JPH03220215A - Grafted substance, its production, and thermoplastic resin composition containing same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a graft modified product, a modified thermoplastic resin composition containing the modified product, a method for producing the same, the modified product, or a thermoplastic resin composition containing the modified product. and engineering plastics and thermoplastic resin compositions. Specifically, dihydroaromatic compounds or polymers thereof, ether compounds, tetrahydroaromatic compounds added as modifiers,
At least one compound selected from cyclopentane compounds and a monomer having a functional group such as a carbonyl group, a cyclic iminoether group, an epoxy group, a hydroxy group, an amino group, or a nitrile group (hereinafter referred to as a functional monomer) and graft-modified products obtained by modifying thermoplastic resins and/or rubber-like substances at a temperature above their melting point or softening point, if necessary in the presence of a radical generator; The present invention relates to a modified thermoplastic resin composition characterized in that it is blended with/or a rubber-like substance, and a method for producing the same.

The present invention further relates to a thermoplastic resin composition using the above modified product or a modified thermoplastic resin composition containing the modified product as a modifier or compatibilizer for engineering plastics.

[Prior Art] A method of grafting a functional monomer for the purpose of modifying a thermoplastic resin has been conventionally known.

In particular, carboxylic acids, carboxylic acid esters, carboxylic acid amides, acid anhydrides, acid halides and other carboxylic acids or their derivatives, ketones, aldehydes, lactones, lactams and other monomers containing carbonyl groups or their derivatives, epoxy-containing monomers, Compositions graft-modified with hydroxy group-containing monomers, amino group-containing monomers, nitrile group-containing monomers, cyclic iminoether group-containing monomers, or their derivatives are highly reactive and can be used as adhesives, impact modifiers, compatibilizers, etc. is used as.

These modified thermoplastic resins also have excellent paintability,
It can be painted without any pretreatment such as a primer, and is useful for automobile parts such as bumpers, home appliances, and electronics.

As a method for graft-modifying such functional monomers, organic peroxides have conventionally been generally used (for example, U.S. Pat. Nos. 4,147,740 and 4,6
Since organic peroxides are very active radical generators, various side reactions occur in addition to the desired graft reaction.

For example, when a peroxide-degradable resin such as polypropylene is used, thermal decomposition of the organic peroxide occurs rapidly, resulting in an unavoidable molecular scission reaction, resulting in a composition with high fluidity and injection molding. However, on the other hand, mechanical properties such as flexural modulus and tensile yield strength, and adhesive properties are deteriorated.

However, when a peroxide crosslinked resin such as polyethylene is used, an extreme crosslinking reaction progresses, resulting in a significant drop in fluidity and, in some cases, gelation, making processing impossible. have a problem

In addition, remaining peroxide deteriorates thermal stability and weather resistance. Furthermore, when these compositions are extruded, there are problems such as deterioration in drawdown resistance due to molecular cutting reactions, roughness on the surface of the molded product due to extreme crosslinking reactions, and insufficient elongation. Furthermore, there are always accompanying problems such as stability and safety during storage and denaturation of free radical generators, and thermal decomposition loss due to adhesion to the inner walls of heated processing machines.

Therefore, it is difficult to obtain a graft-modified product with a good balance between mechanical properties and processability using a method of performing modification using only peroxide.

As described above, various attempts have been made to graft-modify conventional thermoplastic resins, but none of these methods are fully satisfactory in terms of adhesion, mechanical strength, etc. Improvements in modified products have been desired.

[Problems to be Solved by the Invention] In view of the above points, the present invention aims to improve the disadvantages of peroxide modification methods that involve excessive cross-linking reactions or molecular cleavage reactions, and which exhibits a mild modification reaction. A dihydroaromatic compound or its polymer, ether compound, tetrahydroaromatic compound, or cyclopentane compound is used as a modifier, and if necessary, a small amount of a radical generator is used to the extent that mechanical properties and processability are not impaired. A modified product obtained by modifying a plastic resin and/or a rubbery material in the presence of a functional monomer, and a composition containing the modified product, which has improved mechanical properties such as tensile strength and rigidity compared to conventional peroxide modification methods. No deterioration in mechanical strength, heat resistance, etc., outstanding moldability, adhesive,
The object of the present invention is to provide a composition that has extremely excellent performance as an impact modifier, compatibilizer, etc., and also has excellent paintability.

Another object is to provide a thermoplastic resin composition comprising at least one type of engineering plastic and the modified product, which can promote the impact resistance of engineering plastics and the compatibility of engineering plastics with each other, and exhibit mutual properties. A thermoplastic resin composition is provided.

[Means for Solving the Problems] The present inventors have made extensive studies in view of the above problems, and as a result, have arrived at the present invention.

That is, the present invention provides (A) a thermoplastic resin and/or (B) a rubbery substance in the presence of (C) a modifier and/or at least one compound selected from (B) to (C4). (D) The following monomers (D1) to (D6)
A graft modified product obtained by adding at least one monomer containing a functional group, a modified thermoplastic resin composition containing the modified product, and a method for producing the same.

