JPH11158386A - Resin composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a resin composition capable of suppressing the phase separation of a thermosetting resin and a thermoplastic substance and having a high impact resistance in addition to the heat resistance and mechanical strength. SOLUTION: This resin composition is composed of a thermoplastic substance having functional groups containing active hydrogen atoms (a 6-30C aliphatic hydrocarbon compound, a rubber component, a thermoplastic resin or the like having carboxyl groups or the like), a bisoxazoline compound and a thermosetting resin (an epoxy resin or the like). The amount of the bisoxazoline compound is 0.1-5 mol based on 1 mol functional groups in the thermoplastic substance and the amount of the thermoplastic substance is 1-50 pts.wt. based on 100 pts.wt. thermosetting resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition which retains heat resistance and mechanical strength, which are the characteristics of a thermosetting resin, and has high impact resistance, and a method for producing the same.

[0002]

2. Description of the Related Art Many thermosetting resins have high heat resistance and mechanical strength, but have low impact resistance and are brittle. Therefore, the thermosetting resin is modified by modifying it with a monomer having a flexible structure or by blending a soft thermoplastic substance (for example, a rubber component). However, thermosetting resins and thermoplastics are usually incompatible with each other,
Phase separation occurs. Therefore, even if the matrix is made of a thermosetting resin, heat resistance and mechanical strength are reduced, and it is difficult to effectively exhibit the properties of the thermosetting resin.

[0003] JP-A-8-302217 discloses a method for producing a polymer alloy by adding a hydrophobic compound and a bisoxazoline compound to a composition containing a plurality of mutually incompatible polymers. . This document also describes that a reaction product of a hydrophobic compound and a bisoxazoline compound is used as a compatibilizer for a polymer alloy composed of a thermoplastic resin.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition capable of effectively exhibiting the properties of a thermosetting resin even if the thermosetting resin and the thermoplastic substance are incompatible or poorly compatible with each other. An object of the present invention is to provide a product and a method of manufacturing the same. Another object of the present invention is to prevent the occurrence of phase separation even if the matrix is made of a thermosetting resin and the dispersed phase is made of a thermoplastic material, and it has high impact resistance in addition to heat resistance and mechanical strength. An object of the present invention is to provide a resin composition (such as a polymer alloy using a thermosetting resin as a matrix) and a method for producing the same.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and have found that a composition comprising a thermoplastic material such as a rubber component and a thermoplastic resin and a thermosetting resin. It has been found that when a bisoxazoline compound is present, the properties of the thermosetting resin can be effectively exhibited and the impact resistance can be greatly improved, thus completing the present invention. That is, the resin composition of the present invention includes a thermoplastic substance having a functional group containing an active hydrogen atom, a bisoxazoline compound, and a thermosetting resin. In this composition, the thermoplastic may be used as a product of treatment with the bisoxazoline compound or as a reaction product with the bisoxazoline compound. As a thermoplastic, usually,
A compound incompatible with the thermosetting resin is used. Further, the resin composition may contain a powdery or fibrous inorganic substance. The present invention also includes a method for producing a resin composition by mixing the thermoplastic substance, the bisoxazoline compound, and the thermosetting resin.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION [Thermoplastic substance] As the thermoplastic substance, a component capable of imparting properties (impact resistance, flexibility, toughness, etc.) which are not usually present in a thermosetting resin can be used, and a low molecular weight component can be used. And high molecular weight components (oligomers and polymers having a relatively small molecular weight). Thermoplastic materials usually have flexibility and toughness in many cases. In the present invention, a thermoplastic material that is incompatible with the thermosetting resin is usually used in order to develop advantageous properties by being combined with the thermosetting resin. Further, the thermoplastic substance may be a hydrophilic compound, but usually the main chain or the side chain is mainly composed of a hydrocarbon group (such as an aliphatic hydrocarbon group) or a repeating unit containing a hydrocarbon group. It is a hydrophobic compound.

In the thermoplastic substance, the functional group containing an active hydrogen atom includes, for example, a hydroxyl group which may be phenolic, a mercapto group, a carboxyl group, an acid anhydride, and an amino group. The thermoplastic substance may have the same functional group, or may have the same functional group, or may have a plurality of different functional groups. Preferred functional groups include those having a high activity toward oxazoline, such as carboxyl groups, acid anhydride groups and amino groups, especially carboxyl groups.

As the low molecular weight thermoplastic substance, a liquid or solid compound at room temperature can be used.
00 or less (preferably about 100 to 750, and more preferably about 150 to 750). Such compounds are _generally called C _6-30 (preferably C _8-26 , more preferably C _10-24 ) hydrocarbon groups (particularly aliphatic hydrocarbon groups).
Often configured with The low molecular weight thermoplastics may be used in combination of the same or different compounds.

Examples of the low molecular compound having a hydroxyl group include C _10-30 aliphatic alcohols (eg, lauryl alcohol, tetradecyl alcohol, cetyl alcohol, octadecyl alcohol, melisyl alcohol, oleyl alcohol, etc.), phenolic hydroxyl group Compounds having a group (e.g., phenol, alkylphenol (e.g., _C4-20 alkyl-phenol, preferably _C8-14 alkyl-phenol) and the like) and the like. Examples of the low-molecular compound having a mercapto group include thioalcohols corresponding to the aliphatic alcohols.

