JP2001294722A - Transparent, heat-resistant, thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having excellent transparency with reflex index and compatibility adjusted to each other by regulating the constitution and blending ratio for each resin for use, and excellent balance of heat resistance, impact resistance and moldability. SOLUTION: This thermoplastic resin composition comprises (A) a rubber- modified thermoplastic resin, (B) a heat-resistant thermoplastic resin comprising 98-50 wt.% of a methacrylic ester monomer unit, 1-20 wt.% of an aryl maleimide monomer unit, 1-30 wt.% of an alkyl maleimide monomer unit and 0-15 wt.% of a copolymerizable monomer unit, and having a Vicat softening point of >=120 deg.C, and (C) another thermoplastic resin that is to be added optionally, wherein the matrix part of (A) is thermodynamically compatible with the mixture of (B) and (C). The composition is excellent in appearance and heat resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber-modified thermoplastic resin, a maleimide copolymer containing two kinds of maleimide monomer units, and other thermoplastic resins added as necessary. By adjusting the composition and blending of each resin, the composition is made up of, and the refractive index and compatibility are adjusted, and the transparency is excellent, and the heat resistance, impact resistance, and the moldability are excellent in thermoplasticity. The present invention relates to a resin composition. 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] However, the thermoplastic resin compositions described in JP-A-61-91239 and JP-A-61-179252 do not have physical properties excellent in balance of heat resistance, mechanical strength, flowability and the like. However, 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 copolymerization composition of each resin is set so as to bring the refractive index closer to the refractive index of the rubber-grafted portion of the rubber-modified graft polymer by using the coalesced polymer, the content of the maleimide monomer unit is increased. However, there is a problem that heat resistance is lowered due to the inability to carry out or copolymerization of a large amount of aromatic vinyl.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a rubber-modified thermoplastic resin, a maleimide-based copolymer containing two types of maleimide-type monomer units, A composition comprising a thermoplastic resin other than the above, which provides a thermoplastic resin composition having an excellent transparency in which the refractive index and compatibility are adjusted, and further having excellent balance of heat resistance, impact resistance, and moldability. That is the task. In order to solve the problem, a method of adjusting the refractive index and the compatibility of the composition specifically is proposed.

[0007]

Means for Solving the Problems The thermoplastic resin composition of the present invention proposes the following constitution in order to solve the above problems.

It has (A) a rubber-modified thermoplastic resin and (B) a methacrylate monomer unit, an arylmaleimide monomer unit and an alkylmaleimide monomer unit as essential structural units, and has a glass transition temperature of 120 ° C. or higher. The total light transmittance of a molded article obtained by molding a flat plate having a thickness of 3 mm using the thermoplastic resin composition is 75% or more. This is a thermoplastic resin composition characterized by the following. Uses a heat-resistant resin that is a specific maleimide-based copolymer, so it has very good compatibility with the matrix resin part of the rubber-modified thermoplastic resin, and can be obtained by molding as described above even when blended. The total light transmittance of the molded article thus obtained is high, and the molded article has good transparency. In addition, heat resistance can be imparted to the resin composition, and a molded article having high heat resistance can be obtained. Further, since a heat-resistant thermoplastic resin which is a specific maleimide-based copolymer is used, the refractive index can be easily adjusted. In another embodiment of the thermoplastic resin composition of the present invention, (A) a rubber-modified thermoplastic resin and (B)
A thermoplastic resin composition comprising a heat-resistant thermoplastic resin having a glass transition temperature of at least 120 ° C. having a methacrylate monomer unit, an arylmaleimide monomer unit and an alkylmaleimide monomer unit as essential structural units. The glass transition temperature of the thermoplastic resin composition is one observed in a measurement temperature range of 30 ° C. or more, and the thermoplastic resin composition is a thermoplastic resin composition. This is an important physical property indicating that the matrix resin components other than the rubber component of the thermoplastic resin composition of the present invention are in a compatible state. The heat-resistant thermoplastic resin which is a specific maleimide-based copolymer of the present invention, even when blended with a rubber-modified thermoplastic resin, has a compatibility as shown by thermodynamic analysis data as defined above. You can see that it is doing. By being compatible,
The molded article of the obtained resin composition has good transparency and good mechanical strength, specifically, improved impact strength.

More preferably, the above component (B)
A heat-resistant thermoplastic resin which is a maleimide-based copolymer contains 98 to 50% by weight of a methacrylate ester monomer unit, 1 to 20% by weight of an arylmaleimide monomer unit, and 1 to 30% by weight of an alkylmaleimide monomer unit. And a monomer unit copolymerizable with a monomer in an amount of 0 to 15% by weight. Specifically, it is a copolymer obtained by polymerization using a monomer component containing each monomer.

