JP2000143929A - Transparent heat-resistant thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent, heat-resistant thermoplastic resin composition having adjusted refractive index and compatibility, having excellent transparency, and excellent in the balance of heat resistance, impact resistance and molding processability. SOLUTION: This transparent, heat-resistant thermoplastic resin composition consists mainly of (A) a rubber-modified styrenic resin, (B) a heat-resistant resin having a Vicat softening point of >=120 deg.C, and (C) one or more other thermoplastic resins. Therein, the transparent, heat-resistant thermoplastic resin composition satisfies the inequality: |nDA1-nDm|<=0.01, wherein nDm=(wA2×nDA2+wB×nDB+wC×nDC)/(wA2+wB+wC). Therein, nDA1, nDm, nDB, nDC are the refractive indexes of the rubber portions of the component A, the matrix portion of the component A, the component B and the component C, respectively, and wA1, wA2, wB, and wC are the weights (wt.%) of the rubber portion of the component A, the matrix portion of the component A, the component B and the component C, respectively. The matrix of the component A is thermodynamically compatible with a mixture comprising the components B and C. The 3 mm thick flat plate molded product of the thermoplastic resin composition preferably has a whole light transmittance of >=75%. Since the refractive index of the thermoplastic resin composition is adjusted in such the manner as above, the refractive index can easily finely be adjusted.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention comprises a rubber-modified thermoplastic resin, a maleimide-based copolymer and another thermoplastic resin. By adjusting the composition and blending of each resin, the refractive index and the compatibility are improved. The present invention relates to a thermoplastic resin composition excellent in adjusted transparency, and further excellent in heat resistance, impact resistance, and moldability. Further, the present invention comprises a transparent rubber-modified thermoplastic resin, a thermoplastic resin having heat resistance and other thermoplastic resins, and a rubber part and a matrix part of the composition after mixing with each other and mutually compatible thermoplastic resins. The present invention relates to a thermoplastic resin composition having a difference in refractive index of 0.01 or less, excellent in transparency, and further excellent in heat resistance, impact resistance, and moldability.

[0002]

2. Description of the Related Art Conventionally, as a resin composition of a maleimide / methyl methacrylate copolymer and a rubber-modified graft polymer, JP-A-61-91239 discloses a resin composition of methyl methacrylate / N-phenylmaleimide. styrene/
A compatible alloy of acrylonitrile copolymer is disclosed in
1-179252 discloses a resin composition comprising a diene-based graft copolymer and a polymer of methyl methacrylate / N-arylmaleimide, all of which have an excellent balance between heat resistance and mechanical strength or fluidity. A heat-resistant maleimide-based resin composition having physical properties has been obtained.

JP-A-63-243156 discloses that the difference between the refractive index of the graft portion of the rubber-modified graft polymer and the refractive index of a maleimide / methacrylic ester / aromatic vinyl copolymer is within a certain range. The set transparent heat-resistant resin is shown.

[0004]

SUMMARY OF THE INVENTION However, Japanese Patent Application Laid-Open No. Sho 61
-91239 and the thermoplastic resin composition described in JP-A-61-179252 have excellent physical properties such as heat resistance, mechanical strength, and fluid workability.
The final thermoplastic resin composition has a problem that a thermoplastic resin composition having excellent transparency has not been obtained.

Japanese Patent Application Laid-Open No. 63-243156 discloses a maleimide copolymer obtained by copolymerizing a specific maleimide monomer such as N-cyclohexylmaleimide or No-chlorophenylmaleimide with 16% by weight or more of aromatic vinyl. Since the copolymer composition of each resin is set so that the refractive index is close to the refractive index of the rubber-grafted portion of the rubber-modified graft polymer, the control of heat resistance and strength is difficult, and blending is used. Each time the composition of the rubber-modified graft polymer changes and the refractive index changes, it is necessary to synthesize a maleimide-based copolymer having a changed copolymer composition.

[0006]

In order to solve the above problems, the thermoplastic resin composition of the present invention comprises (A) a rubber-modified thermoplastic resin, and (B) a heat-resistant resin having a Vicat softening point of 120 ° C. or more. It is mainly composed of thermoplastic resin, (C) other thermoplastic resin, and the refractive index of (A) rubber part, (A) matrix part, (B), (C) is n _DA1 , n _DA2 ,
n _DB and n _DC, and the weight ratio of each in the resin composition is w
_A1, w _A2, w _B, when formed into a w _C wt%, the following formula (I)
And the matrix part of (A) and (B),
(C) is a thermoplastic resin composition having excellent appearance and heat resistance, wherein the mixture is thermodynamically compatible.

