JPH08109333A - Production of improved resins and their use - Google Patents

Abstract

PURPOSE: To obtain a resin substantially not deteriorated, etc., excellent in flame retardancy, thermal stability, compatibility, surface modifiability, etc., and useful for flame-resistant materials, etc., by reacting a resin with a specific norbornenyl group-containing compound in a prescribed temperature range. CONSTITUTION: (A) A resin is reacted with (B) at least one kind selected from norbornenyl group-containing compounds of the formula [R1 to R9 are H, 1-4C alkyl, phenyl; Y is (substituted) triazinyl amide, carboxylate, oxazolinyl, oxycarbonyl, urethane, cyanuric ester, ether, carbamoyl, carbonyl] [e.g. 2-(bicyclo[2.2.1]hept-5-en-2-yl)-2-oxazoline] at a temperature of 200-450 deg.C, preferably 230-450 deg.C, to obtain the objective resin. The reaction is preferably performed by a reactive processing method.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to modification of resins such as resins, rubbers, waxes and oils, and more specifically, flame retardancy, thermal stability, compatibility and adhesion of such resins. Properties, covering properties,
The present invention relates to a method useful for improving and modifying surface properties such as dyeability and electrical properties, and uses thereof.

[0002]

2. Description of the Related Art In general, resins have excellent electrical properties, mechanical properties, workability, etc., and are used as building materials, electrical materials, automotive and other vehicle materials, textile materials, equipment materials. ,
It is used in a wide range of industrial fields such as household products.

However, these resins are extremely flammable, and as they are used in a wide range, the number of them becoming a major source or fuel source in a fire increases remarkably, and there is a high demand for high safety as an industrial material. Flame retardant,
Insufficient performance such as heat resistance, easy to cause deterioration by heat, light, etc., thermal stability is not sufficient for practical use, poor surface properties such as wettability, adhesiveness, coatability, dyeability, etc. It has defects such as significant restrictions.

With the diversification of uses of such resins,
The required performance and characteristics are remarkably advanced, and it is technically and economically restricted to develop a new type of resin that meets the requirements and deal with it individually. It is desired to improve and impart performance without impairing the existing properties of such resins, and the development of new materials by modifying and compounding resins is an extremely important industrial issue.

A. Conventionally, as a method for improving and imparting the properties of such resins, a method of providing a new type of resin by using a new raw material, synthesis, polymerization technology, etc., and improving various performances by using already obtained resins. A method of imparting and modifying is known.

In the former method, it is not only practically difficult or technically very difficult to create a new type of resin that satisfies the requirements, but also there are drawbacks such as significant economic restrictions. .

On the other hand, the latter method has the advantages that the resins can be easily obtained and the characteristics thereof can be grasped, and the modification by the reaction of introducing a functional group into these resins can be carried out. The method is economically and technically excellent, and many proposals have been made.

As such a modification method, a method of performing a modification reaction or the like using a reactive agent having a functional group is known, but such a functional group is bonded only to the terminal position of the resin having a special structure. And that there is a significant restriction on the amount of functional groups, it is difficult to perform sufficient modification, and it is difficult to perform modification and modification with such functional groups, and further, there are defects such as almost no usefulness. Have.

Further, a functional group is introduced into a resin such as a polyolefin resin having no functional group by using a reactive agent such as maleic anhydride or acrylic acid and a peroxide such as BPO, and further a modification reaction using the functional group. There is also known a method of performing modification by the above. Such a modification method has the advantages of being able to introduce a functional group such as a carboxyl group, which can be easily used for modification and modification secondary modification, and has a relatively easy production method. Since it is required to be used in combination, it causes a remarkable decrease in the molecular weight due to the decomposition of the resins, causes coloration, alteration, etc., it is difficult to introduce a large number of functional groups, and there are restrictions on the modification of the resins, thermal stability. The deterioration of the heat resistance and the like, the decomposition of the resins is remarkably promoted by the elimination of the functional groups, and the reaction products are easily generated due to the polymerization of the reactants themselves used, and the physical properties of the resins are deteriorated. It has a defect that it is easily induced.

Furthermore, it is extremely difficult to introduce a functional group or the like which is excellent in modification and performance imparting, and a method of adding a modifier containing such a functional group or the like can be used. It has a defect that it tends to cause deterioration of physical properties, characteristics, and the like.

These known reforming methods are still insufficient in practical use, and have been severely restricted technically and economically.

The inventors of the present invention have conducted extensive studies to overcome the above-mentioned deficiencies in the method for modifying resins, and as a result, have identified compounds and resins which have completely different structures and characteristics from the known methods. By carrying out the reaction under the reaction conditions, even if a large amount of functional groups are introduced, it is difficult to cause a decrease in the molecular weight of the modified resins, deterioration of physical properties, deterioration, etc. It can be selected, it is easy to control modification, performance addition, etc., it is not necessary to use peroxide etc. together, modification reaction conditions and process are simple, and deterioration due to decomposition of resins by side reaction etc. Is not seen, modification, because it can be introduced into the resins without adding and mixing a compound containing a functional group excellent in performance imparting, it is difficult to impair the physical properties of such resins, Carboxyl group, amino group, double bond For resins that do not contain functional groups such as, it is possible to perform modification such as introduction of functional groups, impart performance, etc., it is difficult to cause deterioration due to heat, etc., and introduction of functional groups that significantly improve heat resistance , Flame retardancy, compatibility, wettability, adhesiveness, coating properties, surface properties such as dyeability, electrical properties, modification by bond introduction of functional groups to improve moldability, performance imparting, etc. It has been found that it is possible to provide a method for producing a modified resin having excellent characteristics such as that

Further, by reacting the modified resins obtained by the above method with epoxides under specific reaction conditions, not only the above-mentioned excellent characteristics but also such resins are obtained. The surface property such as wettability, coatability, adhesiveness, dyeability, chemical resistance, electrical characteristics, moldability, compatibility with different resins, dispersibility, etc. are further improved over a wide range. The inventors have found that a method for producing an epoxy-modified resin, which is also excellent in that it can be used, can be provided, and have reached the present invention.

B. Further, various methods have been proposed to improve the flame retardancy of such resins, for example, a method of adding a flame retardant, a resin using a flame retardant-imparting raw material (halogen-containing monomer, etc.) during resin production. Methods such as incorporation into the skeleton have been proposed.

Of these methods, the method of adding a flame retardant to the former resins is generally used in many cases. As such a flame retardant, a halogen-containing compound, a phosphorus-containing compound, an inorganic compound is used. , Nitrogen-containing compounds and the like are known.

In these known flame retardants, when a halogen-containing compound is used, heat resistance is generally poor, sublimation, bleeding and the like are likely to occur, and it is difficult to obtain the effect unless it is used together with antimony trioxide. There are many drawbacks, such as the discharge of a large amount of extremely harmful halogen-containing gas in case of fire. When a phosphorus-containing compound is used, the effect is small on its own, and it is often used in combination with a halogen-containing compound. Further, when an inorganic compound is used, it is a scarce resource such as antimony trioxide, so there is a problem in raw material acquisition, price, etc., and it is necessary to add a large amount such as aluminum hydroxide because of its small effect. There are defects such as an increase in specific gravity, deterioration of physical properties and moldability, and deterioration of heat resistance due to the water content. Furthermore, when a nitrogen-containing compound is used, typified by a triazine-based compound, sublimation during molding, bleeding and the like are likely to occur, manufacturing is difficult, and the raw material cost is high.
It is easy to cause deterioration of properties, etc., the deterioration of flame retardant effect due to disappearance of such additives with time, dispersion, poor miscibility, etc. is significant, and because a large amount of such additives is required, properties and physical properties of such resins Has a defect such as significantly impairing

In the latter method, a raw material containing bromine, phosphorus and the like is used as a raw material for imparting flame retardancy, and it is known that the raw material is incorporated into resins at the time of production. It is excellent and useful in that the reduction of the effect is small and the physical properties and characteristics of such resins are easily maintained. However, it is difficult to produce such a flame-retardant material,
Raw material costs are high, there are significant restrictions on the availability of raw materials suitable for the production of resins, and it is almost technically difficult to obtain them. There are significant restrictions on providing the required resins because it is extremely difficult or impossible to introduce a bond, and the thermal stability and heat resistance of the obtained resins are poor due to the poor thermal stability of such raw materials. It has inferior properties, such as the discharge of large amounts of harmful gas in the event of a fire.

These known methods for flame retarding resins have not been practically sufficient, and have been severely restricted technically and economically.

The inventors of the present invention have made earnest studies to overcome the above-mentioned deficiencies in the flame retarding method for resins, and as a result, by using the modified resins and epoxy-modified resins obtained by the above method, Since the flame-retardant imparting component is introduced and bonded to the resins, there is no dispersion or miscibility of such components, and the flame retardancy of such resins can be significantly improved, and a flame retardant such as melamine is added. Sublimation compared to the method,
No occurrence of bleeding, generation of char, etc. are extremely good, oil drops, melt dripping, and dropping are extremely small, almost no harmful gas is discharged, excellent characteristics of such resins, Not impairing the physical properties, etc., it is possible to easily bond and introduce such a functional group to the resins in which the introduction of the flame-retardant component is difficult to produce, and it is possible to introduce such a functional group after the production of the resins. It was found that it is possible to provide a flame retarding method for excellent resins, such as that the production is simple and inexpensive, and further, the above-mentioned resins and phosphorus, isocyanuric acids, cyanuric acids, amino groups The inventors have found that a method of flame retarding a resin which can further improve the flame retardancy can be provided by using it together with a contained compound or the like, and have reached the present invention.

C. Such resins are apt to undergo brittleness, decomposition, coloring, etc. due to the presence of heat, light, and other energy supplied from the outside, and further oxygen and heavy metals, and the long-term heat resistance and weather resistance of the resins are insufficient. In addition, since the thermal stability is poor, there are large restrictions on molding processability, and other resin blends etc. are required to improve molding processability, and the properties and physical properties of the resins are impaired. Despite their excellent properties, their industrial use was restricted. Conventionally, various proposals have been made to improve these,
It is still insufficient for overcoming the above-mentioned drawbacks, and in some cases, in some cases, the excellent properties thereof are lost and they are not put to practical use at all.

Specific examples of such conventional heat stabilization methods include benzoates, amines, arylphosphonic diamides, organic phosphites, hindered phenols, melamines, benzoguanamines, phthaloguanamines and spiroguanamines. A method for heat-stabilizing a resin composition obtained by adding a heat stabilizer (JP-B-51)
-47739) and the like have been proposed.

However, these methods are inferior in ultraviolet resistance, weather resistance and the like, and are remarkably discolored, and when molding at a high temperature, they are remarkably colored and discolored, and the heat stability effect is not yet sufficient. However, these thermal stabilizers themselves are susceptible to thermal decomposition during processing, the thermal stability effect is extremely poor, and there is no effect for resins that require high temperature molding processing, thermal stabilization Since the heat stabilizer disappears with the passage of time due to the addition and mixing of the agent, the effect is significantly reduced due to poor dispersion such as bleeding, and further, there is a defect such that it is completely lost. Was still inadequate for practical use, and was severely restricted technically and economically.

The inventors of the present invention have made extensive studies in view of the above-mentioned deficiencies in the heat stabilization method for resins, and as a result, modified resins obtained by bonding and introducing a specific functional group by the above-mentioned production method. By using epoxy-modified resins, UV resistance, weather resistance, thermal stability, and heat resistance are remarkably improved, and since the heat-stabilizing component is introduced into the resins, dispersion, miscibility, etc. may be deteriorated. No, such effects are outstanding, deterioration is suppressed during long-term use at relatively high temperatures, such resins themselves do not easily decompose even at high temperatures, and have excellent long-term heat resistance. Since it is extremely small, it is difficult to cause a decrease in thermal stability effect, it is excellent in maintaining handling, physical properties, properties, etc., remarkably suppressing decomposition and deterioration of resins due to heavy metal ions such as copper, molding at high temperature Place to do In addition, there is little heat deterioration, coloration and discoloration of the resins, and the temperature of such resins, such as 5% heat loss, is remarkably improved, and the thermal stability and heat resistance are remarkably improved, and high temperature molding is extremely easy. Thus, for example, in the conventional technology, in a polyphenylene ether resin or the like, which has a remarkable limitation in high-temperature moldability, it is possible to provide a new material which is inexpensive and has excellent physical properties and characteristics because a moldability improving agent is unnecessary. The inventors have found that it is possible to provide an excellent method for heat stabilization of resins, and have reached the present invention.

D. In addition, such resins have excellent properties and are used in a wide range of industrial fields. As a method, various polymer alloy forming methods have been proposed.

Heretofore, as a method of polymer alloying such resins, there have been proposed a method of modifying and imparting performance to the resins themselves, a method of adding a third component such as a compatibilizer, and the like.

In the former method, the compatibility of resins is
It is useful because it has excellent solubility, and it is easy to obtain a modified resin having uniform performance. However, it has drawbacks such as difficulty in modification reaction of resins, deterioration of properties due to reduction of molecular weight of resins at the time of modification, coloring, deterioration and the like. Further, in the latter method, the heat resistance, weather resistance, water resistance, properties, etc. of the resins are deteriorated by the inclusion of the third component, the manufacturing process of the compatibilizer is complicated, the manufacturing cost is high, Due to poor dispersion of the three components, it is difficult to obtain resins with uniform performance and the like, and further, it is difficult to obtain resins with improved physical properties and characteristics.

The present inventors have conducted extensive studies to overcome the above-mentioned deficiencies in the method of compatibilizing resins, and as a result, by using the modified resins and epoxy-modified resins obtained by the above method, , Of different kinds of resins, excellent in meltability of resins, excellent in heat resistance, weather resistance, water resistance, chemical resistance, etc. They have found that a compatibilizing method can be provided and have reached the present invention.

E. Further, such resins have electrical properties,
It has excellent mechanical properties, workability, etc., and is used in a wide range of industrial fields, but with the diversification and sophistication of applications, it is strongly desired to improve the properties by compounding with different materials. ing. Surface coverage of such resins, adhesion to different materials, wettability, dyeability, surface modification such as water / oil repellency, solvent resistance, electrical properties such as charging property, conductivity, etc. Development of a coating resin composition and an adhesive resin composition useful as materials has become an important industrial issue.

Conventionally, as a method for modifying the surface of such resins, there have been proposed a method for modifying the surface by an oxidizing agent, corona discharge, etc., and a method for modifying the surface with an additive. The former method has drawbacks such that the treatment process is remarkably complicated because the surface treatment is performed after the molding process, it is difficult to treat various shapes, and the modifying effect is not practically sufficient. Further, in the latter method, the effect is remarkably reduced in a short period of time due to the disappearance of the additive with the passage of time, the compatibility between the resin and the additive, poor solubility is likely to occur, and a sufficient surface modification effect is obtained. However, the surface modification method for these resins has not been practically sufficient and has been technically and economically restricted.

The inventors of the present invention have made extensive studies to overcome the above-mentioned deficiencies in the surface modification method of resins, and as a result, use the modified resins and epoxy-modified resins obtained by the above method. Can significantly improve surface properties such as wettability, coatability, adhesiveness, dyeability, water / oil repellency, etc. of such resins, and electric properties such as chargeability and conductivity. Modification of resins themselves Since it is possible to achieve high temperature stability, excellent non-volatility, it is difficult to cause a decrease in effect due to disappearance of the surface-modifying component, etc. It is possible to provide a surface modification method for resins having excellent properties such as polyolefin resin such as polypropylene resin having significant restrictions on surface properties such as coatability and dyeability, and capable of significantly modifying polyolefin fiber. , Such resins are extremely useful to, coating resin composition obtained by using the resins described above, found that it is possible to provide an adhesive resin composition, it has reached the present invention.

[0031]

That is, according to the present invention, (a) resins and formula (1)

[0032]

[Chemical 6] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ ,
R ₈ and R ₉ are species selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms and a phenyl group, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And R ₉ may be the same or different, and Y is a triazinyl group which may have a substituent, an amide group, a carboxylate group, an oxazolinyl group, an oxycarbonyl group, a urethane group, a cyanuric acid ester group, an ether group,
A carbamoyl group or a carbonyl group, which represents a group selected from the group consisting of carbonyl groups) and at least one selected from the group containing norbornenyl group-containing compounds having at least one group in the temperature range of 200 ° C to 450 ° C. A method for producing a modified resin characterized by carrying out a reaction, (b) the norbornenyl group-containing compound in the formula (1) is represented by the formula (2)

[0033]

[Chemical 7] [In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ ,
R ₈ and R ₉ have the same meanings as in formula (1),
R _10, R _11, R ₁₂ and R ₁₃ indicates that a species selected from the group consisting of groups having one or more the number of hydrogen atoms and _{carbon, R 10, R 1 1,} R 12 and R ₁₃ are the same The compound represented by the formula (2), the norbornenyl group-containing compound in the formula (1) is R _{10 of} the formula (2),
The average degree of addition condensation obtained by subjecting a compound in which at least one of the group consisting of R ₁₁ , R ₁₂ and R ₁₃ is a hydrogen atom, and optionally a compound capable of cocondensation, to an aldehyde, is 1 The production method according to (a) above, which is a larger condensate, (d) wherein the norbornenyl group-containing compound in the formula (1) is a group consisting of R ₁₀ , R ₁₁ , R ₁₂ and R _{13 in} the formula (2). An addition-condensation reaction of an aldehyde with a compound in which at least one kind is a hydrogen atom and optionally a compound capable of co-condensing,
Then, by an etherification reaction with at least one selected from alcohols having 1 to 20 carbon atoms, and optionally a condensation reaction at the same time, an etherification condensate having an average addition condensation degree of more than 1 is obtained. A certain manufacturing method according to the above item (a), (e) Y in the formula (1)
The norbornenyl group-containing compound in which is an amide group is an amine having 1 or more carbon atoms and 5-norbornene-2-
The production method according to (a) above, which is at least one selected from the reaction products with carbonyl halides;
The norbornenyl group-containing compound in which Y in the formula (1) is a carboxylate group is at least one selected from the reaction products of alcohols having 4 or more carbon atoms and 5-norbornene-2-carbonyl halide. (G) Y in the formula (1)
A norbornenyl group-containing compound in which is an oxazolinyl group is 2- (bicyclo [2.2.1] hept-5-ene-
2-yl) -2-oxazoline, the production method according to the above item (a), (h) the norbornenyl group-containing compound in which Y in the formula (1) is an amide group is a carboxylic acid having 1 or more carbon atoms. The above (a), which is at least one selected from the reaction product with 2- (bicyclo [2.2.1] hept-5-en-2-yl) -2-oxazoline.
(B) The modified resin according to any one of (b) to (d) above and at least one selected from epoxides are reacted. A method for producing an epoxy-modified resin, which comprises: (n) at least one selected from the group consisting of the modified resins described in (b) to (d) above and the epoxy-modified resin described in (b) above. A method for flame retarding a resin, which comprises using a resin, (l) comprising the modified resin described in the above (b) to (d) and the epoxy modified resin described in the above (b) At least one resin selected from the group, a method for thermally stabilizing resins, (wo) the modified resins described in (a) above, and the epoxy-modified resins described in (ii) above. At least one resin selected from the group consisting of and one or more different resins Compatibilizing method for resins, characterized in that they are made compatible with each other, (wa) above (b)
To (d) modified resins and (i) epoxy-modified resins selected from the group consisting of at least one resin selected from the group consisting of resin surface modification method And (f) at least one resin selected from the group consisting of the modified resins described in (b) to (d) above and the epoxy-modified resin described in (b) above. Coating resin composition to be
To a resin composition for adhesives, which contains at least one resin selected from the group consisting of the modified resins described in (d) and the epoxy modified resin described in (i). Will be provided.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION

A. In the compound containing a norbornenyl group according to the present invention, R ₁ , R ₂ , R ₃ , R ₄ in [Formula (1)]
R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are species selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms and a phenyl group, and R ₁ , R ₂ , R ₃ , R ₄ , R
₅ , R ₆ , R ₇ , R ₈ and R ₉ may be the same or different species, and the number, position and steric configuration thereof are not particularly limited, but among hydrogen atom, methyl group and phenyl group. A norbornenyl group-containing compound consisting of a species selected from the following is preferable from the viewpoint of easy availability of raw materials, easiness of steps for production, purification and the like, and a hydrogen atom is particularly preferable.
Further, such a norbornenyl group-containing compound has at least one group represented by the formula (1), and the number of such groups can be appropriately selected depending on the purpose of use, etc. Usually 1 due to ease of use
It is -10, preferably 1-5, and more preferably 1 or 2. When two or more such groups are included, the groups may be the same or different groups, but the same group is preferable in terms of availability of such compounds.

Y in the formula (1) is a triazinyl group which may have a substituent, an amide group, a carboxylate group, an oxazolinyl group, an oxycarbonyl group, a urethane group, a cyanuric acid ester group, an ether group, a carbamoyl group, a carbonyl group. The group is preferably a triazinyl group which may have a substituent, an amide group, a carboxylate group, and an oxazolinyl group from the viewpoint of easy availability of raw materials, imparting properties to the obtained modified resins, and the like. A triazinyl group is more preferred.

Specific examples of the norbornenyl group-containing compound according to the present invention include 2- (4,6-diamino-1,
3,5-triazin-2-yl) -bicyclo [2.2.
1] Hept-5-ene (norbornene carboguanamine), 2- (4,6-diamino-1,3,5-triazin-2-yl) -7-methyl-bicyclo [2.2.1]
Hepta-5-ene, 2-methyl-2- (4,6-diamino-1,3,5-triazin-2-yl) -5-bicyclo [2.2.1] heptene, 2-carbamoyl-5- Norbornene, N-ethyl-5-norbornene-2-carboxamide, N-phenyl-5-norbornene-2-
Carboxamide, 1,6-bis (5-norbornene-
2-Carboxamide) -hexane, 4,4'-bis (5-norbornene-2-carboxamide) -diphenyl ether, 1,4-bis (5-norbornene-2-
Carboxamido) -benzene, benzoic acid 2- (5-norbornene-2-carboxamide) -ethyl ester, 5-norbornene-2-carboxylic acid octyl ester, 5-norbornene-2-carboxylic acid benzyl ester, 1,6- Bis (5-norbornene-2-carboxylic acid) hexamethylene diester, 5-norbornene-2
-Carboxylic acid methyl ester, 2-methyl-5-bicyclo [2.2.1] heptene-2-carboxylic acid butyl ester, 2- (5-bicyclo [2.2.1] heptene-2
-Yl) -2-oxazoline, benzoic acid (5-norbornen-2-yl) ester, isophthalic acid bis (5-norbornen-2-yl) diester, 5-norbornene-2-methanol acrylate, 5-bicyclo [2 ．
2.1] Hepten-2-yl acetate, 2-benzyloxy-5-norbornene, 5-norbornen-2-yl-phenyl ketone, 5-norbornen-2-ylmethyl ketone, 5-norbornene-2-carbonyl chloride, formula ( 2) norbornene carboguanamines, N-monosubstituted norbornene carboguanamine derivatives, N, N′-disubstituted norbornene carboguanamine derivatives, N, N ′, N ″ -tri-substituted norbornene carboguanamine derivatives, N , N ', N ", N"'-tetra-substituted norbornene carboguanamine derivatives, 2-hydroxy-5-norbornene, 2-amino-5-norbornene, etc. with organic isocyanates, carboxylic acids, cyanuric chloride, etc. Derivative obtained by the reaction, norbornene represented by the formula (2) Examples thereof include addition condensates of carboguanamines and aldehydes, and etherification condensates obtained by etherification reaction with alcohols, and the like. Preferably, the compound represented by the formula (2), 5-norbornene- Derivatives obtained by reaction of 2-carbonyl halide with amines and alcohols, 2- (bicyclo [2.2.1] hept-5-en-2-yl) -2-oxazoline with monocarboxylic acid, dicarboxylic acid And derivatives thereof obtained by reaction with carboxylic acids, addition condensation products of compounds represented by formula (2) and aldehydes, and etherification condensation products obtained by etherification reaction with alcohols. It is not limited to.