[0010] Further, the thermoplastic resin composition of the present invention comprises:
(A) a rubber-modified thermoplastic resin and (B) a heat-resistant heat having a glass transition temperature of 120 ° C. or more having a methacrylic acid ester monomer unit, an arylmaleimide monomer unit and an alkylmaleimide monomer unit as essential structural units. A thermoplastic resin composition comprising a thermoplastic resin, wherein the rubber portion of (A), the matrix portion of (A), and the refractive index of (B) are n _DA1 , n _DA2 , and n _DB , respectively. when the respective weight ratio of the resin composition was w _A1, w _A2 and w _B, a thermoplastic resin composition characterized by satisfying the following calculation equation (I). In this case, the essential resin is a two-component thermoplastic resin composition. (I) | n _DA1 −n _{D m} | ≦ 0.01 where n _{D m} = (w _A2 × n _DA2 + w _B × n _DB ) / (w _A2
+ W _B ) Further, in the embodiment of the present invention, a production method in which the respective components are blended according to the above calculation formula to obtain the thermoplastic resin composition of the present invention is one of the preferred embodiments. The thermoplastic resin composition further contains the rubber-modified thermoplastic resin (A), the heat-resistant thermoplastic resin (B), and another thermoplastic resin (C), and the rubber portion of (A), (A) ), And the refractive indices of (B) and (C) are n
_DA1, n and _DA2, n _DB and n _DC, when the respective weight ratio of the thermoplastic resin composition was w _A1, w _A2, w _B, and w _C, that satisfies the following calculation equation (II) is Characteristic thermoplastic resin composition. In this case, the essential resin is a three-component thermoplastic resin composition. (II) | n _DA1 −n _{D m} | ≦ 0.01 where n _{D m} = (w _A2 × n _DA2 + w _B × n _DB + w _C ×
n _DC ) / (w _A2 + w _B + w _C ) Similarly, in the thermoplastic resin composition of the present invention,
Even if the composition contains the component (C), a method for producing the thermoplastic resin composition of the present invention by blending the components according to the above formula is one of the preferred embodiments. In summary, the thermoplastic resin of the present invention contains a specific heat-resistant thermoplastic resin, so that even if other thermoplastic resins are contained, it is easy to maintain a compatible state, and the molded product has good transparency. have. Further, since it is preferably in a compatible state, it is possible to obtain a molded article having excellent mechanical strength, for example, impact strength.

More preferably, the thermoplastic resin composition of the present invention is a thermoplastic resin composition having excellent heat resistance and having a total light transmittance of 75% or more of a flat molded product having a thickness of 3 mm. The above conditional expressions (I) and (II) mean that the difference in the refractive index between the rubber portion and the matrix portion in the final composition falls within 0.01. More preferably, the rubber-modified thermoplastic resin (A) has a refractive index n _DA1 of a rubber portion of the resin (A),
It is preferable to use a rubber-modified thermoplastic resin in which the difference in the refractive index n _DA2 of the matrix portion is within 0.01 and n _DA1 is in the range of 1.51 to 1.53.

In the present invention, the state in which the heat-resistant thermoplastic resin composition comprising the components (A), (B) and (C) is thermodynamically compatible includes (A), (B) The glass transition temperature of the matrix portion of the heat-resistant thermoplastic resin composition comprising the components (A) and (C) is observed at one point on the chart. More specifically, the glass transition temperature observed in a temperature range of 30 ° C. or more is one point. Although it is the above-mentioned temperature range, more preferably, it is 40
℃ or more, more preferably 50 ℃
This is the above temperature range. Most preferably, it is a temperature range of 60 ° C. or higher. The component (C) is another thermoplastic resin blended as required.

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 total light transmittance of the rubber-modified thermoplastic resin (A) is 75% or more, a thermoplastic resin composition having more excellent transparency can be obtained. More preferably, 8
0% or more. It is more preferably at least 85%. 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. The temperature is more preferably 115 ° C. or higher, further preferably 120 ° C. or higher.

By using the maleimide-based heat-resistant resin (B) having the above structure, the heat resistance can be effectively improved.
Further, (A) as a transparent ABS resin in the rubber-modified thermoplastic resin, a generally used matrix resin, methyl methacrylate-styrene resin, completely compatible, the difference in the refractive index within 0.01 It can be adjusted. Further, as a method for specifically obtaining the transparent heat-resistant resin obtained in the present invention, according to the above formulas (I) and (II),
Adjusting and blending each component is a very effective technique.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described in detail below. The following is
The thermoplastic resin composition of the present invention will be described by way of example of a three-component system in which other thermoplastic resin (C) may be compounded, if necessary, but is limited to the three-component system. It is not something to be done.

The thermoplastic resin composition of the present invention comprises (A) a rubber-modified thermoplastic resin and (B) 98 to 50% by weight of a methacrylate ester monomer unit and 1 to 20% by weight of an arylmaleimide monomer unit. %, From 1 to 30% by weight of an alkylmaleimide monomer unit and from 0 to 15% by weight of a monomer unit derived from another monomer copolymerizable with the monomer. It contains a heat-resistant thermoplastic resin of ℃ or more and (C) other thermoplastic resins that are added as necessary. The rubber portion of (A), (A)
And the refractive indices of (B) and (C) are n _DA1 , n _DA2 , n _DB and n _DC , respectively, and the respective weight ratios in the thermoplastic resin composition are w _A1 , w _A2 , w _B and When w _C is satisfied, it is preferable that the following formula (II) is satisfied. More preferably, a thermoplastic resin composition excellent in appearance and heat resistance, characterized in that a mixture comprising the matrix portion (A) and (B) and (C) is thermodynamically compatible. It is. (II) | n _DA1 −n _{D m} | ≦ 0.01 where n _{D m} = (w _A2 × n _DA2 + w _B × n _DB + w _C ×
n _DC ) / (w _A2 + w _B + w _C ) That is, the thermoplastic resin composition of the present invention uses the resins (A), (B) and (C) defined above, and obtains the refractive index and the refractive index of each resin. This is a thermoplastic resin composition in which the difference between the refractive index of the matrix portion of the final composition determined from the weight ratio and the refractive index of the rubber portion of (A) is 0.01 or less. Further, in the embodiment of the present invention, a production method in which the respective components are blended according to the above calculation formula to obtain the thermoplastic resin composition of the present invention is one of the preferred embodiments. In the above formula (II), when w _C is 0, the formula is inevitable, and the formula is a formula for blending the above-described two-component thermoplastic resin composition of the present invention. (I).