(I) | n _DA1 −n _Dm | ≦ 0.01 where n _Dm = (w _A2 × n _DA2 + w _B × n _DB + w _C ×
n _DC ) / (w _A2 + w _B + w _C ) That is, using the resins (A), (B) and (C) defined above, the matrix of the final composition determined from the refractive index and weight ratio of each resin This is a thermoplastic resin composition obtained by adjusting the type and weight ratio of each resin so that the difference between the refractive index of the portion and the refractive index of the rubber portion of (A) is 0.01 or less.

More preferably, it is a thermoplastic resin composition having excellent heat resistance and having a total light transmittance of 75% or more of a 3 mm-thick flat plate. The above conditional expression (1) means that the difference in the refractive index between the rubber part and the matrix part in the final composition falls within 0.01. More preferably, the resin (A)
However, a rubber-modified styrene-based transparent resin which is a rubber-modified thermoplastic resin in which the difference between the refractive index n _DA1 of the rubber portion of the resin (A) and the refractive index n _DA2 of the matrix portion is within 0.01 may be used.

Further, among the combinations satisfying the above conditions, the matrix part of (A) and (B), (B) and (C), (C)
It is more preferred that the matrix portions of (A) and (A) are mutually compatible. When the rubber-modified thermoplastic resin (A) is a rubber-modified styrene-based transparent resin having a total light transmittance of 80% or more, a thermoplastic resin composition having more excellent transparency can be obtained. Further, the thermoplastic composition mainly comprising (A), (B) and (C) of the present invention has excellent heat resistance, and more preferably has a glass transition temperature of 110 ° C. or higher.

According to the above construction, (B) the heat resistance is improved by the heat-resistant thermoplastic resin, and (B) and (C)
By adjusting the blending amount of the resin composition, the refractive index of the matrix portion of the resin composition obtained can be adjusted to approximate the refractive index of the rubber portion. By adjusting the difference in the refractive index to be within 0.01, excellent transparency can be provided while maintaining heat resistance. Like this 3
In the component system, the refractive index can be finely adjusted by controlling the blending amount, so that a very excellent transparency is obtained, and at the same time, a composition excellent in heat resistance, strength and transparency is obtained. be able to.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below. (A) a rubber-modified thermoplastic resin, (B) a heat-resistant thermoplastic resin having a Vicat softening point of 120 ° C. or higher, (C) other thermoplastic resins, and (A) a rubber portion, (A) Matrix part,
The refractive indexes of (B) and (C) are n _DA1 , n _DA2 , n _DB and n
_DC , each weight ratio in the resin composition is w _A1 ,
When w _A2 , w _B , and w _{C are} % by weight, the following formula (I) is satisfied, and the matrix portion of (A) and (B), (C)
Is a thermoplastic resin composition having excellent appearance and heat resistance, characterized in that a mixture of the following is thermodynamically compatible.

(I) | n _DA1 −n _Dm | ≦ 0.01 where n _Dm = (w _A2 × n _DA2 + w _B × n _DB + w _C ×
n _DC ) / (w _A2 + w _B + w _C ) That is, using the resins (A), (B) and (C) defined above, the matrix of the final composition determined from the refractive index and weight ratio of each resin This is a thermoplastic resin composition obtained by adjusting the type and weight ratio of each resin so that the difference between the refractive index of the portion and the refractive index of the rubber portion of (A) is 0.01 or less.

[0013] More preferably, it is a thermoplastic resin composition excellent in heat resistance, wherein the total light transmittance of a flat plate having a thickness of 3 mm is 75% or more.

For each resin of the resin composition used in the present invention, (A) the rubber-modified thermoplastic resin, the rubber portion includes polybutadiene, styrene-butadiene rubber,
Acrylonitrile-butadiene rubber or the like is dispersed, and the matrix portion is a synthetic resin composed of a continuous phase of a monomer unit resin such as aromatic vinyl represented by styrene, methacrylic acid ester, and unsaturated nitrile. Is raised. Among them, one kind or a combination of two or more kinds can be used. Specifically, as the rubber-modified thermoplastic resin, a rubber-modified styrene-based resin in which a matrix portion contains an aromatic vinyl monomer unit represented by styrene is preferable.

The rubber-modified thermoplastic resin can be produced by a graft polymerization, a blending method, or a graft polymerization-blend method. As the rubber-modified thermoplastic resin according to the present invention, a thermoplastic resin having an appropriate molecular weight and composition may be selected according to the thermoplastic resin composition.

The resins (A), (B), and (C) used in the present invention are thermodynamically compatible when they are mixed, and have the general formula (I) defined above. There is no particular limitation as long as it is a heat-resistant thermoplastic resin having a satisfying refractive index. (B)
Is not particularly limited as long as the thermoplastic resin has a Vicat softening point of 120 ° C. or higher. Preferably, it is a maleimide-based copolymer (1). Specifically, the preferred composition range of (1) is 1 to 50% by weight of a maleimide monomer unit and 50 to 99% by weight of a methacrylate ester monomer unit. A maleimide-based copolymer (1) containing 20% by weight can be mentioned.

