JP2001040228A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition which holds the original characteristics and simultaneously has excellent heat resistance, by compounding a polymer having lactone ring structures in the molecule and a thermoplastic resin except the polymer as thermoplastic resins. SOLUTION: This thermoplastic resin composition contains (A) a polymer having lactone ring structures in the molecule and (B) a thermoplastic resin (for example, polyethyelene) except the component A. The component A preferably has a glass transition temperature of >=100 deg.C, and is preferably obtained by the alcohol-removing reaction of a copolymer containing the units of a monomer of the formula (R1 and R2 are each H or an organic residue). The rate of the lactone ring structures in the component A is preferably >=10 wt.%. The composition contains the components A and B in a component A/B weight ratio of 10/90 to 60/40, and preferably has a haze of <=5%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel thermoplastic composition comprising a plurality of thermoplastic resins and having excellent heat resistance.

[0002]

2. Description of the Related Art Vinyl chloride resin and acrylonitrile-styrene resin have excellent transparency, excellent surface gloss, weather resistance, chemical resistance, mechanical strength, moldability, and the like.
Since the surface hardness is well balanced, it is widely used as a transparent molding material for automobiles, home electric appliances and the like. However, the glass transition temperature (T
Since g) is usually around 70 to 100 ° C., it is difficult to use it in a field where heat resistance is required, and various attempts have been made to improve the heat resistance of these resins.

Hitherto, as a method of improving the heat resistance of a vinyl chloride resin, a method of post-chlorination of a vinyl chloride resin has been known, and Japanese Patent Application Laid-Open Nos. Sho 61-162543 and 3-170542. In the official gazette, maleimide-
A method of blending a polymer having high heat resistance such as a methyl methacrylate-based copolymer or a maleimide-aromatic vinyl-based copolymer has been reported. On the other hand, as a method for improving the heat resistance of a styrene-acrylonitrile resin, Japanese Patent Application Laid-Open No. 57-98536 proposes a method of blending a maleimide-aromatic vinyl copolymer having high heat resistance.

[0004] However, the method of post-chlorinating the vinyl chloride resin has a problem that thermal decomposition is liable to occur and molding processability is impaired. Also,
In the polymer blending method of blending the above-mentioned various high heat-resistant polymers, the obtained resin composition is colored, thereby impairing the original transparency of the resin, or depending on the type of the resin, the phase with the high heat-resistant polymer. There is a problem that the solubility is low and the effect of improving heat resistance cannot be sufficiently obtained. In addition, since the high heat-resistant polymer generally has a tendency that a part of the monomer copolymerized as the heat-resistant component tends to remain, the above-mentioned various high-temperature polymers containing the heat-resistant component having a problem in safety to the human body. The heat-resistant polymer has a problem that its application to uses requiring safety such as food containers is limited.

By the way, as the high heat resistant polymer, Po
lym. Prepr. , 8,1,576 (1967)
Then, a 2- (hydroxymethyl) acrylic acid alkyl ester polymer or α-hydroxymethylstyrene / methyl methacrylate copolymer is heated under reduced pressure with an extruder to cause a dealcoholization reaction, so that the hydroxyl groups of the polymer are Japanese Patent Application Laid-Open No. 9-241323 discloses a method for forming a lactone ring by condensation of ester groups to obtain a heat-resistant resin. A polymer obtained by polymerizing α-hydroxymethyl acrylate is treated at 170 ° C. for 10 hours. A method of obtaining a polymer by lactonization has been reported. However, although the lactonized polymers obtained by these production methods are excellent in heat resistance, any other characteristics such as balance between moldability and mechanical strength could not be expected further. Moreover, as described above, when a high heat-resistant polymer is blended with another thermoplastic resin, heat resistance can be improved, but properties such as transparency and mechanical strength of the other thermoplastic resin are reduced. That is, it is generally recognized as an empirical rule, and it is quite expected that blending the lactonized polymer with another thermoplastic resin in order to impart optional properties in addition to heat resistance. Did not.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a thermoplastic resin which is excellent in heat resistance while maintaining its inherent properties, such as transparency, mechanical strength and moldability. It is to provide a thermoplastic resin composition.