More preferably, the thermoplastic resin composition of the present invention is a thermoplastic resin excellent in heat resistance such that a 3 mm-thick flat molded product obtained by molding has a total light transmittance of 75% or more. A composition. In the thermoplastic resin composition having excellent heat resistance of the present invention, more preferably, the total light transmittance of the molded article of the thermoplastic resin composition containing (A) and (B) is 75% or more, preferably 80%. And more preferably 8
5% or more. It is more preferably at least 88%.
The component (C) is a component that can be added as needed. Therefore, also in the thermoplastic resin composition containing (A), (B) and (C), the total light transmittance of a more preferable molded product is 75% or more, preferably 80% or more, and further preferably 85% or more. It is. More preferably 88
% 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-polybutadiene rubber such as butadiene rubber, ethylene-propylene copolymer rubber, or
Like an ethylene-propylene-non-conjugated diene copolymer rubber, a phase in which an ethylene-α-olefin rubbery polymer or the like is dispersed, a polybutadiene or an ethylene-propylene-non-conjugated diene copolymer rubber may be used. It is preferable from the viewpoint of economy and a resin composition having high impact resistance.
When an ethylene-α-olefin rubbery polymer is used, a resin composition having excellent weather resistance can be obtained.

Examples of the matrix portion include a synthetic resin comprising a continuous phase of a resin of a monomer unit such as aromatic vinyl represented by styrene, methacrylic acid ester and unsaturated nitrile. Among them, one kind or a combination of two or more kinds can be used. Specifically, as a rubber-modified thermoplastic resin, a rubber-modified styrene-based resin in which a matrix portion contains a methacrylate ester monomer unit represented by methyl methacrylate and an aromatic vinyl monomer unit represented by styrene Resins are preferred.

The preferred composition of the matrix portion is 95 to 50% by weight of a methacrylate ester monomer unit, 5 to 50% by weight of an aromatic vinyl monomer unit, and 0 to 20% by weight of a vinyl cyanide monomer unit. %, More preferably 90 to 60% by weight of a methacrylic acid ester monomer unit, 10 to 40% by weight of an aromatic vinyl monomer unit, and 0 to 15% by weight of a vinyl cyanide monomer unit. Specifically, the rubber-modified thermoplastic resin as the component (A) in the present invention is prepared by using a monomer of the unit shown above as a monomer component, for example, using a known production method shown below. And by polymerizing the monomer component. Of course, it is not limited to this manufacturing method.
Any resin modified with a rubber component and exhibiting thermoplasticity can be preferably used as the resin of the component (A) of the present invention.

The rubber-modified thermoplastic resin can be produced by, for example, a graft polymerization, a blending method, or a graft polymerization-blend method. A rubber-modified thermoplastic resin in which a part of a matrix part is grafted on a rubber part is used. By using this, a thermoplastic resin composition having excellent impact resistance can be obtained. 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 above (A) and (B) used in the present invention and
The resin component (C) is not particularly limited as long as it is in a thermodynamically compatible state when mixed, and has a refractive index satisfying the above-defined general formula (I). do not do.

In the present invention, as the heat-resistant thermoplastic resin of the maleimide copolymer (B), the total amount of the resin (B) is 100% by weight, and the methacrylic acid ester monomer units 98 to 98% are used. 50% by weight, 1 to 20% by weight of an arylmaleimide monomer unit, 1 to 30% by weight of an alkylmaleimide monomer unit, and 0 to 15 other monomer units copolymerizable with these monomers. It is not particularly limited as long as it is a heat-resistant thermoplastic resin of a maleimide copolymer having a glass transition temperature of 120% or more by weight. More preferably, the composition range of (B) is 5 to 17% by weight of an arylmaleimide monomer unit and 5 to 2% by weight of an alkylmaleimide monomer unit.
0% by weight, methacrylate monomer unit 90 to 63
%, And preferably from 0 to 12% by weight of other monomer units copolymerizable with these monomers.

In the present invention, the glass transition temperature of the maleimide copolymer of the resin as the component (B) is more preferably 125 ° C. or higher, and more preferably 1 ° C. or higher.
30 ° C. or higher. More preferably, the temperature is 135 ° C. or higher. Most preferably, it is 140 ° C. or higher.

The resin of the component (B) in the present invention is more preferably (B) a methacrylate monomer 98 to 5
0% by weight, 1 to 20% by weight of an arylmaleimide monomer, 1 to 30% by weight of an alkylmaleimide monomer,
Other monomers 0 to 15 copolymerizable with these monomers
It is preferably a resin obtained by polymerizing a monomer component consisting of wt%. More preferably, 5 to 17% by weight of an arylmaleimide monomer unit, 5 to 20% by weight of an alkylmaleimide monomer unit, 90 to 63% by weight of a methacrylate ester monomer unit, and copolymerization with these monomers It is a resin obtained by polymerizing a monomer component comprising 0 to 12% by weight of other possible monomer units.

The method for polymerizing the monomer component is not particularly limited, and for example, solution polymerization, emulsion polymerization, bulk polymerization, and the like can be employed. If necessary, after the various polymerization steps, the resulting polymer can be devolatilized, washed with water, dried, and the like.

If the content of the arylmaleimide monomer unit is more than 20% by weight, the compatibility with the rubber-modified thermoplastic resin (A) may be deteriorated and the coloring may be undesirably increased.

If the maleimide monomer unit (the total amount of arylmaleimide and alkylmaleimide) is less than 15% by weight, the effect of improving heat resistance is low, and the heat resistance of the finally obtained thermoplastic resin composition is low. It may be low, which is not preferable.

When the copolymerizable other component particularly contains an aromatic vinyl monomer unit, the content is preferably less than 12% by weight. When the content is more than 12% by weight, there is a problem that the heat resistance is lowered and the refractive index becomes too high, so that it becomes difficult to contain a large amount of maleimide monomer units. As (C) used when necessary for adjusting the refractive index, when blended with the matrix portion of (A) and (B), a thermodynamically compatible formula for adjusting the refractive index defined in the present invention by being compatible with thermodynamically. There is no particular limitation as long as it falls within the range of the general formula (I). For example, an aromatic vinyl monomer unit is 60 to 85% by weight, and an unsaturated nitrile monomer unit is 15 to 40% by weight. A which is a thermoplastic resin (2) containing 0 to 20% by weight of other monomer units copolymerizable with
S resin, α-methylstyrene-acrylonitrile copolymer, maleimide-styrene copolymer, maleimide-
Styrene-acrylonitrile copolymer and the like can be mentioned.