As (C), the matrix portion of (A) and
When blended with (B), there is no particular limitation as long as it falls within the range of general formula (1) which is thermodynamically compatible and adjusts the refractive index defined in the present invention. A thermoplastic resin containing 60 to 85% by weight of an aromatic vinyl monomer unit, 15 to 40% by weight of an unsaturated nitrile monomer unit, and 0 to 20% by weight of another monomer unit copolymerizable ( 2) AS resin, maleimide-styrene-based copolymer, maleimide-styrene-acrylonitrile-based copolymer, maleimide-methyl (meth) acrylate-based copolymer, and the like.

In order for the thermoplastic resin composition of the present invention to exhibit high transparency, it is necessary that the refractive index of the matrix portion in the final composition be close to the refractive index of the rubber portion, and the transparency is further improved. In order to improve the refractive index, it is necessary to adjust the difference in refractive index to 0.01 or less.

When the difference between the refractive index of the matrix portion of the final composition and the refractive index of the rubber portion is larger than 0.01, light scattering increases in the boundary region between the rubber portion and the matrix portion. However, the transparency of the molded product is undesirably reduced. In the present invention, if the difference in the refractive index is 0.01 or less, a molded article having extremely excellent transparency can be obtained, and more preferably 0.005 or less. On the other hand, if it is 0, a molded article having extremely excellent transparency can be obtained. Since the present invention utilizes a three-component resin, it is easy to reduce the difference in refractive index to 0.01 or less, or to adjust it to zero. It is a preferred embodiment of the present invention that the composition is adjusted so that the difference in refractive index, which is an important point of transparency, becomes zero while maintaining heat resistance.

When a rubber-modified styrene-based transparent resin having a total light transmittance of 80% or more of the rubber-modified thermoplastic resin (A) is used, the difference between the refractive index of the matrix portion and the refractive index of the rubber portion in the final composition. Can be easily adjusted to 0.01 or less or set to 0, and a thermoplastic resin composition having high transparency and excellent heat resistance can be obtained. In this case, the total light transmittance of the thermoplastic resin composition containing the resins (A), (B) and (C) as main components is 75% or more, preferably 80% or more. More preferably, it is at least 85%. More preferably, the resin (A) has a refractive index n _DA1 of a rubber portion and a refractive index n of a matrix portion of the resin (A).
_A rubber-modified styrene-based transparent resin that is a rubber-modified thermoplastic resin having a difference of _DA2 within 0.01 may be used. Specifically, a transparent poly (methyl methacrylate / styrene / butadiene) resin is preferable.

In order for the thermoplastic resin composition of the present invention to have high transparency, heat resistance, impact resistance, and moldability, the matrix portion of (A) and (B)
It is necessary that the mixture comprising (C) is thermodynamically compatible. Also, the matrix part of (A) and (B),
It is more preferable that the matrix parts of (B) and (C), and (C) and (A) are mutually compatible.

In the present invention, the above resins (A), (B) and (C)
Can be confirmed to be thermodynamically compatible by measuring the glass transition point (Tg) of the obtained thermoplastic resin composition. Specifically, in each mixture of the resins, the glass transition point measured by a differential scanning calorimeter is observed at one point, thereby confirming that they are thermodynamically compatible with each other. Further, it is possible to visually determine that a film or a molded product molded from the mixture has transparency, or to evaluate transparency by measuring optical properties such as total light transmittance by a predetermined method. It can be confirmed that they are thermodynamically compatible.

The maleimide copolymer (1) as (B) has a weight average molecular weight of 50,000 to 30.
It is preferably in the range of 0.000. If the weight average molecular weight exceeds the above range, molding processability may be deteriorated. If the weight average molecular weight is below the above range, defects such as heat resistance and mechanical properties may be deteriorated.

The Vicat softening point of the molded product showing the heat resistance of the maleimide copolymer (1) is preferably 120 ° C. or higher, more preferably 125 ° C. or higher. If the temperature is 120 ° C. or lower, it is difficult to impart sufficient heat resistance to the thermoplastic resin composition after blending. The yellowing degree of a molded article of the maleimide-based copolymer (1) is as follows:
It is desirable to be 10 or less, more preferably 5 or less.

Such a maleimide-based copolymer (1)
Can be obtained by polymerization by any polymerization method. However, when the content of the maleimide monomer in a monomer unit exceeds 5% by weight based on the total amount of each monomer component, Legally,
For example, when a suspension polymerization method is used, the amount of the maleimide monomer remaining in the maleimide-based copolymer (1) may increase, and the obtained maleimide-based copolymer (1) may be colored. Transparency may be reduced.