Modifier (C) below: C1 dihydroaromatic compound or polymer thereof C2: Ether compound C3: Tetrahydroaromatic compound C4: Cyclopentane compound (D) Monomer containing a functional group D1: Power Rubonyl group D2: Cyclic iminoether group D3: Epoxy group D4: Hydroxy group D5 Niamino group C6: Nitrile group Other aspects of the present invention include 100 parts by weight of at least one engineering plastic, (A) a thermoplastic resin and/or
Or (B) a rubbery substance is used as a monomer (D1) to (C) in the presence of (C) a modifier and/or at least one compound selected from (B) to (C4) below. D
6) A graft modified product obtained by adding at least one monomer containing a functional group or a thermoplastic resin composition comprising 1 to 100 parts by weight of a modified thermoplastic resin composition containing the modified product. .

Modifier (C) below C1 dihydroaromatic compound or polymer thereof C2: Ether compound C3/tetrahydroaromatic compounds C4: Cyclopentane compound Monomer containing the following (D) functional group: Dl: carbonyl group D2: cyclic iminoether group D3: Epoxy group D4: hydroxy group D5 Niamino group D6; nitrile group The present invention will be explained in detail below.

The thermoplastic resin (A) used in the present invention refers to an α-olefin (co)polymer having 2 to 12 carbon atoms, such as high-medium density polyethylene, high-pressure low-density polyethylene, linear low-density polyethylene, and ultra-low density polyethylene. , polypropylene, poly-1-butene, poly-4-methyl-1-pentene or intercopolymers of α-olefins such as ethylene, propylene, butene-1, hexene-1,4-methyl-1-pentene, ethylene. Polyolefin resins such as copolymers of ethylene and polar monomers such as unsaturated carboxylic acid ester copolymers and ethylene/carboxylic acid unsaturated ester copolymers, polystyrene resins, polyacrylonitrile resins, and polymethacrylate resins. These include resins, polyacetal resins, polyamide resins, polyester resins, polycarbonate resins, polyether resins, polysulfide resins, and polysulfone resins, and these may be used alone or in mixtures.

Among these, polystyrene-based resins and polyolefin-based resins are most preferred, especially ethylene (co)polymers and/or polypropylene-based resins, because they are particularly inexpensive and have a good balance of mechanical strength and the like.

The rubber-like substance (B) used in the present invention is ethylene/α typified by ethylene-propylene random copolymer rubber.
-Olefin random copolymer rubber, ethylene-propylene-diene random copolymer rubber, styrene-butadiene-styrene-block copolymer rubber, styrene-isoprene-styrene-block copolymer rubber, 1.2-
These include polybutadiene rubber, natural rubber, isoprene rubber, butadiene rubber, chloroprene rubber, styrene-butadiene rubber, nitrile rubber, polyisobutylene rubber, and the like.

Among these, ethylene-propylene random copolymer rubber and ethylene-propylene-diene random copolymer rubber are particularly preferred.

These two rubbers have superior thermoplasticity compared to other rubbery substances, are easily dispersed by melt-kneading, and have no unique odor compared to 5BR1 isoprene rubber, nitrile rubber, or butadiene rubber, or are pelletized. Since it is available in a form, it is easy to measure and handle when blending, and it has operational advantages such as a high degree of freedom in selecting the type of composition manufacturing equipment.

As for the diene component of the ethylene-propylene-diene random copolymer rubber, any of ethylidene norbornene, dicyclopentadiene, and 1,4-cyclohexadiene can be used.

The Mooney viscosity of these rubbery substances is MLl, 4=
10 to 100, preferably ML,
4=20-90.

These rubbery substances may be used alone or in a mixture of two or more.

In the present invention, (C) (CI) added as a modifier
A dihydroaromatic compound or a polymer thereof refers to a compound containing one or more aromatic rings in which at least one aromatic ring is dihydrated. Note that the aromatic ring referred to here refers to the definition of aromaticity (for example, Toshio Goto, translated "Basics of Organic Chemistry", pp. 105-106, Tokyo Kagaku Dojin (1976) [Rich+d S, Mon-5on
& john C, 5 hellon;Fundame
nls of O+anic ChemisfBM
acGrav-Old II, INc (1974)] refers to a ring structure in which the number of π-electrons is 4n+2 (n is an integer), and includes, for example, pyridine and quinoline.

Therefore, the dihydroaromatic compounds used in the present invention also include dihydro derivatives of quinoline.

In addition, the dihydroaromatic compound used in the present invention may have a substituent, and may include a substituent with an alkyl group and various other substituents.
Substituted derivatives with elements or functional groups may be used.

Such dihydroaromatic compounds can be synthesized arbitrarily by applying known chemical reactions, but examples of currently available ones include 1,2-dihydrobenzene, cis
-1,2-dihydrocatechol, 1,2-dihydronaphthalene, 9.10 dihydrophenanthrene, etc.
Zosilu 2゜2.4-1-rifthyl-1,2-dihydroquinoline, 6-nitoxy2.2.4-trimethyl-1
, 2-dihydroquinoline, 2.2.4-trinotyl-1
．． Examples include 1,2-dihydroquinoline compounds such as 2-dihydroquinoline. It may also be a polymer of these compounds.