The norbornenyl group-containing compound according to the present invention can be obtained by a known method, and cyclopentadiene such as an alkyl group having 1 to 4 carbon atoms and a phenyl group, such as cyclopentadiene or dicyclopentadiene. Pentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 5-methylcyclopentadiene, methylcyclopentadiene dimer, 5-ethylcyclopentadiene, 1-ethyl-3-methylcyclopentadiene, 3-isopropyl-1-methylcyclopentadiene , 5-isopropylcyclopentadiene,
1,2,3,4-tetraphenylcyclopentadiene,
1,2,4-triphenylcyclopentadiene, 1,4
-Diphenylcyclopentadiene and the like, preferably cyclopentadiene and unsaturated compounds such as (meth) acrylic acid, β-phenylacrylic acid, (meth) acrylic acid ester, vinyl acetate, crotonaldehyde, methyl vinyl ketone, vinyl phenyl ketone and the like To produce a norbornenyl group-containing compound, a hydrogenation reaction, an oxidation reaction, a reduction reaction, an esterification reaction, a transesterification reaction, a halogenation, a urethanization reaction and the like. However, the present invention is not limited to these.

As the norbornenyl group-containing compound, which is a triazinyl group in which Y in the above formula (1) may have a substituent, the compound represented by the formula (2) is particularly useful. For example, it can be obtained by a ring closure reaction between 2-cyano-5-norbornene and dicyandiamide, a ring closure reaction between 5-norbornene-2-carboxylic acid ester and a biguanide, and such a method is extremely useful.

Examples of the norbornenyl group-containing compound in which Y in the above formula (1) is an amide group include amines having 1 or more carbon atoms and 5-norbornene-2-
It is particularly useful because it can be obtained by a method by a known amidation reaction with a carbonyl halide.

As such amines, compounds having one or more amino groups and one or more imino groups each having 1 or more carbon atoms are useful, and aliphatic, alicyclic, aromatic, or heterocyclic amines such as, for example, , Methylamine, ethylamine, butylamine, octylamine, cyclohexylamine, aniline, hexamethylenediamine, 1,4-diaminomethylcyclohexane, 2,5-diaminomethylnorbornane, 1,4-diaminobenzene, and the like. It is not limited.

The norbornenyl group-containing compound in which Y in the above formula (1) is an amide group includes, for example, carboxylic acids having 1 or more carbon atoms and 2- (bicyclo [2.2.1] hept-5). It can also be obtained by a known ring-opening reaction with -en-2-yl) -2-oxazoline, and such a method is also useful. Examples of such carboxylic acids include aliphatic, alicyclic and aromatic carboxylic acids having one or more carboxyl groups, such as propionic acid, cyclohexylcarboxylic acid, benzoic acid, adipic acid and isophthalic acid. It is not limited.

The norbornenyl group-containing compound in which Y in the above formula (1) is a carboxylate group can be obtained, for example, by an esterification reaction of an alcohol having 4 or more carbon atoms with 5-norbornene-2-carbonyl halide. , The above alcohols and 5-norbornene-
It can be obtained by a known method such as a method by transesterification with 2-carboxylic acid methyl ester, and such a method is extremely useful.

Examples of such alcohols are aliphatic, alicyclic and aromatic alcohols having one or more hydroxyl groups, such as butyl alcohol, hexyl alcohol, cyclohexanol, benzyl alcohol, 1,6 hexanediol and 1,4. -Cyclohexanediol and the like are included, but the present invention is not limited thereto.

Further, the norbornenyl group-containing compound having the group represented by the above formula (1) is, for example, 2-
Reaction of hydroxy-5-norbornene with carboxylic acids, isocyanates, etc., Reaction of 2-hydroxy-5-norbornene with sodium alcoholate and halogenated cyanuric acid which may have a substituent, with alkyl halide, 5-norbornene A compound that can be obtained by a known method such as a reaction of 2-carbonyl halide with ammonia or an organic cadmium compound, and Y is an oxycarbonyl group, a urethane group, a cyanuric acid ester group, an ether group, a carbamoyl group, a carbonyl group, or the like. Can be provided.

Further, the norbornenyl group-containing compound according to the present invention is obtained by subjecting the compound represented by the formula (2), an addition condensation product of these compounds and aldehydes, and further an etherification reaction with alcohols. The etherified condensates are flame-retardant, heat-stable, compatible, surface-modifying, coating, adhesive, miscible with additives, and reinforced by the modified resins obtained using these. It is excellent in the improvement of adhesion, dyeing property, electrical properties, etc. with materials, etc., it is difficult to cause discoloration and deterioration during high temperature processing, etc., and has excellent weather resistance, heat resistance, etc. It is particularly preferable because it has an amino group having excellent reactivity, and thus has an excellent point that various modifications and modifications can be performed by reacting with the amino group.

Norbornenyl group-containing compound according to the present invention
In the product [formula (2)], R_Ten, R ₁₁, R₁₂And R
₁₃Is a hydrogen atom and a group having 1 or more carbon atoms.
R is a species selected from the group_Ten, R₁₁, R₁₂And
And R₁₃Can be the same or different species, their numbers,
Although the position and the configuration are not particularly limited,
As the group having 1 or more carbon atoms, a group having 1 or more carbon atoms can be used.
Has a hydroxyl group, ester group, ether group, carboxy
Group, carbonyl group, amide group, imide group, nitro group,
Sulfonic acid group, sulfonic acid amide group, amino group, imino
It may have functional groups such as groups and unsaturated groups, branched chains, etc.
Aliphatic group, alicyclic group, aromatic group, and heterocyclic group are useful
You.

Specific examples thereof include a hydrogen atom,
Methyl, ethyl, isopropyl, n-butyl, 2-ethylhexyl, octadecyl, allyl, oleyl, 4-methylcyclohexyl, phenyl, o-tolyl, α-naphthyl, benzyl, β-phenethyl, o-methoxycarbonylphenyl, p-ethoxy. Carbonylphenyl, methoxymethyl, butoxymethyl, stearyloxymethyl, 4-methoxyphenyl, tetrahydrofurfuryl,
2- (1-piperazinyl) ethyl, 2- (piperazino)
Ethyl, 2- (morpholino) ethyl, 2- (1-pyrrolidinyl) ethyl, 2-pyridinyl, methylol, 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 12-hydroxydodecyl, 1 -(2-Hydroxyethyl) -2-propenyl, 1- (1-hydroxypropyl) -3-pentenyl, 5-hydroxy-3-oxapentyl, 1- (2
-Hydroxyethyl) -4-oxahexyl, 4-hydroxycyclohexyl, 4-hydroxyphenyl, 4-hydroxynaphthyl, 4- (hydroxymethyl) phenyl, 2- (4-hydroxyphenyl) ethyl, 3-hydroxypyridin-2-yl , 8-hydroxyquinoline-
4-yl and the like can be mentioned, but the invention is not limited thereto.

Specific examples of the compound containing the norbornenyl group [formula (2)] according to the present invention include 2- (4,6-diamino-1,3,5-triazin-2-yl) -bicyclo [2.2.1]. ] Hepter 5-ene, 2- (4,6-diamino-1,3,5-triazin-2-yl) -3-methyl-bicyclo [2.2.1] hepter 5-ene, 2-
(4,6-Diamino-1,3,5-triazin-2-yl) -7-methyl-bicyclo [2.2.1] hepter 5
-Ene, 2- (4,6-diamino-1,3,5-triazin-2-yl) -3-phenyl-bicyclo [2.2.
1] Hepter 5-ene, 2- (4,6-diamino-1,
3,5-triazin-2-yl) -7-isopropyl-bicyclo [2.2.1] hepter5-ene, 2- (4
6-Diamino-1,3,5-triazin-2-yl) -4-ethyl-6-methyl-bicyclo [2.2.1] hepter 5-ene, 2- (4,6-diamino-1,3,5-
Triazin-2-yl) -1,4-diphenyl-bicyclo [2.2.1] hepter5-ene, their N-mono (di / tri / tetra) substituted-norbornene carboguanamines, such as N-hydroxymethyi. Runorbornene carboguanamine, N-hydroxymethyl-3-methyl-norbornene carboguanamine, N- (2-hydroxyethyl) -norbornene carboguanamine, N- (5-
Hydroxy-3-oxapentyl) -norbornene carboguanamine, N-methoxymethyl-norbornene carboguanamine, N-butoxymethyl-norbornene carboguanamine, N-stearyloxymethyl-norbornene carboguanamine, N-ethyl-norbornene carboguanamine, N- Octyl-norbornene carboguanamine, N-cyclohexyl-norbornene carboguanamine, N-phenyl-norbornene carboguanamine, N
Examples thereof include-(2-morpholinoethyl) -norbornene carboguanamine, addition condensation products of the compound represented by the formula (2) and aldehydes, and etherification condensation products obtained by etherification reaction with alcohols. However, the present invention is not limited to these.

Examples of the aldehydes used for producing the N-substituted norbornenyl group-containing compound represented by the above formula (2) and condensates thereof include formaldehyde, paraform, hexamethylenetetramine, methyl hemiformal and butyl hemi. Formal, formaldehyde such as sodium formaldehyde bisulfite adduct, glyoxal, acetaldehyde, trimethylolacetaldehyde, acrolein, benzaldehyde, furfural, phthalaldehyde, terephthalaldehyde and the like, preferably formaldehydes, glyoxal, more preferably an aqueous formaldehyde solution, Paraform, but not limited to. or,
The amount of the aldehyde used is usually 0.5 to 20 mol, and more preferably 1 to 20 mol, based on 1 mol of the amino compound consisting of the above-mentioned norbornenyl group-containing compound [formula (2)] and the optional co-condensable compound. Is 0.7 to 10 mol.

The alcohols used for the etherification reaction in the production of these condensates include saturated or unsaturated aliphatic alcohols having 1 to 20 carbon atoms, alicyclic alcohols and ether groups. Alcohol having, alcohol having an aromatic group, etc. are useful,
For example methyl alcohol, iso-propyl alcohol,
n-butyl alcohol, tert-butyl alcohol, 2-
Ethylhexyl alcohol, n-nonyl alcohol, n
-Octadecyl alcohol, n-eicosyl alcohol, cyclohexyl alcohol, cyclohexenyl alcohol, 4-methylhexyl alcohol, ethylene glycol monomethyl ether, propylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, benzyl alcohol and the like, but are not limited thereto. Not something.

The ratio of the norbornenyl group-containing compound [formula (2)] used in the condensate according to the present invention can be appropriately selected according to the desired performance, but the solubility and dispersibility in resins are good. And excellent flame retardancy, thermal stability,
Modified with compatibility, miscibility with additives, surface modification, coating, adhesiveness, dyeability, electrical properties, moldability, solvent resistance, weather resistance, impact resistance, abrasion resistance, etc. In order to obtain the above resins, the amount thereof is preferably 40% by weight or more in the amino compound consisting of the norbornenyl group-containing compound [formula (2)] and the optional co-condensable compound, and further, It is more preferably 60% by weight or more.

Further, in the production of these condensates, a co-condensable compound may be optionally used as described above. Examples of the co-condensable compound include melamine, N-methylmelamine, benzoguanamine, and the like.
Acetoguanamine, cyclohexanecarboguanamine,
Cyclohexenecarboguanamine, norbornanecarboguanamine, CTU-guanamine, adipoguanamine, dicyandiamide, urea, alkylurea, thiourea, alkylthiourea, guanidine, urethane, phenol, p-
Methylphenol, nonylphenol, resole, aniline, tetramethylenediamine, furfural, furfuryl alcohol, p-toluenesulfonic acid amide, o-
Toluenesulfonic acid amide, benzenesulfonic acid amide, tetralin sulfonic acid amide, carboxylic acid amide,
Examples thereof include, but are not limited to, sulfuryl amide and diamido phosphorus nitride low polymer. The amount of the compound used may be in the range that does not impair the significance of using the norbornenyl group-containing compound [formula (2)] according to the present invention, and is preferably less than 60% by weight in the amino compound.

The above-mentioned N-methylol compound of norbornenyl group-containing compound [Formula (2)] is reacted in a solvent, for example, in the presence of a basic compound, if necessary, at pH 8.0 to 13.0, preferably pH 8.5 to 11.5. Temperature 30 ℃ or more, preferably 40
The reaction proceeds rapidly and smoothly when carried out under the condition of -80 ° C to obtain the above-mentioned compound having at least one HOCH ₂ group, and further, it is highly methylolated N-methylol. When obtaining compounds, it is possible to obtain highly pure and good yields by reducing the amounts of water and alcohols, but excessive reduction reduces the stirring effect and makes the reaction temperature non-uniform. And so on, which is not preferable because it hinders a smooth reaction, and a solvent which is substantially insoluble in water and does not hinder the reaction, for example, an aromatic hydrocarbon, an aliphatic hydrocarbon, a halogenated compound, in order to smoothly carry out such a reaction. Method carried out in the presence of hydrocarbons, aliphatic ethers, etc., amines such as alicyclic amines, aliphatic amines, aromatic amines, ammonia and other auxiliary agents are added in an amount of 0.01 to 10 mol% based on the aldehydes. How to do it is useful That is, if the can be appropriately selected, but is not limited to these methods.

The above-mentioned ether compounds of the norbornenyl group-containing compound [Formula (2)] are, for example, the N-methylol compounds obtained above in 40 to 80 under acidic conditions of pH 2 to 4.
It can be obtained by carrying out the reaction in the presence of the above-mentioned alcohols for carrying out the etherification reaction at a temperature of ℃ for 1 to 8 hours. In particular, the water content in the reaction system is reduced as much as possible, and the molar ratio of the charged reaction is N-methylol compound 1
It is preferable to carry out the above-mentioned alcohol in an amount of 10 mol or more per mol.

The method for obtaining the condensate according to the present invention is
Although not particularly limited, a mixture solution obtained by stirring and mixing the above-mentioned amino compound and aldehyde with one or more solvents such as water, alcohols, aromatic compounds and the like, has a pH of 8.0 or less. Or 40 to 1 under pH 13.0 or above
It can be obtained by carrying out the reaction at a temperature of 00 ° C.

Further, the above-mentioned etherification condensate is, for example, the N-methylol compound obtained by the above-mentioned method or the condensate thereof is etherified at a temperature of 50 to 120 ° C. under an acidic condition of pH 1.0 to 5.0. It can be obtained by carrying out an etherification reaction or an etherification reaction and a condensation reaction at the same time in the presence of the above-mentioned alcohols which carry out the reaction, but it is not limited to these methods.

Further, the above-mentioned norbornenyl group-containing compound [formula (2)] and a condensate or etherified condensate thereof are treated with a curing agent such as mineral acids, carboxylic acids, sulfonic acids, ammonium salts thereof, metal and nitric acid. The same applies to condensates, cured products, polymer fine particles, etc. having a high degree of condensation by using compounds that release or form protons under the production conditions of water-soluble metal salts with acids such as sulfuric acid and phosphoric acid. It is useful.

In the production method of the present invention, the amount of the above-mentioned norbornenyl group-containing compound used with respect to the resins can be appropriately selected depending on the purpose of use, etc. Preferably 0.01
-40% by weight. Even when such a norbornenyl group-containing compound is used in a large amount, it is extremely useful in a wide range because it is very unlikely that the modified resins are colored, the physical properties are deteriorated due to a marked decrease in the molecular weight, and the deterioration is not caused.

The method for producing a modified resin according to the present invention is carried out by reacting the resin and the above-mentioned norbornenyl group-containing compound at a temperature in the range of 200 to 450 ° C. Depending on the type of norbornenyl group-containing compound used,
When the norbornenyl group-containing compound described in (h) is used, the reaction is carried out at a temperature of 230 to 450 ° C., preferably 240 to 400 ° C., more preferably 2
It is in the range of 50 to 400 ° C. Above (b) to (h)
When the norbornenyl group-containing compound according to the item is used, 23
When the temperature is lower than 0 ° C, the reaction is remarkably slow and the yield is remarkably low, which is not preferable, and the upper limit temperature may be a temperature within a range where deterioration of the resins is unlikely to occur, and usually 4
The temperature is 50 ° C., preferably 400 ° C. or lower. Even when the reaction temperature exceeds the operating temperature range during the kneading and molding of the raw material resins, the extremely excellent thermal stability and heat resistance of the modified resins cause thermal deterioration. It is difficult to cause the deterioration, coloration and the like of the above, the reaction can be proceeded in good yield, and the modified resin having excellent characteristics and physical properties can be obtained.

The above-mentioned reaction can be carried out in the presence or absence of a solvent, and the solvent can be appropriately selected and used depending on the raw material, the production conditions, etc., but it should be carried out in the absence of the solvent. Is preferred.

The reaction method is not particularly limited and may be any form such as a batch reaction system and a continuous reaction system, and the reaction is carried out by a known solution method, melting method, resin processing step or the like (reactive method). Processing) can be applied and can be appropriately selected depending on the case.However, such a resin and the above-mentioned norbornenyl group-containing compound are mixed in a nitrogen atmosphere in the absence of a solvent under a kneading machine such as a single-screw or twin-screw machine. The method of kneading with an extruder such as an axial screw, a heating roll, a Banbury mixer, a kneader, etc., and extruding after the reaction or while performing the reaction is a one-step process that does not require complicated steps in an extremely short time. It can be performed by extrusion processing,
It is preferable because it is excellent in that it can continuously and consistently obtain modified resins.

The reaction system described above can be carried out under normal pressure or in a closed vessel under autogenous pressure, under pressure or under reduced pressure, and can be appropriately selected as necessary. For degassing of the generated gas such as cyclopentadiene, it is preferable to carry out the reaction by installing a vent port or the like under normal pressure or reduced pressure.

Furthermore, in such a production method, addition of a reaction catalyst, an initiator and the like is not required, but benzoyl peroxide,
An organic peroxide such as lauroyl peroxide or dicumyl peroxide can be optionally added and used as an initiator, and can be appropriately selected within a range not impairing the significance of the present invention. However, when such an initiator is used, mechanical properties due to a decrease in the molecular weight of such resins, deterioration of performance such as electrical properties, thermal deterioration, discoloration, deterioration, heat resistance, deterioration of thermal stability are likely to occur. Due to their defects, their use has significant limitations and it is preferred not to use them. The production method of the present invention is extremely excellent because it is possible to modify the resins without adding such an initiator and the like, and it is free from these defects.

As the resins according to the present invention, any resin containing a hydrocarbon group is useful, and the molecular weight of such resins is from those of high molecular weight materials such as resins and rubbers to waxes. It is useful for low molecular weight materials such as oils and materials having high melt viscosity and Mooney viscosity to low viscosity materials, and can be appropriately selected according to the purpose of use. The method for producing such a modified resin is capable of performing modification by introducing and bonding a functional group and an amount of the functional group which are difficult to introduce and bond during the production of the resin, and therefore, it is possible to improve the properties of resins and rubbers. Molecular weight materials, resins that do not contain functional groups, such as polyolefin resins, E
It is particularly useful for P rubber, olefin thermoplastic elastomers such as EPDM and EOR, hydrocarbon synthetic wax, hydrocarbon oil and the like.

The resins according to the present invention include thermoplastic resins, thermosetting resins, rubbers, blends thereof, modified resins such as block copolymers, graft copolymers and rubber modified polymers, Natural resins, waxes, oils and the like are useful.

Specific examples of such resins include resins such as polystyrene and styrene, and other monomers such as maleic anhydride, α-methylstyrene, butadiene, acrylonitrile, and (meth) acrylic acid ester. Polystyrene resin such as terpolymer, terpolymer, rubber-modified polystyrene, rubber-modified styrene-acrylonitrile copolymer, rubber-modified styrene-maleic anhydride copolymer, polyethylene, polypropylene, polybutyne, poly-3-methylbutene, ethylene- Vinyl acetate copolymer, ethylene-propylene copolymer, polyolefin resin such as EPDM, (meth) acrylic resin such as polymethyl acrylate and polymethyl methacrylate, nylon 4, nylon 6, nylon 12, nylon 66, nylon 612, co Polyester such as polymerized nylon Bromide resin, polyethylene terephthalate, unsaturated polyester resin, poly (2,6-dimethyl-1,4-phenylene) ether, such as polybutylene terephthalate, poly (2-methyl-6-ethyl-1,
4-phenylene) ether, poly (2-methyl-6-chloro-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, 2,6-dimethylphenol Copolymers with 2,3,6-trimethylphenol, polyphenylene ether resins capped at their ends, polyphenylene ether resins such as resins obtained by modifying these with styrene resins, polyamide resins, polyacetal resins, polyvinyl chloride, Polyvinylidene chloride, chlorinated polyethylene,
Chlorinated polypropylene, chlorinated rubber, vinyl chloride and other monomers [eg vinyl acetate, ethylene, propylene, styrene, isobutylene, vinylidene chloride, maleic anhydride, acrylonitrile, butadiene, isoprene, chlorinated propylene, (meth) acrylic acid Ester, etc.], terpolymer, polyvinyl bromide, brominated polyethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene propylene resin, fluororesin, vinyl acetate resin, polyamideimide, polyimide resin , Polyetherimide, polyphenylene sulfide resin, polyether sulfone, polysulfone resin, polyamine sulfone,
Thermoplasticity of polycarbonate, liquid crystal (polyester) polymer, cyclic polyolefin, polyether ether ketone, polyarylate, phenoxy resin, silicone resin and blends of these resins, block copolymers, graft copolymers, rubber modified polymers, etc. Resin, diallyl phthalate, diallyl phthalate resin such as diallyl-2,6-naphthalene dicarboxylate, unsaturated polyester resin such as maleic acid (fumaric acid) -containing polyester-styrene resin, urethane resin, epoxy resin, silicone resin, phenol Resins, furan resins, amino resins, blends of these resins, thermosetting resins such as resins modified with rubbers, petroleum resins, DCPD resins,
Natural resins such as cellulose powder, cellulose acetate, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, polyglutamic acid, and polyterpenes,
These modified resins are exemplified.