When the emulsion polymerization method is used, an emulsifier or the like may remain, and the resulting resin composition may be smeared or thermally colored, resulting in a decrease in transparency. On the other hand, when a solution polymerization method is used as the above polymerization method, the residual amount of the maleimide monomer can be reduced and the above problem can be avoided, so that the method for producing a copolymer (1) having a yellowing degree of 10 or less can be used. It is desirable to use a solution polymerization method.

As the organic solvent used in such a solution polymerization method, generally used organic solvents, for example, toluene, xylene, ethylbenzene, isopropylbenzene, methyl isobutyl ketone, butyl cellosolve, dimethylformaldehyde, 2-methylpyrrolidone, methyl ethyl ketone And the like may be appropriately used.

Various methods have been proposed for separating the maleimide copolymer (1) from the reaction solution from the polymerization solution after polymerization. For example, by devolatilizing with a twin-screw extruder equipped with a vent, the remaining maleimide monomers can be effectively reduced together with the reaction solution, and the above-mentioned maleimide copolymer (1) having a small yellowing degree can be effectively reduced. ) Can be obtained. It is a preferred embodiment of the present invention to use the maleimide-based copolymer (1) having less residual maleimide monomer.

In the present specification, the expression “% by weight” means that each monomer component is blended so that the total amount thereof is always 100% by weight. In the components, when the methacrylic acid ester monomer is blended at 80% by weight, it is uniquely set to 20% by weight of the maleimide monomer, for example, 70% by weight of the methacrylic acid ester monomer is blended. And maleimide monomers 20
% By weight and other monomers by 10% by weight.

According to the general formula (I), which is a formula for adjusting the refractive index specified in the present invention, by appropriately mixing (B) with (A), a heat-resistant and excellent transparency can be obtained. A plastic resin composition is obtained. In addition, (C) other thermoplastic resins are more preferable, if necessary. By mixing with (A) together with (B), fine adjustment of heat resistance and refractive index becomes possible, and heat resistance controlled arbitrarily can be obtained. Thus, a thermoplastic resin composition having properties and transparency can be obtained. The mixing ratio (weight ratio) of (A), (B), and (C) in each thermoplastic resin composition is preferably 1% by weight or more for each thermoplastic resin, and the necessary heat resistance and transparency are required. It is preferred that the compounding ratio be freely changed within the above-mentioned range so as not to impair other physical properties such as impact resistance and molding workability.

(C) is not particularly limited as long as it is a thermoplastic resin which is compatible with (A) and (B) when mixed and further satisfies the general formula (I). In order to use the refractive index, it is preferable to set the refractive index n _{DC as} follows. That is, the relationship between the refractive index n _DA2 of the matrix portion of (A) and the refractive index n _DB of (B) is n _DA2 > n _DB
Case of, n _DA2 <n _DC, become as a (C), n _DA2
In the case of <n _DB , it is preferable to use (C) such that n _DA2 > n _DC .

That is, (C) used for adjusting the refractive index includes the refractive index n of the matrix portion of (A).
If the relationship between the refractive index n _DB and _DA2 (B) is greater than the refractive index n _DB of the refractive index n _DA2 of the matrix portion (A) (B), the refractive index of the matrix portion (A) It is preferable to use (C) having a refractive index higher than n _DA2 .

[0033] Conversely, the relationship between the refractive index n _DA2 of the matrix portion (A) and the refractive index n _DB of (B) is, the refractive index n of the refractive index n _DA2 of the matrix portion (A) is (B) _When it is smaller than _DB, it is preferable to use (C) having a refractive index that is smaller than the refractive index n _DA2 of the matrix portion of (A).

The methacrylic acid ester monomers include:
Methacrylic acid esters having 1 to 18 carbon atoms of an alkyl group including a cyclohexyl group and a benzyl group, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, and methacrylic acid Tert-butyl, amyl methacrylate, isoamyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate,
Cyclohexyl methacrylate, benzyl methacrylate,
2-phenoxyethyl methacrylate, 3-methacrylic acid
Phenylpropyl and the like can be mentioned, and one or a mixture of two or more thereof can be used, and among these, methyl methacrylate is preferable.

The maleimide monomers include maleimide, N-methylmaleimide, N-ethylmaleimide,
-Propylmaleimide, N-isopropylmaleimide,
N-butylmaleimide, N-isobutylmaleimide, N
-Tert-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-laurylmaleimide, N- (2
-Hydroxyethyl) maleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N
-Carboxyphenylmaleimide, N-nitrophenylmaleimide, N-tribromophenylmaleimide and the like.

