JPH03285915A - Production of crosslinked resin - Google Patents

Abstract

PURPOSE:To easily and quickly obtain a crosslinked resin having excellent heat resistance, chemical resistance, mechanical properties, etc., by mixing a specific phenoxy resin with a specific oxazoline derivative and oxazine derivative and reacting the components under heating in the presence of an acidic catalyst. CONSTITUTION:The objective crosslinked resin can be produced by homogeneously mixing (A) a phenoxy resin composed of the recurring unit of formula I (X is halogen, etc.; n is 0-2) with (B) >=0.5wt.% (based on the phenoxy resin) of an oxazoline derivative of formula II (m is 2-4; R is m-valent aliphatic hydrocarbon group, etc. ; Ra, Rb, Rc and Rd are H, <=3C aliphatic hydrocarbon group, etc.) [preferably 2,2'-bis(2-oxazoline), etc.] and/or an oxazine derivative of formula III (Re and Rf are H or <=3C aliphatic hydrocarbon group, etc.) [preferably 2,2'-bis(5,6-dihydro-4H-1,3-oxazine, etc.] and reacting the components under heating in the presence of an acidic catalyst (preferably 3,4,5,6-tetrabromo- phthalic acid, etc.).

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a method for producing a crosslinked resin. The present invention relates to a method for producing the product with a large size and excellent moldability.

<Prior Art> In recent years, with the advancement of technology, there has been a demand for resins that have excellent heat resistance, mechanical properties, and moldability. Among these resins, reactive molding resins using reactive monomers or oligomers, ie, resins in which molding and polymerization are performed simultaneously using raw materials with relatively low viscosity, are attracting particular attention. Such resins include polyurethane resin and polyurea resin.

Nylon resins, epoxy resins, unsaturated polyester resins, etc. are known, and some have been commercialized.

However, each of these resins has its advantages and disadvantages.
For example, polyurethane resins have low heat resistance, and unsaturated polyester resins have drawbacks such as the time required for reaction, that is, molding, and cannot necessarily be said to have sufficient performance and moldability.

In order to improve these problems, the present inventors would like to propose a resin obtained by heat-reacting a composition consisting of a thermoplastic resin and an oxazoline derivative in the presence of a catalyst.
3-248852). However, when polycarbonate or polyester, for example, is used as a thermoplastic resin, the degree of polymerization of these polymers tends to decrease during molding, and it is difficult to say that the toughness of the thermoplastic polymer is fully utilized. For example, when polysulfone or the like is used as the thermoplastic polymer, there is a problem in that the polysulfone and the oxazoline derivative tend to undergo phase separation during the heating reaction, so that the properties of the resulting resin are still insufficient.

<Purpose of the Invention> As a result of intensive research to develop a new resin that improves these problems, the present inventors have discovered that a so-called phenoxy resin does not cause a decrease in the degree of polymerization during molding and is also reactive with oxazoline. Focusing on the fact that phase separation does not occur during heating reactions due to the presence of hydroxyl groups, a composition prepared by blending this phenoxy resin with a polyoxazoline derivative and/or a polyoxazine derivative was heated in the presence of a specific catalyst. It has been discovered that by reacting, a crosslinked resin that is strong and has excellent heat resistance, chemical resistance, etc. can be quickly and easily formed, and the present invention has been achieved.

Therefore, an object of the present invention is to provide a method for producing a crosslinked resin having the above-mentioned properties.

<Configuration of the Invention> The production method of the present invention comprises the following formula (1) and at least 0.5% by weight of the phenoxy resin.
A composition formed by intimately mixing with an oxazine derivative represented by the following formula (II>RaRa)kdRd (III) is subjected to a heating reaction in the presence of a compound that acts as an acid catalyst. This is a method for producing a crosslinked resin.

The present invention will be explained in detail below.

The phenoxy resin used in the present invention has a repeating unit represented by the above formula <I>. In formula (I), X represents a halogen atom or a hydrocarbon group having 1 to 3 carbon atoms. Specifically, examples of the halogen atom include chlorine and bromine, and examples of the hydrocarbon group having 1 to 3 carbon atoms include methyl and ethyl. Further, n represents 0, 1 or 2. This phenoxy resin can be obtained by a conventionally known production method, that is, by reacting the corresponding bisphenol and epichlorohydrin in the presence of an alkaline compound. As the phenoxy resin used in the present invention, various grades of commercially available phenoxy resins can be used as appropriate.