Examples of the low molecular compound having a carboxyl group include carboxylic acids having 6 or more carbon atoms, for example, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, dioxystearic acid. , Behenic acid, C _6-30 saturated fatty acids such as montanic acid, lindelic acid, palmito oleic acid, oleic acid,
Elaidic acid, linoleic acid, linolenic acid, eleostearic acid, arachidonic acid, C _10-24 unsaturated fatty acids such as erucic acid, adipic acid, pimelic acid, azelaic acid, saturated having about 6 to 40 carbon atoms, such as sebacic acid Examples include polycarboxylic acids and dimer acids. Of these carboxylic acids, carboxylic acids having 6 or more carbon atoms, particularly aliphatic monocarboxylic acids, especially higher fatty acids, are often used.
The carbon number of the higher fatty acid is, for example, preferably about 10 to 26 carbon atoms, particularly preferably about 12 to 24 carbon atoms.
The higher fatty acid may be an unsaturated higher fatty acid, but a saturated higher fatty acid is advantageously used.

As the low molecular weight compound having an amino group,
For example, primary amines such as caprylamine, laurylamine, myristylamine, palmitylamine, stearylamine, oleylamine, secondary amines such as didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine and dioctadecylamine Examples thereof include amines and diamines such as hexamethylenediamine.
Preferred amine compounds include long-chain higher amines having about 10 to 26 carbon atoms, preferably about 12 to 24 carbon atoms (for example, about 12 to 18 carbon atoms), particularly primary amines.

Further, the low molecular weight compounds include compounds having different functional groups, for example, compounds having a carboxyl group and an amino group, and compounds having a carboxyl group and a hydroxyl group. Examples of such a compound include aminocarboxylic acids having about 6 to 18 carbon atoms, such as aminocaproic acid and aminoundecanoic acid.

High molecular weight thermoplastic (thermoplastic resin)
May be linear or branched. For example, a rubber component (polybutadiene, polyisobutylene, polyisoprene, chloroprene rubber, ethylene-propylene-diene rubber, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer) , Acrylic rubber, urethane rubber, ethylene-vinyl acetate copolymer, thermoplastic elastomer, etc.), olefin-based polymers (eg, polyethylene, polypropylene, poly (4-methyl-pentene-1), ethylene-propylene copolymer, ethylene) -Vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, homo- or copolymer of _C2-10 olefin such as polybutene), vinyl acetate resin (polyvinyl acetate, vinyl acetate-vinyl chloride copolymer, etc.) ), Vinyl alcohol-based resin (for example, poly Nyl alcohol, ethylene-vinyl alcohol copolymer, etc.), polyvinyl formal (polyvinyl acetal, etc.), chlorine-containing resin (polyvinyl chloride, vinylidene chloride resin, etc.), fluororesin, styrene polymer (polystyrene, styrene-methyl methacrylate) Copolymer, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butacene-styrene block (or graft) copolymer (ABS resin)
Styrene monomers such as homo- or copolymers and hydrogenated products thereof), acrylic resins (polymethyl methacrylate, methyl methacrylate-acrylate copolymer, etc.), polyester resins (polyethylene terephthalate, Polyalkylene terephthalate such as polybutylene terephthalate, homopolyester and copolyester such as polyalkylene naphthalate such as polyethylene naphthalate, and polyamide resin (nylon 6,
Nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, etc.), thermoplastic polyurethane resin, polycarbonate resin (bisphenol A type polycarbonate, etc.), polyacetal, polyphenylene oxide, polyphenylene sulfide, polysulfone,
Polyethersulfone, polyetheretherketone,
Examples include polyoxybenzylene and polyamide imide.

The thermoplastic resin itself may have the above-mentioned functional group containing an active hydrogen atom, and the functional group is introduced into the thermoplastic resin by a conventional method such as copolymerization, grafting, and polymer reaction. You may. For example, in a vinyl polymer, a hydroxyl group-containing monomer (such as allyl alcohol, hydroxyethyl (meth) acrylate, or 2-hydroxypropyl (meth) acrylate), a mercapto group-containing monomer, a carboxyl group, or an acid anhydride Group-containing monomers (acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, 10-undecylenic acid, vinylbenzoic acid, 5-norbornene-2-carboxylic acid, maleic anhydride, etc.), amino group-containing monomer The functional group may be introduced by copolymerization, graft polymerization or polymer reaction of a monomer such as a compound (aminostyrene, vinylamine, allylamine, etc.). In the condensation polymer, a polyfunctional monomer having the above functional group can be copolymerized or a functional group can be introduced by a polymer reaction.

The polymer having the functional group introduced therein includes:
For example, modified olefin resins (polyethylene oxide, polypropylene oxide, maleic anhydride-modified polyolefin, (meth) acrylic acid-modified polyolefin, etc.), modified rubbers (carboxyl group-modified butadiene-based rubber, maleic anhydride-modified butadiene-based rubber, maleic anhydride) Modified S
BR rubber, maleic anhydride-modified ABS resin, etc.), acrylic resin (methyl methacrylate- (meth) acrylate- (meth) acrylic acid copolymer), styrene resin (styrene-maleic anhydride copolymer) Styrene- (meth) acrylic acid copolymer, maleic anhydride-modified AS resin, etc.). Although the molecular weight of the high molecular weight thermoplastic is not particularly limited, for example, a weight average molecular weight of 1,000 to 250,000, preferably 2,000 to 2,000
100,000, more preferably 5000-25000
It is about. As the thermoplastic material, a soft material, particularly a C _6-30 aliphatic hydrocarbon compound (such as a C _6-30 aliphatic carboxylic acid), a rubber component (carboxyl Group, an acid anhydride group-introduced rubber component, etc.), and a thermoplastic resin (modified polyolefin, polyester, polyamide, polysulfone, polyethersulfone, etc.) are often used.