[0007]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, it has been found that a polymer having a lactone ring structure in a molecule has excellent compatibility with other thermoplastic resins, and It has been found that the heat resistance can be improved without impairing the properties such as transparency and mechanical strength of the other thermoplastic resin, and the present invention has been completed.

That is, the thermoplastic resin composition according to the present invention comprises, as a thermoplastic resin, a polymer (A) having a lactone ring structure in a molecule and a thermoplastic resin (B) other than the polymer (A). And

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic resin composition of the present invention comprises:
The thermoplastic resin contains a polymer (A) having a lactone ring structure in the molecule and a thermoplastic resin (B) other than the polymer (A). In the present invention, for example, a resin having desired properties such as transparency and mechanical strength is selected as the thermoplastic resin (B), and the thermoplastic resin (B) is mixed with the polymer (A). The heat resistance can be further provided while maintaining the characteristics of (1).

In the present invention, the polymer (A) is not particularly limited as long as it has a lactone ring structure in the molecule. For example, the polymer (A) is formed by a dealcoholation reaction between a hydroxyl group and an ester group. It is preferable that it is performed. That is, the polymer (A) is obtained by, for example, using a polymer (a) having a hydroxyl group and an ester group in a molecular chain as a raw material and subjecting at least a part of the hydroxyl group and the ester group to condensation cyclization by a dealcoholization reaction. It can be obtained by generating a lactone ring. Less than,
The method for obtaining the polymer (A) in this manner will be described in detail.

The polymer (a) having a hydroxyl group and an ester group in the molecular chain is a polymer having a hydroxyl group and an ester group bonded to the main chain directly or via some atoms. In particular, when the hydroxyl group and the ester group are close to each other, a lactone ring is easily generated, which is preferable. The number of atoms interposed between the hydroxyl group and the ester group is more preferably 6 or less, and most preferably 4 or less. .

The polymer (a) is prepared by, for example, preparing a monomer having a hydroxyl group and an ester group or a mixture of a monomer having a hydroxyl group and a monomer having an ester group at least one of the starting monomers. It can be obtained by polymerizing as a part, or addition reaction of a hydroxyl group to a double bond portion of a copolymer of a diene compound such as butadiene or a polymer having an ester group such as a vinyl acetate copolymer. It can also be obtained by introducing a hydroxyl group or an ester group into the polymer later by a reaction such as hydrolysis or esterification of a polymer having a carboxyl group or an acid anhydride group.

The monomer used as the raw material of the polymer (a) is not particularly limited. At least a part of the raw material is a vinyl monomer having a hydroxyl group and an ester group in the molecule or a hydroxyl group in the molecule. It is preferably a mixture of a vinyl monomer having the compound and a vinyl monomer having an ester group in the molecule. Other than these, other vinyl monomers may coexist.

The vinyl monomer having a hydroxyl group and an ester group in the molecule is not particularly limited.
A monomer represented by the following general formula (1) is preferred. In the general formula (1), examples of the organic residue that is an example of R ₁ and R ₂ include a methyl group, an ethyl group, a propyl group, and a butyl group. As the monomer represented by the general formula (1), specifically, for example, 2- (hydroxymethyl)
Examples thereof include methyl acrylate, ethyl 2- (hydroxymethyl) acrylate, isopropyl 2- (hydroxymethyl) acrylate, normal butyl 2- (hydroxymethyl) acrylate, and tert-butyl 2- (hydroxymethyl) acrylate. . Among these, 2-
Methyl (hydroxymethyl) acrylate and ethyl 2- (hydroxymethyl) acrylate are preferred. These monomers may be used alone or in combination of two or more.

[0015]

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(In the formula, R ₁ and R ₂ are the same or different groups and represent a hydrogen atom or an organic residue.) Examples of the vinyl monomer having a hydroxyl group in the molecule include:
Although not particularly limited, the monomer represented by the general formula (1) or 2- (hydroxyalkyl) acryl such as α-hydroxymethylstyrene, α-hydroxyethylstyrene, methyl 2- (hydroxyethyl) acrylate, etc. Acid ester; 2- (hydroxymethyl) acrylic acid
(Hydroxyalkyl) acrylic acid; and these may be used alone or in combination of two or more.