The oxazoline derivative used in the present invention has the following formula (n
) may be done. Specifically, when R is m=2,
Ethylene, trimethylene, propylene, tetramethylene, hexamethylene, neopentylene.

These are compounds represented by p-phenylene, m-phenylene, and cyclohexa. In the above formula, m represents an integer of 2 to 4, with 2 being preferred.

R represents an m-valent aliphatic, alicyclic, or aromatic hydrocarbon group, and when m = 2, R is a direct bond that represents an aliphatic group having a prime number of 10 or less, an alicyclic group having a carbon number of 10 or less, or a carbon An aromatic hydrocarbon group having a number of 12 or less is preferable.

Ra, Rh, Re and Rd each represent a hydrogen atom, an aliphatic group having 3 or less carbon atoms, or an aromatic hydrocarbon group having 7 or less carbon atoms, and these may be the same or different. Specific examples of the aliphatic hydrocarbon group having 3 or less carbon atoms include methyl group, ethyl group, etc., and examples of the aromatic hydrocarbon group having 7 or less carbon atoms include phenyl group, tolyl group, etc. Ra.

It is preferable that all of Rh, Re and Rd are hydrogen atoms, or any one of them is a methyl group and the rest are hydrogen atoms, and it is particularly preferable that all of them are hydrogen atoms.

Specific examples of the oxazoline derivatives referred to in the present invention include 2
．． 2'-bis(2-oxazoline>, 2.2'ethylenebis(2-oxazoline), 2.2'-tetramethylenebis(2-oxazoline), 2.2'-hexamethylenebis(2-oxazoline) , 2.2'-octamethylenebis(2-oxazoline), 2.2'-1,4-cyclohexylenebis(2-oxazoline), 2.2'-bis(4-methyl-2-oxazoline), 2 .2'-bis(
5-methyl-2-oxazoline), 2.2'-m-phenylenebis(2-oxazoline), 2.2'-p-phenylenebis(2-oxazoline), 2.2'-m-
Phenylenebis(4-methyl-2-oxazoline), 2
．． 2'-m-phenylenebis(5-methyl-2-oxazoline), 2,2'-p-phenylenebis(4-methyl-2-oxazoline), 2,2'-p-phenylenebis(5-methyl- 2-oxazoline), 1,3.5-
Examples include tris(2-oxazolinyl-2)benzene and the like. Among these, 2.2'-bis(2-oxazoline), 2.2'-tetramethylenebis(2-oxazoline), 2.2'-m-fenlenebis(2-oxazoline), 2.2'-p- Phenylenebis(2-oxazoline) is preferred.

Further, the oxazine derivative as used in the present invention is a compound represented by the following formula. In the formula, m, R, Ra.

Rh, Re, and Rd have the same meanings as in the above formula <II), and Re and Rf have the same meanings as in the above formula
.

It is synonymous with Re and Rd.

Specific examples of such oxazine derivatives include 22'-bis(5,6-sihydro48-1,3-oxazine),
2.2'-ethylenebis(5,6-sihydro4H-1
, 3-oxazine), 2,2'-tetramethylenebis(
5,6-sihydro48-1j-oxazine), 2.2
'-hexamethylene bis(5,6-sihydro48-1
．． 3-oxazine), 2,2'-octamethylenebis(
5,6-sihydro48-1,3-oxazine),
2.2'-1,4-cyclohexylenebis(5,6-cyhydro48-1,3-oxazine).

2.2'-bis(4-methyl-5,6-cyhydro4H
1,3-oxazine), 2,2'-bis(5-methyl-
5,6-sihydro-4H-1,3-oxazine).

2.2'-bis(6-methyl-5,6-cyhydro4H
-1,3-oxazine), 2,2'-m-phenylenebis(5,6-sihydro48-1,3-oxazine).