Some of the dihydroaromatic compounds of the present invention are conventionally known as anti-aging agents;
That is, it has not yet been recognized that dihydroaromatic compounds and their polymers induce radicals, or that the combined use of dihydroaromatic compounds and functional monomers promotes mild modification reactions.

The ether compound (C2) used as a modifier in the present invention may be linear or cyclic, and may have a substituent.

Specific examples include cyclic ethers such as 1,3-dioxolane and 1,4 dioxane, linear ethers such as ethyl ether and isopropyl ether, and 3゜4-dihydro-2
-Non-aromatic cyclic vinyl ethers such as pyran and 4H-chromene, furfuryl alcohol, furfuryl aldehyde, benzofuran, furan derivatives such as furfuryl acetate, and linear vinyl ethers such as n-octadecyl vinyl ether and ethyl vinyl ether. vinyl ether compounds, ketene acetals, isopropenyl acetate, vinyl acetate, ketones represented by 1-amino-1-methoxyethylene, esters, lactones, aldehydes, amides,
Enol ethers and enol esters of carbonyl compounds such as lactams. These may have substituents, and substituents with alkyl groups and substituted derivatives with various elements and functional groups are used. Moreover, these may be used alone or as a mixture. Preferably it is vinyl or alkenyl ether.

Further, the (C3) tetrahydroaromatic compound used as a modifier in the present invention refers to a compound in which at least one aromatic ring is tetrahydrated. The aromatic ring referred to herein is the same as the definition of aromaticity described above, and includes, for example, furan, benzene, naphthalene, etc., and excludes pyran. Therefore, the tetrahydroaromatic compounds used in the present invention also include tetrahydro derivatives of naphthalene. Further, the tetrahydroaromatic compound used in the present invention may have a substituent, and substituted derivatives with an alkyl group and various elements or functional groups are used. Such tetrahydroaromatic compounds can be arbitrarily synthesized by applying known chemical reactions, but examples of currently available ones include: 1. 2. 3. 4-
Examples include tetrahydronaphthalene, tetrahydrobenzene, and tetrahydrofuran. It may also be a polymer of these compounds.

The (C4) cyclopentane compound used as a modifier in the present invention is a compound containing at least one cyclopentane, cyclopentene, or cyclopentadiene skeleton, that is, a 5-membered ring constructed from only carbon atoms. It is a ring compound. Specifically, cyclopentane,
These include cyclopentene, cyclopentadiene, dicyclopentadiene, indene, indane, fluorene, and the like. Of course, these may have substituents,
Substituted derivatives with alkyl groups and other substituted derivatives with various elements and functional groups are used. These may be used alone or as a mixture.

The (D) functional group-containing monomer used in the present invention, that is, the D carbonyl group-containing monomer, refers to carboxylic acids, carboxylic acid esters, carboxylic acid amides, acid halides, acid anhydrides, etc. Refers to monomers containing carbonyl groups or their derivatives, such as acids or their derivatives, ketones, aldehydes, lactones, and lactams.

Specifically, α, β-unsaturated ketones such as methyl vinyl ketone, α-, β-unsaturated aldehydes such as acrolein, and δ
Alternatively, ketones, aldehydes, lactones, typified by α, β-unsaturated lactone derivatives such as γ-valerolactone and γ-butenolactone, α, β-unsaturated lactam derivatives such as δ or γ-valerolactam, and γ-butenolactam, Monomers containing carbonyl groups or derivatives thereof, such as lactams.

In more detail, carboxylic acids or derivatives thereof include maleic acid, fumaric acid, citraconic acid, itaconic acid, 5-norbornene-2,3-dicarboxylic acid, 1. 2. 3.
α,β-unsaturated dicarboxylic acids such as 6-titrahydrophthalic acid, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, butenoic acid, pentenoic acid, esters and amides thereof, and dicarboxylic acids is an anhydride, a half-nystere, and a metal salt.

D2: Cyclic imino ether group-containing monomer refers to an alkenyl cyclic imino ether represented by the following structural formula or a derivative thereof.

2 where n is 1.2 and 3, preferably 2 and 3,
More preferably it is 2. Further, RR2, R, and R each represent an inert alkyl group of C7 to CI2 and/or hydrogen, and each alkyl group may have an inert substituent. Inert here means that it does not adversely affect the grafting reaction or the function of its product. Furthermore, all R's do not have to be the same. Preferably R, =
R2=H, R, -H or Me, R-t (i.e. 2-vinyl or 2-isopropenyl-2-oxazoline, 2-vinyl or 2-isopropenyl-5,6-
Sihydro 41 (-1,3-oxazine) These may be used alone or as a mixture. Among these, 2-vinyl and 2-isopropenyl-2-oxazoline are particularly preferred.