The vinyl monomer having an ester group in the molecule is not particularly limited, but may be a monomer represented by the above general formula (1), methyl acrylate, ethyl acrylate or n-acrylate. Acrylates such as -butyl, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, and benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid methacrylates such as t-butyl, cyclohexyl methacrylate, and benzyl methacrylate; and the like, and these may be used alone or in combination of two or more.

The above vinyl monomer having a hydroxyl group and an ester group in the molecule, or a mixture of a vinyl monomer having a hydroxyl group in the molecule and a vinyl monomer having an ester group in the molecule is used in combination. The other vinyl monomer that may be used is not particularly limited, but a monomer represented by the following general formula (2) is particularly preferable. In the general formula (2), examples of the organic residue that is an example of R ₀ include a methyl group, an ethyl group,
Examples include a propyl group and a butyl group. Specific examples of the monomer represented by the general formula (2) include styrene, α-methylstyrene, acrylonitrile, methyl vinyl ketone, ethylene, propylene, and vinyl acetate. And α-methylstyrene are particularly preferable because a polymer (A) having high heat resistance can be easily obtained. These monomers may be used alone or in combination of two or more. The content of these monomers used in combination is preferably 30% by weight or less, more preferably 20% by weight or less, and particularly preferably 10% by weight or less.

[0019]

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(Wherein, R ₃ represents a hydrogen atom or a methyl group, X represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
Phenyl, -OAc group, a -CN group, -COR ₀ group. Here, R ₀ represents a hydrogen atom or an organic residue. In the present invention, a copolymer of alkyl 2- (hydroxymethyl) acrylate and methyl methacrylate represented by the general formula (1) is particularly preferable among the raw material monomers of the polymer (a) described above. Is preferred because the polymer (A) obtained by the dealcoholization reaction has extremely high heat resistance.

The ratio of the hydroxyl group and the ester group in the molecular chain in the polymer (a) is, for example, when 2- (hydroxyalkyl) acrylate is a raw material monomer.
The ratio of the 2- (hydroxyalkyl) acrylate monomer in the polymer (a) is preferably 5% or more, and more preferably 10%.
The above is more preferable, and 20% or more is further preferable. It is particularly preferably at least 30%, and most preferably at least 40%. In the case of a monomer having a hydroxyl group and an ester group separately or a repeating unit, the ratio of the monomer having a smaller equivalent amount in the hydroxyl group and the ester group or the repeating unit ratio is defined as the above ratio. If the proportion of the hydroxyl group and the ester group is small, the proportion of the lactone ring structure in the polymer (A) after the dealcoholation is reduced, and it is not preferable because sufficient heat resistance cannot be imparted to the obtained thermoplastic resin composition.

The polymerization method for obtaining the polymer (a) from the monomer is not particularly limited, but is excellent in hue,
Solution polymerization or bulk polymerization is preferred from the viewpoint that a volatile component is relatively small and a polymer excellent in heat resistance and moldability is easily obtained. The polymerization temperature and the polymerization time may be appropriately set according to various conditions such as the type of the raw material monomer. Also,
During the polymerization reaction, a conventionally known initiator may be added as necessary.

The polymer (A) is obtained, for example, by subjecting the polymer (a) having a hydroxyl group and an ester group in the molecular chain to a dealcoholization reaction. Here, the dealcoholation reaction is a reaction in which at least a part of a hydroxyl group and an ester group present in the molecular chain of the polymer (a) is condensed and cyclized to generate a lactone ring by heating. Alcohol is by-produced. By forming this lactone ring structure in the molecular chain, high heat resistance is imparted to the obtained thermoplastic resin composition.

In the polymer (A), the proportion of the lactone ring structure in the polymer is preferably 10% by weight or more, more preferably 15% by weight or more, further preferably 30% by weight, in the polymer. %, More preferably at least 35% by weight, most preferably at least 50% by weight. If the proportion of the lactone ring structure is less than 10% by weight, sufficient heat resistance tends not to be imparted to the obtained thermoplastic resin composition.