Further, specific examples of such resins include rubbers such as SBR, BR, IR, EP rubber, EPDM rubber, NBR, EOR, chloroprene rubber, IIR, urethane rubber, silicone rubber, polysulfide rubber, and hydrogenated rubber. Nitrile rubber, polyether rubber, fluorine rubber, tetrafluoroethylene / propylene rubber, acrylic rubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber, propylene oxide rubber, ethylene / acrylic rubber, liquid rubber, norbornene rubber, styrene rubber Thermoplastic elastomer, olefin-based thermoplastic elastomer, urethane-based thermoplastic elastomer, polyester-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, 1,2-
Polybutadiene-based thermoplastic elastomer, vinyl chloride-based thermoplastic elastomer, synthetic rubber such as thermoplastic elastomer such as fluorine-based thermoplastic elastomer, natural rubber, waxes such as paraffin wax, microcrystalline wax, Mitsui high wax 800P, 400P, 10
0P, 410P, 220P, 110P, NL800, N
Polyethylene wax such as L500, NL100 [Mitsui Petrochemical Co., Ltd.], NP055, NP105, N
P805 [Mitsui Petrochemical Co., Ltd.] and other polypropylene waxes, Fischer-Tropsch wax and other synthetic waxes, carnauba wax, cane wax, palm wax,
Natural waxes such as wood wax, beeswax, spermaceti wax, montan wax, etc., oils such as hydrocarbon oil, silicone oil, lubricating oil, natural oils and fats, and blended products thereof.
Examples include modified products, but are not limited to these.

Since various functional groups can be introduced into the resins by the production method of the present invention, the modified resins obtained by the above method are used for further modification reaction to promote the modification. That is also useful. The modified resins obtained by using the norbornenyl group-containing compound represented by the formula (2) have active amino groups having excellent reactivity, and include aldehydes, epoxides, carboxylic acids (anhydrides), It is preferable that modification can be promoted by a modification reaction with an isocyanate, an oxazoline, a silane, a silane coupling agent or the like, preferably an epoxide, and various excellent materials can be provided.

In the method for producing an epoxy-modified resin according to the present invention, the modified resin and the epoxide obtained by using the norbornenyl group-containing compound [formula (2)] described above are subjected to specific reaction conditions. By reacting with these resins, the coating properties, adhesion properties, wettability, dyeability, and
Surface properties such as water and oil repellency, solvent resistance, adhesion to reinforcing materials, etc. are significantly modified, compatibility with different resins and dispersibility are further improved, and such resins are stable at high temperatures sex,
Excellent in non-volatility, less generation of sublimation, bleeding, etc., easy to manufacture, etc. Furthermore, it is possible to obtain a new material with improved physical properties as a compatibilizer with different resins. A method for modifying resins can be provided.

The epoxide according to the present invention can be widely used as long as it is a compound having one or more epoxy groups, and there is no particular limitation such as a compound having an aliphatic group, an alicyclic group or a heterocyclic group. .

Specific examples of such epoxides include bisphenol A, bisphenol F, halogenated bisphenol A, bisphenol type epoxy resin having a skeleton of halogenated bisphenol S, cresol novolac type epoxy resin, phenol novolac type epoxy resin, and phenol. Novolac type halogenated epoxy resin, naphthalene type epoxy resin, α-olefin epoxide having 1 to 40 carbon atoms, cyclohexene oxide, cyclopentadiene monoxide, butadiene dioxide, epoxidized linseed oil, styrene epoxide, methyl glycidyl ether, butyl Glycidyl ether,
Allyl glycidyl ether, phenyl glycidyl ether, alkyl phenyl glycidyl ether, 4,4-di (1,2-epoxyethyl) diphenyl ether, diglycidyl ether of resorcin, diglycidyl ether of phloroglysin, triglycidyl ether of p-aminophenol, Tetraglycidyl bis- (aminophenyl) methane, terephthalic acid diglycidyl ether,
1,3,5-tri (1,2-epoxyethyl) benzene, 2,2,4,4-tetraglycidoxybenzophenone, hexanediol diglycidyl ether, 2-ethylhexyl diglycidyl ether, neopentyl glycol diglycidyl ether , Polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, pentaerythritol polyglycidyl ether, vinylcyclohexenedioxide, 3,
4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, fats such as trade names "Celoxide # 2000", "Celoxide # 2021", "Celoxide # 3000", "Celoxide # 4000" [Daicel Chemical Industries, Ltd.] Cyclic epoxy resin, trade name "Epicoat # 1100L" [Okaka Shell Epoxy Co., Ltd.], aromatic amine diglycidyl ether, hydantoin epoxy resin, heterocyclic epoxy resin such as triglycidyl isocyanurate, glycidyl (meth) Epoxy obtained by modifying a polymer of a compound capable of copolymerizing with an epoxy group-containing vinyl monomer such as acrylate, polyphenylene ether resin, polyamide resin, polypropylene resin, saturated polyester resin, etc. with epichlorohydrin, glycidol, etc. Containing resin and the like, but not limited thereto.

The amount of epoxides used in the present invention is
Although it can be appropriately selected depending on the case, it is usually a ratio of 0.1 to 5.0 equivalents of epoxy groups in epoxides with respect to 1 equivalent of triazine-bonded amino groups in the above-mentioned modified resins, The ratio is preferably 0.2 to 3.0 equivalents.

The method for producing the epoxy-modified resin according to the present invention is carried out by heating the modified resin obtained by the above-mentioned method with the epoxide, and the temperature of the heating reaction is 150 ° C. Or more, preferably 150 to 400
C., more preferably 150 to 350.degree. When the reaction temperature is lower than 150 ° C., the reaction is remarkably slow and the yield is remarkably low, which is not preferable.
The temperature may be 0 ° C. or higher, but the temperature may be within a range in which deterioration of the resins is unlikely to occur, and it is usually preferably 350 ° C. or lower. The above reaction and reaction system can be carried out by the solution method, the latex method, the melting method, the reactive processing and the like in the same manner as in the above-mentioned modified resin production method, and may be appropriately selected depending on the case. However, after the above-mentioned modified resins are produced, they are continuously kneaded in the same system in the same system in the absence of a solvent under a nitrogen atmosphere, for example, a single-screw or twin-screw extruder, a heating roll, and a bunber. A method of extruding after kneading with a remixer, a kneader or the like and performing a melt heating reaction or while performing is preferable because it has the same excellent points as described above.

Further, in the above-mentioned method for producing epoxy-modified resins, organic acid metal salts such as tin octylate, reaction promoters such as imidazoles and novolac type phenol resins can be appropriately selected and used depending on the case.

The modified resins and epoxy-modified resins according to the present invention are flame retardant, thermal stable, heat resistant, impact resistant, high strength / high elasticity, resin compatibility, bending / fatigue resistance. , Wear resistance, tear resistance, dimensional stability, stress relaxation, vibration damping,
Heat / cold resistance, solvent resistance (oil, water) resistance, weather resistance, gloss, refractive index change, self-lubricating property, plasticity, gas barrier property and other physical properties, adhesiveness, adhesion with glass fiber reinforcing agents, slippage sex,
Plating properties, coating properties such as paints, dyeing properties of resins and these fibers, antiblocking properties, antistatic properties, conductivity, charging properties, electrical properties such as tracking resistance, fluidity, shrinkability,
Excellent in heat-melting strength, flow moldability, crystallinity, orientation, workability, and other moldability, resource saving, economical improvement such as substitution, etc., construction equipment, interior products, baths, toilets, etc. Housing equipment, instrument panels, pillars, meter clusters, door rims, armrests, defroster garnishes, console boxes, pocket decks,
Bumpers, side sill garnishes, cowl top garnishes, wheel covers, spoilers, headlamps, inner panels, etc. for automobiles and other vehicles such as interior and exterior materials, long and short glass fiber reinforced molding materials, resist materials, electrical insulating materials and other electrical parts, toner, etc. Electrophotographic materials, textile materials,
Textile / paper processing materials, adhesives for hot melts, adhesives, paints for automobiles and home appliances, antifouling, anticorrosion paints, powder paints, traffic paints, adhesives for hot melts, adhesives, industrial materials, etc. Adhesives, etc., IC encapsulants, rubber modifiers, optical materials, leather treatment agents, agricultural materials, medical equipment,
Packaging materials, containers and other food equipment, tents, cloth, clothing and other textiles, gears, packing and other engineering equipment, piping, tanks and other antifouling, corrosion-resistant equipment, heat-resistant equipment, heat insulation, cold insulation materials, oil reforming It is an excellent material that can be used as a material, a flame retardant material, a surfactant, a corrosion / oxidation inhibitor, etc., which is useful in a wide range of industrial applications.

B. In the flame retarding method for resins according to the present invention, use of modified resins comprising the modified resins described in (b) to (d) above and the epoxy modified resins described in (b) above. The amount of the triazine nucleus in the resins may be appropriately selected, and may be 2 to 40% by weight, preferably 4 to 30% by weight. . If it is less than 2% by weight, it is difficult to obtain a sufficient flame retardancy-improving effect. It is not desirable because it causes

In the above flame retarding method for resins,
When phosphorus, which is selected from the group consisting of elemental phosphorus and compounds containing phosphorus atoms, is used together with the modified resins according to the present invention in the resins, a synergistic effect of further improving the flame retardant effect is imparted. It is possible and is especially preferable. This not only facilitates the formation of flame-retardant coatings of relatively low volatility on the surface of the combustion material, but also promotes char formation even more and increases the char layer, which prevents the diffusion of oxygen to the combustion surface. It is considered that such an excellent synergistic effect is produced by functions such as prevention, suppression of generation of flammable gas from the material part, and reduction of heat conduction to the material part.

Examples of such phosphorus include simple phosphorus such as red phosphorus, phosphorus-based compounds such as phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, phosphate, polyphosphate, phosphite and phosphonate. Phosphoric acid esters such as acids, phosphoric acid triesters, polyphosphoric acid esters, acidic phosphoric acid esters and salts thereof, phosphorous acid triesters, phosphorous acid diesters and other phosphorous acid esters, phosphonic acid esters, acidic phosphones Acid esters and phosphonates such as salts thereof, phosphines, phosphine oxides, phosphines such as phosphonium salts, and sulfur-containing phosphorus compounds such as dialkylthiophosphoric acid and salts thereof are useful, but are not limited to these. It is not something that will be done.

Examples of such phosphorus acids include acids such as phosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, etc., and further bases such as ammonia, amine, alkali metal, alkaline earth metal So obtained by neutralizing a part or all, ammonium phosphate, ethylenediamine phosphate, sodium phosphate, calcium phosphate, melamine pyrophosphate, sodium pyrophosphate, ammonium tripolyphosphate, sodium tripolyphosphate, ammonium polyphosphate, Examples thereof include sodium polyphosphate, ammonium phosphite, calcium phosphite, ammonium phosphonate, etc., and the general formula (NH ₄ ) _{m + 2} P _m O
Ammonium polyphosphate represented by _{3m + 1} (wherein m represents an integer greater than 5) is preferable, but not limited thereto.

The above general formula (NH ₄ ) _{m + 2} P _m O
_{In the} ammonium polyphosphate represented by _{3m + 1} (where m is an integer greater than 5), m is sufficiently large to reduce the water solubility in view of the flame retardant effect and the physical properties of resins. Salts in which m is an integer greater than 50 are particularly preferred, and in practice metaphosphate (N
H ₄ PO ₃ ) _m .

As an example of such ammonium polyphosphate, the trade name "Exolit 263",
"Exolit 422" (manufactured by Hoechst), trade name "Phoscheck P"
/ 30 ”(manufactured by Monsanto Chemical Company) and the like.

Examples of such phosphoric acid esters include trimethyl phosphate, tri-n-butyl phosphate, trilauryl phosphate, tristearyl phosphate, trioleyl phosphate, tris (butoxyethyl) phosphate, triphenyl phosphate, tricresyl phosphate, trikisyl phosphate. Silenyl phosphate, cresyl diphenyl phosphate, xylene diphenyl phosphate, tris (isopropylphenyl) phosphate, isopropyl diphenyl phosphate, 2
-Ethylhexyl diphenyl phosphate, stearyl diphenyl phosphate, oleyl diphenyl phosphate, butyl dicresyl phosphate, lauryl dicresyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, Phosphate triesters such as tris (2,3-dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (bromochloropropyl) phosphate, tris (tribromophenyl) phosphate, mono / dimethyl acid phosphate, Mono / diethyl acid phosphate, monobutyl acid phosphate, di-2-ethylhexyl phosphate, mono / diuraryl Ddohosufeto, mono / distearyl acid phosphate, mono / dioleyl acid phosphate, mono / di-2-chloroethyl acid phosphate, mono / dibutoxyethyl acid phosphate, ethylene glycol acid phosphate,
Acidic phosphates such as dibutyl pyrophosphate, mono / diphenyl acid phosphate, mono / dicresyl acid phosphate, mono / dixylenyl acid phosphate, dimethyl phosphate ammonium salt, ethyl phosphate ammonium salt, di-n-butyl phosphate ammonium Salt, dibutoxyethyl phosphate / triethanolamine salt, dioctyl phosphate / morpholine salt, mono-n-butyl phosphate / soda salt, diphenyl phosphate / ammonium salt, diphenyl phosphate / melamine salt, diphenyl phosphate / piperazine salt, phenyl phosphate /
Ammonium salt, dicresyl phosphate / ethylenediamine salt, cresyl phosphate / soda salt, dixylenyl phosphate / melamine salt and other acidic phosphoric acid ester ammonia, amine, melamine, alkali metal, alkaline earth metal salt and the like. However, the present invention is not limited to these.

Examples of such phosphorous acid esters include trimethylphosphite, triethylphosphite,
Tributyl phosphite, tris (2-ethylhexyl) phosphite, trilauryl phosphite, trioleyl phosphite, tristearyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t -Butylphenyl) phosphite, tris (dinonylphenyl) phosphite, bis (nonylphenyl) dinonylphenylphosphite, diphenylmono (2-ethylhexyl) phosphite, diphenylmonodecylphosphite, diphenylmono (tridecyl) phosphite , Phenyl diisooctyl phosphite, tetraphenyl dipropylene glycol diphosphite, poly (dipropylene glycol) phenyl phosphite, diisodecyl pentaerythritol diphosphite , Bis (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, phenyl -4,4'-isopropylidene diphenyl pentaerythritol diphosphite, tetraphenyl tetra (tridecyl) pentaerythritol tetraphosphite, tetra (tridecyl) -4,4'-isopropylidene diphenyl phosphite, hydrogenated bisphenol A / phosphite Polymer, pentaerythritol / hydrogenated bisphenol A / triphenylphosphite polycondensate, tetra (tridecyl) -4,4′-n-butylidene bis (2-t-butyl-5-methyl) Phenol) diphosphite, bis (neopentyl glycol) 1,4
-Cyclohexanedimethylene phosphite, bis (octylphenyl) .bis [4,4'-n-butylidene bis (2-t-butyl-5-methylphenol)] 1,6-
Hexanediol phosphite, tetra (tridecyl)
Phosphorous acid triester such as -1,1,3-tris (2'-methyl-5'-t-butyl-4'-oxyphenyl) butanediphosphite, dimethylhydrogenphosphite, dibutylhydrogenphosphite , Ji (2
-Ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl phosphite, and other phosphite diesters are included, but are not limited thereto.

Examples of such phosphonic acids include dimethyl methylphosphonate, ethyl diethylphosphonoacetate, bis (2-chloroethyl) vinylphosphonate,
Diethyl N, N-bis (2-hydroxyethyl) aminomethylphosphonate, dibutyl butylphosphonate, di-2-ethylhexyl hydroxymethylphosphonate, di-2-ethylhexyl 2-ethylhexylphosphonate, dimethyl phenylphosphonate, diallyl phenylphosphonate , Dioctyl phenylphosphonate, dinaphthyl phenylphosphonate, phosphonate diesters, 2-ethylhexyl phosphonate mono-2-ethylhexyl, phenylphosphonate monooctyl, and other acidic phosphonate esters, 2
-Ethylhexylphosphonic acid mono-2-ethylhexyl ammonium salt, phenylphosphonic acid monooctyl-triethanolamine salt, 2-ethylhexylphosphonic acid mono-2-ethylhexyl-melamine salt, phenylphosphonic acid monooctyl-soda salt, and other phosphonic acid ester salts, etc. However, the present invention is not limited to these.

Examples of such phosphines include triethylphosphine, tri-n-octylphosphine, tris (2-cyanoethyl) phosphine, tris (3-hydroxypropyl) phosphine, tricyclohexylphosphine, triphenylphosphine, tri-p-tolylphosphine, Tri (2,6-dimethoxyphenyl) phosphine, 9-phosphabicyclo [3.3.1], [4.2.
1] Nonane (mixture), bis (1,2-diphenylphosphino) ethane, bis (1,4-diphenylphosphino) butane, diphenyl-p-styrylphosphine, diphenylphosphinas chloride, bis (diphenylphosphino) ferrocene Such as phosphine, triethylphosphine oxide, tri-n-octylphosphine oxide, tris (2-cyanoethyl) phosphine oxide, tris (3-carboxyethyl) phosphine oxide, tris (3-hydroxypropyl) phosphine oxide, triphenylphosphine oxide, etc. Phosphine oxide, tetra-n-butylphosphonium bromide, tri-n-butylallylphosphonium bromide, ethylenebistris (2-cyanoethyl) -phosphonium bromide, Lutriphenylphosphonium bromide, tetraphenylphosphonium bromide, tri-n-octylethylphosphonium bromide, tetra-n-butylphosphonium O, O-diethylphosphorodithioate, tetrakis (hydroxymethyl) phosphonium sulfate, tetra-n-butylphosphonium iodide, ethyl Triphenylphosphonium iodide, triethylbenzylphosphonium chloride, tetra n-
Examples thereof include phosphonium salts such as butylphosphonium chloride, tri-n-butyltetradecylphosphonium chloride, tris (2-cyanoethyl) allylphosphonium chloride, benzyltriphenylphosphonium chloride, bis (triphenylphosphine) iminium chloride, and the like. It is not limited.

Examples of such sulfur-containing phosphorus compounds include dimethylphosphorodithioate, di-n-propylphosphorodithioate, diethylphosphorodithioate / ammonium salt, di-n-propylphosphorodithioate / melamine salt, and dimethylphosphine. Forodithioate ·
Soda salt, trilauryl trithiophosphite, tris (lauryl-2-thioethyl) phosphite, diphenyl bis [4,4'-n-butylidene bis (2-t-butyl-5-methylphenyl)] thiodiethanol diphosphite , Triphenylphosphine sulfide, tris (2-cyanoethyl) phosphine sulfide, tri-n-butylphosphine sulfide, and the like.
It is not limited to these.

The amount of phosphorus used according to the present invention is 5 to 40% by weight, preferably 10 to 10% by weight, based on such resins.
It is 30% by weight. If the amount used is less than 5% by weight,
The synergistic effect of improving flame retardancy is not sufficient, while 40% by weight
If it exceeds the range, it is not preferable in practice because it may affect the physical properties.

Further, such phosphorus may exist separately from the components of the above-mentioned modified resins in such resins, or some or all of them may contain the above-mentioned modified resins and salts. It may be formed and contained. Salts such as phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, ammonium acid polyphosphate, acidic phosphoric acid ester, acidic phosphonic acid ester and the like are contained in the form of salts with the above-mentioned modified resins. In this case, the synergistic effect of improving flame retardancy is more excellent and preferable.

When the above-mentioned modified resins are used in combination with specific isocyanuric acids and / or cyanuric acids in the resins to be used as a flame retardant method for the resins, the flame retardancy of the resins is improved. This is preferable because it can be further improved.

That is, the specific isocyanuric acids and cyanuric acids are represented by the formula (3)

[0091]

Embedded image (In the formula, R ₁₄ , R ₁₅ and R ₁₆ represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an oxyalkyl group having 1 to 3 carbon atoms, a phenyl group or a glycidyl group, and R ₁₄ , R ₁₅ and R ₁₆ may be the same or different, and isocyanuric acids represented by the formula (4)

[0092]

[Chemical 9] [In the formula, R ₁₄ , R ₁₅ and R ₁₆ have the same meanings as in the formula (3)].

The isocyanuric acids according to the present invention have the formula
R is a compound represented by (3) ₁₄, R_Fifteenand
R₁₆ Is a hydrogen atom, an alkyl having 1 to 3 carbon atoms
Group, oxyalkyl group having 1 to 3 carbon atoms, phenyl
A group selected from the group consisting of a vinyl group and a glycidyl group.
Yes, R₁₄, R_FifteenAnd R₁₆Is the same species but different species
However, as a specific example of such isocyanuric acid,
For example, isocyanuric acid, methyl isocyanurate, tris
Methyl isocyanurate, triethyl isocyanurate
G, tris (2-hydroxyethyl) isocyanurate
G, phenyl isocyanurate, diphenyl isocyanurate
Rate, triphenyl isocyanurate, dimethyl phenate
Nyl isocyanurate, triglycidyl isocyanate
However, the present invention is not limited to these.

The cyanuric acid according to the present invention is a compound represented by the formula (4), and R ₁₄ , R ₁₅ and R ₁₆ have the same meanings as in the formula (3). Are, for example, cyanuric acid, methylcyanurate, trimethylcyanurate, triethylcyanurate, tris (2-hydroxyethyl) cyanurate,
Examples thereof include, but are not limited to, phenyl cyanurate, diphenyl cyanurate, triphenyl cyanurate, dimethylphenyl cyanurate, triglycidyl cyanurate, and the like.

The use ratio (triazine nucleus equivalent ratio) of the total amount of isocyanurate acids and cyanuric acids according to the present invention is 0.01 to 5, preferably 0.1 to the triazine nucleus equivalent in the above modified resins. When the usage ratio is less than 0.01, the combined effect is insufficient. On the other hand, when the usage ratio is more than 5, it is not practically preferable because the physical properties are deteriorated.