D3: Epoxy group-containing monomers include glycidyl (meth)allylate, butadiene oxide, isoprene oxide, and the like.

D4. Hydroxy group-containing monomers include 1-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate, and the like.

The D5 niamino group-containing monomer includes aminoethyl (meth)acrylate and the like.

The D6 nitrile group-containing monomer includes acrylonitrile and the like.

The various functional monomers mentioned above may be linear or cyclic;
There may also be substituents that do not inhibit the grafting reaction,
A mixture of substances that do not inhibit the grafting reaction may be used.

Further, derivatives thereof may also be used.

Furthermore, other unsaturated monomers may be present in the graft modification of the functional monomer. Examples of unsaturated monomers having the above properties include propylene, 1-butene, 1-hexene, 1
-Olefins such as decene, 1-octene, and styrene;
Vinyl esters such as vinyl acetate, vinyl propionate, and vinyl benzoate; vinyl chloride; vinyl ethers such as vinyl methyl ether vinyl ethyl ether; and the like.

These (D) functional monomers are graft-reacted with at least one modifier selected from (C1) to (C4), making it possible to impart adhesiveness and reactivity to the modified product. Alternatively, compositions containing the modified product are suitably used in adhesives, impact modifiers, compatibilizers, and the like.

Among these, unsaturated (
Di)carboxylic acid is preferable because it has high graft reactivity when used in combination with (C) modifier.

Alkenyl cyclic imino ethers or derivatives thereof are also preferred because they are highly reactive with various functional groups, have low adhesive properties and reactivity, and are highly effective as adhesives, compatibilizers, and the like.

In the present invention, when obtaining the above-mentioned modified product, a further small amount of (E
) A radical generator can be used in combination.

The radical generator (E) may be a conventional radical generator, such as organic peroxides, azonitrile, oxygen, ozone, and the like.

Organic peroxides include alkyl peroxides, aryl peroxides, acyl peroxides, aroyl peroxides, ketone peroxides, peroxycarbonates, peroxycarboxylates, and the like. Alkyl peroxides include diisopropyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, α, α′-bis(tert-butylperoxyisopropyl)-benzene, and aryl peroxides include dicumyl peroxide, cumyl hydroperoxide, and acyl peroxide. teeth,
Examples of lauroyl peroxide and aroyl peroxide include dibenzoyl peroxide, and examples of ketone peroxide include methyl ethyl ketone peroxide and cyclohexanone peroxide. Examples of azonitrile include azobisisobutyronitrile and azobisisopropionitrile. These may be used alone or as a mixture. By combining an appropriate amount of this (E) radical generator, the function as an adhesive, compatibilizer, etc. is significantly improved.

Furthermore, in the present invention, the periodic table Ia or Il
Carbonates or oxides of group A metals, such as sodium carbonate, potassium carbonate, lithium carbonate, magnesium carbonate,
Calcium carbonate, calcium oxide, sodium oxide, potassium oxide, magnesium oxide, lithium oxide, etc. may be blended during and/or after the above-mentioned modification and modified.

In addition, if necessary, polyfunctional monomers such as methacrylic acid esters represented by trimethylolpropane trimethacrylate and ethylene glycol dimethacrylate, vinyl monomers represented by divinylbenzene, triallyl isocyanurate, and diallyl phthalate can be added. , N, N'm-phenylene bismaleimide, N, N'
- It is possible to blend bismaleimides such as ethylene bismaleimide and crosslink at the same time as modification to increase mechanical strength and improve heat resistance.

These may be used alone or as a mixture, but among them, bismaleimides are preferred because they not only enhance crosslinking reactivity but also serve to impart adhesive properties.

The above-mentioned modification may be carried out by melt kneading such as dynamic heat treatment or reaction in a solvent within a temperature range of not less than the melting point or softening point of the resin and not more than the decomposition point, and is not particularly limited.

In addition, it is preferable to use a mixer that provides a high shear speed for melt mixing, so that radicals are more likely to be generated in the mixture.

The graft modified product of the present invention comprises (A) a thermoplastic resin and (B)
) By appropriately selecting the blending ratio of the rubbery substance, for example, 100-010-100, preferably 95-515-
95, more preferably in the range of 90 to 10/10 to 90, it is possible to satisfy a wide range of required physical properties in combination with the physical properties of the rubbery substance.

The amount of the modifier (C) of the present invention is 0.001 parts by weight per 100 parts by weight of the thermoplastic resin and/or rubbery substance.
~8 parts by weight, preferably 0.01 to 5 parts by weight.

If the amount added is less than 0.001 part by weight, the modification reaction will not proceed sufficiently, and if it exceeds 8 parts by weight, this is not preferable because it will cause discoloration of the resin and/or rubber-like substance or increase in cost.

The amount of the functional monomer (D) is 0.01 parts by weight per 100 parts by weight of the thermoplastic resin and/or rubbery material.
-30 parts by weight.