2,2'-P-phenylenebis(5,6-sihydro48-1,3-oxazine), 2,2'-m-7x
-1:, lembis(4-methyl-5,6-sihydro4
H-1,3=oxazine), 2,2'-m-phenylenebis(5-methyl-5,6-cyhydro 4H-1,3-
oxazine), 2,2'-m-phenylenebis6-methyl56-hydro48-1,3-oxazine).

2,2'-p-phenylenebis(4-methyl-5,6
dihydro48-13-oxazine), 2,2'-pphenylenebis(5-methyl-5,6-dihydro48-
1,3-oxazine), 2,2'-p-phenylenebis(6-methyl-5,6-cyhydro-4H1,3-oxazine), and the like.

Among these, 2,2'-bis(5,6-sihydro4H
-1,3-oxazine), 2,2'-tetramethylenebis(56-sihydro48-1,3-oxazine).

22'-m-phenylene bisque 5,6-sihydro48
-1,3-oxazine) and 2,2'-p-phenylenebis(5,6-sihydro48-1j-oxazine) are preferred.

In the present invention, a part of the oxazoline derivative and/or oxazine derivative is used in place of a monooxazoline compound represented by the following formula (IV) a N-C-Rb d or a monooxazine derivative represented by the following formula. It is also effective for reaction control, adjustment of crosslinking density, etc.

Specifically, such monooxazoline compounds include:
2-Methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-propenyl-2-oxazoline, 2-phenyl-2-oxazoline.

2-Tolyl-2-oxazoline, 2,5-dimethyl 2-
Oxazoline, 2,4-dimethyl-2-oxazoline,
Examples include 2-phenyl-4-methyl-2-oxazoline and 2-phenyl-5-methyl-2-oxazoline. Among these, 2-phenyl-2-oxazoline, 2-tolyl-2-oxazoline, etc. are preferred.

Further, specific examples of monooxazine derivatives include 2-methyl-5,6-cyhydro-48-1,3-oxazine, 2
-Ethyl-5,6-sihydro 48-1゜3-oxazine, 2-propenyl-5,6-sihydro 4H-1,3
-Oxazine, 2-phenyl-5゜6-sihydro 48
-1,3-oxazine, 2-tolyl-5,6-sihydro48-1j-oxazine.

2-phenyl-4-methyl-5,6-sihydro4)I
-1,3-oxazine, 2-phenyl-5-methyl-5
6-Sihydro48-1,3-oxazine.

2-phenyl-6-methyl-5,6-sihydro48-
Examples include 1j-oxazine and the like.

Among these, 2-phenyl-5,6-sihydro 4H-
1,3-oxazine, 2-tolyl-5,6-cyhydro-48-13-oxazine are preferred. The proportion of the monooxazoline and/or monooxazine derivative used is preferably 30 mol% or less, more preferably 25 mol% or less, based on the polyoxazoline derivative and/or polyoxazine derivative represented by formula (II) or <m>. ,
Particularly preferably, it is 20 mol% or less.

In the present invention, a composition obtained by intimately mixing the above-mentioned phenoxy resin and at least 0.59% by weight of an oxazoline derivative and/or an oxazine derivative with respect to the phenoxy resin is subjected to a heating reaction in the presence of an oxazoline ring-opening polymerization catalyst. let Examples of methods for intimately mixing the phenoxy resin and the oxazoline derivative and/or the oxazine derivative include a method of melt-mixing, a method of uniformly dissolving in a solution, and a method of removing the solvent. The phenoxy resin and the oxazoline derivative and/or the oxazine derivative have good compatibility, and a composition in which they are intimately mixed can be easily obtained by these methods.

Here, intimately mixed refers to a state in which the oxazoline derivative and/or oxazine derivative are molecularly dispersed in the phenoxy resin, and this means that when the resulting composition is thermally analyzed, a single transition point is observed. This can be confirmed by methods such as checking whether the Due to the plasticizing effect of the oxazoline derivative and/or oxazine derivative, the composition intimately mixed in this manner has a lower flow initiation temperature and viscosity than that of the phenoxy resin alone, and can be easily molded. . The ratio of the phenoxy resin to the oxazoline derivative and/or oxazine derivative is at least 0 to the phenoxy resin.
．． The content is 5% by weight, preferably 1% by weight or more, more preferably 3% by weight or more, particularly preferably 5% by weight or more. The upper limit is not particularly limited, but is preferably 100% by weight or less, more preferably 70% by weight or less.