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 is increased 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.

When a rubber-modified thermoplastic 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. Further, the obtained thermoplastic resin composition having excellent heat resistance tends to be in a thermodynamically compatible state, and can have excellent transparency. More preferably, a rubber-modified thermoplastic transparent resin having a total light transmittance of 85% or more of the rubber-modified thermoplastic resin (A) is used. Obtained in this case,
The total light transmittance of the thermoplastic resin composition of the present invention containing (A) and (B) is preferably 75% or more, preferably 80% or more, and more preferably 85% or more. It is more preferably at least 88%.

The component (C) is a component that can be added as needed. Therefore, in the thermoplastic resin composition of the present invention obtained by using a rubber-modified thermoplastic transparent resin having a total light transmittance of 85% or more as the component (A), (A), (B) and (C) The total light transmittance of the thermoplastic resin composition of the present invention containing at least 75% is preferably at least 75%, preferably at least 80%, more preferably at least 85%. It is more preferably at least 88%.

In the present invention, the thermoplastic resin composition mainly containing (A) and (B) is used, but the meaning of mainly or the main component means that the thermoplastic resin composition of the present invention has a transparent property. If there is no adverse effect on the properties and heat resistance, other resins and additives may be blended as long as they are in predetermined amounts. Although the amount is not particularly limited, for example, the total amount of the resin components (A) and (B) of the present invention is 100% by weight, and other components may be contained in an amount of 0 to 20% by weight. it can. More preferably, it is 0 to 15% by weight. More preferably, it is 0-10% by weight,
Most preferably, it is 0-5% by weight. If the amount of the other components is more than the above range, the transparency may be remarkably lowered or the heat resistance may not be satisfied. In addition, the compatibility may decrease, and the impact strength may decrease. Also,
As described above, the component (C) in the present invention is a component that can be added as needed.

Therefore, in the present invention, the thermoplastic resin composition mainly containing (A), (B) and (C) is used. If the transparency and heat resistance of the plastic resin composition are not affected, other resins and additives may be blended as long as they are in predetermined amounts. Although the amount is not particularly limited, for example, in this case, the sum of the resin components (A), (B) and (C) of the present invention is 1
As 00% by weight, other components can be present up to 0-20% by weight. More preferably, 0-15% by weight
It is. More preferably, it is 0-10% by weight, most preferably 0-5% by weight. If the amount of the other components is more than the above range, the transparency may be remarkably lowered or the heat resistance may not be satisfied. In addition, the compatibility may decrease, and the impact strength may decrease.

Further, the refractive index n _DA1 of the rubber portion of the resin (A),
By using a rubber-modified thermoplastic resin in which the difference in the refractive index n _DA2 of the matrix portion is within 0.01 and n _DA1 is in the range of 1.51 to 1.53, a thermoplastic resin having excellent transparency can be obtained. Easy and preferred. Specifically, a transparent poly (methyl methacrylate / styrene / butadiene) resin is preferable.

Further, the thermoplastic resin composition of the present invention is blended so that the rubber component portion and the matrix resin portion are preferably compatible in order to maintain transparency.
The resulting thermoplastic resin composition has excellent impact strength, which is an example of mechanical strength. In this case, the notched Izod impact strength measured according to JIS-K7110 is preferably 5 kg · cm / cm or more, and more preferably 8 kg / cm / cm or more.
kg · cm / cm or more. More preferably 10k
g · cm / cm or more.

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

In the present invention, it was confirmed that the resin (A) and the mixture of (B) and (C) were in a thermodynamically compatible state by checking the glass transition point ( T
It can be confirmed by measuring g). Specifically, in each of the resin mixtures, the temperature was increased from normal temperature to 220 ° C. by a measuring differential scanning calorimeter at a rate of 10 ° C.
/ Glass transition point measured under the condition of
In a temperature range of 0 ° C. or higher, the glass transition temperature is 1
Observation at points confirms that they are thermodynamically compatible with each other. More preferably, only one point of the glass transition temperature is observed in the temperature range of 30 ° C. or higher.

The compatibility of the film or the molded article formed from the mixture can be determined by visually discriminating that the film or the molded article has transparency, or by measuring optical properties such as total light transmittance by a predetermined method. It can be confirmed that the composition used preferably has transparency.

In the present invention, by adopting a method in which a specific rubber resin component and a specific polymer component which can be employed are blended so that the refractive index of each rubber portion and the matrix conforms to a certain formula. It is possible to obtain a composition which is transparent, has a Vicat softening temperature of a specific value or more and has heat resistance. More preferably, since the rubber portion and the matrix portion are in a well-mixed state, a resin composition having excellent mechanical properties such as impact strength can be obtained.

The weight average molecular weight of the maleimide copolymer (B) is preferably in the range of 50,000 to 300,000. If the weight average molecular weight exceeds the above range, molding processability may be deteriorated,
When the ratio is below the above range, disadvantages such as deterioration of heat resistance and mechanical properties are caused.

The Vicat softening point of the molded product showing the heat resistance of the maleimide copolymer is preferably 120 ° C. or higher, more preferably 125 ° C. or higher. 1
If the temperature is 20 ° C. or less, it is difficult to impart sufficient heat resistance to the thermoplastic resin composition after blending. It is desirable that the yellowing degree of the molded article made of the maleimide-based copolymer be 10 or less, more preferably 5 or less.

Such a maleimide-based copolymer is obtained by polymerization by an arbitrary polymerization method, and the content of the maleimide monomer in a monomer unit is reduced to the total amount of each monomer component. On the other hand, when the amount exceeds 5% by weight, when a suspension polymerization method is used as the polymerization method, for example, the residual amount of the maleimide monomer in the maleimide-based copolymer may increase, and the obtained maleimide The system copolymer may be colored and the transparency may be reduced.