If the amount added is less than 0.01, the effects on adhesion, reactivity, etc. will be low, and even if added in an amount exceeding 30 parts by weight, the adhesion will not improve any further, and the reactivity will be extremely improved, resulting in hardening. This is not preferable because it may cause problems such as color change or discoloration of the resin.

The amount of the radical generator (E) to be blended is 5 parts by weight or less per 100 parts by weight of the thermoplastic resin and/or rubbery substance. If the amount added exceeds 5 parts by weight, not only a modification reaction but also a molecular cleavage reaction and an excessive crosslinking reaction of the resin will proceed, resulting in a decrease in fluidity and mechanical properties, which is not preferable.

In the present invention, a softener may be added during and/or after the heat treatment.

As the softening agent, not only paraffinic, naphthenic and aromatic oils, but also petroleum fractions thereof, synthetic oils such as liquid polyisobutyne can also be used.

Although the amount of the softener varies depending on the purpose, use, etc., it is usually up to 100 parts by weight per 100 parts by weight of the resin and/or rubber component.

In the present invention, a modified thermoplastic resin composition can be obtained by appropriately blending the above-mentioned unmodified thermoplastic resin component (A) and/or rubber-like material component (B) with the graft modified product.

Further, when the modified thermoplastic resin composition is used as an adhesive, the concentration of the functional monomer (D) in the composition is 0.001% of the thermoplastic resin component and/or the rubbery material component. It is desirable to adjust the amount to fall within the range of ~20% by weight.

If the concentration is less than 0.001% by weight, the adhesive strength will not be sufficient, and if the concentration exceeds 20% by weight, the adhesiveness will not improve any further and there is a risk of discoloration of the resin, which is not preferable.

The modified product or modified thermoplastic resin composition of the present invention has a highly reactive functional group and is therefore effective as an impact modifier for engineering plastics and a compatibilizer for different types of engineering plastics.

Engineering plastics used in the present invention include ultra-high molecular weight polyethylene, polypropylene, poly-1
-butene, poly-4-methyl-1-pentene, polystyrene, styrene/acrylonitrile copolymer, styrene/
Methyl methacrylate/acrylonitrile copolymer, α-
Methylstyrene/styrene/acrylonitrile copolymer, ABS (acrylonitrile/butadiene/styrene copolymer), MBS (methyl methacrylate/butadiene/
Styrene copolymer), AES (acrylonitrile/
EPR/'styrene copolymer), AAS (acrylic rubber/acrylonitrile/styrene copolymer) polystyrene resin, polymethacrylate resin, polyacetal resin, polyamide resin, polycarbonate resin,
Polyphenylene ether resin, polyester resin,
Liquid crystal polyester resin, polysulfone resin, polyether sulfone resin, polyphenylene sulfide resin, polyether/ether ketone, polyarylate resin, polyamideimide resin, polyimide resin, polyetherimide, polyester amide, polyether ester amide, polyether ketone ketone, At least one selected from engineering plastics such as polyaryletherketone, polyetherketone, and fluororesin may be used.

As alloys that combine the above engineering plastics, PA/PPO, PBT/PP01A
BS/PASABS/PBT, ABS/PPO, ABS
/PC,PBT/PC,PPS/PP01PPS/PA
, PS/PPO (PA: polyamide, PPO: polyphenylene oxide, PBT: polybutylene terephthalate, ABS: acrylonitrile/butadiene/
Styrene copolymer, PC: polycarbonate, pps
:Polyphenylene sulfide. PS: It is polysulfone. ) and the like, and the graft modified product or modified thermoplastic resin composition of the present invention has a remarkable effect as a compatibilizer for these.

In the various polymer alloys mentioned above, by appropriately selecting the functional groups of the above-mentioned graft modified product or modified thermoplastic resin composition, the advantages of both can be exhibited without causing phase separation of incompatible different types of engineering plastics. A thermoplastic resin composition can be provided.

Also, modified products or modified thermoplastic resin compositions of the present invention,
Alternatively, stabilizers, antioxidants, ultraviolet absorbers, lubricants, foaming agents, antistatic agents, flame retardants, fillers, plasticizers, dyes, pigments, etc. may be appropriately added to compositions using these materials. be able to.

These additive components may be organic compounds or inorganic compounds, and may have any shape such as powder, scale, needle, spherical, hollow, and fibrous shapes.

More specifically, stabilizers represented by hindered phenol compounds, benzotriazole compounds, hindered amine compounds, and amide compounds; inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide; calcium carbonate, magnesium carbonate, and sulfuric acid. Calcium, calcium silicate, clay, diatomaceous earth, talc, alumina, glass powder, iron oxide, metal powder, graphite, silicon carbide, silicon nitride, silica, borax nitride, aluminum nitride, carbon black, mica, glass plate, sericite, pyro phyllite,
Inorganic fillers such as aluminum flakes, graphite, shirasu balloons, metal balloons, pumice, glass fibers, carbon fibers, graphite fibers, whiskers, metal fibers, silicon carbide fibers, asbestos, wollastonite, etc.; azo dyes, indigo dyes, etc. dyes; pigments such as red iron oxide can be used.