The isocyanuric acids and the cyanuric acids may be present in the resins separately from the components such as the modified resins described above, or some or all of them may be modified as described above. Forming salts with high quality resins,
It may be reacted and contained. In the case of containing and forming a salt, for example, a product salt of isocyanuric acid and the above-mentioned modified resin, a reaction product such as a reaction product of triglycidyl cyanurate and the above-mentioned modified resin, flame retardancy is contained. It is more preferable because of its excellent effect on heat resistance and heat resistance.

As such salts, for example, the above-mentioned isocyanuric acid, the salts obtained by dissolving or dispersing the above-mentioned modified resins in the presence / absence of a solvent and reacting by heating, and the like are useful. Examples thereof include salts obtained by reacting triazine nuclei in the modified resins with isocyanuric acid in an equivalent amount or several equivalent amounts, and a reaction salt mixture thereof, but are not limited thereto.

Further, when the above-mentioned modified resins are used in combination with an amino group-containing compound in a material to be used as a flame retarding method for resins, the flame retardancy of the material can be further improved, preferable.

The amino group-containing compound has an aliphatic group having 2 or more carbon atoms, an alicyclic group, an aromatic group or a heterocyclic group, and preferably an aliphatic group having 2 or more carbon atoms. A group, an alicyclic group, or a heterocyclic group, and more preferably,

[0100]

[Chemical 10] And dicyandiamide, guanidine, and reaction products of these with aldehydes such as formaldehyde or epoxy compounds.

Specific examples of such amino group-containing compounds include 1,2-ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-butylenediamine, 1,6-hexamethylenediamine, Polyalkylenepolyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, cyclohexylamine, cyclohexyldiamine, 1,3-bis (aminomethyl) cyclohexane, aniline, benzylamine, furfurylamine, N- (3- Aminopropyl) morpholine, N-
(2-Aminoethyl) morpholine, N- (2-aminoethyl) piperazine, N- (3-aminopropyl) piperazine, N- (2-aminoethyl) piperidine, N, N '.
-Bis (2-aminoethyl) piperazine, dicyandiamide, guanidine, urea, polyamide resins, reaction products of these with aldehydes such as formaldehyde, for example, ethylenediamine-formaldehyde (1/1) reaction product,
Examples include piperazine-formaldehyde (1/1) reaction product, pentamethylenehexamine, and salts thereof.
It is not limited to these.

The amount of the amino group-containing compound used in the present invention is 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the resins. When the amount used is less than 0.01% by weight, the synergistic effect of improving the flame retardancy is not sufficient, while when it exceeds 10% by weight, there is an effect of causing a decrease in physical properties, which is practically preferable. Absent. Furthermore, in the flame retarding method for resins according to the present invention, by using additives such as phenolic antioxidants, amine antioxidants, sulfur antioxidants, and light stabilizers in combination, The thermal stability and the like can be improved and can be appropriately selected depending on the purpose of use.

As such a phenolic antioxidant,
Known compounds such as 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, octadecyl-
Monophenol compounds such as 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,
2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-ethyl-6-t-butylphenol), 4,4'-thiobis- (3- Methyl-6-t-butylphenol), 4,
Bisphenol compounds such as 4'-butylidene bis- (3-methyl-6-di-t-butylphenol), 1,
1,3-tris- (2-methyl-4-hydroxy-5-
t-Butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-)
Hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3.
Polymeric phenol compounds such as 3′-bis (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester and the like can be mentioned. The amount of these used is 0.001 to 2.0% by weight, preferably 0.05 to 1.0% by weight, based on such resins.

Examples of such amine-based antioxidants include known compounds such as phenyl-1-naphthylamine, phenyl-2-naphthylamine, N, N'-diphenyl-p.
-Phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroxyquinoline, dioctyliminodibenzyl, diethanolamine, triisopropanolamine, octadecyldiethanolamine,
Examples thereof include N, N'-diphenylethylenediamine, triethyltetramine, tridecylamine adduct with 4 mol of ethylene oxide, and hexadecylamine adduct with 20 mol of ethylene oxide. The amount used is 0.02 to 5.0% by weight with respect to such resins.

Examples of the sulfur-based antioxidants include known compounds such as dilauryl-3,3'-thio-di-propionate, dimyristyl-3,3'-thio-di-propionate and distearyl-3,3 '. Examples include -thio-di-propionate, 2-methylmercaptobenzimidazole, pentaerythritol-tetrakis- (β-lauryl-thiopropionate) and the like. The amount used is 0.01 to 4.0% by weight, preferably 0.05 to 2.0% by weight, based on the resin. Examples of the light stabilizer include known compounds such as benzophenone compounds, acetophenone compounds, benzotriazole compounds, benzoate compounds, oxalic acid anilide compounds, cyanoacrylate compounds, organic nickel compounds, hindered amine compounds and the like. However, the present invention is not limited to these.

Further, nucleating agents such as 4-t-butylbenzoic acid, adipic acid and diphenylacetic acid, metal deactivators such as oxanilide, dicarboxylic acid dihydrazide,
Free radical promoters such as salicylic acid hydrazide, eg 2,3
-Dimethyl-2,3-diphenylbutane [trade name Interlocks CC DFB (Peroxide Chemie Gm.
b. H production)], 3,4-dimethyl-3,4-diphenylhexane [trade name Interlocks CC DFH (Peroxide Chemie Gmb H production)], 2,3-dimethyl-2,3- Diphenylhexane or the like can be appropriately selected and used.

In the flame retarding method for resins according to the present invention, the method for producing such resins is not particularly limited, and the production method usually used when mixing powdery additives with such resins is applicable. Is. For example, in the case of a thermoplastic resin or the like, a resin pellet or powder and additives are premixed at room temperature and then melt-mixed using an extruder, a heating roll, a kneader, etc. Resins are manufactured in advance, and a manufacturing method in which this and ordinary resins are melt-kneaded and then molded, or in the case of a thermosetting resin, a monomer before curing, a prepolymer or a reinforcing material is added to these. Examples of the method include, but are not limited to, a production method in which the essential components according to the present invention are added to the dope or compound and the mixture is kneaded and then molded.

In the flame retarding method for resins according to the present invention, other additives such as a plasticizer, a dye / pigment, a dispersant, an organic chelating agent, a stabilizer, and the like are added within a range not impairing the effects of the present invention. Foaming agent, anti-fog agent, matting agent, surface treatment agent,
Fluorescent agent, antifungal agent, bactericidal agent, antioxidant, ultraviolet absorber,
Antimony trioxide, barium metaborate, zirconium dioxide, lead oxide, zinc borate, ammonium salts such as aluminum hydroxide, ammonium sulfate, ammonium carbonate, reaction products of cyanuric chloride / amines, triazine nucleus-containing compounds such as melamine derivatives, etc. Flame retardant, flame retardant aid, higher fatty acid, higher fatty acid ester, higher fatty acid metal salt, lubricant such as bisamide, sulfonic acid, quaternary ammonium salt, polyhydric alcohol ester, alkylamide, alkylamine, conductive carbon black, etc. Antistatic agent, reinforcing material such as glass fiber, carbon fiber, talc, clay, calcined clay, mica, calcium silicate, calcium sulfate, calcium carbonate, glass beads, molybdenum disulfide, graphite and the like filler, nucleating agent , Processing aids, mold release agents, other polymers etc. are required Flip and can be included. In the flame-retardant method for resins of the present invention, it is preferable to contain at least one selected from the group consisting of phosphorus as a simple substance and a compound containing a phosphorus atom as a component. Examples of phosphorus include red phosphorus and phosphorus. Acid, polyphosphoric acid, phosphorous acid, phosphonic acid, phosphate, polyphosphate,
More preferred are phosphites, phosphonates, phosphates, phosphites, phosphonates, phosphines, and sulfur-containing phosphorus compounds, and polyphosphates having the general formula (NH ₄ ) More preferably, it is an ammonium polyphosphate represented by _{m + 2} P _m O _{3m +1} (wherein m represents an integer greater than 5). Further, it is preferable to contain at least one selected from the isocyanuric acids and cyanuric acids represented by the formulas (3) and (4) as a component.

Further, it is preferable that at least one selected from the amino group-containing compounds is contained as a component, and the amino group-containing compound is

[0110]

[Chemical 11] More preferably, it is a compound having cis, dicyandiamide, guanidine and a reaction product thereof with an aldehyde or an epoxy compound.

Further, it is particularly preferable to contain the above-mentioned phosphorus and amino group-containing compound as a component.

Further, the resins are preferably thermoplastic resins, thermosetting resins, and thermoplastic elastomers, and the thermoplastic resins are polyolefin resins, polyamide resins,
Polystyrene resin, polyphenylene ether resin, polyacrylic resin, saturated polyester resin, polycarbonate resin, thermosetting resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, urethane resin,
More preferably, the thermoplastic elastomer is an olefinic thermoplastic elastomer.

Further, among such polyolefin resins, polypropylene resin and polystyrene resin are extremely difficult to be flame retarded, and the prior art requires a large amount of additives such as triazine compounds and phosphorus compounds.
Although it has defects such as poor miscibility of the additives and remarkable deterioration of physical properties, on the other hand, when the modified resin according to the present invention is used, an aminotriazinyl group is introduced and bonded to the resin. Therefore, these defects can be remarkably improved, and the flame retardant method according to the present invention is particularly useful for such a resin.

C. The heat stabilization method for resins according to the present invention is at least one selected from the group consisting of the modified resins described in (b) to (d) above and the epoxy-modified resins described in (b) above. By including seeds,
It is possible to provide excellent molded products, etc., in which the thermal stability, ultraviolet resistance, long-term heat resistance, weather resistance, etc. of resins are remarkably improved, and there is little heat deterioration, coloring, discoloration of resins during high temperature processing. , The above-mentioned modified resins are excellent in high-temperature stability and non-volatility, are excellent in handling, etc., and can further suppress decomposition and deterioration of resins due to heavy metal ions such as copper, A reforming method can be provided.

Furthermore, since the temperatures of 1% and 5% heat loss of such resins are remarkably improved, high temperature processing becomes easy and various molding processing can be carried out. For example, a polyphenylene ether resin is a resin such as a polystyrene resin, which is conventionally poor in moldability because it induces decomposition, gelation, etc. during high-temperature molding processing despite having excellent physical properties when heated at high temperatures. For example, a method of improving the molding processability by blending with other compounds is used, and the excellent heat characteristics originally possessed by the resin are impaired, and in some cases it cannot be utilized at all. The modified resins according to the present invention have such an excellent property that the thermal stability is remarkably improved, high-temperature molding is possible, and the blending with other resin is extremely small, or unnecessary, and the like. We can also provide new materials.

In the heat stabilization method for resins according to the present invention, the amount of the above-mentioned modified resins comprising the modified resins and the epoxy-modified resins may be the total amount or a partial amount in the resins. The content of the triazine nucleus in the resin is 0.01 to 10% by weight, preferably 0.02 to 5% by weight, although it can be appropriately selected. 0.
When the amount is less than 01% by weight, it is difficult to obtain the sufficient effect of improving stability against heat, light, etc., and when the amount is more than 10% by weight, the effect of improving stability is not particularly improved, and the economy is improved. Is not preferable.

As the resins which can be the object of the heat stabilization method for the resins of the present invention, the resins which are the objects of the flame retardant method can be mentioned in almost the same manner. Further, in the heat stabilization method for resins according to the present invention, the above-mentioned phenolic antioxidant, amine antioxidant, sulfur antioxidant, light stabilizer, nucleating agent, other additives, etc. are added. By using the same amount of the agent in the same amount as the above amount and by using the following phosphite type antioxidant in combination, it is possible to further improve the effect of improving stability according to the present invention, depending on the purpose of use. Can be appropriately selected.

Examples of phosphite antioxidants include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, diphenyldecyl phosphite, 2 -Ethylhexyl diphenyl phosphite,
Phenyldiisodecyl phosphite, diphenyl acid phosphite, tridecyl phosphite, tris (2-
Ethylhexyl) phosphite, tributyl phosphite, dilauryl acid phosphite, ditridecyl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-t
-Butylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, phenyl 4,4'-isopropylidenediphenol pentaerythritol diphosphite, trilauryltrithiophos Fight, Tris (Lauryl-2
-Thioethyl) phosphite, diphenyl bis [4,
4'-n-butylidene bis (2-t-butyl-5-methylphenol)] thiodiethanol diphosphite, bis (neopentyl glycol) 1,4-cyclohexanedimethylene phosphite, hydrogenated-4,4'-isopropyi Ridenediphenol polyphosphite, bis (octylphenyl) .bis [4,4'-n-butylidene bis (2-t-butyl-5-methylphenol)] 1,6-
Hexanediol diphosphite, tetratridecyl-
4,4'-n-butylidene bis (2-t-butyl-5-
Methylphenol) diphosphite, tetratridecyl-1,1,3-tris (2'-methyl-5'-t-butyl-4'-oxyphenyl) butanediphosphite, tetra ( _C12-15 mixed alkyl) 4 , 4'-isopropylidene diphenyl diphosphite and the like. The amount of these used is preferably 0.01 to 10% by weight with respect to the resins.

In the heat stabilization method for resins according to the present invention, the method for producing such resins and the use of other additives can be carried out in the same manner as in the above-mentioned flame retardation method for resins. However, it is not limited thereto.

In the heat stabilization method for resins according to the present invention, the resins are preferably thermoplastic resins, thermoplastic elastomers, synthetic waxes, and polyphenylene ether resins, polyacrylic resins, polystyrene resins, polyamides. More preferably, it is at least one selected from the group consisting of resins, polyolefin resins, olefin-based thermoplastic elastomers, and hydrocarbon-based synthetic waxes, and the polyolefin resin comprises polyethylene resin, polypropylene resin, and ethylene-propylene copolymer. More preferably, it is at least one selected from the group.

D. The method for compatibilizing resins according to the present invention comprises at least one resin selected from the group consisting of the modified resins described in (a) above and the epoxy-modified resins described in (i) above, By compatibilizing two or more different resins, not only the compatibility and dispersibility of different resins are significantly improved, but also the physical properties are improved and new materials can be provided. Deterioration, coloring,
Little discoloration, excellent stability at high temperature of such materials, non-volatility, less sublimation, bleeding, etc., easy handling, large solubility parameter difference, improved compatibility and dispersibility between different resins Therefore, a wide selection of types of such resins can be provided, and various new materials can be provided. Since such materials have almost no degradation of the molecular weight due to decomposition or gelation of the original resins, alterations, etc. It is excellent in that it can easily maintain the properties of
Further, the thermal stability of the material obtained by compatibilization is also improved, and an excellent method for modifying resins can be provided.

In the method for compatibilizing resins according to the present invention, the amount of the above-mentioned modified resins and epoxy-modified resins to be used may be the total amount or a partial amount of the corresponding kind of resins, and depending on the case, Can be selected. The amount of the modified resin used is usually 0.1 to 30% by weight as the content of the reaction residue of the norbornenyl group-containing compound described above in the resin of the corresponding species, and is appropriately selected depending on the case. However, if the amount is less than 0.1% by weight, it is difficult to obtain a sufficient effect of improving the compatibility.
If the amount is larger, the improvement effect is not particularly improved, and it is not economically preferable. The amount of the epoxy-modified resin used is usually 0.1 to 40% by weight, preferably 0.5 to 30% by weight, as the content of the reaction residue of the above-mentioned epoxide in the corresponding type of resins. It can be appropriately selected depending on the case, but if it is less than 0.1% by weight, it is difficult to obtain a sufficient effect of improving the compatibility.
When the content is more than 10% by weight, not only the improvement effect is not particularly improved, but also the deterioration of the properties of the resins is easily caused, which is not preferable.

In the method for compatibilizing resins according to the present invention, a method of incorporating at least one resin selected from the group consisting of the above-mentioned modified resins and epoxy-modified resins and one or more resins different from them. , 2 different selected from the group consisting of modified resins and epoxy-modified resins
A method of incorporating one or more species is useful, but not limited to these.

The modified resins according to the present invention are
Since materials containing various functional groups can be provided, they can be used for further modification, and these can be used in the compatibilizing method according to the present invention like the above-mentioned modified resins and the like. be able to. The modified resins obtained by using the norbornenyl group-containing compound represented by the formula (2) have active amino groups excellent in reactivity,
Not only the above epoxides, but also carboxylic acids (anhydrides) such as maleic anhydride-modified polypropylene resin, isocyanates such as polyurethane resin, oxazolines such as styrene-2-vinyl-2-oxazoline copolymer,
The modification can be promoted by a modification reaction with an aldehyde or the like such as terephthalcarbaldehyde, and these are useful in the compatibilizing method according to the present invention like the above-mentioned modified resins and the like.

As the resins which can be the object of the method for compatibilizing the resins according to the present invention, the resins which are the objects of the above-mentioned modified resin production method can be mentioned in almost the same manner. However, the polyolefin resins and the polyphenylene ethers can be used. Resins, saturated polyester resins, polyamide resins, polycarbonate resins, polystyrene resins, and thermoplastic elastomers are preferred. Specific examples of the two or more different resins include, for example, different kinds of binary resins such as polyolefin resin and polyamide resin, polyphenylene ether resin, polystyrene resin, polyimide resin, saturated polyester resin, multi-component resin, polyphenylene ether resin and polyamide resin, Polyimide resin, polyaramide resin, heterogeneous binary with saturated polyester resin, multi-component resin, elastomer and polyolefin resin, polyamide resin, polyphenylene ether resin, polystyrene resin, polyimide resin, heterogeneous binary resin with saturated polyester resin, etc., Examples include, but are not limited to, heterogeneous binary and multi-component resins such as saturated polyester resin and other resins.

Further, in the compatibilizing method of resins according to the present invention, the method for producing the modified resin and the epoxy-modified resin described above and the method for compatibilizing the different resins are performed in parallel. It is useful to separately obtain modified resins and epoxy-modified resins, and then use these to make them compatible with different resins and the like, which can be appropriately selected depending on the case. It is not limited to.

Further, the method for producing such a material is not particularly limited, and a solution method, a latex method, a melting method and the like which are usually used in the compatibilizing method of such resins can be applied. For example, pellets of resins or After premixing the powder at room temperature, a kneading machine, for example, a single-screw, twin-screw extruder or the like, a heating roll, a Banbury mixer, a method of melt-mixing using a kneader, and the like can be mentioned. It is not limited.

The method for compatibilizing resins according to the present invention includes the above-mentioned phenolic antioxidant, amine antioxidant, sulfur antioxidant, phosphite antioxidant, light stabilizer, and stabilizer. Additives such as a nucleating agent and other additives may be used in the same amount as the above amount, and can be appropriately selected according to the purpose of use.

E. The surface modification method for resins according to the present invention is at least one selected from the group consisting of the modified resins described in (b) to (2) above and the epoxy modified resins described in (b) above. By using the above resins, high-molecular-weight resins, not low-molecular-weight additives, are improved in wettability, adhesiveness, coatability, dyeability, water / oil repellency, solvent resistance, etc. of such resins. Since it can be modified and modified, it is excellent in high temperature stability and non-volatility, and it is difficult to reduce the effect due to the disappearance of the modified component over time, heat, etc. Furthermore, due to poor compatibility with resins, etc. It is possible to provide a method for modifying resins, which is excellent in that separation and disappearance of the modifying component are unlikely to occur, and wettability of the surface can be appropriately selected according to the purpose of use.

The surface modification method for resins according to the present invention is as follows:
It is particularly useful for polyolefin resins such as polypropylene resins that have significant restrictions on surface properties such as adhesiveness, coating properties, and dyeability. Such a resin has remarkable physical properties and characteristics, but has serious restrictions on its use due to such serious drawbacks, but it is possible to overcome these drawbacks by the above-mentioned method and expand to a wider range of applications. Became.

Further, although polypropylene fibers have excellent properties such as lightness, strength, warmness, and easy drying, they have a serious defect in surface properties such as markedly poor dyeability, and therefore, their use is considerably restricted.

As a method for improving the dyeability, many proposals have been made such as addition of the modifier and use of maleic acid-modified polypropylene fiber. However, such a method is that sufficient dyeability cannot be obtained, and the modifier is used. And the compatibility is insufficient, the heat resistance is significantly reduced, and the weather resistance is poor.

The surface modification method for resins according to the present invention is as follows:
Since the required amount of functional groups that significantly improve dyeability can be introduced into such resins by bonding, excellent dyeability, dispersion and compatibility are not a concern, and heat resistance and weather resistance are excellent. Further, it is extremely excellent in modifying the dyeability, such as deterioration of the molecular weight of resins and the like, and remarkably little heat deterioration.

The modified fiber can be produced and dyed by a known spinning method, dye, dyeing condition, soaping method or the like. The modified fiber has an aminotriazinyl group. Dyes such as acid dyes are useful because they are bonded and introduced, but the dyes are not limited thereto.

In the surface modification method for resins according to the present invention, the resin surface provided from the modified resin obtained by using the norbornenyl group-containing compound represented by the formula (2) is Since the active amino group with excellent reactivity is remarkably exposed, aldehydes, epoxides, carboxylic acids (anhydrides), isocyanates, oxazolines, chlorosilanes, alkoxysilanes, silazanes, special silyl groups are used on the surface of these resins. The surface can be further modified by reaction with a silane such as an agent, a silane coupling agent such as vinyl silane, epoxy silane, fluorine-containing silane, or the like, and such a method is also very useful.

Furthermore, in the resin composition for coating and adhesive, a resin composition modified from the above (b) to (d) and an epoxy modified resin described in the above (b) is selected. By using at least one kind of resin selected, since it contains a segment having good compatibility with such resins, it has excellent adhesion to the material, good solvent resistance, water resistance, etc. The resin composition for coating having excellent coating properties, and also having a segment having good compatibility with such resins and a segment having excellent adhesiveness to other base material, Has good adhesion to
It is possible to provide a resin composition for an adhesive, which is excellent in that it can provide a composite material using various materials and has good adhesiveness.

In the method for surface modification of resins according to the present invention, the amount of the modified resins and the epoxy modified resin used may be the total amount or a partial amount of the resins, or may be a mixture or a mixture thereof. It is also particularly preferable to use epoxy-modified resins because the adhesiveness with various materials can be appropriately selected according to the purpose of use and excellent surface modification can be performed. For example, resins such as polyolefin resins and polystyrene resins are usually used in combination with rubbers such as olefinic thermoplastic elastomers for the purpose of improving their physical properties, etc., but their surface properties such as wettability, adhesiveness, and coatability are At the time of modification, both or both of the modified resin and the modified rubber described above can be used to modify the surface characteristics by a method of using the whole amount or a partial amount, It can be appropriately selected according to the purpose of use.