One or a mixture of two or more of these can be used. In particular, among the above maleimide monomers (a), N-phenylmaleimide or N-cyclohexylmaleimide is preferable in order to impart desired heat resistance and transparency, and the heat resistance improving effect is more preferably high. N-phenylmaleimide is desirable in this respect. When N-tribromophenylmaleimide is used, the thermoplastic resin composition can also be imparted with flame retardancy.

Examples of the aromatic vinyl monomers include styrene, α-methylstyrene, paramethylstyrene, isopropenylstyrene, vinyltoluene, and chlorostyrene. One or more of these may be used. Mixtures can be used, of which styrene is particularly preferred.

However, when a large amount of an aromatic vinyl monomer is used, the refractive index of the maleimide copolymer (1) as (B) becomes high, and the copolymer composition of the maleimide monomer is increased. , It is difficult to set the content at a high level, and heat resistance tends to be insufficient. When the maleimide-based copolymer (1) having such a high refractive index is used, it becomes difficult to satisfy the general formula (1) for obtaining the transparent resin composition of the present invention. Therefore, when copolymerizing an aromatic vinyl monomer as necessary, the amount is preferably 15% by weight or less, more preferably 10% by weight or less, and most preferably 5% by weight.
It is as follows.

As the unsaturated nitrile monomers, acrylonitrile, methacrylonitrile, ethacrylonitrile,
Phenylacrylonitrile and the like can be mentioned. Other copolymerizable monomers include aromatic vinyls;
Unsaturated nitriles; acrylates having 1 to 18 carbon atoms in alkyl groups including cyclohexyl and benzyl groups; olefins; dienes; vinyl ethers;
Vinyl esters; vinyl fluorides; allyl esters or methacrylic esters of saturated fatty acid monocarboxylic acids such as allyl propionate; poly (meth) acrylates; polyarylates; glycidyl compounds; And one or a mixture of two or more thereof can be used.

The acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, tertiary butyl acrylate, amyl acrylate, isoamyl acrylate, acrylic Octyl acid, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate, cyclohexyl acrylate,
Benzyl acrylate and the like can be mentioned.

The olefins include ethylene,
Propylene, isobutylene, diisobutylene and the like can be mentioned. Examples of the dienes include butadiene and isoprene. Examples of the vinyl ethers include methyl vinyl ether and butyl vinyl ether. Examples of the vinyl esters include vinyl acetate and vinyl propionate. Examples of the vinyl fluorides include vinylidene fluoride.

The polyvalent (meth) acrylates include ethylene glycol (meth) acrylate, diethylene glycol (meth) acrylate, divinylbenzene, diallyl phthalate, trimethylolpropane tri (meth) acrylate, hexanediol tri, pentaerythritol tetra ( (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, di (meth) acrylate of ethylene oxide or propylene oxide adduct of bisphenol A, di (meth) acrylate of ethylene oxide or propylene oxide adduct of halogenated bisphenol A, isocyanate Examples thereof include di- or tri (meth) acrylate of ethylene oxide of nurate or adduct of propylene oxide.

Examples of the polyvalent acrylates include triallyl isocyanurate. Examples of the glycidyl compound include glycidyl (meth) acrylate and allyl glycidyl ether. Examples of the unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and half-esters and anhydrides thereof.

(A) a rubber-modified styrenic resin of the present invention,
(B) a heat-resistant resin having a Vicat softening point of 120 ° C. or higher,
As described above, the thermoplastic resin composition mainly composed of (C) another thermoplastic resin and having excellent heat resistance has not only excellent transparency but also heat resistance. By blending the specific heat-resistant thermoplastic resin (B) into the composition, a thermoplastic resin composition having a sufficiently high glass transition temperature and excellent transparency can be obtained. If the resin composition of the present invention satisfies the general formula (I) for adjusting the refractive index, the glass transition temperature of the thermoplastic resin composition having excellent heat resistance of the present invention is not particularly limited. However, the glass transition temperature of the thermoplastic resin composition having excellent heat resistance of the present invention is preferably 110 ° C or higher, more preferably 115 ° C or higher, and most preferably 120 ° C or higher.

Next, an example of a method for producing the thermoplastic resin composition of the present invention will be described. Each monomer component containing at least a methacrylic acid ester monomer and a maleimide monomer is preferably dissolved in a solution. It is preferable to obtain a thermoplastic resin composition by mixing the maleimide copolymer (1) obtained by copolymerization with (A) a rubber-modified thermoplastic resin and (C) another thermoplastic resin. According to the above method, even when the maleimide monomer used in the maleimide-based copolymer (1) is used in an amount exceeding 5% by weight, the maleimide-based copolymer (1) is obtained by using solution polymerization. )), The residual amount of the maleimide monomer can be reduced, and a decrease in the optical properties due to the residual maleimide monomer can be suppressed.