Particularly when filling with the above-mentioned inorganic compound, one surface-treated with a silane coupling agent, an organic titanate coupling agent, a metal salt of fatty acid, etc. may be used.

In addition, the modified products or modified thermoplastic resin compositions modified with unsaturated carboxylic acids or derivatives thereof by the method of the present invention have particularly polar groups, so high loading of compounding agents such as inorganic fillers is possible. It is possible.

Although these filler components can be blended at any time, it is preferable to knead them at the same time during melt-kneading.

Furthermore, although the graft-modified product or modified thermoplastic resin composition of the present invention has excellent paintability, in order to further improve the effect, it may be irradiated with high-energy light such as ultraviolet rays or plasma.

[Effects of the Invention] As described above, the graft modified product or modified thermoplastic resin composition obtained by the present invention is obtained by adding a thermoplastic resin or a rubbery substance to a dihydroaromatic compound, a polymer thereof, or an ether as a modifier. By grafting a functional monomer in the presence of a compound, a tetrahydroaromatic compound, a cyclopentane compound, and if necessary a radical generator, the resin itself has excellent mechanical strength, thermal properties, and moldability. It is possible to dramatically improve the adhesiveness and reactivity while maintaining the properties, and the properties as an adhesive, impact modifier, compatibilizer, etc. are extremely excellent, and the coating properties can also be significantly improved.

[Uses of the present invention] The modified product of the present invention and the modified thermoplastic resin composition containing the modified product have excellent adhesive properties, and therefore can be used as resin materials in applications requiring painting, printing, and adhesion. In addition, engineering plastics using the modified product and the modified thermoplastic resin composition containing the modified product have excellent properties, such as those used in textiles, electricity, electronics, automobiles, ships, etc.
It is used as panels, packaging materials, furniture, household goods, etc. in various fields such as aircraft, architecture, and civil engineering, and can be molded by any plastic molding method such as injection molding, extrusion molding, and compression molding. More specifically, (1) rear finisher, sill, rear coater panel, engine hood, trunk lid, fender door panel, protector, bumper fascia, energy absorber, air spoiler, side molding, weather strip,
Auto parts such as shock absorber dust boots, vacuum connectors, rack and pinion boots, instrument panels, armrests, door liner seat backs, duct covers, mudguards, etc.(2) Home appliance parts such as the interior and exterior of coolers and refrigerators, etc. 3) Housing materials such as roof panels and insulation walls (4)
Dining tables, desk surfaces, furniture panels, kitchen cabinets,
Daily necessities such as ice boxes, furniture, etc. (5) Refrigerated truck interior materials, freezer parts such as freezer walls, etc. (6) Other molding applications such as extrusion molded products such as sheets and films, and injection molded products include resin compositions. It is used as a product or masterbatch.

In addition, the modified product or modified thermoplastic resin composition can be laminated as an adhesive resin with other materials (for example, metals, inorganic materials, plastics, etc.) in a molten state to form a strongly bonded laminated structure. It becomes possible.

[Examples and Comparative Examples] Hereinafter, the present invention will be specifically explained using Examples, but the present invention is not limited thereto.

Examples 1 to 6, Comparative Examples 1 to 7 (A) thermoplastic resin (B) rubbery substance, (C) modifier, (D) functional monomer (E) radical generator in the proportions shown in Table 1. Table 1 shows the results of melt-kneading and evaluation. Unless otherwise specified, test pieces were obtained by injection molding and subjected to annealing treatment.

The method for producing the composition, the conditions for producing a test piece by injection molding, and the test method are as follows.

Method for producing a composition 1) (A) a thermoplastic resin and/or (B) a rubbery substance, (C) a modifier, and (D) a functional motumer, if desired, (E) a radical generator are mixed in a blending ratio. Mixed in a Henschel mixer.

2) The mixture obtained above was passed through a twin-screw continuous kneading extruder (3
0 mmφ, manufactured by Plastic Engineering Research Institute (■)), the mixture was melt-kneaded at a resin temperature of 180 to 260° C. and a rotational speed of 200 pm, and pelletized. In addition, when kneading, vent (-70
0+n+iHg) to completely remove unreacted monomers. If it was necessary to inject the softener, it was added from a reciprocating metering pump connected to the ventro.

Injection molding conditions Molding machine 1s-90B (manufactured by Toshiba Machine ■) Injection pressure 1,000 kg/c/molding temperature
180-260°C Mold temperature 50°C Test/Measurement method (1) Melt flow rate (VFR) Measured according to JIS K-6760, 6758.

2. Flexural modulus Measured according to ASTM D-790.

3.Izotsu impact strength Measured according to JIS K-6758.