[Bisoxazoline compound] As the bisoxazoline compound, a compound represented by the following formula (I) can be used.

[0017]

Embedded image(In the formula, D is an alkylene which may have a substituent.
Group, a cycloalkylene group which may have a substituent or
An arylene group which may have a substituent; ¹,
R^Two, R^ThreeAnd R^FourAre the same or different
A substituent, an alkyl group which may have a substituent or a substituent.
The following shows an aryl group which may be possessed. The bisoxazoline compound represented by the formula (I)
As the alkylene group for D, for example, C_1-10Archi
Len groups (eg, methylene, ethylene, trimethylene,
Propylene, tetramethylene, etc.)
The alkylene group includes, for example, C_5-10Cycloalkylene group
(For example, 1,3-cyclopentylene, 1,3-cyclo
Hexylene, 1,4-cyclohexylene group, etc.)
included. Arylene groups include C_6-12Arylene group (example
For example, 1,3-phenylene, 1,4-phenylene, 1,
5-naphthylene, 2,5-naphthylene group, etc.)
I will. The alkylene group, cycloalkylene group and ant
-Halene group is a halogen atom, C _1-6Alkyl group, C_1-6
It may have a substituent such as an alkoxy group. Preferred
Is an aryl group which may have a substituent, particularly
A phenylene group which may have a substituent (for example, 1,
3-phenylene group or 1,4-phenylene group)
included.

In the above formula (I), R ¹ , R ² , R ³
And alkyl groups represented by R ⁴ include, for example, C _1-10 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl and hexyl groups. . Preferred alkyl groups include C _1-6 alkyl groups, especially C _1-4 alkyl groups. Aryl groups include phenyl, 1-naphthyl,
And a 2-naphthyl group.

The alkyl group and the aryl group may have a substituent. Examples of the alkyl group having a substituent include dichloromethyl, trichloromethyl, trifluoromethyl, 2,2,2-trichloroethyl, 2,2,2
-Halogenated C _1-4 alkyl groups such as trifluoroethyl and pentafluoroethyl. Aryl groups having a substituent include, for example, 2-chlorophenyl, 3
Phenyl group having a halogen atom such as -chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 3,5-dichlorophenyl group, 2-methylphenyl, 3
A C _1-4 alkyl-phenyl group such as -methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 3,5-dimethylphenyl, 4-ethylphenyl group, 2-methoxyphenyl, 3-methoxyphenyl, C _1-4 such as -methoxyphenyl, 2,4-dimethoxyphenyl, 3,5-dimethoxyphenyl, 4-ethoxyphenyl, etc.
An alkoxy-phenyl group and the like.

Preferred R ¹ , R ² , R ³ and R ⁴ include a hydrogen atom or a C _1-4 alkyl group. Especially,
At least ^one of R ¹ and R ² (particularly R ² ) is a hydrogen atom,
Preferably, at least one of R ³ and R ⁴ (particularly R ⁴ ) is a hydrogen atom. More preferably, R ¹ , R ² , R
³ and R ⁴ are both hydrogen atoms.

Preferred bisoxazoline compounds include compounds represented by the following formula (Ia).

[0022]

Embedded image (In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and each represent a hydrogen atom or a C _1-4 alkyl group.) As the compound represented by the formula (Ia), R ¹ , R ² , R
Compounds in which ³ and R ⁴ are hydrogen atoms are often used.

Specific examples of preferred compounds of the formula (I) include, for example, 1,6-bis (1,3-oxazoli-2-yl) hexane, 1,8-
Bis (1,3-oxazoli-2-yl) octane, 1,
10-bis (1,3-oxazoli-2-yl) decane,
1,3-bis (1,3-oxazoli-2-yl) cyclohexane, 1,4-bis (1,3-oxazoli-2-yl) cyclohexane, 2,2 ′-(1,3-phenylene) -bis (2-oxazoline), 2,2 '-(1,4
-Phenylene) -bis (2-oxazoline), 2,2 '
-(1,2-phenylene) -bis (2-oxazoline), 2,2 '-(1,3-phenylene) -bis (4-
Methyl-2-oxazoline), 2,2 '-(1,4-phenylene) -bis (4-methyl-2-oxazoline),
2,2 '-(1,2-phenylene) -bis (5-methyl-2-oxazoline), 2,2'-(1,3-phenylene) -bis (5-methyl-2-oxazoline), 2,
2 '-(1,4-phenylene) -bis (5-methyl-2
-Oxazoline), 2,2 '-(1,3-phenylene)
-Bis (4-methylphenyl-2-oxazoline),
2,2 '-(1,4-phenylene) -bis (4-methylphenyl-2-oxazoline), 2,2'-(1,3-
Phenylene) -bis (4-chlorophenyl-2-oxazoline), 2,2 '-(1,4-phenylene) -bis (4-chlorophenyl-2-oxazoline) and the like. The bisoxazoline compound represented by the formula (I) can be used alone or in combination of two or more. The bisoxazoline compound can be produced by a conventional method, for example, by reacting a fatty acid or its methyl ester with ethanolamine in the presence of a catalyst to form a 5-membered heterocyclic compound (“Plastic Age”, p. 114, Mar. 1995), by reacting a dicarboxylic acid or a lower alkyl ester thereof corresponding to X in the above formula (I) with ethanolamine or a derivative thereof to form a 5-membered heterocyclic compound.

