JPH05140377A - Transparent resin composition - Google Patents

Abstract

(57) [Summary] [Purpose] To provide a resin composition having excellent transparency, heat resistance, high rigidity and other mechanical properties. [Structure] a) Maleimide-based copolymer 0.5 to 99.5
A resin composition comprising 9 parts by weight, b) a), and 99.5 to 0.5 parts by weight of a thermoplastic resin having a refractive index difference of 0.01 or less at a wavelength of 589 nm.

Description

Detailed Description of the Invention

[0001]

The present invention relates to N-substituted maleimide-
The present invention relates to a resin composition comprising an olefin-based copolymer and a thermoplastic resin having substantially the same refractive index as that of the resin composition, which is excellent in transparency, heat resistance, impact resistance and other mechanical properties.

[0002]

2. Description of the Related Art Conventionally, glass has been generally used as a transparent material, but in recent years, polymeric materials have come to be used in view of productivity, weight reduction, cost and the like.
As such a transparent material, polystyrene (hereinafter P
Abbreviated as S) and polystyrene resin, transparency AB
S (acrylonitrile / styrene / butadiene copolymer), polymethylmethacrylate (hereinafter abbreviated as PMMA), impact resistant PMMA and polycarbonate (hereinafter abbreviated as PC), and amorphous nylon are used. There is.

However, PS, PMMA, and copolymers and resin compositions containing them are excellent in transparency, but their heat distortion temperature (HDT) is around 100 to 120 ° C., so that mechanical properties such as heat resistance and impact resistance are high. Is insufficient and its use is restricted. PC has a relatively high heat resistance with an HDT of around 135 ° C and is excellent in impact resistance as well, but it has optical properties, especially large birefringence and inferior to PMMA, low surface hardness and easily scratched, poor weatherability, molding There are problems such as poor sex. Although amorphous nylon has excellent toughness, it has problems with water absorption, rigidity, and heat resistance.

On the other hand, maleimide copolymers have various heat resistances, and therefore various studies have been made. For example, a method of copolymerizing N-aromatic substituted maleimide with methyl methacrylate is disclosed in JP-B-43-9753 and JP-A-61-
No. 141715, JP-A-61-171708 and JP-A-62-109811 disclose methods of copolymerizing N-aromatic substituted maleimide with styrene resin in JP-A-47-6891. It is known from JP-A-61-76512 and JP-A-61-276807. However, the resin obtained by this method has better heat resistance as the N-aromatic substituted maleimide content increases, but it is very brittle and has poor processability and coloration. It is only used in a small amount as an improving agent.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition having excellent transparency, heat resistance, high rigidity and other mechanical properties.

[0006]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of this problem, and as a result, a resin composition comprising an N-substituted maleimide-olefin copolymer and amorphous nylon satisfies the above object. The present invention has been completed.

That is, in the present invention, the constituent component (I) shown below is 30 to 98 mol% of the whole polymer and the constituent component (II) is 2 to 70 mol% of the whole polymer, and the weight average polystyrene equivalent. Molecular weight is 1 × 10 ³ or more 5 × 1
0 0.5 to 99.5 parts by weight of the resin ⁶ or less, transparency, characterized in that a thermoplastic resin 99.5 to 0.5 parts by weight, heat resistance, high stiffness and other resins having excellent mechanical properties It relates to a composition.

[0008]

[Chemical 3] (Here, R ¹ represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a halogen-substituted phenyl group)

[0009]

[Chemical 4] (Here, R ² is hydrogen or an alkyl group having 1 to 8 carbon atoms, and R ³ and R ⁴ each represent an alkyl group having 1 to 8 carbon atoms.) The maleimide copolymer described above is, for example, N- It can be obtained by a radical copolymerization reaction of a substituted maleimide and an olefin.

The compounds which give the component (I) are N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn.
-Butyl maleimide, N-i-butyl maleimide, N-
s-Butyl maleimide, Nt-butyl maleimide, N
-N-pentyl maleimide, N-n-hexyl maleimide, N-n-heptyl maleimide, N-n-octyl maleimide, N-lauryl maleimide, N-stearyl maleimide, N-cyclopropyl maleimide, N-cyclobutyl maleimide, N -Cyclohexylmaleimide, N
-Phenylmaleimide, N- (2-methylphenyl) maleimide, N- (2-ethylphenyl) maleimide, N
-(2-Isopropylphenyl) maleimide, N- (3
-Methylphenyl) maleimide, N- (3-ethylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (4-ethylphenyl) maleimide, N-
(2,6-Dimethylphenyl) maleimide, N- (2,
6-diethylphenyl) maleimide, N- (2,6-diisopropylphenyl) maleimide, N- (2,4,6)
-Trimethylphenyl) maleimide, N-carboxyphenylmaleimide, N- (2-chlorophenyl) maleimide, N- (2,6-dichlorophenyl) maleimide,
N-substituted maleimides such as N- (2-bromophenyl) maleimide, N- (perbromophenyl) maleimide, N- (2,4-dimethylphenyl) maleimide, paratolylmaleimide, among which N-methylmaleimide , N-ethylmaleimide, N-isopropylmaleimide or N-cyclohexylmaleimide are preferably used. These can be used alone or in combination of two or more.