When used in a ratio outside the above range, it becomes difficult to obtain a molded product that has both the heat resistance and toughness that are the objectives of the present invention.

The crosslinked resin of the present invention can be obtained by subjecting the above-mentioned composition to a heating reaction in the presence of a compound that acts as an acidic catalyst. The following compound group can be exemplified as the compound that acts as an acidic catalyst used here.

(i) A protonic acid with a pKa of 2.5 or less.

(ii) Esters of protic acids with pK a of 1.0 or less.

(i) A salt of a protonic acid with a pKa of 2.5 or less.

W Lewis acids and their complexes.

M Alkyl halide.

M Iodine.

Halogen phenols represented by the following formula (Vl) Acupuncture Halogenophthalic acids represented by the following formula (■) Sulfonic acids, phosphonic acids or inorganic acids are preferred, e.g. phosphonic acids such as organic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid; sulfuric acid, phosphoric acid, sulfuric acid, phosphine. Mention may be made of inorganic acids such as acids and perchloric acid.

As the protic acid ester (11) having a pKa of 1.0 or less, organic sulfonic acid esters and inorganic protic acid esters are preferable. As the alcohol component forming the ester, an aliphatic alcohol having 1 to 10 carbon atoms is preferably used. Examples of the ester include methyl benzenesulfonate, ethyl benzenesulfonate, P
- Sulfonic acid esters such as methyl toluenesulfonate, ethyl p-toluenesulfonate and ethyl trifluoromethanesulfonate; esters of inorganic protonic acids such as dimethyl sulfate;

Examples of the protonic acid salt C11D having a pKa of 2.5 or less include the above-mentioned protonic acid (i) salt, hexamethylene diamine, piperazine, m-xylylene diamine, 4゜4'
-diaminodiphenylmethane, pyridine, 2.2'-m
Salts of organic amine compounds such as -phenylenebis(2-oxazoline), trifluoromethanesulfonic acid, and the like are preferably used.

Examples of Lewis acids and their complexes CM include Lewis acids such as titanium tetrachloride, tin tetrachloride, zinc chloride, aluminum chloride, and boron trifluoride; or complexes of these Lewis acids with ethers or phenols, such as trifluoride. Preferred examples include boron ether complexes.

As the alkyl halide M, alkyl iodide or alkyl bromide is particularly preferred. Further, the number of carbon atoms in the alkyl group is preferably 1 to 10, and the alkyl group may be substituted with phenyl. As alkyl halide M,
For example, methyl iodide.

Ethyl iodide, propyl iodide, butyl iodide.

Preferred examples include benzyl iodide and benzyl bromide.

Iodine M is simple iodine.

The halogenophenol neck represented by the above formula (VI) is also one of the suitable catalysts.

In the above formula (Vl), Xl and X2 are the same or different and are halogen atoms. As the halogen atom, for example, a chlorine atom and a bromine atom are particularly preferred. p
is a number of 0, 1 or 2.

Preferably, p is 1. Also, in that case (p=1)
It is particularly preferable that X2 is bonded to the ortho position with respect to the hydroxyl group in formula (VI).

Y is -802R1, -COR2, ~CN or -NO2
It is.

The above formula (Vl) can be represented by the following formulas depending on the definition of Y.

1 Alkyl may be linear or branched.

Alkyl having 1 to 10 carbon atoms is preferred. Such alkyls include, for example, methyl, ethyl, n-propyl, i
go-propyl, n-butyl, is.

-butyl, 5ec-butyl, tert-butyl, n
~Pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, etc. can be mentioned. These alkyl groups may be substituted with substituents such as halogen, hydroxyl group, carboxyl group, nitro group, cyano group, amine group, alkoxy group, alkoxycarbonyl group, acyl group, and acyloxy group.