Further, the oxazoline compound is combined with a powdery or fibrous substance (carrier) having a reactive group (particularly, a substance (carrier) treated with an oxazoline compound and, if necessary, a surface treatment agent having a reactive group). )), And may be used as a carrier having an oxazoline group. For example, (1) a method in which a carrier (A) having a reactive group (for example, carbon black or the like) having a reactive group without being treated with a surface treating agent is reacted with a bisoxazoline compound using the reactive group, ) A method of treating an inert carrier (A) with a surface treating agent (B) for introducing a reactive group and reacting with a bisoxazoline compound using the generated reactive group; Carrier with (A)
An oxazoline group-containing carrier obtained by, for example, a method of reacting a oxazoline compound with a carrier (A) having a surface treated with a surface treating agent (B) to introduce a reactive group with an oxazoline compound can also be used.

As the carrier (A), any of organic or inorganic substances can be used as long as the properties of the thermosetting resin are not deteriorated. However, in order to improve the advantages of the thermosetting resin, usually, heat resistance, reinforcing property, etc. An inorganic substance (inorganic carrier) which is advantageous in this respect is used.

Examples of inorganic substances include carbon, silica sand, silica, silicon dioxide, glass, mica, talc, clay, diatomaceous earth, carbonates (such as calcium carbonate and magnesium carbonate), and metal sulfates (such as barium sulfate). , Metal oxides (silicon oxide, aluminum oxide (alumina),
Titanium oxide, copper oxide, silver oxide, iron oxide Fe ₂ O ₃ , Fe ₃
O ₄ , zinc oxide, zirconium oxide, magnesium oxide, etc., metal hydroxide (aluminum hydroxide, etc.), metal sulfide (cadmium sulfide, zinc sulfide, etc.), non-oxide ceramics (silicon carbide, boron carbide, etc.) Carbides, titanium nitride, boron nitride, aluminum nitride, nitrides such as silicon nitride, silicides, borides, etc.), potassium titanate, aluminum borate, molybdenum disulfide, metals (aluminum, copper, nickel, tungsten, gold, Silver, platinum, cadmium, zinc, lead, etc.).

Although the shape of the carrier (A) is not particularly limited, it is advantageous that the carrier is in the form of powder or granules or fibrous in order to impart high reinforcing properties. Specific examples of such carriers include:
Inorganic powder (silica, silica sand, silicon dioxide, calcium carbonate, titanium oxide, aluminum oxide, carbon black, etc.), inorganic fiber (glass fiber, carbon fiber, rock wool,
Silica fiber, alumina fiber, potassium titanate fiber, silicon carbide fiber, whisker, etc.). The average particle size of the powder is, for example, about 1 nm to 50 μm, preferably about 5 nm to 30 μm, and particularly about 10 nm to 20 μm. The average diameter of the fiber is, for example, 0.1 to 150 μm,
Preferably, the average fiber length is, for example, about 10 μm to 5 mm, preferably about 5 to 50 μm.
It can be selected from a range of about 0 μm to 3 mm, particularly about 100 μm to 2 mm.

As the surface treating agent (B) for introducing a reactive group by treating the carrier (A), a coupling agent can be used. Examples of the coupling agent include an organic metal compound having a hydrolyzable organic group, for example, a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent. Preferred coupling agents include organosilicon compounds such as silane coupling agents, for example, halogen atoms, hydroxyl groups, mercapto groups,
Carboxyl group, amino group, mono or di C _1-4 alkylamino group, epoxy group, isocyanate group, vinyl group,
It includes a silicon compound having at least one kind of functional group selected from (meth) acryloyl groups, a hydrolyzable group (alkoxy group) and a silyl group. The silane coupling agent may have one or more kinds of reactive groups.

The alkoxy group of the silane coupling agent includes, for example, a C _1-4 alkoxy group, especially a methoxy group or an ethoxy group. The number of the alkoxy groups in the silane coupling agent is about 1 to 3 (particularly 2 or 3). When the carrier (A) is a metal, the surface treatment agent (B)
A compound having a functional group capable of coordinating with at least a metal (coordinating compound), for example, a mercapto alcohol (such as mercaptoethanol), a sulfur- or nitrogen-containing compound (such as cysteine and histidine), and a mercapto group-containing silane cup. A ring agent (such as mercaptopropyltrimethoxysilane) can be used. For example, in the case of mercaptoethanol, since the mercapto group forms a coordination bond with the above-described metals (gold, platinum, etc.), the remaining hydroxyl groups can be used for the reaction with the oxazoline compound.

Surface treatment agent based on 100 parts by weight of carrier (A)
(B) is used in an amount of 0 to 100 parts by weight (for example, 0.1 to 100 parts by weight).
75 parts by weight), preferably from 1 to 50 parts by weight, more preferably from about 1 to 25 parts by weight.

The ratio of the thermoplastic substance to the bisoxazoline compound is, for example, 0.1 mol of the bisoxazoline compound per 1 mol of the functional group having an active hydrogen atom of the thermoplastic substance.
It can be selected from a range of about 1 to 5 mol, preferably about 0.5 to 3 mol, and more preferably about 0.7 to 2 mol. Normal,
An amount in which the oxazoline group is excessive relative to the functional group having an active hydrogen atom, for example, 0.7 to 1.5 moles of a bisoxazoline compound, preferably 1 mole of the functional group having an active hydrogen atom of the thermoplastic substance. Is often about 0.8 to 1.3 mol (e.g., 0.9 to 1.2 mol).