In the present invention, the ratio of the lactone ring structure in the polymer (A) can be calculated, for example, as follows. That is, in the thermal analysis (TG-DTA) of the polymer (A), the weight loss rate between 150 ° C. and 275 ° C. is measured, and the obtained measured weight loss rate is defined as (X). On the other hand, based on the composition of the polymer, the theoretical weight loss rate when assuming that all the hydroxyl groups contained in the polymer composition are involved in the formation of a lactone ring to be converted into alcohol and dealcoholized (that is, 100% in the composition) % (Weight loss rate calculated assuming that a dealcoholization reaction has occurred). More specifically, the theoretical weight loss rate (Y) is, more specifically, the molar ratio of the raw material monomer having a structure (hydroxyl group) involved in the dealcoholation reaction in the polymer and the raw material unit in the polymer composition. It can be calculated from the content of the monomer. These values (X, Y)
Is substituted for 1- (measured weight loss rate (X) / theoretical weight loss rate (Y)), and its value is obtained. When expressed in%, the dealcoholization reaction rate is obtained. Then, assuming that the predetermined lactone cyclization has been performed by the dealcoholization reaction rate, the content (unit ratio) of the raw material monomer having a structure (hydroxyl group) involved in lactone cyclization in the polymer composition is determined. By multiplying by the dealcoholation reaction rate, the ratio of the lactone ring structure in the polymer can be calculated.

As an example, the ratio of the lactone ring structure in the polymer (A-1) obtained in Production Example 1 described below is calculated. Theoretical weight loss rate (Y) of this polymer (A-1)
When the molecular weight of methanol is 32,
-The molecular weight of methyl (hydroxymethyl) acrylate is 1
Since the content (unit ratio) of this 2- (hydroxymethyl) methyl acrylate in the polymer (A-1) is 20.0% in composition, (32/116) × 20.
0 ≒ 5.52% by weight. On the other hand, since the measured weight loss rate (X) measured by TG-DTA was 0.10% by weight, when these values were applied to the above-described alcohol removal calculation formula, 1- (0.10 / 5.52) Since it is 0.98, the dealcoholization reaction rate is 98%. Then, in the polymer (A-1), it is assumed that the predetermined lactone cyclization has been performed by the amount corresponding to the dealcoholization reaction rate, and that methyl 2- (hydroxymethyl) acrylate in the polymer (A-1) By multiplying the content (20.0%) by the dealcoholation reaction rate (98% = 0.98), the polymer (A-
The ratio of the lactone ring structure in 1) was 19.6 (= 2
0.0 × 0.98)% by weight.

As seen above, the proportion occupied by the lactone ring structure is determined by the dealcoholation reaction rate. Therefore,
In order to make the proportion of the lactone ring structure 10% by weight or more, the dealcoholization reaction rate is preferably 90% or more,
It is more preferably at least 95%, most preferably at least 98%. If the dealcoholation reaction rate is low, not only does the heat resistance of the obtained thermoplastic resin composition not sufficiently improve,
Problems such as foaming during molding also occur.

In order to obtain the polymer (A), usually, after the above-mentioned dealcoholization reaction, in order to remove volatile components such as solvents and residual monomers, and by-produced alcohol, if necessary, heating under reduced pressure is carried out. , A devolatilization process is performed. The dealcoholation reaction and the devolatilization treatment may be performed separately or simultaneously. The apparatus for simultaneously performing the dealcoholation reaction and the devolatilization treatment is not particularly limited, but a devolatilization apparatus or a vented extruder including a heat exchanger and a devolatilization tank, or the devolatilization apparatus and the extruder are connected in series. It is preferable to use those arranged, and it is particularly preferable to use a vented extruder alone. In this case, the number of vents may be one or more, but it is preferable to have a plurality of vents.

When performing the dealcoholation reaction and the devolatilization treatment, if necessary, an esterification catalyst such as p-toluenesulfonic acid or a transesterification catalyst may be used as a catalyst for the dealcoholization reaction, and And / or may be added during the process. The total residual volatile content in the polymer (A) obtained as described above is preferably 1500
It is preferably at most ppm, more preferably at most 1,000 ppm. If the amount is larger than this, coloring, foaming, and molding failure such as silver are likely to occur due to deterioration during molding.