When the emulsion polymerization method is used, an emulsifier or the like remains, 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 polymerization method, the residual amount of the maleimide monomer can be reduced and the above problem can be avoided. Therefore, as a method for producing a copolymer having a yellowing degree of 10 or less, a solution It is desirable to use a polymerization method.

As the organic solvent used in such a solution polymerization method, generally used organic solvents such as 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-based copolymer from the reaction solution after the polymerization. For example, by devolatilizing with a vented twin-screw extruder, the remaining maleimide monomers can be effectively reduced together with the reaction solution, and the above-mentioned maleimide copolymer having a small yellowing degree can be obtained. be able to. It is a preferred embodiment of the present invention to use a maleimide-based copolymer having a small amount of residual maleimide monomer.

In this 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. Means that it is uniquely set as 20% by weight of maleimide monomer and 10% by weight of other monomers.

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, if necessary, can be mixed with (A) together with (B) to enable fine adjustment of heat resistance and refractive index.
A thermoplastic resin composition having arbitrarily controlled heat resistance and transparency can be obtained. The mixing ratio (weight ratio) of (A) and (B) in each of the above thermoplastic resin compositions is 1% by weight or more of each thermoplastic resin. To the extent that other physical properties such as workability are not impaired, it is possible to freely change the mixing ratio and add,
In particular, in order to obtain a thermoplastic resin composition having excellent heat resistance, it is preferable to blend the final composition so that the glass transition point thereof is 110 ° C. or higher. In order to obtain a thermoplastic resin composition having excellent impact resistance, the rubber content in the final composition is preferably 5% or more, more preferably 10% or more.

In the present invention, the components (A), (B) and (C)
Specific preferred compounding ratios are (A) 20 to 99% by weight and (B) 1 to 100% by weight of the total amount of the components (A), (B) and (C).
80% by weight, (C) 0 to 30% by weight, more preferably (A) 50 to 95% by weight, (B) 5 to 50% by weight, (C) 0
-20% by weight. Still more preferably, the component (C) is from 0 to 10% by weight. More preferably, (C)
The components are 0-5% by weight.

More specifically, it is preferable to use a maleimide heat-resistant resin as the component (B). The component (B) contains 98 to 50% by weight of a methacrylic acid ester monomer and 1 to 2 of an arylmaleimide monomer.
0% by weight, 1 to 30% by weight of alkylmaleimide monomers
And, if necessary, it can be obtained by polymerization using a monomer component composed of other monomer weight% which can be copolymerized with these monomers. A more preferable range of the monomer component is 5 to 17% by weight of an arylmaleimide monomer, 5 to 20% by weight of an alkylmaleimide monomer, 90 to 63% by weight of a methacrylate monomer, and Other monomers are 0 to 12% by weight. Further, more preferably, it is a polymer obtained by polymerization using these monomer components, and is not particularly limited as long as it is a thermoplastic resin having a Vicat softening point of 120 ° C. or higher.

The methacrylic acid ester monomers include methacrylic acid esters having 1 to 18 carbon atoms in an alkyl group including a cyclohexyl group and a benzyl group, and include methyl methacrylate, ethyl methacrylate, and propyl methacrylate. Isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, methacrylic Examples thereof include benzyl acrylate, 2-phenoxyethyl methacrylate, and 3-phenylpropyl methacrylate. Among them, one or a mixture of two or more thereof can be used. Methyl methacrylic acid are preferred.

The above arylmaleimide monomers include N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide,
-Methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N-tribromophenylmaleimide and the like.

The above-mentioned alkylmaleimide monomers include N-methylmaleimide, N-ethylmaleimide,
-Propylmaleimide, N-isopropylmaleimide,
N-butylmaleimide, N-isobutylmaleimide, N
-Tert-butylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (2-hydroxyethyl) maleimide and the like.

As the maleimide-based heat-resistant thermoplastic resin of the present invention, one kind or two or more kinds are selected from the above-mentioned arylmaleimide monomers and alkylmaleimide monomers, respectively. It is preferable to use a mixture of two or more kinds as a monomer unit.

Specifically, as the maleimide-based monomer,
It is preferable to use two types of maleimide monomers, an arylmaleimide monomer and an alkylmaleimide monomer. By using these two types of maleimide-based monomers in combination and polymerizing them as a monomer component, they can be well compatible with the component (A) or the component (C) of the present invention (B). The components can be obtained. As a result, it is possible to obtain a resin composition that is preferable in terms of balance among heat resistance, compatibility, and refractive index. As a result, a resin composition having good transparency can be obtained.

N-phenylmaleimide is used as the arylmaleimide monomer unit, and N-cyclohexylmaleimide is used as the alkylmaleimide monomer unit in terms of the balance between heat resistance, compatibility and refractive index. Is most preferred.

Other copolymerizable monomers include aromatic vinyls; unsaturated nitriles; cyclohexyl group,
Acrylic esters having 1 to 18 carbon atoms in an alkyl group including a benzyl group; olefins; dienes; vinyl ethers; vinyl esters; vinyl fluorides; allyl esters of saturated fatty acid monocarboxylic acids such as allyl propionate. Or methacrylic esters; poly (meth) acrylates; polyarylates; glycidyl compounds; unsaturated carboxylic acids, and the like, and one or a mixture of two or more of these can be used.

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

However, when a large amount of the aromatic vinyl monomer is used, the refractive index of the maleimide-based copolymer (B) becomes high, and the content of the maleimide monomer unit may be set high. Since it becomes difficult to perform, heat resistance tends to be insufficient. It is not preferable to use such a maleimide-based copolymer having a high refractive index because it becomes difficult to satisfy the general formula (I) for obtaining the transparent resin composition of the present invention. Therefore, when copolymerizing an aromatic vinyl monomer as required, the content is preferably 15% by weight or less, more preferably 1% by weight or less.
It is at most 2% by weight, most preferably at most 10% by weight.