The ratio of the thermoplastic substance to the oxazoline group-containing carrier is, for example, 0.05 to 2.5 mol of bisoxazoline group of the carrier per mol of the functional group having an active hydrogen atom of the thermoplastic substance. Can be selected from the range of about 0.25 to 1.5 mol, more preferably about 0.3 to 1 mol.

The thermoplastic substance and the oxazoline compound may be used alone or may be used as a treated product obtained by treating a thermoplastic substance with an oxazoline compound or as a reaction product of a thermoplastic substance and an oxazoline compound. Good. The processed product and the reaction product also have a high function as a compatibilizer. Further, the thermoplastic substance, the oxazoline compound and the carrier may be used alone, respectively, and may be used as a processed product obtained by treating a thermoplastic substance with an oxazoline-containing carrier or as a reaction product of a thermoplastic substance and an oxazoline-containing carrier. May be. That is, the thermoplastic substance, the bisoxazoline compound, and the inorganic substance are directly or indirectly (via the residue of the surface treating agent) on the surface of the inorganic substance, It may be composed of a bound carrier (compatibilizer).

The treatment of the thermoplastic substance with the oxazoline compound or the oxazoline-containing carrier and the reaction of the thermoplastic substance with the oxazoline compound or the oxazoline-containing carrier are carried out at an appropriate temperature (for example, in the presence or absence of a solvent inert to the reaction). (About 30 to 350 ° C.) by dry or wet mixing, but is often performed by kneading, particularly by melt mixing such as melt kneading. Such a treated product or reaction product may have a free oxazoline group.

[Thermosetting Resin] The bisoxazoline compound is allowed to coexist in a resin system composed of the thermoplastic substance and the thermosetting resin, or the thermosetting resin is mixed with the processed product or the reaction product. When coexisting, phase separation between the thermoplastic substance and the thermosetting resin is suppressed, and the alloy can be effectively formed. Therefore, it is possible to obtain a resin composition having properties (impact resistance, toughness, etc.) not possessed by thermosetting resins, while maintaining excellent heat resistance and mechanical strength, which are characteristics of thermosetting resins.

As the thermosetting resin, various resins, for example, epoxy resin (such as aromatic epoxy resin such as bisphenol A type epoxy resin), phenol resin, amino resin (such as urea resin and melamine resin), furan resin,
Silicone resin, polyurethane resin, polyimide resin,
Examples thereof include a vinyl ester resin (a reaction product of an epoxy resin and (meth) acrylic acid), an unsaturated polyester resin, a diallyl phthalate resin, and the like. These thermosetting resins can be used alone or in combination of two or more.

The proportion of the thermoplastic substance can be selected from a range in which the thermosetting resin forms a matrix and the properties of the thermosetting resin are effectively exhibited.
1 to 50 parts by weight, preferably 5 to 4 parts by weight, per 100 parts by weight
0 parts by weight, more preferably about 10 to 30 parts by weight.

The resin composition of the present invention may contain various additives depending on the type of thermosetting resin, for example, a curing agent, a curing accelerator, a crosslinking agent, and a stabilizer (an antioxidant, an ultraviolet absorber, etc.). , A reinforcing agent (a powdery or fibrous reinforcing agent), a flame retardant, an antistatic agent, a release agent, a filler, a coloring agent, and the like.

[Production Method] The resin composition of the present invention can be produced by mixing the thermoplastic substance, an oxazoline compound (or an oxazoline group-containing carrier) and a thermosetting resin. At that time, as described above, the thermoplastic substance and the oxazoline compound (or the oxazoline group-containing carrier)
May be used as a processed product or a reaction product of a thermoplastic substance with a bisoxazoline compound (or an oxazoline group-containing carrier), and may be mixed with a thermosetting resin. In particular, the resin composition of the present invention can be prepared by compatibilizing a thermosetting resin and a thermoplastic material that are incompatible with each other by a simple polymer blending operation such as melt mixing and alloying.

The resin composition of the present invention can be molded into a predetermined shape by a conventional molding method of a thermosetting resin, for example, an injection molding method, a laminating molding method, a casting molding method and the like.

The molded product obtained from the resin composition of the present invention has no phase separation between the thermosetting resin and the thermoplastic material, can form a homogeneous or superdifferential acid system, and has high transparency. Also,
Since the adhesive strength at the interface between the two is high, it is possible to impart flexibility, toughness, impact resistance, etc. of the thermoplastic material while maintaining the high heat resistance and mechanical strength of the thermosetting resin. When a soft polymer or a tough polymer is used as the thermoplastic substance, characteristics such as vibration damping and sound insulation can be imparted. Therefore, it is useful for producing various molded articles requiring high performance.

[0042]

According to the present invention, a thermoplastic material, a bisoxazoline compound and a thermosetting resin are combined.
Even if the thermosetting resin and the thermoplastic material are incompatible or poorly compatible with each other, the properties of the thermosetting resin can be effectively exhibited. In particular, even if the matrix is made of a thermosetting resin and the dispersed phase is made of a thermoplastic material, phase separation can be prevented, and the impact resistance can be improved in addition to heat resistance and mechanical strength. A polymer alloy serving as a matrix can be obtained.

[0043]

EXAMPLES The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples. Comparative Example 1 (Epoxy resin alone) Bisphenol A type epoxy resin (Yuika Shell Epoxy Co., Ltd., Epicoat 828, epoxy equivalent 188-1)
94) To 50 g, 49 g of a curing agent [acid anhydride-based curing agent (Epicure YH-306, manufactured by Yuka Shell Epoxy Co., Ltd., 117 g of amine nitrogen content)], and a curing catalyst [Oyaka Shell Epoxy Co., Ltd., Epicure EMI-24,2-ethyl-4-methylimidazole] at 120 ° C.
For 4 hours and then at 150 ° C. for 2 hours.