4. Paint evaluation 1. on the flat plate obtained using the injection molding machine. 1. After 1° trichloroethane steam cleaning (1 minute), apply only one-component urethane top coat to a film thickness of 35 μm, dry at 120°C for 30 minutes, and leave at room temperature for 24 hours.
A paintability test piece was obtained after being left for a period of time. The paint film of this test piece was cut with a cutter into 100 base grains of vertical III and 11 horizontal IM, and cellophane tape was attached, and then the cellophane tape was suddenly peeled off and the proportion of the base grains in the remaining paint film was determined as a percentage. This evaluated the coating film adhesion.

In addition, in practical use, the peel strength of the paint film is an important factor, and the paintability test pieces obtained in the same manner as described above, except that the film thickness was 100 μm, were used for the peel strength test of the paint film. Using. A strip-shaped cutter with a width of 10Tm was used to cut out this test piece, and a portion was forcibly peeled off from one end.Then, the peeling angle was set at a tensile speed of 50w/min using a tensile testing machine used for tensile testing of plastics, etc. The coating film was peeled off under the conditions of 180° C. and room temperature of 23° C., and the peeling strength of the coating film at that time (g/10 mm) was determined.

5. A sample was injection molded into a mold having a flow mark size of 100 mm x 200 mm x 3 mm under the following conditions, and the molded product was visually judged.

Injection molding conditions Molding machine 1s-90B (manufactured by Toshiba Machine ■) Injection pressure 1. 000kg/cnf molding temperature
180-260°C Mold temperature 50°C Visual judgment was given in four stages from ◎◎△△ in descending order.

Examples 7 to 11, Comparative Examples 8 to 12 (A) thermoplastic resin, (B) rubbery substance, (D2) functional monomer (cyclic imino ether derivative), (C) modifier in the proportions shown in Table 2. , If desired, (E) a radical generator was melt-kneaded. Unless otherwise specified, test pieces are 2
A plate with a thickness of 2 mm was press-molded at 30° C., and the plate obtained by press-molding was annealed, and desired test pieces were punched out and used. In particular, Examples 10 and 11,
Flow mark evaluation was also conducted for Comparative Examples 11 and 12.

The manufacturing method and testing method for the composition are as described above.

Examples 12 to 15, Comparative Examples 13 to 16 Table 3 shows the low density polyethylene (A5), the oxazoline modified thermoplastic resin prepared in Example 7.8゜9, and the maleic anhydride modified thermoplastic resin prepared in Example 6. After tri-blending at a ratio of , the mixture was melt-kneaded using a twin-screw extruder. The obtained pellets were made into a film with a thickness of about 80 μm, and the same as the polypropylene sheet (A2) with a thickness of about IM, about III
Sandwiched between polyester (A7) and ethylene vinyl alcohol copolymer (A8) sheets with a thickness of I11,
Heat-sealing was performed at 230° C. for 20 seconds using a press molding machine to obtain a three-layer film laminate. The polypropylene sheet and various polymer sheets were peeled off in a 180 degree direction and their strength was measured. The peel rate was 50 strokes/min. Note that unmodified polymers were used in each of the comparative examples.

Examples 16 to 19 and Comparative Examples 17 to 20 (A) a thermoplastic resin, (B) a rubbery substance, (C) a modifier, and (D) a functional monomer were melt-kneaded in the proportions shown in Table 4. The obtained pellets were made into plates by press molding, and the results of coating evaluation were shown in Table 4.

Examples 20 to 24 and Comparative Examples 21 to 25 (C2
) 1 part by weight of dihydropyran, (Dl) 3 parts by weight of maleic anhydride
Parts by weight were blended and melt-kneaded using the aforementioned twin-screw extrusion machine to produce maleic acid-modified low-density polyethylene (MAn-LDP).
E) was obtained.

Additionally, 1 part by weight of dihydropyran (C2) and (D
3) 3 parts by weight of glycidyl methacrylate was blended and melt-kneaded using the twin-screw extrusion machine described above to produce glycidyl methacrylate-modified ultra-low density polyethylene (GMA-VLDPE).
) was obtained.

Table 5 shows the results of evaluating the impact resistance modification and compatibility of the following engineering plastics using the above modified products.
It was shown to.

Charpy impact test: Compliant with JIS K7111 The (A) thermoplastic resin, (B) rubbery substance, (C) modifier, and (D) functional monomer used in the present invention are as follows.

(A) Thermoplastic resin; A1: Polypropylene (PP) (Product name: Nippon Seki Polypro J880G.

Made by Nippon Petrochemical ■, MFR=40) A2: Polypropylene (pp) (Product name: 8 stone polypro J650G.

Manufactured by Nippon Petrochemical ■, VFR=8.0) A3: Polypropylene (p p) (Product name: 8 stone polypro J420G.