The unsaturated nitrile monomers include acrylonitrile, methacrylonitrile, ethacrylonitrile,
Phenylacrylonitrile and the like can be mentioned.

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 allylate 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.

The rubber-modified thermoplastic resin (A) of the present invention and the monomer unit (B) of the methacrylate ester 98 to 50
Vicat softening point of 1-20% by weight of an arylmaleimide monomer unit, 1-30% by weight of an alkylmaleimide monomer unit and 0-15% by weight of a copolymerizable monomer unit is 120 ° C. The above-mentioned heat-resistant resin, the thermoplastic resin composition having excellent heat resistance mainly comprising (C) other thermoplastic resins, as described above, together with excellent transparency,
It also has heat resistance.

By blending the specific heat-resistant thermoplastic resin (B) in a preferable composition, the glass transition temperature is sufficiently high,
In addition, a thermoplastic resin composition having 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, for example, the preferred glass transition temperature is 1
The temperature can be 10 ° 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 containing at least a methacrylate monomer, an arylmaleimide monomer, and an alkylmaleimide monomer is described. A maleimide copolymer obtained by copolymerizing a monomer component, preferably by solution polymerization, and (A) a rubber-modified thermoplastic resin, and (C) another thermoplastic resin to form a thermoplastic resin composition. The method of obtaining is preferred. According to the above method, even when the amount of the arylmaleimide monomer and the alkylmaleimide monomer used in the maleimide-based copolymer exceeds 15% by weight, the solution polymerization is used to obtain the above-mentioned maleimide-based monomer. It is preferable because the residual amount of the maleimide monomer in the copolymer can be reduced, and a decrease in optical properties due to the remaining maleimide monomer and a maleimide monomer that volatilizes during heat processing can be suppressed.

The order of mixing the components (A), (B), and (C) may be, for example, a method of mixing all of them at the same time, a method of mixing two kinds in advance, and then mixing the other one. And the like. Such mixing can be performed by a conventionally known method.

As a method of mixing all of them at the same time, using a single-screw or twin-screw melt extruder, (A)
(B), (C) and, if necessary, various additives described later can be added and melt-mixed. After mixing the two components in advance, as a method of mixing with the other component, after pre-mixing (B) and (C) using a single-screw or twin-screw extruder, It can be melt-mixed with (A) again using a single-screw or twin-screw melt 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 according to 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 components of the glass fiber and the like, the amount of the glass fiber and the length thereof can be adjusted so as not to hinder the effects of the present invention. For example, it is preferable to use a milled fiber or the like. Glass powder or the like can also be used. The amount of the filler and the type thereof can be similarly selected and used.

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

[0074]

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”. First, as a working reference example, a polymerization example of a maleimide-based copolymer used as the component B of the present invention and physical properties thereof will be described.

Reference Example 1 A unit composed of 7.5 parts of N-phenylmaleimide, 5.0 parts of N-cyclohexylmaleimide, 34.0 parts of methyl methacrylate, 3.5 parts of styrene, and 50.0 parts of toluene Using body components, and t
-Butyl peroxyisopropyl carbonate 0.05
After performing the solution polymerization using the reaction mixture, the obtained reaction solution is introduced into a twin-screw extruder to remove volatile components, and to obtain a weight average molecular weight of 23.
A maleimide copolymer (B-1) having 10,000, 68.3% of methyl methacrylate units, 15.2% of N-phenylmaleimide units, 9.5% of N-cyclohexylmaleimide units, and 7.0% of styrene units was obtained. Was. The copolymer (B-1)
Had a glass transition temperature of 144 ° C., a Vicat softening temperature of 141 ° C., a refractive index of 1.517 and a yellowing degree of 1.9.

Example 2 The starting material composition was 5.0 parts of N-phenylmaleimide and 1 part of N-cyclohexylmaleimide.
The same operation as above was performed except that the parts were changed to 0.0 part, 30.0 parts of methyl methacrylate, 5.0 parts of styrene, 50.0 parts of toluene, and 0.05 part of t-butylperoxyisopropyl carbonate. Weight average molecular weight 24
A maleimide copolymer (B-2) having 59.9% of methyl methacrylate units, 10.5% of N-phenylmaleimide units, 19.7% of N-cyclohexylmaleimide units, and 9.9% of styrene units was obtained. Was. The copolymer (B-
In 2), the glass transition temperature was 143 ° C, the Vicat softening temperature was 141 ° C, the refractive index was 1.518, and the yellowing degree was 2.2.

(Comparative Reference Example 3) The raw material composition was 12.5 parts of N-phenylmaleimide, 31.5 parts of methyl methacrylate.
Parts, styrene 6.0 parts, toluene 50.0 parts and t
-Butyl peroxyisopropyl carbonate 0.05
Parts by weight, the same operation as described above was carried out, except that the weight average molecular weight was 223,000, methyl methacrylate unit was 62.0%,
A maleimide copolymer (B-3) having 25.3% of N-phenylmaleimide units and 12.7% of styrene units was obtained.
The glass transition temperature of the copolymer (B-3) is 144 ° C.,
The Vicat softening temperature was 141 ° C., the refractive index was 1.534, and the degree of yellowing was 4.2.

(Comparative Reference Example 4) The raw material composition was 12.5 parts of N-cyclohexylmaleimide, and 2 parts of methyl methacrylate.
The same operation as above was carried out except that 8.5 parts, 9.0 parts of styrene, 50.0 parts of toluene and 0.05 part of t-butylperoxyisopropyl carbonate were used, and the weight average molecular weight was 185,000 and methacryl was obtained. Methyl acid unit 5
7.5%, N-cyclohexylmaleimide unit 26.0
%, A styrene unit of 16.5% of a maleimide copolymer (B-4). The glass transition temperature of the copolymer (B-4) was 127 ° C, the Vicat softening temperature was 123 ° C, the refractive index was 1.518, and the yellowing degree was 2.0.