The bending test was performed on the obtained molded product according to JI.
When the Izod impact test was performed in accordance with JIS K-7113, the results shown in the table were obtained. As shown in the table, the molded product has low impact strength, poor toughness, and is brittle.

Comparative Example 2 (Epoxy resin + rubber component) Bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 828, epoxy equivalent 188-1)
94) 50 g of carboxy-terminated butadiene-acrylonitrile rubber (HYCAR CT Polymer C manufactured by Ube Industries, Ltd.)
10 g of TBN 1300 × 31, molecular weight of about 3500), and a curing agent [acid anhydride-based curing agent (Yukaka Epoxy Co., Ltd.)
Manufactured by Epicur YH-306, amine nitrogen content 117
g)], 49 g, curing catalyst [Yukaka Epoxy Co., Ltd.]
EMI-24, 2-Ethyl-4-methylimidazole], and cured at 120 ° C. for 4 hours and then at 150 ° C. for 2 hours.

Observation of the cross section of the obtained molded product with an electron microscope revealed that rubber components were precipitated and the compatibility was poor. When the molded article was subjected to the same test as in Comparative Example 1, the impact strength was improved as compared with the epoxy resin alone (Comparative Example 1), but the bending strength and the flexural modulus were compared with those of the epoxy resin alone (Comparative Example 1). Dropped.

Example 1 (Epoxy resin + rubber component x oxazoline) Carboxy-terminated butadiene-acrylonitrile rubber (manufactured by Ube Industries, Ltd., HYCAR CT polymer CTBN1300x)
31, molecular weight of about 3500) and 100 g of 2,2'-
(1,3-phenylene) -bis (2-oxazoline)
5 g (1,3-BPO manufactured by Takeda Pharmaceutical Co., Ltd.)
The mixture was stirred and mixed at 0 ° C. for 30 minutes to obtain a reaction product.

10 g of the above reaction product was added to 50 g of a bisphenol A type epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalents 188 to 194).
Curing agent [Acid anhydride curing agent (Yuka Shell Epoxy Co., Ltd.)
Manufactured by Epicur YH-306, amine nitrogen content 117
g)], 49 g, curing catalyst [Yukaka Epoxy Co., Ltd.]
EMI-24, 2-Ethyl-4-methylimidazole], and cured at 120 ° C. for 4 hours and then at 150 ° C. for 2 hours.

When the cross section of the obtained molded article was observed with an electron microscope, it was found to be uniform and transparent, and high compatibility was observed. When the molded article was subjected to the same test as in Comparative Example 1,
The flexural strength and flexural modulus were equivalent to the epoxy resin alone (Comparative Example 1), and the impact strength was improved and the toughness was improved as compared with the epoxy resin alone (Comparative Example 1).

Comparative Example 3 (Epoxy resin + long-chain fatty acid) Bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 828, epoxy equivalent 188-1)
94) 50 g, lauric acid (manufactured by Nacalai Tesque, Inc.) 10 g, and a curing agent [acid anhydride curing agent (Yuika Shell Epoxy Co., Ltd., EpiCure YH-306, amine nitrogen content 117 g)] 49 g, Curing catalyst [Epure EMI-24,2-ethyl-, manufactured by Yuka Shell Epoxy Co., Ltd.]
4-methylimidazole] at 120 ° C.
Cured at 150 ° C. for 2 hours and then at 150 ° C. When the obtained molded article was subjected to the same test as in Comparative Example 1, the Izod impact strength was reduced, the toughness was poor, and the article was brittle.

Example 2 (epoxy resin + long-chain fatty acid × oxazoline) 100 g of lauric acid (manufactured by Nacalai Tesque, Inc.)
2,2 '-(1,3-phenylene) -bis (2-oxazoline) (1,3-BPO, manufactured by Takeda Pharmaceutical Co., Ltd.) 1
And 00g with stirring at 150 ° C. for 30 minutes to obtain a reaction product.

10 g of the above reaction product was added to 50 g of a bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 828, epoxy equivalent: 188 to 194).
Curing agent [Acid anhydride curing agent (Yuka Shell Epoxy Co., Ltd.)
Manufactured by Epicur YH-306, amine nitrogen content 117
g)], 49 g, curing catalyst [Yukaka Epoxy Co., Ltd.]
EMI-24, 2-Ethyl-4-methylimidazole], and cured at 120 ° C. for 4 hours and then at 150 ° C. for 2 hours.

When the cross section of the obtained molded article was observed with an electron microscope, it was found to be uniform and transparent, and high compatibility was observed. When the molded article was subjected to the same test as in Comparative Example 1,
The flexural strength and the flexural modulus were equivalent to those of the epoxy resin alone (Comparative Example 1), and the impact strength was improved and toughened compared to the epoxy resin alone (Comparative Example 1).

Example 3 (Epoxy resin + modified polyolefin × oxazoline) Maleic anhydride-modified polypropylene (Sanyo Chemical Co., Ltd.)
, Umex 1010) 50g and 2,2'-
(1,3-phenylene) -bis (2-oxazoline)
10 g (1,3-BPO, manufactured by Takeda Pharmaceutical Co., Ltd.) was melt-kneaded at 200 ° C. by a twin screw extruder to obtain a reaction product.