Examples of the aryl having 6 to 12 carbon atoms for R1 include phenyl, tolyl, naphthyl, and the like. These aryl groups may be substituted with the same substituents as the above substituents exemplified as substituents for alkyl groups.

The group represented by R1 -NR3R4 optionally substituted alkyl having 1 to 12 carbon atoms and 6 to 12 carbon atoms
As the aryl of 12, the same groups as mentioned above for R1 can be exemplified. Also, the carbon number of a reptile or mountain is 5
-10 cycloalkyl is, for example, cyclopentyl, cyclohexyl.

As a compound of the above formula (■+1), for example, bis(3,5
-dichloro-4-hydroxyphenyl) sulfone, bis(3,5-dibromo-4-hydroxyphenyl) sulfone, 3,5-dichloro-4-hydroxybenzenesulfonic acid amide, 3,5-dibromo-4-hydroxybenzenesulfone Acid amide.

Examples include 3,5-dibromo-4-hydroxybenzenesulfonic acid N-methylamide.

In the above formula (■+2), the optionally negatively substituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, and aryl having 6 to 12 carbon atoms include the formula (■+1
The same groups as the above-mentioned groups can be exemplified. Also, as the group -NRI, R7, the group -NR3R4
The same groups as the above-mentioned groups can be exemplified.

As the group -0R5, the same groups as those exemplified above for the groups R3 and R4 can be exemplified.

As a compound of the above formula (■+2), for example, bis(3,5
-dichloro-4-hydroxyphenyl)ketone, bis(
3,5-dibromo-4-hydroxyphenyl)ketone,
Methyl 3,5-dichloro-4-hydroxybenzoate, 3
, methyl 5-dibromo-4-hydroxybenzoate, 3,
Methyl 5-dibromo-4-hydroxybenzoate, 3,5
-dibromo-4-hydroxybenzoic acid amide, 3,5-
Dibromo-4-hydroxybenzoic acid N-ethylamide, 3
．． Examples include 5-dibromo-4-hydroxybenzoic acid.

Examples of the compound of the above formula (■+3) include 3,5 dichloro-4-hydroxy-benzonitrile.

Examples include 35-dibromo-4-hydroxy-benzonitrile.

Examples of the compound of the above formula (■+4) include 3,5-dichloro-4-hydroxynitrobenzene and 3.5-dibromo-4-hydroxynitrobenzene.

Among the halogenophenols represented by the above formula (VI Particularly preferred are compounds such as (3,5-dibromo-4-hydroxyphenyl)sulfone.

Halogenophthalic acids represented by the above formula (■) and/
Alternatively, halogenophthalic anhydride represented by the above formula (■) is also one of the suitable catalysts.

In formula (■), X and X4 are the same halogen atoms as defined for X, such as chlorine or bromine. q is a number of 0, 1, 2 or 3. Of these,
q is preferably 1, 2 or 3, particularly preferably 2 or 3. In the formula <■>, Ryo has the same definition as the mother of the above formula (Vl), and therefore, as the island, the same group as exemplified for Ai can be exemplified.

Furthermore, in the formula (■), the definitions of X3, X4, and ρ are the same as those in the above formula (■).

As compounds represented by formula (■) and formula (■),
For example, the following compounds can be exemplified.

(i) dicarboxylic acids and their anhydrides; e.g. 3.
456-tetrabromo (or tetrachloro) phthalic acid, 3,4,5.6-tetrabromo (or tetrachloro)-phthalic anhydride, 3,4.5-)ribromo (or trichloro)-phthalic acid, 3.4.5 = tribrome (or trichlor)-phthalic anhydride, 3,4.6
-) Ribrome (or trichloro)-phthalic acid, 3,4
．． 6-tribromo (or trichloro)-phthalic anhydride and the like.

(11) Dicarboxylic acid monoester; e.g. 3.4
．． 5.6-tetrabromo (or tetrachlor)-phthalic acid monomethyl ester, 3,4,5.6-tetrabromo (or tetrachlor)-phthalic acid monoethyl ester, 3,4,5.6-tetrabromo (or tetrachlor)-phthal Acid monopropyl ester, 3,4,5
．． 6-tetrabromo (or tetrachloro)-phthalic acid monoisopropyl ester.

