JP2002322268A - Method for producing oxetane resin comprising multifunctional oxetane compound and cyclic carboxylic acid anhydride - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new method for producing an oxetane resin. SOLUTION: This method for producing the oxetane resin is characterized by subjecting a multifunctional oxetane compound and a cyclic carboxylic acid anhydride.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel method for producing an oxetane resin.

[0002]

2. Description of the Related Art In recent years, due to the miniaturization and weight reduction of electronic devices represented by mobile phones and notebook personal computers, the momentum of high integration and high functionality of semiconductors is remarkable. Accordingly, characteristics required for a sealing material, such as protecting a semiconductor element from an external environment such as moisture and heat, and facilitating mounting on a substrate, have become strict. Most of the semiconductor encapsulating materials use an epoxy resin using a cyclic carboxylic anhydride as a curing agent. The reason is that an epoxy resin using a cyclic carboxylic anhydride has extremely low water absorption because it does not contain a hydroxyl group in a side chain, and thus the epoxy resin is excellent in electric insulation. Taking advantage of these advantages, they are often used for electric insulating materials, and are also used in various other fields such as paints and adhesives. However, epoxy resins are known to be unstable and irritating to the skin under alkaline conditions, which not only lowers the stability of the product but also poses a problem in safety from the viewpoint of work.

On the other hand, it has been reported that an oxetane compound having a four-membered cyclic ether structure forms a three-dimensional network structure by a crosslinking reaction with a curing agent like an epoxy compound. Oxetane compounds require relatively high curing temperatures due to their lower reactivity than epoxy compounds, but are stable under alkaline conditions and have no skin irritation. Also, from the viewpoint of the structure of the oxetane ring, the resulting cured product is expected to have a smaller volume shrinkage than the cured product of the epoxy compound. Furthermore, since the number of methylene chains generated with the opening of the oxetane ring is larger than that of epoxy, there is a high possibility that the polymer material will have improved brittleness of a cured product, which is a drawback of epoxy resins. As described above, oxetane resins are expected to be used industrially, whereas epoxy resins have been actively researched, but so far, oxetane resins have hardly been researched. .

[0004]

An object of the present invention is to provide a novel method for producing an oxetane resin,
Specifically, it is a method for producing an oxetane resin in which a polyfunctional oxetane compound and a cyclic carboxylic anhydride are subjected to a thermosetting reaction.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, by applying a specific catalyst and specific reaction conditions, a polyfunctional oxetane compound and a cyclic carboxylic acid anhydride are obtained. Have been found to undergo a thermosetting reaction, and the present invention has been completed. That is, the present invention is a method for producing a polyester, which comprises thermally curing a polyfunctional oxetane compound and a cyclic carboxylic acid compound.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION As the polyfunctional oxetane compound in the present invention, any compound having two or more oxetane rings in a molecule can be used without any particular limitation. Specific examples include oxetane compounds represented by the following formulas (1) to (9). Among these, from the viewpoint of reactivity with a cyclic carboxylic anhydride, they are represented by the following formula (1). 1,4-bis (3-ethyl-3-oxetanylmethoxymethyl) benzene is a particularly preferred compound.

[0007]

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[0008]

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[0009]

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[0010]

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[0011]

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[0012]

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[0013]

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[0014]

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[0015]

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The cyclic carboxylic anhydride in the present invention includes, for example, phthalic anhydride, succinic anhydride, cis-
1,2-cyclohexanedicarboxylic anhydride and 2,
2′-biphenyldicarboxylic anhydride and the like,
Of these, phthalic anhydride is preferred from the viewpoint of reactivity with the oxetane compound.

The production method of the present invention comprises subjecting the above-mentioned polyfunctional oxetane compound and a cyclic carboxylic anhydride to a thermosetting reaction. Used as a catalyst,
The reaction is preferably performed in the presence of these. Among these catalysts, the use of a quaternary onium salt and a crown ether complex is preferred from the viewpoint of the reactivity between the polyfunctional oxetane compound and the cyclic carboxylic acid anhydride. As the quaternary onium salt, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, tetraethylammonium bromide, tetraethylchloride, tetraethyliodide, n-dodecyltrimethylammonium bromide, octadecyltrimethylammonium bromide,
Trimethylbenzylammonium bromide, cetyldimethylbenzylammonium chloride, cetyldimethylbenzylammonium bromide, cetylpyridium sulfate, tetraethylammonium acetate,
Trimethylbenzylammonium benzoate, trimethylbenzylammonium borate, 5-benzyl-
Quaternary ammonium salts such as 1,5-diazabicyclo [4,3,0] -5-nonenium chloride and 5-benzyl-1,5-diazabicyclo [4,3,0] -5-nonenium tetrafluoroborate; And ammonium tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, tetraphenylphosphonium chloride, benzyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, triphenylmethoxymethylphosphonium chloride, triphenylmethyl Carbonylmethylphosphonium chloride, triphenylethoxycarbonylmethylphosphonium chloride, trioctybenzylbenzyl Mukuroraido, trioctyl methyl phosphonium chloride, trioctyl ethyl phosphonium acetate, tetra-octyl phosphonium chloride, quaternary phosphonium salts such as trioctyl ethyl phosphonium dimethyl phosphate and the like. Of these, quaternary phosphonium salts are preferably used, and tetrabutylphosphonium bromide is particularly preferred.