10 g of the above reaction product was added to 50 g of a bisphenol A type epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent: 188 to 194), and the mixture was melt-mixed at 150 ° C. To this mixture, a curing agent [acid anhydride-based curing agent (Epicure YH-306, manufactured by Yuka Shell Epoxy Co., Ltd., amine nitrogen content: 117 g)]
49 g of a curing catalyst [Epure EMI-24, 2-ethyl-4-methylimidazole, manufactured by Yuka Shell Epoxy Co., Ltd.] is mixed, and the mixture is mixed at 120 ° C. for 4 hours, and then mixed with 150 g.
Cured for 2 hours at ° C.

When the cross section of the obtained molded article was observed with an electron microscope, it was found to be uniform and high compatibility. When the molded product was subjected to the same test as in Comparative Example 1, the bending strength and the flexural modulus were equivalent to those of the epoxy resin alone (Comparative Example 1), and the impact strength was improved as compared with the epoxy resin alone (Comparative Example 1). And toughened. Even when the maleic anhydride-modified polypropylene and the bisphenol A-type epoxy resin were melt-mixed at 150 ° C. without being modified with the oxazoline compound, they could not be mixed uniformly.

Comparative Example 4 (Epoxy Resin) Phenol novolac type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 1009, epoxy equivalent: 24)
5 g of a curing agent [diaminophenylmethane (manufactured by Sumitomo Chemical Co., Ltd., melting point: 89 ° C.)] is mixed with 100 g of the resin (00 to 3300, softening point: 144 ° C.), and cured at 120 ° C. for 4 hours and then at 150 ° C. for 2 hours I let it. When the obtained molded article was subjected to the same test as in Comparative Example 1, the Izod impact strength was reduced, the toughness was poor, and the article was brittle.

Example 4 (Epoxy resin + polyamide × oxazoline) Polyamide 6 (T-800, manufactured by Toyobo Co., Ltd.) 100
g and 2,2 '-(1,3-phenylene) -bis (2-
Oxazoline) (1,3-BP, manufactured by Takeda Pharmaceutical Co., Ltd.)
O) 5 g with 240 g by twin screw extruder
The mixture was melted and kneaded at ℃ to obtain a reaction product.

Phenol novolak type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 1009, epoxy equivalent 2400-3300, softening point 144 ° C.) 100
Then, 10 g of the above reaction product was added to the resulting mixture, and the mixture was melt-kneaded at 200 ° C. using a twin screw extruder to obtain a mixture. After pulverizing this mixture, a hardener [diaminophenylmethane (manufactured by Sumitomo Chemical Co., Ltd., melting point 89 ° C.)] is added to the pulverized material.
5 g and mixed at 120 ° C. for 4 hours, then 150 ° C. for 2 hours.
Cured for hours. When the cross section of the obtained molded article was observed with an electron microscope, it was uniform and high compatibility was recognized. When the molded product was subjected to the same test as Comparative Example 1, the flexural strength and flexural modulus were superior to the epoxy resin alone (Comparative Example 4), and the impact strength was improved as compared to the epoxy resin alone (Comparative Example 4). , Could be strengthened. Even if the polyamide 6 and the epoxy resin were melt-mixed without being modified with the oxazoline compound, they could not be mixed uniformly.

Comparative Example 5 (Epoxy resin + polysulfone) Bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 828, epoxy equivalent 188-1)
94) 50g and polysulfone (UDEL P-1700, manufactured by Teijin Amoko Engineering Plastics Co., Ltd.) 1
0 g was dissolved and mixed in 300 ml of tetrahydrofuran. When tetrahydrofuran was removed from this mixture using an evaporator, a white liquid was obtained.

A curing agent [acid anhydride-based curing agent (Epicure YH- manufactured by Yuka Shell Epoxy Co., Ltd.) is added to 50 g of the liquid material.
306, amine nitrogen content 117 g)] 49 g, curing catalyst [Yuika Shell Epoxy Co., Ltd., EpiCure EMI-
24,2-ethyl-4-methylimidazole], and cured at 120 ° C. for 4 hours and then at 150 ° C. for 2 hours.

When the cross section of the obtained molded article was observed with an electron microscope, precipitation of polysulfone particles of about 50 μm was observed, and no adhesion was observed at the interface with the matrix of the epoxy resin. When the obtained molded article was subjected to the same test as Comparative Example 1, the bending strength and the flexural modulus were superior to those of the epoxy resin alone (Comparative Example 1).
The impact strength was equivalent to that of the epoxy resin alone (Comparative Example 1), and it was not brittle because it could not be toughened.

Example 5 (Epoxy resin + polysulfone × oxazoline) 100 g of polysulfone (UDEL P-1700, manufactured by Teijin Amoko Engineering Plastics Co., Ltd.)
5 g of 2 '-(1,3-phenylene) -bis (2-oxazoline) (1,3-BPO, manufactured by Takeda Pharmaceutical Co., Ltd.) is melt-kneaded at 320 ° C. by a twin screw extruder to produce a reaction. I got something.

50 g of a bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 828, epoxy equivalent: 188 to 194) and 10 g of the above reaction product were dissolved and mixed in 300 ml of tetrahydrofuran. When tetrahydrofuran was removed from this mixture using an evaporator, a transparent liquid was obtained.