In the present invention, the glass transition temperature (Tg) of the polymer (A) is preferably at least 100 ° C., more preferably at least 120 ° C., particularly preferably at least 140 ° C. The glass transition temperature (Tg) is one index indicating heat resistance. If Tg is less than 100 ° C., it is not preferable because sufficient heat resistance cannot be imparted to the obtained thermoplastic resin composition.

The molecular weight of the polymer (A) is not particularly limited, but the weight average molecular weight is preferably from 1,000 to 1,000,000, more preferably from 5,000 to 500,000. If the molecular weight is lower than the above range, there is a problem that the mechanical strength is reduced and the material becomes brittle. If the molecular weight is higher than the above range, there is a problem that the fluidity is reduced and molding becomes difficult.

In the present invention, the thermoplastic resin (B) comprises:
There is no particular limitation as long as it is a thermoplastic resin other than the polymer (A), and a resin having desired characteristics can be appropriately selected. Specific examples of the thermoplastic resin (B) include olefin-based polymers such as polyethylene, polypropylene, ethylene-propylene copolymer, and poly (4-methyl-pentene-1); vinyl chloride, chlorinated vinyl resin Halogen-containing polymers such as polymethacrylate; acrylic polymers such as polymethyl methacrylate; styrene polymers such as polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene block copolymer;
Polyesters and polyarylates such as polyethylene terephthalate and polybutylene terephthalate; nylon 6,
Polyamides such as nylon 66 and nylon 610; polyacetal; polycarbonate; polyphenylene oxide; polyphenylene sulfide; polysulfone; polyether sulfone; polyetheretherketone; polyoxybenzylene;
These may be used alone or in combination of two or more.

When imparting transparency to the thermoplastic resin composition of the present invention, the thermoplastic resin (B) which is compatible with the polymer (A) having a lactone ring structure in the molecule and has transparency. If there is, it can be used without particular limitation.
Even if the compatibility is low, a transparent thermoplastic resin having a refractive index similar to or close to that of the polymer (A) has little effect on transparency, and can be preferably used similarly. From such a viewpoint, among the thermoplastic resins (B) listed above, acrylic polymers such as polymethyl methacrylate, polystyrene, polycarbonate, styrene-methyl methacrylate copolymer, A vinyl chloride resin and a styrene-acrylonitrile resin are preferable, and a vinyl chloride resin and a styrene-acrylonitrile resin are particularly preferable in terms of excellent compatibility.

The selection of the thermoplastic resin (B) to be added to the transparent thermoplastic resin composition of the present invention is carried out, for example, by measuring the haze of a test piece obtained by molding the resin composition. You can do it. The degree of compatibility between the polymer (A) and the thermoplastic resin (B) was evaluated by a haze evaluation method described below, and a thermoplastic resin having a haze of 5% or less was evaluated.
The thermoplastic resin (B) used in the thermoplastic resin composition of the present invention is selected. As long as the thermoplastic resin (B) has a haze value of 5% or less, it can be used without any particular problem. In this manner, transparency can be imparted to the thermoplastic resin composition of the present invention as well as heat resistance.

In the present invention, a rubbery polymer may be used as the thermoplastic resin (B). As the rubbery polymer, for example, ABS containing polybutadiene rubber is used.
Resin, ASA resin containing acrylic rubber, AES resin or HIPS containing polyolefin rubber; thermoplastic elastomer such as polyolefin, polyester, etc.
Elastomers such as BS and SIS; and the like. These rubbery polymers may be used alone or in combination of two or more, and may be used in combination with the thermoplastic resins exemplified above.

In the thermoplastic resin composition of the present invention, when transparency is particularly desired, for example, an acrylonitrile-styrene copolymer or a vinyl chloride resin is used as the thermoplastic resin (B). As A), a polymer containing 50% by weight or more of methacrylic acid esters may be used. By these combinations, good compatibility is obtained, and a resin composition having excellent transparency and high heat resistance is obtained. The thermodynamic compatibility of the polymer (A) and the thermoplastic resin (B) is confirmed by measuring the glass transition point of a thermoplastic resin composition obtained by mixing them. be able to. Specifically, since only one glass transition point measured by a differential scanning calorimeter is observed for the mixture of the polymer (A) and the thermoplastic resin (B), the glass transition point is thermodynamically compatible. It can be said that.