3,4.5.6-tetrabrome (or tetrachlor)
Phthalic acid monobenzyl ester, 3,4,5,6-tetrabromine (or tetrachloro)-phthalic acid monophenyl ester, and the like.

(io dicarboxylic acid monoamide: e.g. 3,4.5
．． 6-tetrabrome, (manahatetrachlor)-phthalic acid monoamide, N-methyl-3,4,5,6-tetrabromo (or tetrachlor)-phthalic acid monoamide, N
-Ethyl-3,4,5,6-tetrabromo (or tetrachlor)-phthalic acid monoamide.

N-propyl-3,4,5,6-tetrabromo (or tetrachlor)-phthalic acid monoamide, N-decyl-3
,4,5,6-tetrabrome (or tetrachlor)-
Phthalic acid monoamide, N-phenyl-3,4,5,6-
Tetrabromo (manahatetrachlor)-phthalic acid monoamide, etc.

M Ketocarboxylic acid; e.g. 2-carboxy-3°4,
5.6-tetrabromo (or tetrachlor)-phenylmethylketone, 2-carboxy-3°4,5.6-tetrabromo (or tetrachlor)-phenylethylketone, etc.

Among these, the above dicarboxylic acids and their anhydrides are preferred, and tetrachlorophthalic acids, tetrabromophthalic acids and their anhydrides are more preferred, especially 3.4
．． Particularly preferred are 5,6-tetrabromo (or tetrachloro)-phthalic acid and 3,4,5,6-tetrabromo (or tetrachloro)-phthalic anhydride. In the method of the present invention, the above catalysts may be used alone or in combination of two or more.

The amount of the catalyst used is usually 0.01 to 20 mol%, based on the oxazoline derivative and/or oxazine derivative.
The amount is preferably about 0.1 to 10 mol%.

The method of blending the catalyst is not particularly limited, but includes a method of melt-blending the catalyst with a composition consisting of a phenoxy resin and an oxazoline derivative and/or an oxazine derivative;
Examples include a method in which a catalyst is added at the same time when the composition is prepared by a melting method. Fibers and films in the case of melt blending method.

It is preferable that a catalyst-containing composition in the form of a sheet or molded article can be directly obtained. At this time, melt molding is performed using oxazoline derivatives and/or
Alternatively, it can be carried out at a relatively low temperature due to the plasticizing action of the oxazine derivative, and it can be carried out without being accompanied by the thermal crosslinking reaction described below.

When a solution method is used, it is preferable to simultaneously dissolve the phenoxy resin, the oxazoline derivative and/or the oxazine derivative, and the catalyst in a solvent, and then remove the solvent.

The crosslinked resin of the present invention can be obtained by subjecting the above composition to a heating reaction. The heating reaction temperature at this time is preferably 150°C or higher, more preferably 160°C or higher, particularly preferably 180°C or higher.

The reaction time may be sufficient as long as it is sufficient to harden the target resin, and this time varies depending on the type of raw materials used, the proportion used, the reaction temperature, etc., but is preferably 1.
The time is about 0 seconds to 60 minutes, more preferably 20 seconds to 45 minutes, particularly preferably about 30 seconds to 30 minutes. The reaction can be carried out under normal pressure to increased pressure.

The thus obtained crosslinked polymer is a crosslinked polymer of oxazoline and/or oxazine, a phenoxy resin, and a structure in which the hydroxyl group in the phenoxy resin is partially reacted with the oxazoline and/or oxazine, which are dispersed or entangled in the molecular form. It is a resin that has excellent heat resistance and chemical resistance while maintaining the mechanical properties of phenoxy resin, which is a thermoplastic resin.

The crosslinked resin of the present invention can be preferably used not only as a resin alone, but also as a matrix resin for composite materials, for example. When used for this purpose, it may be impregnated into fibers by a solution method, or the composition before heat curing may be melt-molded into fibers or sheets, and this and reinforcing fibers may be formed into a so-called F/F composite. Methods such as stacking or stacking are also preferred.