The amount of the modified resin used is usually 0.1 to 30% by weight as the content of the reaction residue of the norbornenyl group-containing compound described above in the resin of the corresponding species. Can be appropriately selected by
When the amount is less than 0.1% by weight, it is difficult to obtain a sufficient effect of surface modification, and when the amount is more than 30% by weight, the improvement effect is not particularly improved, and the properties of resins are deteriorated. It is easy and economically unfavorable.

The amount of the epoxy-modified resin used is usually 0.1 to 30% by weight as the content of the reaction residue of the above-mentioned epoxide in the corresponding kind of resin, and may be appropriately adjusted depending on the case. It can be selected, but if it is less than 0.1% by weight, it is difficult to obtain a sufficient effect of surface modification, and if it is more than 30% by weight, it is easy to cause deterioration of the properties of such resins. , Not preferable.

Further, in the surface modification method for resins according to the present invention, the method for producing such resins and the use of other additives can be carried out in the same manner as in the above-mentioned flame retardation method for resins. However, it is not limited thereto.

In the above-mentioned coating resin composition, the amount of the modified resin and the epoxy-modified resin used may be the total amount or a partial amount of the resin composition, or may be a mixture or a mixture thereof. However, epoxy-modified resins are particularly preferable because they have excellent coating properties such as adhesion to various resins, solvent resistance, and water resistance. Further, epoxy-modified resins obtained by using bisphenol-A, bisphenol-F, and compounds having a naphthalene skeleton as epoxides are preferable.

In the above adhesive resin composition,
The amount of modified resins and epoxy-modified resins used is
The whole amount or a partial amount of such a resin composition may be used, and it is useful even if these are mixed or used alone. Epoxy-modified resins are particularly preferable because they have excellent adhesiveness to various materials. Furthermore, epoxy-modified resins obtained by using bisphenol-A, bisphenol-F, and compounds having a naphthalene skeleton as epoxides are particularly preferable because they have excellent adhesiveness to a wide range of materials.

Further, the resin composition for adhesives may be of any type such as solvent type, solventless type, solid melt use type such as hot melt type adhesive, room temperature flow type such as adhesive, and the like. Can be selected as appropriate.

The following effects of the invention are brought about in the above-described method for producing the modified resin and the like according to the present invention and its use.

The method for producing a modified resin according to the present invention is modified by reacting the above-mentioned norbornenyl group-containing compound with the resin under a specific condition, without impairing the molecular weight, physical properties and the like. Excellent in modifying surface properties such as flame retardancy, thermal stability, heat resistance, compatibility, wettability, adhesiveness, coating properties, dyeability, molding properties, electrical properties, gloss, etc. It is an excellent one that can bond and introduce a functional group. Furthermore, the method for producing the epoxy-modified resins of the present invention is
By reacting the above-mentioned specific modified resins and epoxides under specific conditions, the production is simple, and the surface of the resins such as wettability, coatability, adhesiveness, dyeability, etc. It is excellent in that it can significantly improve properties, molding characteristics, electrical characteristics, etc., and that it can provide resins that further improve compatibility and dispersibility between different resins. This is an invention that is extremely excellent in industry.

The method of making the resins flame-retardant according to the present invention comprises the above-mentioned norbornenyl group-containing compound [formula (2)], a condensate thereof, and a modified resin obtained by using an etherification condensate, This is a method in which the flame retardancy of resins can be significantly improved by using epoxy-modified resins. Sublimation compared to the method of adding flame retardants such as melamine,
No occurrence of bleeding, etc., because flame retardancy-imparting components are incorporated into resins, these components disappear over time, and dispersion defects such as bleeding do not easily occur, so long-term effects are maintained. It is possible to remarkably improve the flame retardancy of such resins, and further not to impair the characteristics and physical properties, and the char generation is extremely good, and oil drops, melt dripping, and falling are extremely small, and Is excellent in the effect of improving the flame retardancy of resins such as the fact that no extremely harmful gases are emitted during combustion, and further, the above materials and phosphorus, isocyanuric acids, cyanuric acids, amino By using in combination with a group-containing compound, it is possible to provide a flame retarding method for resins that can obtain further improved flame retardancy due to a synergistic effect, and it becomes possible to expand the resins to wider applications, Industrial Umate is an excellent invention.

Further, the method for heat-stabilizing resins according to the present invention is a modified resin obtained by using the above-mentioned norbornenyl group-containing compound [formula (2)] or a condensate or etherification condensate thereof. UV resistance, thermal stability, heat resistance, etc. are significantly improved by using epoxy resins and epoxy modified resins, and thermal stability, heat resistance and heat resistance are low even when molding at high temperature with little heat deterioration, coloration or discoloration. Is improved,
Deterioration is suppressed and retention of physical properties is remarkably improved when used at a relatively high temperature for a long time, disappearance over time due to incorporation of a heat stability-providing component into resins, poor dispersion of bleeding, etc. Can be maintained for a long period of time because it is difficult to induce, and is extremely excellent in such effects. Stability against isotherm, light, etc. is remarkable, and the effects are shown for a long period of time, and secondary effects are induced. In addition, the fact that heavy metal ions such as copper promote decomposition and degradation of resins is significantly suppressed, thermal stability and heat resistance are significantly improved, and high-temperature molding processing is extremely easy. It is extremely excellent in the effect of improving the thermal stability of resins, such as being able to provide new materials having characteristics, and it is possible to expand the applications of resins to a wider range of uses, making it an excellent industrial invention. so That.

Furthermore, the method for compatibilizing resins according to the present invention can be applied to two or more different resins including the above-mentioned modified resins and epoxy-modified resins so that the compatibility of different resins can be improved. , Not only the dispersibility is remarkably improved, but new properties such as impact resistance, rigidity, flame retardancy, heat resistance, chemical resistance, barrier property, pearl luster, molding processability, adhesiveness, and covering property are added. Can provide a new material, which has less coloring and discoloration of resins during high temperature processing, has excellent high temperature stability and non-volatility, has less occurrence of sublimation and bleeding, and has excellent adhesiveness, electrical characteristics, etc. It is easy to handle and manufacture, and the compatibility and dispersibility between different resins with large differences in solubility parameters are also improved, so a wide selection of types of such resins can be selected. Decrease in molecular weight due to It is easy to maintain the properties of such resins because there are almost no such compounds, and it is possible to obtain resins modified with different resins that can be compatibilized, epoxy-modified resins, and low molecular weight compounds for compatibilization. Since it does not require the use of a third component such as, it is possible to provide an extremely excellent new material, and further it is possible to improve the thermal stability, water resistance, chemical resistance, etc. of the material obtained by compatibilization. This makes it possible to develop resins for a wider range of applications and is an extremely excellent invention in industry.

Further, the surface modification method for resins according to the present invention uses the modified resins composed of the above-mentioned modified resins and epoxy-modified resins to improve the wettability and adhesiveness of the resins. , Surface properties such as coatability, dyeability, and water / oil repellency can be remarkably improved, and the use of a third component such as a surface modifier is not required, so the effect is reduced due to the disappearance of the surface-modified component. Is difficult to cause, the physical properties of such resins are not likely to deteriorate, and since it is not necessary to perform surface modification after molding or the like, good uniform surface modification can be performed on various shapes.
In particular, it is possible to bond and introduce such a functional group into a resin such as a polyolefin resin, which has significant restrictions on the surface properties such as adhesiveness, coatability, and dyeability, to remarkably improve the surface properties of such resin or fiber. It has excellent points such as being able to do so.

Furthermore, the present invention can provide a resin composition for coating and a resin composition for adhesive which are prepared by using the above-mentioned modifying material, and the resin composition for coating adheres to resins. The adhesive resin composition is a segment having excellent compatibility with such resins and a segment having excellent adhesiveness with other base materials. Since it also has excellent adhesiveness to various materials and can provide new materials as well, it is possible to develop resins for a wider range of uses and is an extremely excellent invention in industry.

[0151]

EXAMPLES Next, the present invention will be explained in detail by reference examples and examples. However, the description of these reference examples and examples does not limit the scope of the present invention thereto. Reference Example 1 Synthesis of norbornene carboguanamine-formaldehyde condensate: 2- (4,6-diamino-1,3,5-triazin-2-yl) -bicyclo [2.2.1] hepta-
To 203.0 g (1 mol) of 5-ene (hereinafter abbreviated as norbornene carboguanamine), 243.2 g (3.0 mol) of 37% formalin solution was added, and the mixture was adjusted to pH 10.5 with a 20% aqueous potassium hydroxide solution while stirring. It was adjusted. The mixture was heated at a temperature of 70 ° C. for 1 hour with stirring.
After completion of heating, a 20% aqueous nitric acid solution was added to this reaction mixture to adjust the pH to 2.0. Further, when the reaction mixture was heated with stirring at a temperature of 70 ° C., it gradually became cloudy and a heating reaction was carried out for 3 hours. After heating, the reaction mixture is mixed with 2
The pH was adjusted to 8.0 with a 0% aqueous potassium hydroxide solution, and the precipitate was filtered off. This was thoroughly washed with distilled water and dried under reduced pressure to give a white solid. As a result of analyzing this solid content, it was a condensate having an average addition condensation degree of 3.8. Reference Example 2 Synthesis of norbornene carboguanamine-formaldehyde condensate: norbornene carboguanamine 203.0 g
(1 mol), 243.2 g of 37% formalin solution
(3.0 mol) was added, and the pH was adjusted to 10.5 with a 20% aqueous potassium hydroxide solution while mixing and stirring. The mixture was heated at a temperature of 70 ° C. for 30 minutes with stirring. After heating, add 20% nitric acid aqueous solution to the reaction mixture to adjust the pH.
It was adjusted to 4.0. Further, the reaction mixture is heated to a temperature of 60 ° C.
When heated with stirring, the mixture gradually became cloudy, and a heating reaction was carried out for 1 hour. After completion of heating, the reaction mixture was adjusted to pH 7.0 with a 20% aqueous potassium hydroxide solution. To this reaction mixture, 200 g of benzene was added and heated to effect debenzene, and then the precipitate was filtered off. This was thoroughly washed with distilled water and dried under reduced pressure to give a white solid. As a result of analyzing this solid content, it was a condensate having an average addition condensation degree of 1.6. Reference Example 3 Synthesis of etherified condensate of norbornene carboguanamine: 203.0 g (1 mol) of norbornene carboguanamine and 131.3 paraformaldehyde (80% product).
g (3.5 mol) and 500 ml of n-butanol were added, and the pH was adjusted to 1 with a 20% aqueous potassium hydroxide solution while mixing and stirring.
Adjusted to 1.0. This mixture was heated at a temperature of 60 ° C. for 30 minutes with stirring, and then a 20% nitric acid aqueous solution was added to adjust the pH to 3.0. Further, this reaction mixture was heated under stirring at reflux temperature for 3 hours while performing reflux dehydration. After heating, the reaction mixture was adjusted to pH 8.0 with a 20% aqueous potassium hydroxide solution, and the precipitate was filtered. As a result of removing the solvent from this solution to obtain a resinous substance and analyzing it, it was found to be an etherified condensate containing a butyl ether group and having an average addition condensation degree of 2.3. Reference Example 4 Synthesis of epoxidized polyphenylene ether resin: Polyphenylene ether resin (number average molecular weight 21,000) was placed in a 2 liter autoclave equipped with a stirrer and an insertion port.
After charging 20 g and 1 liter of epichlorohydrin and replacing the inside of the system with nitrogen, the temperature was gradually raised to 100 ° C. While maintaining the internal temperature at 100 ° C., the mixture was stirred and dissolved.
Next, 5 cc of 10% aqueous sodium hydroxide solution was added to this, and the reaction was carried out at an internal temperature of 100 ° C. for 5 hours. After completion of the reaction, the remaining amount of epichlorohydrin was distilled off under reduced pressure, and chloroform was added to the obtained solid content to dissolve it. The insoluble matter of this solution was removed by filtration, a methanol-water mixed solvent was added, and the deposited precipitate was filtered off. The precipitate was thoroughly washed with the above mixed solvent and dried under reduced pressure to obtain an epoxidized polyphenylene ether resin. As a result of analysis of this, the epoxy equivalent was 24000. Example 1 Production of modified polypropylene resin: polypropylene resin Mitsui Noblen JS-G [manufactured by Mitsui Toatsu Chemicals, Inc.]
100 parts by weight, 10 parts by weight of norbornene carboguanamine and 0.1 parts by weight of dilauryl thiodipropionate were thoroughly mixed with a Henschel mixer, and then fed to a twin screw extruder with a 20 mmφ vent equipped with a nitrogen seal and fed with 260 The kneading reaction was performed under the condition of staying at 0 ° C. for 10 minutes, and then pelletized.

The pellets were melted with hot xylol,
After filtering through a membrane filter (pore size 1.0 μm), methyl cellosolve was poured into this filtrate, and the deposited precipitate was separated by filtration. After thoroughly washing this with methyl cellosolve,
It was dried under reduced pressure to obtain a white solid. As a result of analyzing this solid content, (4,6-diamino-1,3,5-triazine)
It was a modified polypropylene resin having 4.9% by weight of the skeleton attached. The results of elemental analysis and infrared absorption spectrum analysis of this solid content are shown below.

Elemental analysis C H N measurement value: 83.1% 13.8% 3.1% Infrared absorption spectrum analysis Absorption based on NH ₂ 3320, 3150 cm ⁻¹ Absorption based on C = N 1630, 1550 cm ^-1 Triazine Nucleus based absorption 815 cm ^-1 Example 2 Preparation of modified polypropylene resin: Example except that 10 parts by weight of norbornene carboguanamine in Example 1 was replaced with 25 parts by weight of the above compound. The kneading reaction was performed in the same manner as in 1, and then pelletized.

Using this pellet, a solvent treatment was carried out in the same manner as in Example 1. The solid content thus obtained was dried under reduced pressure and analyzed to find that it was a modified polypropylene resin having 10.9% by weight of (4,6-diamino-1,3,5-triazine) skeleton bonded thereto. The results of elemental analysis of this solid content are shown below.

The MI value of this pellet was measured and found to be 1.8. On the other hand, as a comparative example, the one obtained by kneading only the above polypropylene resin in the same manner has MI
The value was 2.3, and the production method according to the present invention was excellent in that it was extremely difficult to cause a decrease in the molecular weight of resins and discoloration.

Elemental analysis C H N measured value: 80.1% 13.0% 6.9% Example 3 Production of modified polypropylene resin: polypropylene resin in Example 1 Mitsui Noblene JS-G [Mitsui Toatsu] Chemical Chemicals Co., Ltd.], a kneading reaction was performed in the same manner as in Example 1 except that a low polymerization degree polypropylene resin having an MI value of 100 was used, and then pelletized.

Using the pellets, solvent treatment was carried out in the same manner as in Example 1. The solid content thus obtained was dried under reduced pressure and analyzed to find that it was a modified polypropylene resin having a (4,6-diamino-1,3,5-triazine) skeleton of 4.9% by weight bonded thereto. The results of elemental analysis of this solid content are shown below.

Elemental analysis C H N measured value: 83.2% 13.7% 3.1% Comparative Example 1 Modification test of polypropylene resin: Norbornene carboguanamine 10 parts by weight in Example 1 was used instead of 2-
A kneading reaction was performed in the same manner as in Example 1 except that 10 parts by weight of (4,6-diamino-1,3,5-triazin-2-yl) -bicyclo [2.2.1] heptane was used, and then pellets were used. Turned into

Using this pellet, solvent treatment was carried out in the same manner as in Example 1. After drying the obtained solid content under reduced pressure, elemental analysis, infrared absorption spectrum analysis results,
The (4,6-diamino-1,3,5-triazine) skeleton was not found to be contained or bonded, which was the same as the raw material polypropylene resin, and the raw material polypropylene resin was not modified. The results of elemental analysis of this solid content are shown below.

Elemental analysis C H N measurement value: 85.6% 14.4% 0.0% Comparative Example 2 Polypropylene resin modification test: polypropylene resin Mitsui Noblen JS-G [manufactured by Mitsui Toatsu Chemicals, Inc.] 100
Parts by weight, 10 parts by weight of 5-norbornene-2,3-dicarboxylic anhydride and dilaurylthiodipropionate 0.
After thoroughly mixing 1 part by weight with a Henschel mixer, the mixture is fed to a nitrogen-sealed twin-screw extruder with a 20 mmφ vent, and a kneading reaction is carried out at a kneading temperature of 240 ° C. for 10 minutes, followed by pelletization. did.

The pellets were melted with hot xylol,
After filtering with a membrane filter (pore size 1.0 μm), methanol was poured into this filtrate, and the deposited precipitate was separated by filtration. This was thoroughly washed with methanol and dried under reduced pressure to obtain a white solid. As a result of infrared absorption spectrum analysis of this solid content, absorption based on carboxyl group and its anhydride (1710, 1770, 1785, 1860 cm ^-1 etc.)
Was not observed, and the polypropylene resin was not modified at all.

Further, the kneading reaction, treatment and analysis were carried out in the same manner as above except that the kneading reaction was carried out at a kneading temperature of 260 ° C. or 280 ° C. instead of the above kneading temperature of 240 ° C. Even under the conditions, the polypropylene resin was not modified at all. Comparative Example 3 Modification test of polypropylene resin: 5 in Comparative Example 2
A kneading reaction was performed in the same manner as in Comparative Example 2 except that 10 parts by weight of maleic anhydride was used instead of 10 parts by weight of norbornene-2,3-dicarboxylic acid anhydride, and then pelletized.

The pellets were treated in the same manner as in Comparative Example 2 to obtain white solids. As a result of infrared absorption spectrum analysis of this solid content, absorption (1710, 1770, 1785, 18) based on a carboxyl group and its anhydride was obtained.
60 cm ^-1 ) was not observed, and the polypropylene resin was not modified at all. Example 4 Production of Modified Polyethylene Resin: Instead of the polypropylene resin Mitsui Noblene JS-G [manufactured by Mitsui Toatsu Chemicals, Inc.] in Example 2, polyethylene resin Hi-Zex 6200BP [manufactured by Mitsui Petrochemicals] A kneading reaction was carried out in the same manner as in Example 1 except that was used, and then pelletized.

Using this pellet, a solvent treatment was carried out in the same manner as in Example 1. After drying the obtained solid content under reduced pressure, elemental analysis, infrared absorption spectrum analysis results,
(4,6-Diamino-1,3,5-triazine) skeleton 1
It was 1.3% by weight bonded modified polyethylene resin. The results of elemental analysis of this solid content are shown below.

Elemental analysis C H N measurement: 79.8% 13.0% 7.2% Example 5 Preparation of modified polyphenylene ether resin: Poly2, with an intrinsic viscosity [η] of 0.42. 6-dimethyl-1,
After thoroughly mixing 100 parts by weight of 4-phenylene ether, 10 parts by weight of norbornene carboguanamine and 0.1 part by weight of dilauryl thiodipropionate with a Henschel mixer, use a 20 mmφ vented twin screw extruder equipped with a nitrogen seal. The mixture was fed and kneaded at 310 ° C. for 10 minutes to carry out a kneading reaction, and then pelletized.

The pellet was dissolved in chloroform,
After filtering through a membrane filter (pore size 1.0 μm), methyl cellosolve was poured into this filtrate, and the deposited precipitate was separated by filtration. After thoroughly washing this with methyl cellosolve,
Drying under reduced pressure gave a yellow solid. As a result of analyzing this solid content, (4,6-diamino-1,3,5-triazine)
It was a modified polyphenylene ether resin having a skeleton of 4.9% by weight bonded (containing 0.1% by weight of nitrogen in the resin before modification). The results of elemental analysis of this solid content are shown below.

The molecular weight of the pellets was measured by GPC. As a result, it was almost the same as the raw material polyphenylene ether resin before the kneading reaction described above. It was an excellent product that was extremely unlikely to cause such problems. Elemental analysis CHN measured value: 77.8% 6.6% 3.2% Example 6 Production of modified polystyrene resin: polystyrene resin Topolex 570-02 [manufactured by Mitsui Toatsu Chemicals, Inc.]
100 parts by weight, norbornene carboguanamine 5 parts by weight and tris- (2-methyl-4-hydroxy-5-t-
After thoroughly mixing 0.1 part by weight of butylphenyl) butane with a Henschel mixer, the mixture was fed to a nitrogen-sealed twin-screw extruder equipped with a 20 mmφ vent, and 250
The kneading reaction was carried out under the condition of staying at 15 ° C. for 15 minutes, and then pelletized.

The pellet was dissolved in chloroform,
After filtering through a membrane filter (pore size 1.0 μm), methyl cellosolve was poured into this filtrate, and the deposited precipitate was separated by filtration. After thoroughly washing this with methyl cellosolve,
It was dried under reduced pressure to obtain a white solid. As a result of analyzing this solid content, (4,6-diamino-1,3,5-triazine)
It was a modified polystyrene resin having 2.5% by weight of the skeleton attached. The results of elemental analysis and infrared absorption spectrum analysis of this solid content are shown below.

Elemental analysis C H N measurement value: 90.7% 7.7% 1.6% Infrared absorption spectrum analysis NH ₂ based absorption 3310, 3160 cm ⁻¹ C = N based absorption 1630, 1550 cm ^-1 Triazine Nucleus based absorption 818 cm ^-1 Example 7 Preparation of modified saturated polyester resin: Saturated polyester resin Teijin PBT resin TRB-H [Teijin Co., Ltd.
100 parts by weight, norbornene carboguanamine 10
Parts by weight and tris- (2-methyl-4-hydroxy-5)
After thoroughly mixing 0.1 part by weight of -t-butylphenyl) butane with a Henschel mixer, a nitrogen seal was applied 20.
Feed into a twin screw type extruder with mmφ vent,
Perform the kneading reaction under the condition of staying at 260 ° C. for 15 minutes,
It was then pelletized.

The pellet was dissolved in dichloroethane, filtered through a membrane filter (pore size 1.0 μm), methylcellosolve was poured into the filtrate, and the deposited precipitate was separated by filtration. This was thoroughly washed with methyl cellosolve and dried under reduced pressure to obtain a white solid. As a result of analyzing this solid content, it was a modified saturated polyester resin having 4.3% by weight of (4,6-diamino-1,3,5-triazine) skeleton bonded thereto. The results of elemental analysis and infrared absorption spectrum analysis of this solid content are shown below.

Elemental analysis C H N measurement value: 64.5% 5.5% 2.7% Infrared absorption spectrum analysis Absorption based on NH ₂ 3320, 3160 cm ⁻¹ C = N based absorption 1630, 1550 cm ^-1 Triazine Nucleus-based absorption 816 cm ^-1 Example 8 Preparation of modified polyamide resin: Polyamide resin Toyobo Nylon T-802 [manufactured by Toyobo Co., Ltd.] 100 parts by weight and norbornene carboguanamine 10 parts by weight After sufficiently mixing with a Henschel mixer, the mixture was fed to a nitrogen-sealed twin-screw extruder with a 20 mmφ vent, and a kneading reaction was carried out under the condition of staying at 250 ° C. for 15 minutes, and then pelletized.