In the thermoplastic resin composition of the present invention, when impact resistance is particularly desired, as the thermoplastic resin (B), a thermoplastic resin containing a rubber component, for example, ABS resin, ASA resin, AES resin It is preferable to use a vinyl chloride resin containing MBS resin. By using these as the thermoplastic resin (B), a resin composition having both excellent mechanical strength and high heat resistance can be obtained.

In the present invention, as described above, when the transparent resin is used as the thermoplastic resin (B), the compatibility between the polymer (A) and the thermoplastic resin (B) is excellent. The haze value measured by a method according to ASTM-D-1003 using a test piece obtained by molding the obtained thermoplastic resin composition of the present invention has a low value of 5% or less and high transparency. Can be demonstrated. In particular,
For example, when a vinyl chloride resin and / or an acrylonitrile-styrene resin or the like is used as the thermoplastic resin (B), the test piece molded with the thermoplastic resin composition of the present invention has a haze value of 5% or less. The haze as a measure of transparency is more preferably 4% or less, particularly preferably 2% or less. Such a combination of the polymer (A) and the thermoplastic resin (B) includes, for example, transparent optical lenses, optical elements, pickup lenses, various sensors, O
It can be suitably used for applications requiring optical characteristics such as transparent parts such as A-devices and automobiles. In particular, the thermoplastic resin composition of the present invention can be suitably used in application fields where both optical properties and heat resistance are desired.

In the present invention, the blending ratio of the polymer (A) and the thermoplastic resin (B) is such that the ratio of polymer (A) / thermoplastic resin (B) = 1/99 to 99/1 (weight ratio) ), Preferably 10 / 90-9.
A range of 0/10 is good. In particular, when the properties of the thermoplastic resin (B) are maximized and the heat resistance is also to be improved, the polymer (A) / the thermoplastic resin (B) = 10/9
It is preferable to set the range of 0 to 80/20 (weight ratio). More preferably, the range is 10/90 to 70/30 (weight ratio), and particularly preferably, the range is 10/90 to 60/30.
A range of 40 (weight ratio) is good.

The thermoplastic resin composition of the present invention may be a mixture comprising only the polymer (A) and the thermoplastic resin (B), or may contain various additives as necessary. It may be. Specific examples of the various additives include, for example, hindered phenol-based, phosphorus-based, and sulfur-based antioxidants and stabilizers; reinforcing materials such as glass fiber or carbon fiber; phenyl salicylate, 2- (2 '-Hydroxy-5-methylphenyl) benzotriazole, 2
Ultraviolet absorbers such as hydroxybenzophenone; tris (dibromopropyl) phosphate, triphenylphosphate, triallylphosphate, ethylene tetrabromide,
Flame retardants such as antimony oxide and zinc borate; antistatic agents such as anionic, cationic, nonionic and amphoteric surfactants; coloring agents such as inorganic pigments, organic pigments and dyes; fillers and other resins But is not particularly limited. The content of these additives is not particularly limited as long as the properties of the obtained thermoplastic resin composition are not impaired.Specifically, in the thermoplastic resin composition of the present invention, The total content of the polymer (A) and the thermoplastic resin (B) contained is 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and most preferably 20% by weight. It is preferable to make the above.

In a preferred embodiment of the present invention, the degree of improvement in heat resistance, which is indicated by the glass transition temperature of the thermoplastic resin composition, depends on the glass transition temperature of the thermoplastic resin (B) used as a raw material of the composition. When X ° C., 1.0
It is preferable that the temperature be 3X ° C or higher. The upper limit may be set as desired in consideration of mechanical strength and other physical properties, and is not particularly limited, but is preferably 1.4X ° C or less, more preferably 1.3X ° C or less, and particularly preferably. Is preferably 1.2X ° C. or less. It is possible to increase the glass transition temperature of the thermoplastic resin composition to more than 1.4X ° C by increasing the amount of the polymer (A) added. Since there is a possibility of inhibiting the physical properties of the plastic resin (B),
Not preferred.

