of the other with the spinning direction aligned, and then heated at 190°C under normal pressure and then at 21°C.
Hot pressing was carried out at 0° C. under a pressure of 30k19/i for 30 minutes. This hot-pressed product was further post-cured at 220° C. for 3 hours to obtain a laminate. This product.

The laminated plate did not contain any air bubbles and had very good defoaming properties. Test piece of the obtained laminate at 4250℃
The weight loss was measured by leaving the pot open for 50 hours, 100 hours, and 300 hours, and the weight loss was 0.41% by weight.
, 0.52% by weight, and 0.72% by weight.

As mentioned above, it is also clear that the copolymers of hydroxystyrenes and maleimides obtained by the production method of the present invention and modified products thereof are useful as photoresists, synthetic materials, coatings, and laminates.

(Effects of the Invention) According to the method of the present invention, copolymers of hydroxystyrenes and maleimides, which are novel polymers, can be easily obtained, and these copolymers have excellent heat resistance, film-forming properties, It is a resin with excellent adhesive properties and a good hue, and as mentioned above, it can be suitably used in many applications such as photoresists, molding materials, paints, and laminates.

[Brief explanation of drawings]

Figure 1 is the IR spectrum of the product obtained in Exp, 1 of Example 1, and Figure 2 is its 13C-
This is an NMR spectrum. Procedure Amendment Book February 7, 1985

Claims (1)

[Claims] (1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (However, R_1, R_2, and R_3 represent hydrogen or an alkyl group having 1 to 4 carbon atoms, and R_6 represents hydrogen, an aralkyl group, or Represents an acetyl group, Z has 1 carbon number
-4 alkyl group, m is 0, 1, 2 or 3, and the R_6O group is at the meta or para position with respect to the vinyl group. ) Hydroxystyrenes represented by the general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (However, R_4 and R_5 are hydrogen or have 1 to 1 carbon atoms.
4 alkyl group, R_7 is hydrogen, carbon number 1-1
0 alkyl group, phenyl group, aralkyl group or acetoxy group. ) and a radical initiator, with a molar ratio of the hydroxystyrenes and the maleimides in the range of 10:90 to 90:10.
At least one of acid, base, light, heat, and radiation is used to contain 1% or more of water as a copolymerization solvent, and
When containing 0%, in the temperature range of 120 to 350°C,
When containing 80% or more of water, the polymer chain characterized by copolymerization in the temperature range of 0 to 50°C is essentially the general formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) and general formula (IV) ▲Mathematical formulas, chemical formulas, tables, etc.▼(IV) (However, R_1, R_2, R_3, R_4, R_5,
R_6, R_7, m and Z are the same as above, and R_
The 6O group is at the meta or para position with respect to the main chain. )
A method for producing a copolymer of hydroxystyrene and maleimide formed by linearly bonding the structural units represented by