Made by Nippon Petrochemical ■, MFR = 1.5) A4: Very low density polyethylene (VLDPE) (Product name - 8 stone Softlex D9550, manufactured by Nippon Petrochemical ■, MFR = 5.0, Density = 11.907 g/am ' ) A5: Low-density polyethylene (LDPE) (Product name: 8 stone Xuron F22, manufactured by Nippon Petrochemical ■, MIi'R = 1.0) Density = (
1,924g/cnf) A6: Polystyrene (Psi) (Product name: Toporex 525, manufactured by Mitsui Toatsu Chemical ■) A7: Polybutylene terephthalate (PBT) (Product name: Halox 310, manufactured by Engineering Plastic ■, A8: Ethylene-vinyl Alcohol copolymer (EVOH
) Product name: EVAL EP-FIOI, manufactured by Kuraray ■) A9: Polyphenylene oxide (PPO) (Product name:
Noryl 534J-801 manufactured by EPL ■) AIO: Ethylene-ethyl acrylate copolymer (EE
A) (Product name: 8 stones Xuron EEA.

A11: Polyamide (PA) (Product name: Nylon-6, manufactured by Ube Industries) A12: Polyethylene terephthalate (PET) (Product name: MA-5)
21X.

Made by Mitsubishi Rayon) Al1: polycarbonate (pc) (Product name: Nipperex 7025A.

(manufactured by Mitsubishi Kasei ■) (B) Rubber-like substance; B1: Ethylene-propylene-diene random copolymer rubber (EPDM) (iodine value 15, ML, .4=88°; trade name: EP57p.

B2: Ethylene-propylene random copolymer (EPR)
) (ML+, 4=70. Product name: EP07P.

(manufactured by Japan Synthetic Rubber) (C) Modifier: (CI) Dihydroaromatic compound C1l: Poly(2,2,4-trimethyl-1゜2-
Dihydroquinoline) (Product name: Tsukrak 224 S.

CI2: 9.10-dihydrophenanthrene manufactured by Tokyo Kasei ■ (C2) Ether compound C2-1 + dihydropyran Tokyo Kasei (Kiki C2-2: Isopropenyl acetate manufactured by Tokyo Kasei ■ (C3) Tetrahydro Aromatic compounds 03-I: 1,2,3.4-Tetrahydronaphthalene manufactured by Tokyo Kasei ■ C3-2: Tetrahydrobenzene manufactured by Tokyo Kasei ■ C3-3: Tetrahydrofuran manufactured by Tokyo Chemical ■ (C4) Cyclopentane compound C4: (D) Functional monomer manufactured by Inden Tokyo Kasei ■ Dl: Maleic anhydride (trade name: Crystalman, manufactured by Asahi Petrochemical ■) B2-1: 2-isopropenyl 2-2 3 4 5 6 2-oxazoline: 2 -Vinyl-2-oxazoline: Glycidyl methacrylate: Hydroxyethyl acrylate: Aminoethyl acrylate: Acrylonitrile (E) Radical generator; α, α′-Bis(tertiary-butylperoxyisopropyl)-benzene (others) Softener; Super Oil C9 Japan Filler made from petroleum; Made by Talc FFR Asada Flour Milling

Claims (3)

[Claims] (1) Using (A) a thermoplastic resin and/or (B) a rubbery substance as a (C) modifier, the following (C1) to (C4) are used.
(D) in the presence of at least one compound selected from
A graft modified product obtained by adding at least one monomer containing the following functional groups (D1) to (D6) as a monomer, or a modified thermoplastic resin composition containing the modified product. The following (C) modifier: C1: Dihydro aromatic compound or its polymer C2: Ether compound C3: Tetrahydro aromatic compound C4: Cyclopentane compound The following (D) Monomer containing a functional group: D1 : Carbonyl group D2: Cyclic iminoether group D3: Epoxy group D4: Hydroxy group D5: Amino group C6: Nitrile group (2) Using (A) a thermoplastic resin and/or (B) a rubbery substance as a (C) modifier, the following (C1) to (C4) are used.
(D) in the presence of at least one compound selected from
A graft-modified product characterized by modifying at least one monomer containing the following functional groups (D1) to (D6) at a temperature equal to or higher than the melting point or softening point of the resin or rubber. A method for producing a modified thermoplastic resin composition containing a modified substance. The following (C) modifier: C1: Dihydro aromatic compound or its polymer C2: Ether compound C3: Tetrahydro aromatic compound C4: Cyclopentane compound The following (D) Monomer containing a functional group: D1 : Carbonyl group D2: Cyclic iminoether group D3: Epoxy group D4: Hydroxy group D5: Amino group C6: Nitrile group (3) 100 parts by weight of at least one engineering plastic; (A) a thermoplastic resin and/or (
B) A rubber-like substance is used as a (C) modifier as shown in (C1) below.
Obtained by adding at least one monomer containing the following functional groups (D1) to (D6) as the (D) monomer in the presence of at least one compound selected from ~(C4) A thermoplastic resin composition comprising 1 to 100 parts by weight of a graft modified product or a modified thermoplastic resin composition containing the modified product. The following (C) modifier: C1: Dihydro aromatic compound or its polymer C2: Ether compound C3: Tetrahydro aromatic compound C4: Cyclopentane compound The following (D) Monomer containing a functional group: D1 : Carbonyl group D2: Cyclic iminoether group D3: Epoxy group D4: Hydroxy group D5: Amino group C6: Nitrile group