Further, as the crown ether complex, 1
2-crown-4, 15-crown-5, 18-crown-6, dibenzo-18-crown-6, 21-crown-7, 24-crown-8 and the like, and these include KF, KCl, KBr. , CsF, CsCl, CsB
r, used as a complex with inorganic or organic salts such as potassium thiocyanate, sodium phenoxide, potassium phenoxide, sodium benzoate, potassium benzoate, sodium acetate and potassium acetate.
Among these, dibenzo-18-crown-6 is preferred. Further, tertiary amines include diethylaminopropylamine, N-aminoethylpiperazine, benzyldimethylamine, and tris (dimethylaminomethyl) phenol.

The reaction conditions in the production method of the present invention are slightly different depending on the types of the polyfunctional oxetane compound and the cyclic carboxylic anhydride used in the reaction, but it is preferable to carry out the reaction under the following conditions. The reaction can be carried out either in a continuous system or in a batch system. The reaction in the production method of the present invention is a thermosetting reaction between the polyfunctional oxetane compound and the cyclic carboxylic acid anhydride, and varies depending on the number of functional groups of the oxetane compound. For example, in the case of a bifunctional oxetane compound, a cyclic carboxylic anhydride is used in an amount of from 0.8 to 1 mol per mol of the polyfunctional oxetane compound.
It is preferably 2.8 mol.

Catalyst Concentration As mentioned above, the reaction is preferably performed in the presence of a catalyst. The use amount of these catalysts is preferably 1 to 20 mol%, more preferably 2 to 10 mol%, based on the polyfunctional oxetane compound. When the amount of the catalyst is less than 1 mol%, the reaction hardly proceeds, and on the other hand, even if it is used in a proportion exceeding 20 mol%, no particular effect is recognized.

Reaction temperature and reaction time The reaction temperature is preferably in the range of 100 to 300 ° C., particularly preferably 180 to 250 ° C. on the other hand,
Although the reaction time is not particularly limited, a reaction time of 1 to 10 hours is appropriate in consideration of the reaction temperature.

Reaction Solvent In the above reaction, a reaction solvent can be used.
Reaction solvents include, but are not limited to, toluene, anisole, N, N-dimethylacetamide, N-methylpyrrolidone, chlorobenzene, and dimethylsulfoxide. Further, the reaction can be carried out without a solvent.

The oxetane resin obtained by the production method of the present invention is obtained by copolymerizing a polyfunctional oxetane compound and a cyclic carboxylic anhydride into a fine network structure. As a result, mechanical properties (such as tensile strength) and electric It is a resin with excellent mechanical properties (such as electrical insulation), heat resistance, chemical resistance, and adhesion, and is expected to be used in various applications. Hereinafter, the present invention will be specifically described with reference to examples.

[0024]

EXAMPLES Example 1 0.010 g (0.03 mmol) of tetrabutylphosphonium bromide (hereinafter referred to as TBPB) and 1,4-bis (3-ethyl-3-oxetanylmethoxymethyl) represented by the above formula (1) ) 0.033 g (0.1 mmol) of benzene (hereinafter referred to as BEOB) and 0.030 g (0.2 mm) of phthalic anhydride (hereinafter referred to as PAn)
ol) was placed in a sample bottle, a small amount of DMF was added and mixed well. After heating this at 220 ° C. for 2 hours, 3.
0 mL of DMF was added and left for 24 hours. Thereafter, the gelled portion was washed once with DMF and acetone, and then collected on a glass filter, dried with a desiccator and a reduced-pressure drier (60 ° C.), and the gelation rate after the reaction was determined.
The gelation ratio after the reaction was 92%.