The pellet was dissolved in m-cresol, filtered through a membrane filter (pore size 1.0 μm), methylcellosolve was poured into the filtrate, and the deposited precipitate was separated by filtration. This was thoroughly washed with methyl cellosolve and dried under reduced pressure to obtain a white solid. As a result of analyzing this solid content, it was a modified polyamide resin in which 4.8 wt% of (4,6-diamino-1,3,5-triazine) skeleton was bonded. The results of elemental analysis of this solid content are shown below.

Elemental analysis CHN measured value: 62.5% 9.5% 14.7% Example 9 Production of modified polymethacrylic resin: polymethacrylic resin Parapet HR [manufactured by Kyowa Gas Chemical Industry Co., Ltd. ] 10
After thoroughly mixing 0 part by weight and 10 parts by weight of norbornene carboguanamine with a Henschel mixer, the mixture was fed to a nitrogen-sealed twin-screw extruder with a 20 mmφ vent, and a kneading reaction was performed under the condition of staying at 260 ° C. for 15 minutes. Done and then pelletized.

The pellet was dissolved in methyl ethyl ketone, filtered through a membrane filter (pore size 1.0 μm), methanol was poured into the filtrate, and the deposited precipitate was separated by filtration. This was thoroughly washed with methanol and dried under reduced pressure to obtain a white solid. As a result of analyzing this solid content,
It was a modified polymethacrylic resin having 4.7% by weight of (4,6-diamino-1,3,5-triazine) skeleton bonded thereto. The results of elemental analysis of this solid content are shown below.

Elemental analysis C H N measurements: 55.4% 6.9% 3.0% Example 10 Preparation of modified EP rubber: EP rubber JSR EP01
100 parts by weight of P [manufactured by Japan Synthetic Rubber Co., Ltd.] and 10 parts by weight of norbornene carboguanamine were fed into a kneader type kneader with a vent equipped with a nitrogen seal, and the temperature was 240 ° C.
The kneading reaction was performed for 30 minutes, and then the kneaded product was taken out.

The kneaded product was dissolved in hot xylol, filtered through a membrane filter (pore size 1.0 μm), and then methylcellosolve was poured into the filtrate to separate solids by filtration. This was thoroughly washed with methyl cellosolve and dried under reduced pressure to obtain a white solid. As a result of analyzing this solid content,
It was a modified EP rubber in which 4.4% by weight of (4,6-diamino-1,3,5-triazine) skeleton was bonded.
The results of elemental analysis of this solid content are shown below.

Elemental analysis C H N measurement value: 83.4% 13.8% 2.8% Example 11 Production of modified PP wax: PP wax Mitsui High Wax NP055 (manufactured by Mitsui Petrochemical Co., Ltd.) 100 parts by weight and 20 parts by weight of a norbornenecarboguanamine condensate obtained by the method of Reference Example 1 were fed to a kneader type kneader with a vent equipped with a nitrogen seal, and the kneading reaction was performed at 260 ° C. for 20 minutes. Then, the kneaded product was taken out.

The kneaded product was dissolved in hot xylol and filtered through a membrane filter (pore size 1.0 μm). Methyl cellosolve was poured into the filtrate to separate the resinous substance. After repeating this treatment twice, the resinous material was dried under reduced pressure to obtain a white solid. As a result of analyzing this solid content, it was a modified PP wax to which 8.8% by weight of (4,6-diamino-1,3,5-triazine) skeleton was bonded. The results of elemental analysis of this solid content are shown below.

Elemental analysis CHN measurements: 81.3% 13.1% 5.6% Examples 12-16 Preparation of modified polypropylene resins: Table 1 instead of norbornene carboguanamine in Example 1. A kneading reaction was carried out in the same manner as in Example 1 except that the norbornenyl group-containing compound shown in 1 was used, and then pelletized.

The pellets were subjected to a solvent treatment in the same manner as in Example 1. The obtained solid content was dried under reduced pressure, and then the N content (elemental analysis) was performed. The results are shown in Table-1.
Shown in

As shown in Table 1, the polypropylene resin modified by the reaction with the norbornenyl group-containing compound according to the present invention was excellent in that it could be easily produced with a high yield.

[0182]

[Table 1] Example 17 Production of modified polyethylene resin: polyethylene resin Lextron J79-4F25 (manufactured by Nisseki Chemical Co., Ltd.) 1
After thoroughly mixing 00 parts by weight, 20 parts by weight of norbornene carboguanamine and 0.1 parts by weight of dilauryl thiopropionate with a Henschel mixer, the mixture was fed to a 20 mmφ vented twin-screw extruder equipped with a nitrogen seal and 280 The kneading reaction was performed under the condition of staying at 0 ° C. for 10 minutes, and then pelletized. Dissolve the pellets with hot xylol and use a membrane filter (pore size 1.0μ).
After filtering with m), methylcellosolve was poured into this filtrate, and the deposited precipitate was separated by filtration. This was thoroughly washed with methyl cellosolve and dried under reduced pressure to obtain a white solid. As a result of analyzing this solid content, (4,6-diamino-1,3,3
It was a modified polyethylene resin in which 9.1% by weight of 5-triazine) skeleton was bonded. The results of elemental analysis of this solid content are shown below.

Elemental analysis CHN measured value: 80.9% 13.3% 5.8% Example 18 Production of modified polyethylene resin: polyethylene resin Hi-Zex 6200BP [manufactured by Mitsui Petrochemical Co., Ltd.] 1
00 parts by weight, 5 parts by weight of a reaction product of 5-norbornene-2-carbonyl chloride and isophthalic acid (2/1 molar ratio) and 0.1 part by weight of dilauryl thiopropionate were thoroughly mixed with a Henschel mixer, and then nitrogen was added. The mixture was fed to a sealed twin-screw extruder with a 20 mmφ vent, and a kneading reaction was performed under the condition of staying at 260 ° C. for 10 minutes, and then pelletized.

The pellets were melted with hot xylol,
After filtration through a membrane filter (pore size 1.0 μm), m-cresol was poured into this filtrate, and the deposited precipitate was filtered off. This was thoroughly washed with m-cresol and then dried under reduced pressure to obtain a white solid. As a result of infrared absorption spectrum analysis of this solid content, it was a modified polyethylene resin having an ester bond and a phenyl skeleton. Example 19 Production of modified polyethylene resin: Polyethylene resin HiZex 6200BP [manufactured by Mitsui Petrochemical Co., Ltd.] 1
00 parts by weight, a reaction product of 2-norbornene-2-carbonyl chloride and diaminodiphenyl ether (2/1
(Mole ratio) 5 parts by weight and 0.1 part by weight of dilauryl thiopropionate are thoroughly mixed in a Henschel mixer,
The mixture was fed to a 20 mmφ vented twin-screw extruder equipped with a nitrogen seal, and a kneading reaction was performed under the condition of staying at 260 ° C. for 10 minutes, and then pelletized.

The pellet was melted with hot xylol,
After filtration through a membrane filter (pore size 1.0 μm), m-cresol was poured into this filtrate, and the deposited precipitate was filtered off. This was thoroughly washed with m-cresol and then dried under reduced pressure to obtain a white solid. As a result of infrared absorption spectrum analysis of this solid content, it was a modified polyethylene resin having an amide bond and a phenyl skeleton. Example 20 Preparation of modified polyethylene resin: 2- (bicyclo [2.2] instead of the reaction product of 5-norbornene-2-carbonyl chloride and diaminodiphenyl ether in Example 19 (2/1 molar ratio) .1] hept-5
A kneading reaction was carried out in the same manner as in Example 19 except that a reaction product (1/1 mol ratio) of en-2-yl) -2-oxazoline and benzoic acid was used, and then pelletized.

Using this pellet, a solvent treatment was carried out in the same manner as in Example 19. As a result of infrared absorption spectrum analysis of the obtained solid content, it was a modified polyethylene resin having an amide bond, an ester bond and a phenyl skeleton. Example 21 Production of modified paraffin wax: 100 parts by weight of paraffin wax 155 (manufactured by Nippon Seiro Co., Ltd.), 10 parts by weight of norbornene carboguanamine and 0.1 part by weight of dilauryl thiopropionate, vented, It was put into a 500 ml autoclave equipped with a stirrer and a cooler.
After replacing the inside of this system with nitrogen, the internal temperature was set to 250 ° C.
The reaction was carried out with stirring for a minute. After the reaction was completed, the reaction mixture of the resinous material was taken out. The resinous material was dissolved in hot toluene, filtered through a membrane filter (pore size 1.0 μm), and then methylcellosolve was poured into the filtrate to separate the resinous material. After repeating this treatment twice, the resinous material was dried under reduced pressure to obtain a white solid. As a result of analyzing this solid content, (4, 6-
Diamino-1,3,5-triazine) skeleton 4.7% by weight
It was a modified paraffin wax bonded with. The results of elemental analysis of this solid content are shown below.

Elemental analysis C H N Measured value: 83.2% 13.8% 3.0% Example 22 Preparation of EP modified polypropylene resin: Pellets of modified polypropylene resin obtained by the method of Example 1. 10
After thoroughly mixing 0 part by weight and 20 parts by weight of Epoxy resin Epicoat # 1009 (produced by Yuka Shell Epoxy Co., Ltd.) with a mixer, the mixture was fed to a nitrogen-sealed twin-screw extruder with a 20 mmφ vent and heated at 260 ° C. The mixture was kneaded under the condition of staying for 10 minutes, and then pelletized.

The pellets were melted with hot xylol,
After filtering through a membrane filter (pore size 1.0 μm), methyl cellosolve was poured into this filtrate, and the deposited precipitate was separated by filtration. After thoroughly washing this with methyl cellosolve,
It was dried under reduced pressure to obtain a white solid. As a result of analyzing this solid content, it was an EP-modified polypropylene resin having a bisphenol A skeleton. The results of elemental analysis and infrared absorption spectrum analysis of this solid content are shown below.

Elemental analysis C H N measurement: 82.2% 13.0% 2.7% Infrared absorption spectrum analysis Phenyl core based absorption 1603, 1500 cm ^-1 Example 23 Preparation of EP modified EP rubber: carried out 100 parts by weight of the kneaded product of the modified EP rubber obtained by the method of Example 10 and epoxy resin Epicoat # 1004 [Yukaka Shell Epoxy Co., Ltd.]
[Production] After thoroughly mixing 10 parts by weight with a mixer, the mixture is fed to a vented kneader type extruder with a nitrogen seal,
The kneading reaction was carried out under the condition of 230 ° C. for 30 minutes, and then the kneaded product was taken out.

The kneaded product was dissolved with hot xylol, filtered through a membrane filter (pore size 1.0 μm), and then methylcellosolve was poured into the filtrate to separate a resinous product. After repeating this treatment twice, the resinous material was dried under reduced pressure to obtain a white solid. As a result of analyzing this solid content, EP modified EP having a bisphenol A skeleton
It was rubber. The results of elemental analysis and infrared absorption spectrum analysis of this solid content are shown below.

Elemental analysis C H N measurement: 82.8% 13.3% 2.6% Infrared absorption spectrum analysis Phenyl core-based absorption 1603, 1501 cm ^-1 Example 24 Preparation of EP-modified PP wax: carried out 100 parts by weight of the kneaded product of the modified PP wax obtained by the method of Example 11 and 20 parts by weight of epoxy resin Epicoat # 1010 [Okaka Shell Epoxy Co., Ltd.] were thoroughly mixed with a mixer, and then a nitrogen seal was performed. The mixture was fed to the kneader type extruder with a vent, and a kneading reaction was performed under the conditions of 230 ° C. for 20 minutes, and then the kneaded product was taken out.

The kneaded product was dissolved with hot xylol, filtered through a membrane filter (pore size 1.0 μm), and methyl ethyl ketone was poured into the filtrate to separate the resinous material. After repeating this treatment twice, the resinous material was dried under reduced pressure to obtain a white solid. As a result of analyzing this solid content, EP-modified P having a bisphenol A skeleton
It was P wax. The results of elemental analysis and infrared absorption spectrum analysis of this solid content are shown below.

Elemental analysis C H N measurement: 80.7% 12.5% 5.0% Infrared absorption spectrum analysis Phenyl core based absorption 1601, 1500 cm ^-1 Example 25 Preparation of EP modified polyethylene resin: carried out 100 parts by weight of modified polyethylene resin pellets obtained by the method of Example 4 and p-benzylphenylglycidyl ether 10
After thoroughly mixing parts by weight with a mixer, the mixture was fed into a nitrogen-sealed twin-screw extruder with a 20 mmφ vent, and a kneading reaction was carried out under the condition of staying at 230 ° C. for 20 minutes, and then pelletized.

The pellets were melted with hot xylol,
After filtering through a membrane filter (pore size 1.0 μm), methyl cellosolve was poured into this filtrate, and the deposited precipitate was separated by filtration. After thoroughly washing this with methyl cellosolve,
It was dried under reduced pressure to obtain a white solid. As a result of analyzing this solid content, it was an EP-modified polyethylene resin having a phenyl skeleton. The results of elemental analysis and infrared absorption spectrum analysis of this solid content are shown below.

Elemental analysis C H N measurement: 79.8% 12.6% 6.7% Infrared absorption spectrum analysis Phenyl core-based absorption 1600, 1502 cm ^-1 Example 26 Preparation of EP-modified polypropylene resin: carried out Modified polypropylene resin pellets 10 obtained by the method of Example 1
After thoroughly mixing 0 part by weight and 20 parts by weight of the pellet of the epoxidized polyphenylene ether resin obtained by the method of Reference Example 4 with a mixer, the mixture was fed to a 20 mmφ vented twin-screw extruder equipped with a nitrogen seal, and 280 ℃
The mixture was kneaded under the condition of staying for 10 minutes, and then pelletized.

The pellets were melted with hot xylol,
After filtering with a membrane filter (pore size 1.0 μm), chloroform was poured into this filtrate, and the deposited precipitate was separated by filtration. This was thoroughly washed with chloroform and dried under reduced pressure to obtain a solid content. After remelting this solid content in hot xylol, methyl cellosolve was poured and the deposited precipitate was filtered off and treated in the same manner as above to obtain a solid content. As a result of analyzing this solid content, it was an EP-modified polypropylene resin having a polyphenylene ether resin skeleton. The results of elemental analysis of this solid content are shown below.

Elemental analysis C H N Measured value: 82.8% 13.0% 2.8% Example 27 99 parts by weight of modified polypropylene resin pellets obtained by the method of Example 2, dilaurylthio A polypropylene resin composition consisting of 0.6 parts by weight of dipropionate and 0.4 parts by weight of pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] was mixed with 210 by mixing rolls. ℃
The mixture was kneaded under the condition of -6 minutes, and then kneaded with an extruder to form pellets. This is molded with an injection molding machine and the thickness is 1/1
A 6-inch test piece for measuring flammability was prepared.

Using this test piece, Under Wr, USA
iters Laboratories Inc. Of S
As a result of performing the test based on the vertical combustion test method shown in the object 94, it is level V-1, there is no molten fallen object at the time of combustion, and the shape retention state of the combustion object is good, and the above polypropylene resin composition is It had excellent flame retardancy. Example 28 80 parts by weight of pellets of the modified polypropylene resin obtained by the method of Example 1, 19 parts by weight of ammonium polyphosphate "Exorit 422" (manufactured by Hoechst), 0.6 part by weight of dilauryl thiodipropionate Parts and pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.4
A polypropylene resin composition consisting of parts by weight was used in Example 2
A test piece was prepared in the same manner as in 7.

Using this test piece, a flammability test was conducted in the same manner as in Example 27. As a result, the level was V-0 and the shape retention state of the burned material was good. Furthermore, it has been found that when the modified polypropylene resin according to the present invention and phosphorus are used in combination, the flame retardancy is further improved by the synergistic effect, and the polypropylene resin composition described above has excellent flame retardancy. Met. Examples 29 to 32 A polyethylene resin composition comprising 85 parts by weight of modified polyethylene resin pellets obtained by the method of Example 4 and 15 parts by weight of phosphorus shown in Table 2 was heated at 180 ° C. with a mixing roll. The mixture was kneaded under the condition of 6 minutes and then kneaded with an extruder to form pellets. A test piece for combustion measurement was prepared and tested in the same manner as in Example 27. The results are shown in Table-2.

As shown in Table 2, it was found that when the modified polyethylene resin according to the present invention and phosphorus were used in combination, the flame retardancy was further improved and the flame retardancy was excellent.

[0201]

[Table 2] Example 33 Using the modified polyamide resin pellets obtained by the method of Example 8, the pellets were molded with an injection molding machine to prepare flammability measuring test pieces having a thickness of 1/16 inch.

Using this test piece, a test was conducted in the same manner as in Example 27. As a result, the combustion product, which had a level of V-1 and was excellent in char-forming property, had a good shape-retaining state and was modified as described above. The polyamide resin had excellent flame retardancy. Example 34 A polyamide resin composition consisting of 96 parts by weight of modified polyamide resin pellets obtained by the method of Example 8 and 4 parts by weight of isocyanuric acid was mixed thoroughly in a mixer, then the cylinder temperature was set to 260 ° C. Kneaded in an extruder and pelletized. This is molded with an injection molding machine,
A test piece for measuring flammability having a thickness of 1/16 inch was prepared.

Using this test piece, a test was conducted in the same manner as in Example 27. As a result, the level was V-0, and the shape retention state of the combustion product was good. Furthermore, it was found that the combined use of the modified polyamide resin according to the present invention and isocyanuric acids further improves the flame retardancy improvement due to the synergistic effect, and the above polyamide resin composition has excellent flame retardancy. there were. Example 35 A polyester resin composition comprising 93 parts by weight of pellets of the modified polyester resin obtained by the method of Example 7 and 7 parts by weight of tris (2-hydroxyethyl) isocyanurate was thoroughly mixed in a mixer, and then mixed. The mixture was kneaded and pelletized with an extruder set to a cylinder temperature of 280 ° C. This was molded by an injection molding machine to prepare a test piece for measuring flammability having a thickness of 1/16 inch.

Using this test piece, a test was conducted in the same manner as in Example 27. As a result, the level was V-0, and the shape-retaining state of the combustion product was good. Furthermore, it was found that the combined use of the modified polyester resin according to the present invention and isocyanuric acids further improves the flame retardancy improvement due to a synergistic effect, and the polyester resin composition described above has excellent flame retardancy. there were. Example 36 EP-modified PP wax 30 obtained by the method of Example 24
Part by weight and 5 parts by weight of cyanuric acid were premixed with a hot roll. This is then followed by Epoxy Resin Epicoat # 828
[Oilized Shell Epoxy Co., Ltd.] 40 parts by weight and methylhexahydrophthalic anhydride 25 parts by weight were added and mixed with a hot roll to obtain an epoxy resin composition. This was poured into a casting plate and cured to prepare a flammability measuring test piece having a thickness of 1/16 inch.

Using this test piece, a test was conducted in the same manner as in Example 27. As a result, the level was V-0, and the shape-retaining state of the combustion product was good.

As shown in Examples 34 to 36, the method of flame retarding resins according to the present invention shows excellent flame retardancy in a wide range of resins such as thermoplastic resins and thermosetting resins. It has been found that the combined use of the modified resins and / or EP-modified resins according to the invention with isocyanuric acids and cyanuric acids further improves the flame retardancy by a synergistic effect. Example 37 45 parts by weight of modified polyphenylene ether resin obtained by the method of Example 5, 30 parts by weight of modified polystyrene resin obtained by the method of Example 6, 1 part of isocyanuric acid
A polyphenylene ether resin composition consisting of 0 parts by weight and 15 parts by weight of ammonium polyphosphate "Exorit 422" (manufactured by Hoechst) was mixed with a Henschel mixer, and then kneaded into pellets with an extruder. This was molded by an injection molding machine to prepare a test piece for measuring flammability having a thickness of 1/16 inch.

Using this test piece, a test was carried out in the same manner as in Example 27. As a result, it was level V-0, and the shape retention of the combusted material was good, and the above-mentioned polyphenylene ether resin composition was excellent and difficult. It was flammable. Example 38 A kneading reaction was performed in the same manner as in Example 5 except that 20 parts by weight of norbornenecarboguanamine was used in place of 10 parts by weight in Example 5. Then, pelletized to obtain a modified polyphenylene ether resin.
Also, norbornene carboguanamine 5 in Example 6
A kneading reaction was carried out in the same manner as in Example 6 except that the same 15 parts by weight was used instead of the parts by weight. Then, pelletized to obtain a modified polystyrene resin.

A polystyrene resin composition consisting of 20 parts by weight of the modified polyphenylene ether resin, 67 parts by weight of the modified polystyrene resin, 9 parts by weight of triphenyl phosphate and 4 parts by weight of ammonium sulfate was thoroughly mixed with a mixer. Then cylinder temperature 250 ℃
It was kneaded and pelletized by the extruder set to. This was molded by an injection molding machine to prepare a test piece for measuring flammability having a thickness of 1/16 inch.

Using this test piece, a test was conducted in the same manner as in Example 27. As a result, the level was V-0, and the shape retention of the combustion product was good, and the polystyrene resin composition described above was excellent in flame retardancy. It had a nature. Examples 39 to 47 78 parts by weight of pellets of the modified polypropylene resin obtained by the method of Example 1, 18 parts by weight of ammonium polyphosphate "Exolit 422" (manufactured by Hoechst), Table-
3% by weight of the amino group-containing compound shown in 3 above, 0.6 part by weight of dilaurylthiopropionate, and pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.4 A polypropylene resin composition consisting of parts by weight was treated and tested in the same procedure as in Example 27. The results are shown in Table-3.

As shown in Table 3, in the flame retarding method for resins according to the present invention, the composition comprising the modified resins according to the present invention is extremely excellent in self-extinguishing property and combustible substances. It was found that when the shape-retaining state is good and the phosphorus-containing compound and the amino group-containing compound are used in combination, the flame retardancy is further improved by the synergistic effect.

[0211]

[Table 3] Example 48 Thermal stability test of modified polyphenylene ether resin: Using the modified polyphenylene ether resin obtained by the method of Example 5, thermogravimetric measurement (TG) was performed in an air atmosphere at a heating rate of 10 ° C. As a result of carrying out under the condition of / min, the temperature was 434 ° C when the mass reduction rate was 5% by weight.