The compounds which give the component (II) are isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1-hexene and 1-methyl-1-.
With olefins such as heptene, 1-isooctene, 2-methyl-1-octene, 2-ethyl-1-pentene, 2-methyl-2-butene, 2-methyl-2-pentene, 2-methyl-2-hexene Of these, isobutene is preferably used. These can be used alone or in combination of two or more.

The content of the constituent component (I) is 30 to 98 mol%, 40 to 85 mol%, especially 4
5-80 mol% is preferable. When the constituent component (I) exceeds 98 mol%, the polymer produced becomes brittle, which is not preferable.

The maleimide copolymer of the present invention may be modified with a reactive group. As the reactive group, carboxylic acid and its derivative or metal salt,
Acid anhydride group, epoxy group, amino group, hydroxyl group,
Examples thereof include a thiol group, an alkoxysilyl group, and an isocyanate group, and the content of the reactive group is 0 to 30 mol%, preferably 0 to 20 mol%, more preferably 0, relative to the maleimide copolymer. ~ 5 mol%. If the reactive group exceeds 30 mol%, the thermal stability and mechanical strength of the resin produced may be reduced.

The method for producing these modified maleimide copolymers is as follows:
Maleic anhydride, citraconic anhydride, itaconic anhydride,
(Meth) acrylic acid, itaconic acid, fumaric acid, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate
G, triethoxysilylpropyl (meth) acrylate
It can be produced by copolymerizing an unsaturated compound such as glutamine and allylamine. Further, as described below, when the maleimide copolymer of the present invention is obtained by post-imidization of a maleic anhydride and an olefin copolymer, the acid anhydride unit can remain by adjusting the imidization amount. ..

Further, if necessary, the above copolymer may be copolymerized with another vinyl monomer and used within a range not impairing the object of the present invention. Other vinyl monomers include styrene, α-methylstyrene, vinyltoluene, 1,3-butadieneisoprene and their halogen-substituted derivatives, methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, methacrylic acid. Methacrylic acid esters such as benzyl, acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, vinyl esters such as vinyl acetate and vinyl benzoate, Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, vinyl chloride, vinylidene chloride, acrylonitrile, ethylene, propylene, 1-butene, 2-butene. Compound 1 or more selected from 1-hexene and the like.

For the polymerization of these monomers, any of known polymerization methods such as bulk polymerization method, solution polymerization method, suspension polymerization method and emulsion polymerization method can be adopted.

Examples of the polymerization initiator include benzoylperoxide, laurylperoxide, octanoylperoxide, acetylperoxide, di-t-butylperoxide, t-butylcumylperoxide, dicumylperoxide, t-butylperoxyacetate.
, An organic peroxide such as t-butylperoxybenzoate, or 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-butyronitrile), 2,2 ′ -Azobisisobutyronitrile, dimethyl-2,2'-azobisisobutyrate, 1,1'-
Azo-based initiators such as azobis (cyclohexane-1-carbonitrile) may be mentioned.

Solvents usable in the solution polymerization method include benzene, toluene, xylene, ethylbenzene,
Cyclohexane, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, dimethylformamide,
Examples include isopropyl alcohol and butyl alcohol.

The polymerization temperature can be appropriately set according to the decomposition temperature of the initiator, but it is generally preferable to carry out the polymerization in the range of 40 to 150 ° C.

The above-mentioned resin can also be obtained by post-imidizing a resin obtained by copolymerization of maleic anhydride and olefins with an alkylamine or the like. For example, maleic anhydride-isobutene copolymer is dissolved or dispersed in a molten state or in an alcohol solvent such as methanol, ethanol and propanol, or an aromatic solvent such as benzene and toluene. And a primary amine such as methylamine is reacted at a temperature of 100 to 350 ° C.