Examples 2 to 13 The reaction was carried out in the same manner as in Example 1 except that the catalysts shown in Table 1 below were used instead of TBPB.
And a thermosetting reaction product of PAn. The abbreviations in Table 1 are as follows. TBPC: tetrabutylphosphonium chloride TPPC: tetraphenylphosphonium chloride TPPB: tetraphenylphosphonium bromide 18-C-6 / KCl: 18-crown-6-ether / KCl 18-C-6 / KBr: 18-crown-6-ether / KBr 18-C-6 / PhOK: 18-crown-6-ether / Phok DB18-C-6 / KCl: dibenzo 18-crown-
6-ether / KCl DB18-C-6 / KBr: dibenzo 18-crown-
6-ether / KBr DB18-C-6 / PhOK: dibenzo 18-crown-6-ether / PhOK DCH18-C-6 / KCl: cis-dicyclohexano 18-crown-6-ether / KCl DCH18-C-6 / KBr: cis-dicyclohexano 18-crown-6-ether / KBr DCH18-C-6 / PhOK: cis-dicyclohexano 18-crown-6-ether / PhOK

[0026]

[Table 1]

Examples 14 to 30 The same reaction as in Example 1 was carried out except that the polyfunctional oxetane and the cyclic carboxylic anhydride shown in Table 2 were used, and the heat of the polyfunctional oxetane compound and the cyclic carboxylic anhydride was A cured reaction product was obtained. The abbreviations in Table 2 are as follows. (Polyfunctional oxetane compound) TEOPE: 1,1,1-tris-4- (3) represented by the above formula (8)
-ethyl-3-oxetanyl phenoxy) -ethane PNOX: phendic novolac o represented by the above formula (9)
xetane TM-BEOBP: 3,3 ′, 5,5 ′ represented by the above formula (2)
-tetramethyl-4,4 '-[bis (3-ethyl-3-oxetanyl) bipheny
l] 4,4'-BEOBP: 4,4'-BEOBP represented by the above formula (3)
[bis (3-ethyl-3-oxetanyl) methoxy] biphnyl 2,2′-BEOBP: 2,2′- represented by the above formula (4)
[bis (3-ethyl-3-oxetanyl) methoxy] biphnyl BEOMB: 1,4-bis [3-ethyl represented by the above formula (5)
-3-oxetanyl] methoxyl] benzene 1,3-BEOMB: 1,3-bis represented by the above formula (6)
[3-ethyl-3-oxetanyl] methoxyl] benzene 1,2-BEOMB: 1,2-bis represented by the above formula (7)
[3-ethyl-3-oxetanyl] methoxyl] benzene (cyclic carboxylic anhydride) SAn: succinic anhydride CHAn: cis-1,2-cyclohexanedicarboxylic anhydride DPAn: 2,2′-biphenyldicarboxylic anhydride

[0028]

[Table 2]

[0029]

The oxetane resin obtained by the production method of the present invention has excellent mechanical strength, electrical properties, heat resistance, chemical resistance, etc., and is suitable for various industrial uses as a substitute for epoxy resin. The use of is expected.

Continued on the front page (72) Inventor Tadaomi Nishikubo 3-6-8 Motofujisawa, Fujisawa City, Kanagawa Prefecture (72) Inventor Atsushi Kameyama 1-10-3-705 Nishi-Kanagawa, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture (72) Inventor Kuriyama A No. 1 Funami-cho, Minato-ku, Nagoya-shi, Aichi Prefecture F-term within Toagosei Co., Ltd. 4C048 TT02 UU05 XX01 4J005 AA11 AB02 BA00 BB02 4J029 AA01 AB04 AC02 AE11 AE13 CA04 CB04A CD03 HB06 JB231 JB232 JC091 JC73

Claims (4)

[Claims] 1. A method for producing an oxetane resin, which comprises subjecting a polyfunctional oxetane compound and a cyclic carboxylic anhydride to a thermosetting reaction. 2. A polyfunctional oxetane compound represented by the following formula (1):
The method for producing an oxetane resin according to claim 1, which is any compound represented by (9). Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image 3. The method of claim 1, wherein the cyclic carboxylic anhydride is phthalic anhydride, succinic anhydride, cis-1,2-cyclohexanedicarboxylic anhydride or 2,2′-biphenyldicarboxylic anhydride. A method for producing the oxetane resin according to claim 2. 4. The process for producing an oxetane resin according to claim 1, wherein the thermosetting reaction is carried out in the presence of a quaternary onium salt, a crown ether complex or a tertiary amine.