On the other hand, as a result of thermogravimetric measurement using the raw material polyphenylene ether resin used in Example 5 under the same conditions as above, the temperature at a mass reduction rate of 5% by weight was 40.
It was 1 ° C. Example 49 Thermal Stability Test of Modified Polystyrene Resin: Example 6
Using the modified polystyrene resin obtained by the method of
As a result of thermogravimetric measurement under the same conditions as in Example 48, the temperature was 334 ° C. when the mass reduction rate was 5% by weight.

On the other hand, as a result of thermogravimetric measurement using the raw material polystyrene resin used in Example 6 under the same conditions as above, the temperature was 299 ° C. when the mass reduction rate was 5% by weight. Example 50 Thermal stability test of modified polymethacrylic resin: Using the modified polymethacrylic resin obtained by the method of Example 9, thermogravimetric measurement was performed under the same conditions as in Example 48. As a result, the temperature when the mass reduction rate was 5% by weight was 303 ° C.

On the other hand, as a result of thermogravimetric measurement using the raw material polymethacryl resin used in Example 9 under the same conditions as above, the temperature was 285 ° C. when the mass reduction rate was 5% by weight. Example 51 Thermal stability test of modified polypropylene resin: Results of thermogravimetric measurement under the same conditions as in Example 48 using the modified polypropylene resin obtained by the method of Example 1. The temperature at a mass reduction rate of 5% by weight was 283 ° C.

On the other hand, the raw material polypropylene resin used in Example 1 was subjected to thermogravimetric measurement under the same conditions as above. As a result, the temperature was 267 ° C. when the mass reduction rate was 5% by weight. Example 52 Thermal stability test of modified polyethylene resin: Example 1
The modified polyethylene resin obtained by the method of Example 7 was subjected to thermogravimetric measurement under the same conditions as in Example 48. As a result, the temperature at a mass reduction rate of 5% by weight was 385 ° C.

On the other hand, as a result of thermogravimetric measurement using the raw material polyethylene resin used in Example 17 under the same conditions as above, the temperature was 297 ° C. when the mass reduction rate was 5% by weight. As shown in Examples 48 to 52, the modified resins according to the present invention have a significantly improved temperature of 5% by weight in terms of thermal mass reduction rate as compared with unmodified resins, and have a thermal stability. It was a significant improvement. Example 53 Thermal stability test of modified polyphenylene ether resin: Using the modified polyphenylene ether resin obtained by the method of Example 5, this pellet was dissolved in chloroform and a membrane filter (pore size 1.0 μm) was used. ), And chloroform insoluble matter was obtained. Next, this chloroform-insoluble matter was poured into hot methyl cellosolve and filtered in the same manner as above to obtain an insoluble solid matter. The insoluble solid content was dried under reduced pressure, and the weight was measured. As a result, the insoluble solid content was 0.05% by weight based on the modified polyphenylene ether resin.
Met.

The raw polyphenylene ether resin before kneading used in Example 5 was treated in the same manner as above, and as a result, the insoluble solid content was 0.03% by weight based on the resin.

As described above, the modified polyphenylene ether resin according to the present invention is kneaded under high temperature heating,
Even after the molding process, the insoluble solid content was remarkably small and was almost the same as the raw material resin before the kneading, and the thermal stability during the kneading and the molding process was remarkably excellent. Comparative Example 4 Polyphenylene ether resin thermal stability test: Example 5
Kneading was performed in the same manner as in Example 5 except that 10 parts by weight of norbornene carboguanamine in Example 2 was removed.
It was then pelletized.

This pellet was treated in the same manner as in Example 53, and the weight of the insoluble solid content was measured. As a result, the insoluble solid content was 4.61% by weight based on the kneaded resin.

As described above, the unmodified polyphenylene ether resin has an insoluble solid content remarkably increased due to the kneading under high temperature heating and the molding process, and the thermal stability is poor. I had one. Example 54 Thermal stability test of polyphenylene ether resin: Poly2,6-dimethyl-1,4 having an intrinsic viscosity [η] of 0.58
A polyphenylene ether resin composition comprising a polyphenylene ether resin comprising 42 parts by weight of the phenylene ether component, 52 parts by weight of the modified polystyrene resin obtained by the method of Example 6 and 6 parts by weight of the hydrogenated SBS rubber component in a mixer. After mixing, they were melt-kneaded and pelletized by a twin-screw extruder set to a cylinder temperature of 280 ° C.
Using this, an injection molding machine in which the cylinder temperature was set to 280 ° C. was used to prepare a test piece for measuring Izod impact strength having a thickness of 1/8 inch. This test piece was left for 200 hours in a hot air circulating constant temperature bath set at 130 ° C. to perform an aging test.
ASTM Izod impact strength before and after the aging test
It measured based on D256, and the result is shown in Table-4. Comparative Example 5 The same procedure as in Example 54 was carried out except that the modified polystyrene resin obtained in the method of Example 6 in Example 54 was replaced by the unmodified polystyrene resin. I went. The results are shown in Table-4.

[0221]

[Table 4] (Note 1) The figures in parentheses indicate the retention rate of Izod impact strength before and after aging in%. Examples 55-56 Polyphenylene ether resin thermal stability test: Example 5
The polyphenylene ether resin composition in 4 was treated and tested in the same procedure as in Example 54 except that the following additives were added. The results are shown in Table-5.

[0222]

[Table 5] (Note 1) Indicates the weight% based on the polyphenylene ether resin. Example 57 Polyethylene resin thermal stability test: Polyethylene resin HiZex 6200BP [Mitsui Petrochemical Co., Ltd.] 94
A polyethylene resin composition consisting of 1 part by weight, 1 part by weight of fine copper powder and 5 parts by weight of the modified polyethylene resin obtained by the method of Example 4 was mixed at 160 ° C. with a mixing roll.
Kneading under the condition of -6 minutes, then 150 ° C, 200 kg /
A sheet film was obtained by compression molding for 5 minutes under the condition of cm ² .

[0223] Using this sheet film, the temperature is 150 ° C.
The accelerated heating deterioration test was performed in an air atmosphere in the hot pack oven set to. The time when the color of this test piece changed was regarded as the start of deterioration, and the thermal stability of the resin composition was judged by the time until this time. The results are shown in Table-6.

The above polyethylene resin composition was treated and tested in the same procedure as above except that 5 parts by weight of the modified polyethylene obtained by the method of Example 4 was not added. Is shown as "Comparative Example-6".
6 is shown.

[0225]

[Table 6] Example 58 Polypropylene resin thermal stability test: Polypropylene resin Mitsui Noblen JS-G [manufactured by Mitsui Toatsu Chemicals, Inc.] 9
A polypropylene resin composition consisting of 4 parts by weight, 1 part by weight of copper fine powder and 5 parts by weight of the modified polypropylene resin obtained by the method of Example 1 was mixed with a mixing roll to form 2 parts.
Knead at 10 ° C for 6 minutes, then 190 ° C, 200
A sheet film was obtained by compression molding for 5 minutes under the condition of kg / cm ² .

Using this sheet film, treatment and testing were carried out in the same procedure as in Example 57, and the results are shown in Table-7.

The polypropylene resin composition was treated and tested in the same procedure as above except that 5 parts by weight of the modified polypropylene resin obtained by the method of Example 1 was not added. The results are shown in Table 7 as "Comparative Example-7".

[0228]

[Table 7] Example 59 Polyphenylene ether resin-polyamideimide resin binary system compatibilization test: 80 parts by weight of the modified polyphenylene ether resin pellets obtained by the method of Example 5, polyamideimide resin Torlon 4203T [manufactured by Amoco]
20 parts by weight were mixed by a Henschel mixer, and then melt-kneaded and pelletized by a twin-screw type extruder set at a cylinder temperature of 330 ° C.

As a result of observing this binary resin composition with an electron microscope, it was found that the resin-melted structure had a sea-island structure and the spherical particles controlled to have a diameter of about 2.7 μm were uniformly dispersed. Was excellent. Example 60 Polyphenylene ether resin-EP rubber binary compatibilization test: 70 parts by weight of modified polyphenylene ether resin pellets obtained by the method of Example 5 and modified by the method of Example 10. 30 parts by weight of EP rubber was mixed with a Henschel mixer, and then the cylinder temperature was 330 ° C.
Was melt-kneaded and pelletized by the twin-screw type extruder set to.

As a result of observing this binary resin composition with an electron microscope, it was found that the resin-melted structure had a sea-island structure and the spherical particles controlled to have a diameter of 1.6 μm were uniformly dispersed. Was excellent. Example 61 Polyamide resin-polyphenylene ether resin-polystyrene resin Compatibilization test of ternary system: Modified polyphenylene ether resin pellet 4 obtained by the method of Example 5
A resin composition consisting of 5 parts by weight, polystyrene resin 50 parts by weight, and hydrogenated SBS rubber 5 parts by weight was mixed by a Henschel mixer, and then melt-kneaded and pelletized by a twin-screw extruder set at a cylinder temperature of 300 ° C. . After 50 parts by weight of the pellets were finely pulverized, 50 parts by weight of the modified polyamide resin obtained by the method of Example 8 was added thereto, the resin composition was mixed with a Henschel mixer, and then the cylinder temperature was adjusted to 280 ° C. It was melt-kneaded and pelletized by the set twin screw type extruder.

As a result of observing this ternary resin composition with an electron microscope, it was found that the resin-melted structure had a sea-island structure and the spherical particles controlled to have a diameter of 1.6 μm were uniformly dispersed. It was excellent. Example 62 Compatibilization test of polyphenylene ether resin-polypropylene resin binary system: 80 parts by weight of poly 2,6-dimethyl-1,4-phenylene ether having an intrinsic viscosity [η] of 0.42 and Example 26 20 parts by weight of the EP-modified polypropylene resin obtained by the method was mixed by a mixer, and then melt-kneaded and pelletized by a twin-screw extruder set to a cylinder temperature of 330 ° C.

As a result of observing this binary resin composition with an electron microscope, it was found that the resin-melted structure had a sea-island structure and the spherical particles controlled to have a diameter of about 1.1 μm were uniformly dispersed. Was excellent. Example 63 Compatibilization test of saturated polyester resin-polypropylene resin binary system: saturated polyester resin Teijin PBT resin T
80 parts by weight of RB-H [manufactured by Teijin Ltd.] and 20 parts by weight of the modified polypropylene resin obtained by the method of Example 2 were mixed in a Henschel mixer, and then twin-screw set to a cylinder temperature of 260 ° C. It was melt-kneaded and pelletized by a screw type extruder.

As a result of observing this binary resin composition with an electron microscope, it was found that the resin-melted structure had a sea-island structure and the spherical particles controlled to have a diameter of approximately 2.3 μm were uniformly dispersed. It was excellent. Example 64 Compatibilization test of a polyamide resin-polypropylene resin binary system: Polyamide resin Toyobo Nylon T-802 [manufactured by Toyobo Co., Ltd.] 70 parts by weight, polypropylene resin Mitsui Noblen JS-G [Mitsui Toatsu Chemicals, Inc.] Made] 30 parts by weight,
After thoroughly mixing 3 parts by weight of a reaction product of 5-norbornene-2-carbonyl chloride and hexamethylenediamine (2/1 molar ratio) and 0.1 part by weight of dilaurylthiopropionate with a Henschel mixer, a nitrogen seal was applied. The mixture was fed to the twin-screw extruder equipped with a 20 mmφ vent, and a kneading reaction was performed under the condition of staying at 250 ° C. for 20 minutes, and then pelletized.

As a result of observing this binary resin composition with an electron microscope, it was found that the resin-melted structure had a sea-island structure and the spherical particles controlled to have a diameter of about 0.6 μm were uniformly dispersed. Was excellent. Example 65 Polyphenylene ether resin-polyamide resin binary system compatibilization test: poly-2 having an intrinsic viscosity [η] of 0.42
80 parts by weight of 6-dimethyl-1,4-phenylene ether, 20 parts by weight of polyamide resin Toyobo Nylon T-802 [manufactured by Toyobo Co., Ltd.] and norbornene carboguanamine-formaldehyde condensate 3 obtained by the method of Reference Example 2 After sufficiently mixing parts by weight with a Henschel mixer, the mixture was fed to a nitrogen-sealed twin-screw extruder with a 20 mmφ vent, and a kneading reaction was performed under the condition of staying at 280 ° C. for 20 minutes, and then pelletized.

As a result of observing this binary resin composition with an electron microscope, it was found that the resin-melted structure had a sea-island structure and the spherical particles controlled to have a diameter of about 0.5 μm were uniformly dispersed. Was excellent.

As shown in Examples 59 to 65, in the compatibilizing method of resins according to the present invention, the use of the modified resins of the present invention significantly improves the compatibilization of different resins. I understood. Example 66 Compatibilization test of polyamide resin-polypropylene resin binary system: Polyamide resin Toyobo Nylon T-802 [manufactured by Toyobo Co., Ltd.] 70 parts by weight and EP-modified polypropylene resin pellets 30 obtained by the method of Example 22 Parts by weight are mixed in a Henschel mixer, then cylinder temperature 22
It was melt-kneaded and pelletized by a twin-screw extruder set at 0 ° C.

As a result of observing the binary resin composition with an electron microscope, it was found that the resin-melted structure had a sea-island structure and the spherical particles controlled to have a diameter of 1.1 μm were uniformly dispersed, and the compatibility was high. It was excellent. Example 67 Polystyrene resin-polyethylene resin binary system compatibilization test: polystyrene resin Topolex 570-02 [manufactured by Mitsui Toatsu Chemicals, Inc.] 80 parts by weight and the EP-modified polyethylene resin obtained by the method of Example 25 20 parts by weight of the pellets were mixed by a Henschel mixer, and then melt-kneaded and pelletized by a twin-screw type extruder set at a cylinder temperature of 230 ° C.

As a result of observing this binary resin composition with an electron microscope, it was found that the resin-melted structure had a sea-island structure and the spherical particles controlled to have a diameter of about 2.7 μm were uniformly dispersed. It was excellent.

As shown in Examples 66 and 67, in the compatibilizing method of resins according to the present invention, it was found that the use of the EP-modified resins of the present invention significantly improves the compatibilization of different resins. It was Comparative Example 8 Instead of the EP-modified polypropylene resin pellet obtained by the method of Example 22 in Example 66, polypropylene resin Mitsui Noblen JS-G [Mitsui Toatsu Chemicals, Inc.]
[Production] was used and treated in the same manner as in Example 66 to obtain a pelletized resin composition.

As a result of observing this resin composition with an electron microscope, the resin-melted structure has a sea-island structure, but a spherical object having a wide range of 5-100 μm in diameter which is not controlled at all,
The ellipsoid was dispersed, and the compatibilization was extremely poor. Example 68 Surface wettability test of modified polypropylene resin: The polypropylene resin pellet obtained by the method of Example 1 was dissolved in hot xylol, filtered through a membrane filter (pore size 1.0 μm), and the filtrate was obtained. Methyl cellosolve was poured into and the deposited precipitate was filtered off. This was washed with methyl cellosolve (10 parts) and dried under reduced pressure to give a white solid. Next, this solid content is heated at a temperature of 220 ° C. and a pressing pressure of 50.
Press molding was carried out under the condition of kg / cm ² -5 minutes to obtain a molded plate having a thickness of 1 mm.

Using this molded plate, "wetting index standard solution" for wettability test [manufactured by Wako Pure Chemical Industries, Ltd.] was applied in a strip shape with a cotton swab, and the surface wettability test was carried out. As a result, 36 dyne / cm ( 23
Even when the standard solution (± 2 ° C.) was applied, it remained in the initially applied band shape even after aging, and the surface remained wet.

On the other hand, using the raw material polypropylene resin pellets used in Example 1, a molded plate was prepared under the same conditions as above. A surface wettability test was conducted in the same manner as above using this molded plate. As a result, 32 dyne / cm (23 ± 2
Even when the standard solution of (° C.) was applied, it immediately became a bead and was not wet at all.

As described above, the modified polypropylene resin of the present invention had remarkably good surface wettability as compared with the unmodified polypropylene resin. Comparative Example 9 Surface wettability test of polypropylene resin composition: polypropylene resin Mitsui Noblene JS-G [manufactured by Mitsui Toatsu Chemicals, Inc.] 100 parts by weight, adipoguanamine 10 parts by weight and dilauryl thiodipropionate 0.1. After thoroughly mixing 1 part by weight with a Henschel mixer, the mixture is fed to a nitrogen-sealed twin-screw extruder with a 20 mmφ vent, kneaded at 230 ° C. for 10 minutes, and then pelletized to form a polypropylene resin composition. Got

Then, using these pellets, a molded plate was prepared in the same manner as in Example 68, and a surface wettability test was conducted. As a result, the molded plate was 32 dyne / cm (23 ± 2
The surface did not get wet even when the standard solution (° C.) Was applied, and it was about the same as the unmodified polypropylene resin, and the surface wettability was not excellent. Example 69 Coverability test of modified polypropylene resin composition: polypropylene resin Mitsui Noblene BJ5H [manufactured by Mitsui Toatsu Chemicals, Inc.] 48 parts by weight, modified polypropylene resin obtained by the method of Example 1 22 parts by weight, EP rubber JS
22 parts by weight of REP01P [manufactured by Japan Synthetic Rubber Co., Ltd.],
8 parts by weight of crushed EPDM rubber JSR EP33 [manufactured by Japan Synthetic Rubber Co., Ltd.] and Irganox 1010
[Ciba Geigy Co., Ltd.] 0.05 part by weight was thoroughly mixed with a Henschel mixer, and then the cylinder temperature was 210 ° C.
The mixture was kneaded into pellets with a twin-screw extruder set to. This was molded by an injection molding machine to prepare a test plate for coating having a thickness of 1/8 inch. Using this test plate,
The surface was washed and dried, and 100 parts by weight of Orestar Q186 [Mitsui Toatsu Chemicals, Inc., nonvolatile content 50%], Orestar NP2000 [Mitsui Toatsu Chemicals, Inc., nonvolatile content 75]
%] 18 parts by weight of a two-component curing type polyurethane resin was applied to a film thickness of 15 μm and then cured at 80 ° C. for 50 minutes.

The coating film of the coating test plate was very good, with no cissing or blistering observed, and no peeling was observed in the adhesion test (tape peeling test of burdock eyes). Example 70 Coverability test of modified polypropylene resin composition: Polypropylene resin Mitsui Noblene BJ5H [manufactured by Mitsui Toatsu Chemicals, Inc.] 48 parts by weight, JS-G [manufactured by Mitsui Toatsu Chemicals, Inc.] 22 Parts by weight, 22 parts by weight of the modified EP rubber obtained by the method of Example 10, 8 parts by weight of crushed EPDM rubber JSR EP33 [manufactured by Nippon Synthetic Rubber Co., Ltd.] and Irganox 1010 [Ciba Geigy Co., Ltd.] Made]
A test plate was prepared in the same manner as in Example 69 using 0.05 part by weight, and the test plate was coated.

The coating film of the coating test plate was very good, with no cissing or blistering observed, and no peeling was observed in the adhesion test (tape peeling test of burlap).

Comparative Example 10 Polypropylene Resin Composition Coverability Test: Instead of 20 parts by weight of the modified polypropylene resin obtained by the method of Example 1 in Example 69, polypropylene resin Mitsui Noblene JS-G [Mitsui Toatsu Chemical Co., Ltd.] was used to prepare a test plate in the same manner as in Example 69, and the test plate was coated.

The coating film of the coating test plate was completely peeled off in the adhesion test (goggles peeling test), and the covering property was extremely poor.

As shown in Examples 69 and 70, when the modified resins according to the present invention are used, the polypropylene resin composition has an excellent coating property as compared with the unmodified composition. It was. Example 71 80 parts by weight of EP-modified polypropylene resin pellets obtained by the method of Example 22 and 20 parts by weight of EP-modified EP rubber obtained by the method of Example 23 were thoroughly mixed with a mixer,
Then, the mixture was kneaded into pellets by a twin-screw extruder set to a cylinder temperature of 240 ° C. This was molded by an injection molding machine to prepare a test plate for coating having a thickness of 1/8 inch.

Using this test plate, a urethane paint Orestar M83-42CX [manufactured by Mitsui Toatsu Chemicals, Inc.] having a film thickness of 2 was used.
After being applied to a thickness of 4 μm, it was cured at 80 ° C. for 5 hours.

The coating film of the test plate did not show cissing or blistering, and had an adhesion test (tape peeling test of scoring).
However, no peeling was observed and it was extremely good. Example 72 80 parts by weight of the modified polyethylene resin pellet obtained by the method of Example 4 and 20 parts by weight of the modified EP rubber obtained by the method of Example 10 were thoroughly mixed with a mixer.
Then, the mixture was kneaded and pelletized by a twin-screw type extruder set to a cylinder temperature of 250 ° C. This was molded by an injection molding machine to prepare a test piece for measuring tensile shear strength having a thickness of 1/8 inch.

Then, using the adhesive composition obtained by mixing 50 parts by weight of the epoxy resin Konishi bond "QUICK MENDER" [manufactured by Konishi Co., Ltd.] main component and 50 parts by weight of the curing agent, the above test piece and the iron metal test were conducted. The piece was adhered under the condition of 100 ° C. for 24 hours to prepare a test body conforming to JIS K 6850.

Using this test piece, the tensile shear strength was set to J
As a result of measurement according to IS K 6850, 41 Kgf /
The adhesive strength was cm ² , and good adhesion was exhibited. Example 73 EP modified polypropylene resin pellets obtained by the method of Example 22 were molded by an injection molding machine set at a cylinder temperature of 240 ° C. to obtain a test piece for measuring tensile shear strength having a thickness of 1/8 inch. Created.

Then, using this test piece, a test body was prepared in the same procedure as in Example 72, and the tensile shear strength was measured. As a result, an adhesive strength of 87 Kgf / cm ² was obtained.
It showed very good adhesion.

A test piece was prepared in the same procedure as above except that the original polypropylene resin not modified / EP modified was used in place of the EP modified polypropylene resin described above, and the tensile shear strength was changed. It was measured. as a result,
The adhesive strength was 8 Kgf / cm ² , and the adhesiveness of such a material was extremely poor.

As shown in Examples 69 to 73, in the surface modification method of resins according to the present invention, by using the modified / EP modified resins of the present invention, coating property, adhesive property and the like can be improved. It has been found that the surface properties are significantly improved. Example 74 Surface modification test of polypropylene resin: Using the modified polypropylene resin molded plate obtained by the method of Example 68, a silane cuffing agent phenyltrichlorosilane was applied to the surface thereof under a nitrogen atmosphere at room temperature-1. The reaction was carried out by applying under the conditions of time. Next, the surface of this coated molded plate was washed with toluene and then dried with hot air.