A curing agent [acid anhydride-based curing agent (Epicure YH- manufactured by Yuka Shell Epoxy Co., Ltd.) was added to 50 g of the liquid material.
306, amine nitrogen content 117 g)] 49 g, curing catalyst [Yuika Shell Epoxy Co., Ltd., EpiCure EMI-
24,2-ethyl-4-methylimidazole], and cured at 120 ° C. for 4 hours and then at 150 ° C. for 2 hours. Observation of the cross section of the obtained molded article with an electron microscope revealed that the polysulfone particles had been refined to about 5 μm, and high compatibility was recognized. When the molded article was subjected to the same test as in Comparative Example 1, the bending strength and the flexural modulus were superior to the epoxy resin alone (Comparative Example 1), and the impact strength was improved as compared to the epoxy resin alone (Comparative Example 1). , Could be strengthened.

Example 6 (Epoxy resin + lauric acid + silica + oxazoline compound) 100 g of silicon dioxide powder [manufactured by Nacalai Tesque Co., Ltd., average particle diameter 5 μm] was added to 1000 ml of ethyl alcohol [manufactured by Nacalai Tesque Co., Ltd.]. Stir and disperse, and add carboxymethyltriethoxysilane [Chisso Corporation,
SIC2264.5] (0.255 g) and reacted under reflux for 8 hours. After cooling the reaction mixture, the powder particles were separated by filtration, sufficiently washed with tetrahydrofuran, and dried under reduced pressure. 2,2 '-(1,3
0.131 g of -phenylene) -bis (2-oxazoline) (1,3-BPO, manufactured by Takeda Pharmaceutical Co., Ltd.) was added, reacted at 200 ° C. for 30 minutes, and then lauric acid (Nippon Oil & Fats Co., Ltd.) (NAA-122), and reacted at 200 ° C. for 30 minutes to obtain a powder having oxazoline groups and long-chain alkyl groups on the surface. When the above reaction with lauric acid was traced by FT-IR (manufactured by JASCO Corporation), the absorption near the 1650 cm ^{-1 of} the oxazoline ring and the 1720 c
The absorption near m ^-1 decreased, and the absorption of the amide group near 1550 cm ^-1 due to the reaction between the two increased.

To 50 g of a bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 828, epoxy equivalent: 188 to 194), 10 g of the above powder, and a curing agent [an acid anhydride-based curing agent (Yuka Shell Epoxy Co., Ltd.) ), Epicure YH-306, amine nitrogen content 117 g)]
49 g and 1 g of a curing catalyst [Epicure EMI-24,2-ethyl-4-methylimidazole manufactured by Yuka Shell Epoxy Co., Ltd.] were mixed at 120 ° C. for 4 hours, and then 150 minutes.
Cured for 2 hours at ° C.

When the cross section of the obtained molded article was observed with an electron microscope, the silica particles were uniformly dispersed and transparent.
High compatibility was observed. When the molded article was subjected to the same test as in Comparative Example 1, the flexural strength and flexural modulus were equal to or higher than that of the epoxy resin alone (Comparative Example 1), and the impact strength was higher than that of the epoxy resin alone (Comparative Example 1). Improved and toughened.

Example 7 (Epoxy resin + modified polyolefin + silica + oxazoline) A molded article was obtained in the same manner as in Example 6, except that 0.3 g of the maleic anhydride-modified polypropylene of Example 3 was used instead of lauric acid. .

The results are shown in the table.

[0071]

[Table 1]

Claims (11)

[Claims] 1. A resin composition comprising a thermoplastic substance having a functional group containing an active hydrogen atom, a bisoxazoline compound, and a thermosetting resin. 2. The resin composition according to claim 1, wherein the thermoplastic substance and the bisoxazoline compound are formed by treating a thermoplastic substance with a bisoxazoline compound or a reaction product of the thermoplastic substance and a bisoxazoline compound. Stuff. 3. The functional group of the thermoplastic material is at least one selected from a hydroxyl group, a mercapto group, a carboxyl group, an acid anhydride group and an amino group.
The resin composition as described in the above. 4. The thermoplastic material is incompatible with a thermosetting resin and is at least one selected from a C _6-30 aliphatic hydrocarbon compound, a rubber component, and a thermoplastic resin. 2. The resin composition according to 1. 5. A bisoxazoline compound represented by the following formula:(In the formula, D is an alkylene which may have a substituent.
Group, a cycloalkylene group which may have a substituent or
An arylene group which may have a substituent; ¹,
R^Two, R^ThreeAnd R^FourAre the same or different
A substituent, an alkyl group which may have a substituent or a substituent.
Represents an aryl group which may be present)
The resin composition according to claim 1, wherein 6. The resin composition according to claim 1, wherein the proportion of the bisoxazoline compound is 0.1 to 5 mol per 1 mol of the functional group containing the active hydrogen atom of the thermoplastic substance. 7. The method according to claim 1, wherein the proportion of the thermoplastic substance is
The resin composition according to claim 1, wherein the amount is 1 to 50 parts by weight based on 00 parts by weight. 8. The resin composition according to claim 1, further comprising a granular or fibrous inorganic substance. 9. A compatibilizer comprising a thermoplastic substance, a bisoxazoline compound and an inorganic substance, wherein the thermoplastic substance is bonded directly or indirectly to the surface of the inorganic substance via a residue of the bisoxazoline compound. The resin composition according to claim 8, wherein 10. A method for producing a resin composition comprising mixing a thermoplastic substance having a functional group containing an active hydrogen atom, a bisoxazoline compound, and a thermosetting resin. 11. A thermoplastic substance and a bisoxazoline compound are mixed with a thermosetting resin in the form of a processed product of the thermoplastic substance with the bisoxazoline compound or a reaction product of the thermoplastic substance and the bisoxazoline compound. A method for producing the resin composition according to claim 10.