The order of mixing the above components (A), (B) and (C) may be, for example, a method of mixing all at the same time, a method of mixing two types in advance, and then mixing the other component. And the like. Such mixing can be performed by a conventionally known method. Among these methods, all are mixed at the same time, or (B) and (C)
Is preliminarily mixed, and then (A) is preferably mixed.

As a method of mixing all of them at the same time, (A),
(B), (C) and, if necessary, various additives described below are added and melt-mixed. As a method of mixing two components in advance and then mixing with the other component, (B)
And (C) are previously mixed using a single-screw or twin-screw extruder, and then melt-mixed with (A) again using a single-screw or twin-screw extruder. Various additives described below can be added as needed, but the mixing of the additives may be performed at any of the first stage and the second stage.

The thermoplastic resin composition of the present invention includes:
Various additives may be added as needed. Such various additives include glass fiber, metal fiber, aramid fiber, ceramic fiber, potassium whisker, carbon fiber, fibrous reinforcing agents such as asbestos, talc, calcium carbonate, mica, clay, titanium oxide, and aluminum oxide. , Glass flakes, milled fiber, metal flakes, various fillers such as metal powder, heat stabilizers such as phosphate esters and phosphites or catalyst deactivators, oxidation stabilizers, light stabilizers, Additives such as a lubricant, a pigment, a flame retardant, a flame retardant aid, and a plasticizer may be appropriately compounded.

The resin composition of the present invention can be obtained by molding methods such as injection molding, extrusion molding, vacuum molding or the like, or by molding, and sheets and films having high heat resistance and transparency, and other impact resistance. And excellent in moldability.

[0050]

EXAMPLES Specific examples and comparative examples of the present invention will be shown below, but the present invention is not limited to the following examples. Unless otherwise specified, “parts” are “parts by weight” and “%” are “% by weight”.

Reference Example 1 N-phenylmaleimide
0 parts, 45.0 parts of methyl methacrylate, 50.50 parts of toluene.
0 parts, 0.02 parts of n-dodecyl mercaptan and t
After performing solution polymerization using 0.2 parts of -butylperoxyisopropyl carbonate, the obtained reaction solution was introduced into a twin-screw extruder to remove volatile components, and the weight-average molecular weight was 100,000.
A maleimide-based copolymer of 90.2% of methyl methacrylate units and 9.8% of N-phenylmaleimide units (B-
1) was obtained. The glass transition temperature of the copolymer (B-1) was 132 ° C., the Vicat softening temperature was 129 ° C., the refractive index was 1.501, and the yellowing degree was 3.0.

Reference Example 2 The starting material composition was 7.5 parts of N-phenylmaleimide, 37.5 parts of methyl methacrylate, 5.0 parts of styrene, 50.0 parts of toluene, 0.02 part of n-dodecyl mercaptan, and A weight average molecular weight of 120,000, methyl methacrylate unit 75.3%, N-phenylmaleimide unit 1
A maleimide copolymer (B-2) having 4.8% and 9.9% of styrene units was obtained. The glass transition temperature of the copolymer (B-2) was 135 ° C., the Vicat softening temperature was 133 ° C., the refractive index was 1.515, and the yellowing degree was 3.3.

Reference Example 3 The starting material composition was 6.0 parts of N-cyclohexylmaleimide and 41.0 parts of methyl methacrylate.
Parts, 3.0 parts of styrene, 50.0 parts of toluene and t
-Butyl peroxyisopropyl carbonate 0.03
Parts by weight, the same operation as above was performed, except that the weight average molecular weight was 185,000, methyl methacrylate unit was 83.0%,
A maleimide copolymer (B-3) having 12.1% of N-cyclohexylmaleimide units and 4.9% of styrene units was obtained. The glass transition temperature of the copolymer (B-3) is 123.
° C, Vicat softening temperature 121 ° C, refractive index 1.50
The yellowing degree was 0.

Reference Example 4 The raw material composition was 12.5 parts of N-phenylmaleimide, 31.5 parts of methyl methacrylate, 6.0 parts of styrene, 50.0 parts of toluene, and 0.1 part of t-butylperoxyisopropyl carbonate. The same operation as above was performed except that the weight average molecular weight was changed to 2 parts.
23,000, methyl methacrylate unit 62.0%, N-phenylmaleimide unit 25.3%, styrene unit
7% of a maleimide-based copolymer (C-1) was obtained. The glass transition temperature of the copolymer (C-1) was 144 ° C., the Vicat softening temperature was 141 ° C., and the refractive index was 1.534.