As a result of X-ray photoelectron spectroscopy (ESCA) using this coated molded plate, the Si _{2 P} / C _1S spectrum of the surface was remarkably large and the surface was modified. Example 75 Dyeability test of modified polypropylene resin: Example 1
The modified polypropylene resin pellets obtained by the method of 1. were dissolved with hot xylol, filtered through a membrane filter (pore size 1.0 μm), methylcellosolve was poured into this filtrate, and the deposited precipitate was separated by filtration. . This was washed with methyl cellosolve (10 parts) and dried under reduced pressure to give a white solid. Further, using this solid content, a resin temperature of 250
The resin was obtained by spinning at a temperature of 10 minutes for a residence time of 10 minutes and a winding speed of 500 m / min.

Next, this fiber was adjusted to pH 5 with 30% acetic acid.
Acid dye Amiryl Blue E-PR adjusted to
L [Sumitomo Chemical Co., Ltd.] 5% solution, bath ratio 1:40,
Immersion dyeing was performed under the conditions of 90 ° C. and 60 minutes. Furthermore,
2g / of this powder of Emar 40 powder [manufactured by Kao Corporation]
A dyeing test was carried out by soaping with a liter solution at a bath ratio of 1:30 and 60 ° C. for 5 minutes.

The dyeability of the fiber obtained from this modified polypropylene resin was visually judged, and the result was good and the dyeability was remarkably modified. Comparative Example 11 Polypropylene resin dyeability test: Raw material polypropylene resin used in Example 1 instead of the modified polypropylene resin obtained by the method of Example 1 in Example 75 Mitsui Noblen JS-G [Mitsui A fiber of the resin was obtained in the same manner as in Example 75 except that Toatsu Chemical Co., Ltd.] was used, and a dyeing test was performed on the fiber.

The dyeability of the fiber obtained from this polypropylene resin was visually judged to be extremely poor. Example 76 Epoxy group-containing resin Almatex # 7610 [manufactured by Mitsui Toatsu Chemicals, Inc.] 80 parts by weight, 12 parts by weight of the modified PP wax obtained by the method of Example 11 and 1,4-bis ( 8 parts by weight of 4,6-diamino-s-triazin-2-yl) -cyclohexane was fed to a kneader-type kneader set at a cylinder temperature of 110 ° C. and kneaded to obtain a solid resin. This solid resin is roughly crushed by a coarse crusher,
Then, it was pulverized with an atomizer. This was sieved with a 150 mesh sieve, and the pass product was used as a resin composition for powder coating in the test. Using this composition, a zinc phosphate chemical conversion treated dull steel sheet was electrostatically coated so as to have a film thickness of about 50 μm, and heat-treated at 210 ° C. for 30 minutes.

The coating film of this heat-treated coated steel sheet had good coating film smoothness (visual judgment), and the coating film was peeled off even after rubbing the coating film surface 50 times with a cloth impregnated with n-butanol. No adhesiveness was observed, and further adhesion test (tape tape peeling)
However, no peeling was observed and the coating film was good. Example 77 Epoxy resin Epokey 815 [manufactured by Mitsui Toatsu Chemicals, Inc.]
85 parts by weight and EP modified P obtained by the method of Example 22
15 parts by weight of P wax was thoroughly mixed with a mixer to prepare a coating resin composition. This composition was applied to a galvanized steel sheet and then heat-cured at 160 ° C. for 20 minutes.

The coating film of this coated steel sheet had good coating smoothness (visual judgment), and peeling of the coating film was observed even when the coating film surface was rubbed 50 times with a cloth impregnated with n-butanol. Moreover, no peeling was observed in the adhesion test (peel-eye tape peeling), and the coating film was good.

As shown in Examples 76 and 77, by using the modified / EP-modified resins of the present invention in the coating resin composition of the present invention, the coating smoothness, adhesion, etc. The coatability was extremely good. Example 78 30 parts by weight of modified polypropylene resin pellets obtained by the method of Example 3, 30 parts by weight of modified EP rubber obtained by the method of Example 10 and obtained by the method of Example 11 40 parts by weight of the modified PP wax was thoroughly mixed with a mixer, and then fed into a twin-screw type extruder set at a cylinder temperature of 200 ° C. and kneaded to prepare a resin composition for adhesives.

Using this resin composition and a hot-melt coating gun set at 180 ° C., a polypropylene resin Mitsui Noblen JS-G [manufactured by Mitsui Toatsu Chemicals, Inc.] with a thickness 1/8 inch test plate was used. A test piece conforming to JIS K 6850 was prepared by coating and adhering on an aluminum metal test plate.

Using this test piece, the tensile shear strength was set to J
As a result of measurement according to IS K 6850, 48 Kgf /
The adhesive strength was cm ² , and good adhesion was exhibited. Example 79 Epoxy resin Epicoat # 828 [produced by Yuka Shell Epoxy Co., Ltd.] 80 parts by weight and 20 parts by weight of EP-modified PP wax obtained by the method of Example 24 were thoroughly mixed with a mixer, and then 4, 4'-diaminodiphenylmethane 3
0 parts by weight were added and mixed to prepare a resin composition for adhesives.

Using this resin composition, a polypropylene resin Mitsui Noblen JS-G [manufactured by Mitsui Toatsu Chemicals, Inc.] test plate having a thickness of 1/8 inch and a metal test plate made of iron were heated to 120 ° C.
Bonding was carried out under the condition of -6 hours to prepare a test body conforming to JIS K 6850. Using this test piece, the tensile shear strength was measured according to JIS K 6850. As a result, the adhesive strength was 96 Kgf / cm ² , and the good adhesiveness was exhibited.

As shown in Examples 78 and 79, in the resin composition for adhesives according to the present invention, by using the modified / EP-modified resins of the present invention, the adhesiveness of different materials is remarkably increased. It turned out to be improved.

[0268]

INDUSTRIAL APPLICABILITY According to the production method of the present invention, it is possible to introduce and bond a functional group which is hard to cause deterioration of resins and is excellent in flame retardancy, thermal stability, compatibility and surface modification property. , By using these, flame-retardant materials with good char-forming ability, heat-stable materials with slow thermal deterioration of molded products, new materials with excellent miscibility with different resins, adhesiveness, and coatability A surface-modified material excellent in wettability and dyeability, a resin composition for coating, a resin composition for adhesives and the like can be obtained.

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[Procedure amendment]

[Submission date] August 9, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0075

[Correction method] Change

[Correction content]

The modified resins and epoxy-modified resins according to the present invention are flame retardant, thermal stable, heat resistant, impact resistant, high strength / high elasticity, resin compatibility, bending / fatigue resistance. , Wear resistance, tear resistance, dimensional stability, stress relaxation, vibration damping,
Heat and cold resistance, solvent (oil, water) resistance, adhesiveness, adhesion to reinforcing agents such as glass fiber, slipperiness, plating property, coating properties such as paint, electrical properties such as antistatic property, tracking resistance, Liquidity,
Shrinkability, hot melt strength, flow moldability, crystallinity, orientation,
Excellent in workability and other molding processability, resource saving, and economical improvement such as substitution. Construction equipment, interior products, bath,
Toilet and other housing equipment, instrument panels, pillars, meter clusters, door rims, armrests,
Defroster garnish, console box, pocket deck, bumper, side sill garnish, cowl top garnish, wheel cover, spoiler,
Headlamps, inner panels, etc. for vehicles such as automobiles, exterior and exterior materials, long and short glass fiber reinforced molding materials, resist materials, electrical insulating materials and other electrical parts, toner and other electrophotographic materials,
Textile materials, textile / paper processing materials, paints for automobiles / home appliances, antifouling, anticorrosion paints, powder paints, traffic paints, resins and dyeability of these fibers, blocking prevention, antistatic property, conductivity , Adhesiveness, adhesives for hot melt, adhesives, adhesives for structural adhesives such as industrial materials, IC sealing materials,
Rubber modifiers, optical materials, leather treatment agents, agricultural materials, pharmaceutical equipment, packaging materials, food equipment such as containers, textiles such as tents, cloth, clothing, gears, engineering equipment such as packing, piping, tanks, etc. Dirt, corrosion resistance equipment, heat resistance equipment, heat insulation, cold insulation material,
It is an excellent material that can provide materials useful in a wide range of industrial applications such as oil modifiers, flame retardants, surfactants, and corrosion / oxidation inhibitors.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0182

[Correction method] Change

[Correction content]

[0182]

[Table 1] Example 17 Production of modified polyethylene resin: polyethylene resin Lextron J79-4F25 (manufactured by Nisseki Chemical Co., Ltd.) 1
After thoroughly mixing 00 parts by weight, 20 parts by weight of norbornene carboguanamine and 0.1 parts by weight of dilauryl thiodipropionate with a Henschel mixer, the mixture was fed to a 20 mmφ vented twin-screw extruder equipped with a nitrogen seal and 280 The kneading reaction was performed under the condition of staying at 0 ° C. for 10 minutes, and then pelletized. Dissolve the pellets with hot xylol and use a membrane filter (pore size 1.0μ).
After filtering with m), methylcellosolve was poured into this filtrate, and the deposited precipitate was separated by filtration. This was thoroughly washed with methyl cellosolve and dried under reduced pressure to obtain a white solid. As a result of analyzing this solid content, (4,6-diamino-1,3,3
The results of elemental analysis of the 5-triazine) component are shown below. It was a modified polyethylene resin having 9.1% by weight of the skeleton attached. The results of elemental analysis of this solid content are shown below.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0183

[Correction method] Change

[Correction content]

Elemental analysis CHN measured value: 80.9% 13.3% 5.8% Example 18 Production of modified polyethylene resin: polyethylene resin Hi-Zex 6200BP [manufactured by Mitsui Petrochemical Co., Ltd.] 1
00 parts by weight, reaction product of 5-norbornene-2-carbonyl chloride and benzyl alcohol (1/1 molar ratio)
5 parts by weight and 0.1 part by weight of dilauryl thiodipropionate After thoroughly mixing with a Henschel mixer, the mixture was fed to a twin-screw extruder with a 20 mmφ vent equipped with a nitrogen seal and stayed at 260 ° C. for 10 minutes. A kneading reaction was carried out at, and then pelletized.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0184

[Correction method] Change

[Correction content]

The pellets were melted with hot xylol,
After filtration through a membrane filter (pore size 1.0 μm), m-cresol was poured into this filtrate, and the deposited precipitate was filtered off. This was thoroughly washed with m-cresol and then dried under reduced pressure to obtain a white solid. As a result of infrared absorption spectrum analysis of this solid content, it was a modified polyethylene resin having an ester bond and a phenyl skeleton. Example 19 Production of modified polyethylene resin: Polyethylene resin HiZex 6200BP [manufactured by Mitsui Petrochemical Co., Ltd.] 1
00 parts by weight, 5 parts by weight of a reaction product of 5-norbornene-2-carbonyl chloride and 4,4' -diaminodiphenyl ether (2/1 molar ratio) and dilaurylthiodipro
After thoroughly mixing 0.1 parts by weight of pionate with a Henschel mixer, the mixture was fed to a twin-screw extruder equipped with a nitrogen-sealed 20 mmφ vent, and a kneading reaction was performed under the condition of staying at 260 ° C. for 10 minutes, and then pellets Turned into

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0185

[Correction method] Change

[Correction content]

The pellet was melted with hot xylol,
After filtration through a membrane filter (pore size 1.0 μm), m-cresol was poured into this filtrate, and the deposited precipitate was filtered off. This was thoroughly washed with m-cresol and then dried under reduced pressure to obtain a white solid. As a result of infrared absorption spectrum analysis of this solid content, it was a modified polyethylene resin having an amide bond and a phenyl skeleton. Example 20 Preparation of modified polyethylene resin: 5-norbornene-2-carbonyl chloride in Example 19 and 4,
Reaction product with 4' -diaminodiphenyl ether (2/1
Molar ratio), except that a reaction product of 2- (bicyclo [2.2.1] hept-5-en-2-yl) -2-oxazoline and benzoic acid (1/1 molar ratio) is used. A kneading reaction was carried out in the same manner as in Example 19, and then pelletized.

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0186

[Correction method] Change

[Correction content]

Using this pellet, a solvent treatment was carried out in the same manner as in Example 19. As a result of infrared absorption spectrum analysis of the obtained solid content, it was a modified polyethylene resin having an amide bond, an ester bond and a phenyl skeleton. Example 21 Production of modified paraffin wax: Paraffin wax 155 [manufactured by Nippon Seiro Co., Ltd.] 100 parts by weight, norbornene carboguanamine 10 parts by weight and dilaurylthio.
After substituting 0.1 part by weight of dipropionate in the system with nitrogen, the reaction was carried out while stirring at an internal temperature of 250 ° C. for 30 minutes. After the reaction was completed, the reaction mixture of the resinous material was taken out. The resinous material was dissolved in hot toluene, filtered through a membrane filter (pore size 1.0 μm), and then methylcellosolve was poured into the filtrate to separate the resinous material. Obtained. As a result of analyzing this solid content, it was a modified paraffin wax to which 4.7% by weight of (4,6-diamino-1,3,5-triazine) skeleton was bonded. The results of elemental analysis of this solid content are shown below. After repeating this treatment operation twice, the resinous material was dried under reduced pressure and the white solid content was put into a 500 ml autoclave equipped with a vent, a stirrer and a cooler.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0196

[Correction method] Change

[Correction content]

The pellets were melted with hot xylol,
After filtering with a membrane filter (pore size 1.0 μm), chloroform was poured into this filtrate, and the deposited precipitate was separated by filtration. This was thoroughly washed with chloroform and dried under reduced pressure to obtain a solid content. This solid content was redissolved in hot xylol, methylcellosolve was poured, and the deposited precipitate was filtered off and treated in the same manner as above to obtain a solid content. As a result of analyzing this solid content, it was an EP-modified polypropylene resin having a polyphenylene ether resin skeleton. The results of elemental analysis of this solid content are shown below.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0209

[Correction method] Change

[Correction content]

Using this test piece, a test was conducted in the same manner as in Example 27. As a result, the level was V-0, and the shape retention of the combustion product was good, and the polystyrene resin composition described above was excellent in flame retardancy. It had a nature. Examples 39 to 47 78 parts by weight of pellets of the modified polypropylene resin obtained by the method of Example 1, 18 parts by weight of ammonium polyphosphate "Exolit 422" (manufactured by Hoechst), Table-
3 parts by weight of the amino group-containing compound shown in 3 , dilaurylthio
A polypropylene resin composition containing 0.6 parts by weight of dipropionate and 0.4 parts by weight of pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] was prepared in the same manner as in Example 27. Processed and tested according to procedure. The results are shown in Table-3.

Claims (38)

[Claims] 1. A resin and a compound of formula (1): (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ ,
R ₈ and R ₉ are species selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms and a phenyl group, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And R ₉ may be the same or different, and Y is a triazinyl group which may have a substituent, an amide group, a carboxylate group, an oxazolinyl group, an oxycarbonyl group, a urethane group, a cyanuric acid ester group, an ether group,
A carbamoyl group or a carbonyl group, which is a group selected from the group consisting of) and at least one selected from the group containing norbornenyl group-containing compounds having at least one group represented by the formula (2) at a temperature of 200 ° C to 450 ° C. A method for producing a modified resin, which comprises carrying out a reaction. 2. R in formula (1)₁, R₂, R₃, R
_Four, R_Five, R₆, R ₇, R₈ And R₉ Is a hydrogen atom
The method for producing the modified resin according to claim 1. 3. The norbornenyl group-containing compound in formula (1) has the formula (2): [In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ ,
R ₈ and R ₉ have the same meanings as in formula (1),
R _10, R _11, R ₁₂ and R ₁₃ indicates that a species selected from the group consisting of groups having one or more the number of hydrogen atoms and _{carbon, R 10, R 1 1,} R 12 and R ₁₃ are the same Or a different species] may be used. The method for producing a modified resin according to claim 1, wherein the compound is a compound represented by the formula: 4. The norbornenyl group-containing compound of formula (1) is the compound of formula (2) wherein R ₁₀ , R ₁₁ , R ₁₂ and R _{13 are used.}
A condensate having an average degree of addition condensation of more than 1 obtained by subjecting a compound in which at least one of the group consisting of 1 is a hydrogen atom, and optionally a compound capable of cocondensation, to an aldehyde. 1. The method for producing the modified resin according to 1. 5. The norbornenyl group-containing compound in formula (1) is the compound of formula (2) wherein R ₁₀ , R ₁₁ , R ₁₂ and R _{13 are used.}
At least one selected from the group consisting of alcohols having 1 to 20 carbon atoms, which is obtained by subjecting a compound in which at least one kind is a hydrogen atom and a compound capable of co-condensation to an aldehyde, The method for producing a modified resin according to claim 1, which is an etherification condensate having an average addition condensation degree of greater than 1 obtained by subjecting a seed to an etherification reaction and optionally a condensation reaction at the same time. 6. A norbornenyl group-containing compound in which Y in the formula (1) is an amide group is at least selected from the reaction products of amines having 1 or more carbon atoms and 5-norbornene-2-carbonyl halide. The method for producing a modified resin according to claim 1, which is one kind. 7. The norbornenyl group-containing compound in which Y in the formula (1) is a carboxylate group is selected from the reaction products of alcohols having 4 or more carbon atoms and 5-norbornene-2-carbonyl halide. The method for producing a modified resin according to claim 1, which is at least one kind. 8. The norbornenyl group-containing compound in which Y in the formula (1) is an oxazolinyl group is 2- (bicyclo [2.2.1] hept-5-en-2-yl) -2-oxazoline. Item 2. A method for producing a modified resin according to Item 1. 9. A norbornenyl group-containing compound in which Y in the formula (1) is an amide group is a carboxylic acid having 1 or more carbon atoms and 2- (bicyclo [2.2.1] hept-
The method for producing a modified resin according to claim 1, wherein the modified resin is at least one selected from the reaction product with 5-en-2-yl) -2-oxazoline. 10. The method for producing a modified resin according to claim 1, wherein the reaction is carried out at a temperature of 230 to 450 ° C. 11. The method for producing a modified resin according to claim 1, wherein the reaction is carried out by reactive processing. 12. The method for producing a modified resin according to claim 1, wherein the resin is at least one selected from the group consisting of resins, rubbers, waxes and oils. 13. The resin is a thermoplastic resin.
2. The method for producing the modified resin according to 2. 14. The modified resin according to claim 13, wherein the thermoplastic resin is at least one selected from the group consisting of polyolefin resin, polyphenylene ether resin, saturated polyester resin, polyamide resin, polyacrylic resin and polystyrene resin. Resin manufacturing method. 15. A method for producing an epoxy-modified resin, which comprises reacting the modified resin according to claim 3 with at least one selected from epoxides. . 16. The method for producing an epoxy-modified resin according to claim 15, wherein the reaction is performed at a temperature of 150 to 400 ° C. 17. The method for producing an epoxy-modified resin according to claim 15, wherein the reaction is performed by reactive processing. 18. A resin comprising at least one resin selected from the group consisting of the modified resins according to claim 3 and the epoxy modified resin according to claim 15. Flame retardant method. 19. The flame-retardant method according to claim 18, wherein at least one selected from phosphorus consisting of a simple substance of phosphorus and a compound containing a phosphorus atom is contained as a component. 20. Phosphorus is red phosphorus, phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, phosphate, polyphosphate,
The flame retardant method according to claim 19, which is a phosphite, a phosphonate, a phosphoric acid ester, a phosphorous acid ester, a phosphonic acid ester, a phosphine, or a sulfur-containing phosphorus compound. 21. The polyphosphate has the general formula (NH ₄ ) _{m + 2}
21. The flame-retardant method according to claim 20, which is ammonium polyphosphate represented by P _m O _{3m + 1} (where m represents an integer greater than 5). 22. Formula (3): (In the formula, R ₁₄ , R ₁₅ and R ₁₆ represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an oxyalkyl group having 1 to 3 carbon atoms, a phenyl group or a glycidyl group, and R ₁₄ , R ₁₅ and R ₁₆ may be the same or different, and an isocyanuric acid represented by the formula (4) 19. At least one selected from the cyanuric acids represented by the formula: wherein R ₁₄ , R ₁₅ and R ₁₆ have the same meanings as in formula (3), as a component. Flame retardant method. 23. The flame-retardant method according to claim 18, wherein an amino group-containing compound is contained as a component. 24. The amino group-containing compound is represented by: The flame retardant according to claim 23, which is at least one selected from the group consisting of a compound containing at least one selected from the group represented by: dicyandiamide, guanidine, and a reaction product of these compounds with an aldehyde. Method. 25. The flame-retardant method according to claim 18, wherein phosphorus and an amino group-containing compound are contained as components. 26. A resin comprising at least one resin selected from the group consisting of the modified resins according to claim 3 and the epoxy modified resin according to claim 15. Thermal stabilization method. 27. The heat stabilizing method according to claim 26, wherein the resin is at least one selected from the group consisting of a polyolefin resin, a polyphenylene ether resin, a polyamide resin, a polyacrylic resin, a polystyrene resin, and an olefin-based thermoplastic elastomer. . 28. At least one resin selected from the group consisting of the modified resin according to claim 1 and the epoxy-modified resin according to claim 15, and one or more different resins. A method for compatibilizing resins, which comprises solubilizing. 29. A resin characterized by compatibilizing at least two different resins selected from the group consisting of the modified resin according to claim 1 and the epoxy-modified resin according to claim 15. Compatibilization method. 30. The resin is at least one selected from the group consisting of polyolefin resin, polyphenylene ether resin, saturated polyester resin, polyamide resin, polycarbonate resin, polystyrene resin, polyether sulfone and thermoplastic elastomer.
The compatibilization method described. 31. The resin is at least one selected from the group consisting of a polyolefin resin, a polyphenylene ether resin, a saturated polyester resin, a polyamide resin, a polycarbonate resin, a polystyrene resin, a polyether sulfone, and a thermoplastic elastomer.
The compatibilization method described. 32. A resin comprising at least one resin selected from the group consisting of the modified resin according to claim 3 and the epoxy modified resin according to claim 15. Surface modification method. 33. The surface modification method according to claim 32, wherein the coating property of the resins is modified. 34. The surface modification method according to claim 32, wherein the adhesiveness of the resins is modified. 35. The surface modification method according to claim 32, wherein the dyeability of the resins is modified. 36. The surface modification method according to claim 32, wherein the resin is a polyolefin resin. 37. A coating comprising at least one resin selected from the group consisting of the modified resins according to claim 3 and the epoxy modified resin according to claim 15. Resin composition. 38. An adhesive containing at least one resin selected from the group consisting of the modified resins according to claims 3 to 5 and the epoxy-modified resin according to claim 15. Resin composition.