Here, the weight average molecular weight (Mw) of the resin produced is determined by gel permeation chromatography.
(GPC). The molecular weight of the maleimide copolymer is 1 × 10 ³ or more and 5 × 10 ⁶ or less, and particularly,
It is preferably 1 × 10 ⁵ or more and 1 × 10 ⁶ or less. When the molecular weight exceeds 5 × 10 ⁶ , moldability becomes poor and 1
If it is less than × 10 ³ , the obtained resin tends to be brittle.

Further, in the resin composition of the present invention, a thermoplastic resin having a refractive index difference of 0.01 or less at a wavelength of 589 nm is 0.5 to 99.5 parts by weight of the copolymer. 99.5 to 0.5 parts by weight are included. Here, when the amount of the copolymer is less than 0.5 part by weight, the rigidity and elastic modulus of the resin composition decrease. On the other hand, if the amount is more than 99.5 parts by weight, the impact strength decreases, which is not preferable. Further, the difference in refractive index between the copolymer and the thermoplastic resin is preferably 0.01 or less, more preferably 0.005 or less. The refractive index difference is 0.
When it exceeds 01, the molded body becomes milky white due to the light scattering phenomenon, and the light transmittance, that is, the transparency is reduced, which is not preferable.

Examples of such thermoplastic resin include amorphous nylon. Unlike the linear aliphatic nylon such as nylon 6 and nylon 66, this amorphous nylon is a nylon in which the crystallization of the polymer hardly occurs or the crystallization rate is very small.

The comonomers constituting the amorphous nylon include dicarboxylic acids such as isophthalic acid, terephthalic acid, adipic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid as acid components and 1,6 as diamine components.
-Hexamethylenediamine, trimethylhexamethylenediamine, 4,4'-diamino-dicyclo-hexylenemethane, 4,4'-diamino-3,3'-dimethyl-dicyclo-hexylenemethane, 4,4'-diamino- Examples thereof include dicyclo-hexylene propane, isophorone diamine, lactam components such as caprolactam and laurolactam, and isocyanate components such as 4,4′-diphenylmethane-diisocyanate. In the resin composition of the present invention, the compounding ratio (weight ratio) of the maleimide-olefin copolymer and the amorphous nylon is 1 to 50:99 to 50, particularly 3 to 30:97 to 70, and further 5 to 15 :. 95-85
Is preferred.

The refractive index of amorphous nylon is 1.53 to 1.
54. On the other hand, the maleimide copolymer used in the present invention has a refractive index of 1. depending on the type of maleimide.
Since it can be arbitrarily changed from 50 to 1.58, it has high transparency with a light transmittance of 85% or more and heat resistance, high rigidity, etc. It can be used as a transparent resin composition having excellent mechanical properties.

The composition of the present invention can also be used by adding a third component compatible with both the maleimide copolymer and / or the amorphous nylon as a compatibilizing agent.

It is also possible to add a maleimide copolymer and / or a third component capable of reacting with the reactive group of the amorphous nylon to form a block or graft copolymer at the interface between the two components.

Further, when the reactive group of the maleimide polymer and / or the amorphous nylon is introduced, various catalysts can be added for the purpose of promoting the reaction.

The transparent resin composition of the present invention may be further mixed with other thermoplastic or thermosetting resin having substantially the same refractive index, or solid or liquid rubber. It is also possible to polymerize the above maleimide and olefins in the presence of amorphous nylon and use it as a graft polymer.

If necessary, the resin composition obtained in the present invention contains glass fibers having substantially the same refractive index,
It is also possible to mix an inorganic filler such as a glass microrod, a glass microbead, or a glass powder. Further, a heat stabilizer such as a hindered phenol, an organic phosphoric acid ester, a benzotriazole type or a hinder.
An ultraviolet stabilizer such as a doamine-based stabilizer, a flame retardant, a foaming agent, an antistatic agent, various lubricants and the like may be added. These additives may be used in combination.

There is no particular limitation on the method for producing the resin composition of the present invention. For example, powdery or pelletized maleimide-olefin copolymer and amorphous nylon and other additives are mixed or mixed. Examples of the method include a method of supplying to an extruder without performing melting and kneading, a method of dissolving a maleimide-olefin copolymer, amorphous nylon and other additives in a solvent and mixing them to remove the solvent.

As a method for molding the transparent resin composition of the present invention, usual molding methods such as injection molding method, extrusion molding method, compression molding method, blow molding method, cast molding method and spin cast molding method are used. Can be mentioned.

The obtained molded product is a case for various electric parts,
It can be used for illumination covers, automobile lenses, signal lenses, instrument panels, windshields, goggles, window glasses, daylighting plates and the like.

[0034]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

The molecular weight of the produced polymer is GPC (Tosoh
It was determined by polystyrene conversion using HLC-802A manufactured by Co., Ltd.