The transparent rubber-modified thermoplastic resin (A-1) has a butadiene content of 20%, a methyl methacrylate content of 55%, a styrene content of 20%, an acrylonitrile content of 5% and a weight average molecular weight of 13 As a transparent rubber-modified thermoplastic resin (A-2), an ethylene-α-olefin rubbery polymer was used as E.
PDM rubber content 20%, methyl methacrylate content 5
5%, styrene content 20%, acrylonitrile content 5%, matrix having a weight average molecular weight of 150,000, rubber-modified thermoplastic resin (A-3) having butadiene content 26%, methyl methacrylate 73%, A matrix having a weight average molecular weight of 120,000 and a styrene content of 27%
AS resin (C) used as other thermoplastic resin has a styrene content of 81% and an acrylonitrile content of 1
A 9%, weight average molecular weight of 120,000 was used.

The measured value of the glass transition temperature of the matrix portion of (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%.
Met. The glass transition temperature of the matrix portion of (A-2) was 106 ° C., the refractive index was 1.520, the refractive index of the rubber portion was 1.518, and the total light transmittance of the molded product was 88%.
Similarly, the measured value of the glass transition temperature of the matrix portion of (A-3) is 100 ° C., the refractive index is 1.518, the refractive index of the rubber portion is 1.517, and the total light transmittance of the molded product is 89%. there were. Similarly, the glass transition temperature of (C-3) is 105
° C and the refractive index were 1.580. Further, as (B-5), the glass transition temperature is 145 ° C., and the Vicat softening temperature is 1
A polycarbonate resin having a refractive index of 41 ° C. and a refractive index of 1.585 was used.

Hereinafter, methods for measuring various physical properties in the present invention will be described.

Glass transition temperature (Tg) The glass transition temperatures of the above copolymers and the compositions of the following examples were measured using a differential scanning calorimeter (trade name, manufactured by Rigaku Corporation).
DSC-8230) and a temperature of 220 ° C. from room temperature using α-alumina as a reference under a nitrogen gas atmosphere.
DSC (Differenti) measured at a heating rate of 10 ° C./min.
al Scanning Calorimeter) from the curve.

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.).

Resin yellowing degree (YI) The resin was dissolved in chloroform to prepare a 15% by weight chloroform solution, and the resin was measured by a transmission method according to JIS-K-7103. 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 JI
Measured by SK7103.

Analysis of Thermoplastic Resin Structure In the present invention, the content (% by weight) of component (B) as a monomer structural unit derived from the arylmaleimide monomer (A) component in the thermoplastic resin structure and The content as a monomer structural unit derived from the alkylmaleimide-type monomer (B) component is determined based on the nitrogen content (% by weight) of a polymer obtained by polymerizing a predetermined monomer component. ) And ¹ H-NMR.

Vicat Softening Point (VST) The Vicat softening point of the above copolymer is determined according to ASTM D152.
5 was measured under the condition of a load of 1 kg. Impact Resistance The impact resistance was measured in accordance with JIS K7110 using the Izod impact strength (I
zod).

(Example 1) (A-1) 60 parts, Reference Example 1
After mixing 40 parts by weight of the maleimide copolymer (B-1) obtained in the above with an omni mixer, the mixture was melt-kneaded using a 30 mmφ twin-screw extruder in which the cylinder temperature was controlled at 240 ° C. A thermoplastic resin composition of Example 1 was obtained. The glass transition temperature of the matrix portion of the thermoplastic resin composition, that is, the glass transition temperature other than the rubber region is 1
At 23 ° C., the glass transition temperature was observed to be one point, indicating that they were compatible. As described in the text, the glass transition temperature outside the rubber region is specifically 30.
Indicates a temperature range of ℃ or more. This example showed that the rubber-modified thermoplastic resin and the specific maleimide copolymer of the present application easily became compatible.

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 light transmittance measurement) was formed.
× 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 6) Next, other embodiments of the present invention will be described below as Embodiments 2 to 6. In each of Examples 2 to 6, the thermoplastic resin composition of each of Examples 2 to 6 was prepared in the same manner as in Example 1 at the compounding amounts shown in Table 1. 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 showing the features of the present invention will be described as comparative examples 1 to 3, as follows.

(Comparative Examples 1 to 3)
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 3, the difference in the refractive index between the matrix portion and the rubber portion was greater than 0.01, indicating that the transparency was significantly poor.

Further, in the comparative composition 1, since the N-phenylmaleimide polymer is used as the component (B), the compatibility between the resins in the matrix portion is poor and the Tg is 2
Because of the point observation and incompatibility, the transparency and impact resistance are significantly reduced. Due to poor compatibility, the Izod impact strength is also low. Comparative composition 2
Although the transparency and impact resistance are somewhat maintained, the compatibility is good because the N-cyclohexylmaleimide polymer is used as the component (B),
Only compositions having low glass transition temperature and Vicat softening temperature and low heat resistance have been obtained.

The polymers used in the above Examples and Comparative Examples, their compositions, and various physical property data are summarized in Table 1. In the table, (A-1) to (A-3) are rubber-modified thermoplastic resins, (B-1) to (B-5) are thermoplastic resins having a Vicat softening point of 120 ° C. or more, and (C) ) Represents other thermoplastic resins.

Table 1 is shown below.