Reference Example 5 The raw material composition was 55.6 styrene.
Parts, N-phenylmaleimide 11.4 parts, toluene 3
3.0 parts On the other hand, the same operation as above was carried out except that the amount was changed to 0.06 parts of t-butyl peroxyisopropyl carbonate, and the weight average molecular weight was 160,000, N-phenylmaleimide unit was 39.5%, and styrene unit was 51.6. %, Acrylonitrile unit 8.9% maleimide copolymer (C-2)
I got The glass transition temperature of the copolymer (C-2) is 1
67 ° C, Vicat softening temperature 163 ° C, refractive index 1.5
88.

The transparent rubber-modified thermoplastic resin (A-1) has a butadiene content of 20%, a methyl methacrylate content of 56%, a styrene content of 20%, an acrylonitrile content of 4% and a matrix weight average molecular weight of 13%. The rubber-modified thermoplastic resin (A-2) contains butadiene content of 26%, styrene content of 55%, acrylonitrile content of 19%, and a weight average molecular weight of the matrix of 1%.
As the AS resin (C-3) used as a thermoplastic resin, a styrene content of 77%, an acrylonitrile content of 23%, and a weight average molecular weight of 100,000 were used.
used.

The glass transition temperature of the matrix portion (A-1) was 107 ° C., the refractive index was 1.520, the refractive index of the rubber portion was 1.517, and the total light transmittance of the molded product was 87%. The glass transition temperature of the matrix portion of (A-2) is 1
05 ° C, the refractive index is 1.574, the refractive index of the rubber part is 1.5
14. The total light transmittance of the molded product was 23%. (C
The glass transition temperature of -3) is 105 ° C and the refractive index is 1.57.
It was 5. Further, as (B-4), the glass transition temperature is 145 ° C, the Vicat softening temperature is 141 ° C, and the refractive index is 1.
585 polycarbonate resin was used.

Glass transition temperature (Tg) The glass transition temperature of the above copolymer was determined by using a differential scanning calorimeter (trade name: DSC-8230, manufactured by Rigaku Corporation) in a nitrogen gas atmosphere under an atmosphere of α-alumina. (Differential Scanning Colorimetr) measured from normal temperature to 220 ° C at a rate of 10 ° C / min using
y) It was calculated from the curve by the midpoint method.

Weight average molecular weight (Mw) The weight average molecular weight of the above copolymer was determined by GPC (Gel Permea
The calculated weight average molecular weight was calculated by standard styrene for molecular weight measurement using the Chromatography.

Refractive index The refractive index of the copolymer was measured using an Abbe refractometer (2T, manufactured by Atago Co., Ltd.).

Optical Properties The total light transmittance of the test piece was measured according to ASTM D1003, and the yellowing degree (YI) of the test piece was measured by JI.
It was measured according to SK7103.

The content (% by weight) of the maleimide monomer (A) in the thermoplastic resin composition as a monomer unit
And content of maleimide monomer (B) component Measurement of nitrogen content N (% by weight) of thermoplastic resin composition by elemental analysis and infrared absorption spectrum (IR)
It was measured based on the measurement.

Vicat Softening Point (VST) The Vicat softening point of the above copolymer is determined according to ASTM D152.
According to No. 5, the measurement was performed under the condition of a load of 1 kg.

Impact resistance The impact resistance was measured according to JIS K7110, with a notch 1
Izod impact strength (Iz)
od).

Example 1 (A-1) 80 parts, Reference Example 1
After mixing 16 parts by weight of the maleimide copolymer (B-1) and 4 parts by weight of the AS resin (C-3) obtained by the above with an omni mixer, a 30 mmφ twin screw extruder controlled at a cylinder temperature of 240 ° C. To obtain a thermoplastic resin composition of Example 1. The glass transition temperature of the matrix portion of this thermoplastic resin composition is compatible with 110 ° C.

This thermoplastic resin composition was molded using an injection molding machine controlled at a cylinder temperature of 240 ° C. and a mold temperature of 60 ° C., and a test piece (50) for measuring light transmittance was obtained.
× 50 × 3 mm) and various test pieces for measuring physical properties. Each physical property of this test piece was measured by each of the above evaluation methods. The results are shown in Table 1. Also,
The refractive index of the matrix was calculated from the refractive index and the compounding ratio of each resin, and the results are shown in Table 1. Embodiments 2 to 7 Next, other embodiments of the present invention will be described as Embodiments 2 to 7 as follows. In each of Examples 2 to 7, each thermoplastic resin composition of each of Examples 2 to 7 was prepared in the same manner as in Example 1 at the compounding amounts shown in Table 2. Each physical property value of each of the above thermoplastic resin compositions was measured in the same manner as in Example 1, and the results are shown in Table 1.

Next, comparative examples for illustrating the features of the present invention will be described as comparative examples 1 and 2, respectively.