The composition of the produced polymer was determined by elemental analysis and NMR.
The measurement was performed.

The light transmittance was measured according to ASTM 1746, and the refractive index was measured using an Abbe refractometer.

As a mechanical property, a tensile test was conducted according to ASTM D638M. However, the following examples, the breaking elongation shown in the comparative example, the elastic modulus is a value obtained by dividing the moving distance of the crosshead by the length of the parallel portion of the tensile test piece as the strain, .. Impact strength is A
It carried out based on STM D256.

In the following Reference Examples and Examples,
"Parts" and "%" indicate parts by weight and% by weight, unless otherwise specified.

Reference Example Synthesis of Maleimide-Olefin Copolymer A-1 30 equipped with stirrer, nitrogen inlet tube, thermometer and degassing tube
1180 g of N-methylmaleimide in 1 g of autoclave,
167 g of glycidyl methacrylate, 8 g of perbutyl neodecanoate and a toluene / methanol mixed solvent (1
(1/1 weight ratio) was charged, and after purging with nitrogen several times, 8.5 l of liquefied isobutene was charged and the reaction was carried out at 60 ° C. for 12 hours.

The particulate polymer obtained by the reaction was separated by centrifugation and dried under reduced pressure at 60 ° C. for 2 hours. The yield was 1770 g.

The polymer obtained was purified by reprecipitation with a chloroform / methanol system solvent, and subjected to elemental analysis and ¹ H-NM.
As a result of analysis by R, the maleimide unit in the produced polymer was 49.5 mol%, the glycidyl methacrylate unit was 0.8 mol%, and the isobutene unit was 49.7 mol%. The molecular weight (Mw) determined by GPC was 263,000. The refractive index was 1.525.

A-2 N-methylmaleimide 118 was placed in the reaction vessel described in A-1.
0 g, 23 g of maleic anhydride, 8 g of perbutyl neodecanoate and 15 l of a toluene / methanol mixed solvent (1/1 weight ratio) were charged, and after purging with nitrogen several times, 8.5 l of liquefied isobutene was charged, The reaction was carried out at 60 ° C for 12 hours.

The particulate polymer obtained by the reaction was separated by centrifugation and dried under reduced pressure at 60 ° C. for 24 hours.
The yield was 1750 g.

Based on the results of elemental analysis of the obtained polymer and the results of elemental analysis and ¹ H-NMR analysis of a sample obtained by methyl-esterifying the maleic anhydride portion of the obtained polymer, the maleimide unit in the produced polymer was 49 Mol%, maleic anhydride 1 mol%, isobutene unit 50 mol%. The obtained polymer has a molecular weight (Mw) of 27,000.
It was 0. The refractive index was 1.525.

Amorphous Nylon B-1 Commercially available amorphous nylon (manufactured by Ems Japan KK: T
R55-LX) was used. The refractive index was 1.529.

Styrenic Copolymer Resin C-1 A commercially available styrene-acrylonitrile copolymer (manufactured by Mitsubishi Kasei Polytech Co., Ltd .: Sunlex) was used. The refractive index was 1.570.

Examples and Comparative Examples Copolymers and amorphous nylon having the compositions shown in Table 1 were premixed with powder or pellets and kneaded with a twin-screw extruder (Laboplast Mill, Toyo Seiki Co., Ltd.). Extrusion was performed and pelletized. The obtained pellets were molded using an injection molding machine (Panajection, manufactured by Matsushita Electric Industrial Co., Ltd.) to obtain a physical property measurement sample. The results obtained are shown in Table 2.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

As is apparent from the examples, the resin composition of the present invention has good transparency and further has excellent mechanical properties such as elongation at break, elastic modulus and impact strength. Extremely useful.

Claims (3)

[Claims] 1. A) Component (I) shown below is a polymer.
30 to 98 mol% of the whole, the constituent (II) is a polymer
0.5 to 99.5 parts by weight of maleimide-based copolymer having a polystyrene-equivalent weight average molecular weight of 1 × 10 ³ or more and 5 × 10 ⁶ or less, and b) a) and wavelength. A resin composition comprising 99.5 to 0.5 parts by weight of a thermoplastic resin having a difference in refractive index of 0.01 or less at 589 nm. [Chemical 1] (Here, R ¹ represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a halogen-substituted phenyl group.) (Here, R ² is hydrogen or an alkyl group having 1 to 8 carbon atoms, and R ³ and R ⁴ each represent an alkyl group having 1 to 8 carbon atoms) 2. The resin composition according to claim 1, wherein the thermoplastic resin is amorphous nylon. 3. A transparent material comprising the resin composition according to claim 1 or 2.