[0095]

[Table 1]

[0096]

The thermoplastic resin composition having excellent heat resistance according to the present invention comprises (A) a rubber-modified thermoplastic resin and (B) a methacrylate ester monomer unit of 98 to 5 as follows.
0% by weight, 1 to 20% by weight of arylmaleimide monomer units, 1 to 30% by weight of alkylmaleimide monomer units
And a glass transition temperature of from 0 to 15% by weight of a copolymerizable monomer unit, which is mainly composed of a heat-resistant thermoplastic resin having a temperature of 120 ° C. or more, and (C) other thermoplastic resins added as necessary. The rubber part of (A), the matrix part of (A), and the refractive indices of (B) and (C) are denoted by n _{D A1} and n _D , respectively.
_DA2, and n _DB and n _DC, when the respective weight ratio of the thermoplastic resin composition was _{w A 1, w A2, w} B , and w _C, satisfy the following calculation equation of (II), preferably, Further, it is a thermoplastic resin composition excellent in appearance and heat resistance, characterized in that a mixture comprising the matrix part (A) and (B) and (C) is thermodynamically compatible. This is a characteristic configuration. (II) | n _DA1 −n _{D m} | ≦ 0.01 where n _{D m} = (w _A2 × n _DA2 + w _B × n _DB + w _C ×
n _DC ) / (w _A2 + w _B + w _C ) In the above formula (II), when w _C is 0, the above formula (II)
Denotes the formula (I), which is a formula corresponding to the two-component thermoplastic resin composition of the present invention described above.
Further, in the embodiment of the present invention, a production method in which the respective components are blended according to the above calculation formula to obtain the thermoplastic resin composition of the present invention is one of the preferred embodiments. As the component (B), for example, by using a maleimide-based heat-resistant resin, it is possible to effectively improve heat resistance, and further to obtain a thermoplastic resin composition having excellent transparency and compatibility. it can. That is, the thermoplastic resin composition of the present invention comprises (A) a rubber-modified thermoplastic resin and (B) a methacrylate monomer unit, an arylmaleimide monomer unit and an alkylmaleimide monomer unit as essential structural units. A thermoplastic resin composition comprising a heat-resistant thermoplastic resin having a glass transition temperature of 120 ° C. or higher and (C) another thermoplastic resin added as needed, wherein the thermoplastic resin composition Is a thermoplastic resin composition characterized in that the molded article has a total light transmittance of 75% or more when a flat plate having a thickness of 3 mm is molded using the above. By molding this thermoplastic resin composition, a molded article having good transparency is obtained.

More specifically, (A) a rubber-modified thermoplastic resin and (B) a methacrylate monomer unit 9
8 to 50% by weight, arylmaleimides monomer unit 1 to 1
20% by weight, alkylmaleimides monomer unit 1 to 30
% By weight and a heat-resistant thermoplastic resin having a glass transition temperature of 120 ° C. or more, which is composed of 0 to 15% by weight of a copolymerizable monomer unit, and (C) other thermoplastic resins added as necessary. Wherein the glass transition temperature of the thermoplastic resin composition is one observed in a measurement temperature range of 30 ° C. or more. This state indicates a state where the matrix resin portion of the thermoplastic resin composition of the present invention is thermodynamically compatible. It becomes a thermoplastic resin composition for obtaining a molded article having stable mechanical strength such as impact strength.

Claims (5)

[Claims] A glass transition temperature of (A) a rubber-modified thermoplastic resin and (B) a methacrylate ester monomer unit, an arylmaleimide monomer unit and an alkylmaleimide monomer unit as essential structural units. A thermoplastic resin composition containing a heat-resistant thermoplastic resin having a total temperature of 75% or more when a flat plate having a thickness of 3 mm is molded using the thermoplastic resin composition. A thermoplastic resin composition, characterized in that: 2. The glass transition temperature of (A) a rubber-modified thermoplastic resin and (B) a methacrylate monomer unit, an arylmaleimide monomer unit and an alkylmaleimide monomer unit as essential structural units is 120 ° C. A thermoplastic resin composition containing the above heat-resistant thermoplastic resin, wherein one glass transition temperature of the thermoplastic resin composition is observed in a measurement temperature range of 30 ° C. or more. Plastic resin composition. 3. The heat-resistant thermoplastic resin contains 98 to 50% by weight of a methacrylate monomer unit, 1 to 20% by weight of an arylmaleimide monomer unit, 1 to 30% by weight of an alkylmaleimide monomer unit, and 3. The thermoplastic resin composition according to claim 1, comprising 0 to 15% by weight of other monomer units copolymerizable with these monomers. 4. A glass transition temperature having (A) a rubber-modified thermoplastic resin and (B) a methacrylic acid ester monomer unit, an arylmaleimide monomer unit and an alkylmaleimide monomer unit as essential structural units is 120 ° C. A thermoplastic resin composition comprising the above heat-resistant thermoplastic resin, wherein the refractive index of the rubber portion of (A), the matrix portion of (A), and the refractive index of (B) are n _DA1 , n _DA2 , and n _DB , respectively. ,age,
The weight ratio of each of the thermoplastic resin compositions to w _A1 , w _A2
And when a w _B, a thermoplastic resin composition characterized by satisfying the following calculation equation (I). (I) | n _DA1 −n _{D m} | ≦ 0.01 where n _{D m} = (w _A2 × n _DA2 + w _B × n _DB ) / (w _A2
+ W _B) 5. The thermoplastic resin composition further comprises the rubber-modified thermoplastic resin (A) and a heat-resistant thermoplastic resin.
(B) and other thermoplastic resins (C), wherein the rubber part of (A), the matrix part of (A), and the refractive indices of (B) and (C) are n _DA1 , n _DA2 , and n _DB , respectively. And n _DC, and the respective weight ratios in the thermoplastic resin composition are w _A1 , w _A2 ,
A thermoplastic resin composition which satisfies the following formula (II) when w _B and w _C are satisfied. (II) | n _DA1 −n _{D m} | ≦ 0.01 where n _{D m} = (w _A2 × n _DA2 + w _B × n _DB + w _C ×
n _DC ) / (w _A2 + w _B + w _C )