Comparative Examples 1 to 4 In Comparative Examples 1 to 4,
The thermoplastic resin compositions of Comparative Examples 1 to 3 were prepared in the same manner as in Example 1 with the blending amounts described in the above section, respectively. Each physical property value of each of the above thermoplastic resin compositions was measured in the same manner as in Example 1, and the results are shown in Table 1. In addition,
In Comparative Composition 1 and Comparative Composition 4, the difference in the refractive index between the matrix part and the rubber part was larger than 0.01, indicating that the transparency was significantly poor. In Comparative Composition 2, the compatibility between the resins in the matrix portion was poor, two points of Tg were observed, and the transparency was significantly reduced due to incompatibility. In Comparative Composition 3, only a composition having low heat resistance was obtained, although some transparency was maintained.

Table 1 summarizes the polymers used in the above Examples and Comparative Examples, their compositions, and various physical property data. (A-1) and (A-2) in the table are rubber-modified thermoplastic resins, (B-1) to (B-4) are thermoplastic resins having a Vicat softening point of 120 ° C. or more, and (C) -1) to (C-
Up to 2) represents other thermoplastic resins.

[0070]

[Table 1]

[0071]

As described above, the thermoplastic resin composition having excellent heat resistance according to the present invention comprises (A) a rubber-modified styrene resin, (B) a heat-resistant resin having a Vicat softening point of 120 ° C. or more, (C) Other thermoplastic resins, mainly consisting of
(A) rubber part, (A) matrix part, (B),
The refractive index of (C) is _defined as n _DA1 , n _DA2 , n _DB , and n _DC, and the respective weight ratios in the resin composition are w _A1 , w _A2 , w
_B, when formed into a w _C% by weight, satisfying the following calculation equation of (I), and a matrix portion (A) (B), that the mixture is thermodynamically compatible consisting (C) and It is a characteristic thermoplastic resin with excellent heat resistance. More preferably, the total light transmittance of a 3 mm-thick flat molded product of the thermoplastic resin composition is 75% or more.

(I) | n _DA1 −n _Dm | ≦ 0.01 where n _Dm = (w _A2 × n _DA2 + w _B × n _DB + w _C ×
n _DC ) / (w _A2 + w _B + w _C ) Therefore, by adopting the above configuration, it is possible to obtain a thermoplastic resin having both heat resistance and transparency, and also having an excellent balance of various physical properties such as strength. Can be. Since the refractive index is adjusted by using a three-component system, it is simple and the refractive index can be easily adjusted. A composition having transparency and excellent in various physical properties such as heat resistance, strength, and moldability can be easily obtained.

Continued on the front page F term (reference) 4J002 BC051 BC063 BG052 BG122 BG123 BH022 BN141 BN161 4J026 AA17 AA49 AA68 AC10 AC11 AC12 AC32 AC36 BA05 BA27 BA31 BB01 BB02 BB10 GA01 GA09

Claims (6)

[Claims] (A) a rubber-modified thermoplastic resin, (B) a heat-resistant thermoplastic resin having a Vicat softening point of 120 ° C. or more, (C)
The resin is mainly composed of other thermoplastic resin, and the refractive index of the rubber part of (A), the matrix part of (A), (B) and (C) is n _DA1 , n _DA2 , n _DB and n _DC , respectively. The weight ratio of each of the components in the composition is represented by w _A1 , w _A2 , w _B , w _C % by weight.
In the heat resistance, the following formula (I) is satisfied, and a mixture of the matrix portion of (A) and (B) and (C) is thermodynamically compatible. Excellent thermoplastic resin composition. (I) | n _DA1 −n _Dm | ≦ 0.01 where n _Dm = (w _A2 × n _DA2 + w _B × n _DB + w _C ×
n _DC ) / (w _A2 + w _B + w _C ) 2. The resin (A) has a difference in refractive index n _DA1 of a rubber part and a refractive index n _DA2 of a matrix part of the resin (A) of _0.1 .
The thermoplastic resin composition having excellent heat resistance according to claim 1, wherein the thermoplastic resin composition is a rubber-modified thermoplastic resin having a particle size of 01 or less. 3. A molded article formed of a thermoplastic composition mainly comprising (A), (B) and (C) having a thickness of 3 mm and having a total light transmittance of 75% or more. The thermoplastic resin composition having excellent heat resistance according to claim 1 or 2, wherein: 4. The thermoplastic resin composition mainly comprising (A), (B) and (C), wherein the glass transition temperature is 110 ° C. or higher. The thermoplastic resin composition according to claim 1 or 2. 5. The resin according to claim 1, wherein said resin (B) is a heat-resistant resin containing at least a maleimide monomer unit and a methacrylate ester monomer unit. Item 10. The thermoplastic resin composition according to Item 1. 6. The thermosetting resin according to claim 1, wherein the resin (C) is a thermoplastic resin containing an aromatic vinyl monomer unit and an unsaturated nitrile monomer unit. Plastic resin composition.