<Examples> Hereinafter, the present invention will be described in detail with reference to Examples, but the Examples are for illustrative purposes and the present invention is not limited thereto.

In addition, "parts" in the examples mean "parts by weight."

Example 1 and Comparative Example 1 60 parts of phenoxy resin (manufactured by Tobu Kasei Co., Ltd., YP-50) and 40 parts of m-phenylenebis(2-oxazoline) were tri-blended using a ■ type blender, and a 25 mm
Using a φ2-axis extruder, the resin temperature was 180℃,
When melt extruded under conditions of an average residence time of about 6 minutes, a pale yellow transparent homogeneous composition was obtained.

After cooling and grinding the composition, 1.
8 parts of ethyl p-toluenesulfonate were triblended, and this was injection molded under the conditions of a polymer temperature of 120°C and a mold temperature of 180°C, and was held in the mold for 25 minutes to form a light brown, transparent crosslinked product. A molded product was obtained.

For the physical properties of the molded product and for comparison, the base resin phenoxy resin was used at a polymer temperature of 240'C1 mold temperature of 50.
Table 1 shows the physical properties of samples injection molded at ℃.

As is clear from Table 1, it can be seen that the crosslinked resin of the present invention has significantly improved heat resistance and solvent resistance while retaining the toughness inherent to phenoxy resin.

Example 2 60 parts of the same phenoxy resin as obtained in Example 1, m-
1.4 parts of benzenesulfonic acid was triblended to 100 parts of a composition consisting of 40 parts of phenylenebis(2-oxazoline), and this was mixed with CuStom Scientific.
SCI-Max manufactured by Instruments Inc.
Temperature 130℃ using MixingExtruder
A pale yellow transparent monofilament was obtained by melt extrusion through an lnwnφ nozzle with a residence time of about 2 minutes. The monofilament was stretched 2.5 times at 60'C and the strength was 1.1 g/d.
e. A drawn yarn with an elongation of 12% was obtained. The obtained fiber has a basis weight of 1
00 g/rrr plain weave fabric, 11 plies of the fabric and 198 g/rrf carbon fiber plain weave fabric (Trading Card T-3
00') 10 plies were laminated alternately and heated to 190°C.
It was heat-cured for 30 minutes using a hot press at a pressure of 5 dazzles/aa. The obtained molded product is strong and does not deform even at a temperature of 230°C, and can be easily stained with acetone at room temperature.
methanol.

I immersed it in chloroform, dioxane, and xylene, but there was no change at all.

Examples 3-8 Phenoxy resin (YP-50 manufactured by Tobu Kasei Co., Ltd.) 50 parts.

0.5 part of ethyl p-)luenesulfonate and m-phenylenebis(2-oxazoline) in the amounts shown in the table below were dissolved in 250 parts of chloroform.Then, a film was obtained from the solution by a casting method, and an additional 200 parts of ethyl The film was cured by heating for 15 minutes using a hot press at ℃.The resulting film was flexible and did not completely dissolve in chloroform.Table 2 shows the amount of insolubility in chloroform as the degree of crosslinking. .

Claims (1)

[Claims] The following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) [In the formula, X represents a halogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and n is 0, 1 or 2. ] A phenoxy resin having a repeating unit represented by the following formula (II) in an amount of at least 0.5% by weight based on the phenoxy resin ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) [In the formula, m is represents an integer of 2 to 4, R is an m-valent aliphatic,
Indicates alicyclic and aromatic hydrocarbon groups. However, when m=2, R may be a direct bond. Ra, Rb, Rc and Rd each represent a hydrogen atom, an aliphatic hydrocarbon group having 3 or less carbon atoms, or an aromatic hydrocarbon group having 7 or less carbon atoms, and these may be the same or different. ] Oxazoline derivatives represented by and/or the following formula (
III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) [However, in the formula, m, R, Ra, Rb, Rc, and Rd are the above (I
I) Synonymous with expression. Re, Rf are the above Ra, Rb, Rc, R
Synonymous with d. ] A method for producing a crosslinked resin, which comprises subjecting a composition formed by intimately mixing the oxazine derivative represented by the following formula to a heating reaction in the presence of a compound that acts as an acidic catalyst.