The thermoplastic resin composition of the present invention can be easily obtained by mixing the polymer (A) and the thermoplastic resin (B) and, if necessary, various additives. Can be. A polymer (A) and a thermoplastic resin (B),
The method of mixing the various additives, if necessary, is not particularly limited. For example, a method of extruding and kneading the obtained mixture after preblending them with a mixer such as an omni mixer can be adopted. . In this case, the kneader used for extrusion kneading is not particularly limited, and for example, a conventionally known kneader such as an extruder such as a single screw extruder or a twin screw extruder or a pressure kneader can be used. .

The thermoplastic resin composition of the present invention can be easily formed into various shapes such as a plate, a molded product, a film, and a sheet by a molding method such as injection molding, blow molding, extrusion molding, or cast molding. Can be molded into The molding method is not particularly limited. The molding temperature during molding may be appropriately set according to the properties of the resin such as heat resistance, and is not particularly limited, but is preferably 150 to 350 ° C, more preferably 200 to 300 ° C.

[0044]

EXAMPLES Examples and comparative examples according to the present invention will be described below, but the present invention is not limited by these examples. In the following text, “parts” means “parts by weight”.
Represents Each physical property and evaluation of the polymer (A) and the thermoplastic resin composition were measured by the following methods.

Analysis of Polymerization Reaction Rate of Polymer (A), Polymer Composition Analysis The reaction rate at the time of polymerization reaction and the content of specific monomer units in the polymer were determined by measuring the unreacted monomer in the obtained polymerization reaction mixture. The amount of the monomer was measured and determined using gas chromatography (manufactured by Shimadzu Corporation, device name: GC-14A). -Weight average molecular weight of polymer (A) The weight average molecular weight of the polymer is GPC (GPC manufactured by Tosoh Corporation).
System) in terms of polystyrene.

The degree of coloring YI of the polymer (A) is determined by dissolving the polymer in chloroform and adding 15%
The solution was put in a quartz cell, and measured using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., device name: SZ- # 90). -Thermal analysis of the polymer (A) (5% weight loss temperature, glass transition temperature) The thermal analysis was performed by using a sample of about 10 mg and a heating rate of 10 ° C / mi.
n, using a TG (manufactured by Rigaku, device name: TG-8110) and DSC (manufactured by Rigaku, device name: DSC-8230) under the conditions of a nitrogen flow of 50 cc / min.

Measurement of Volatile Content in Polymer (A) The residual volatile content contained in the resin was measured by gas chromatography (manufactured by Shimadzu Corporation, device name: GC-14A). -Heat resistance The obtained thermoplastic resin composition was measured for glass transition temperature (Tg) by the above-mentioned DSC measurement, and evaluated by the glass transition temperature. That is, the higher the glass transition temperature, the better the heat resistance.

Compatibility The glass transition temperature (Tg) of the obtained thermoplastic resin composition was measured by the above-mentioned DSC measurement. Was evaluated as ×. -Haze value The obtained thermoplastic resin composition is injection-molded and subjected to ASTM.
It measured according to D1003.

Transparency A tetrahydrofuran solution of the obtained thermoplastic resin composition is applied on a glass plate so as to have a uniform thickness, and then dried to form a cast film. It was visually observed and evaluated as follows. That is, a case where there was no turbidity and it was colorless and transparent was evaluated as ○, and a case where it became white and turbid was evaluated as ×.

Hereinafter, a production example of the polymer (A) will be described. (Production Example 1) A 30 L reactor equipped with a stirrer, a temperature sensor, a cooling pipe, a nitrogen introduction pipe, and a dropping pump was charged with 2
5 parts of methyl- (hydroxymethyl) acrylate, 20 parts of methyl methacrylate, and 25 parts of toluene were charged and heated to 100 ° C. while passing nitrogen. Then, 0.075 part of tertiary butyl peroxyisopropyl carbonate as an initiator was added, and at the same time, 5 parts of methyl 2- (hydroxymethyl) acrylate and 20 parts of methyl methacrylate were added.
, 25 parts of toluene and 0.075 parts of initiator were added dropwise over 3 hours and a half, solution polymerization was carried out at 100 to 110 ° C, and aging was carried out for 1 hour and a half. The polymerization reaction rate was 91.8%, and the ratio of methyl 2- (hydroxymethyl) acrylate unit in the polymer was 20.0%. The weight average molecular weight of this polymer is 13,000.
It was 0.

The obtained polymer solution was heated at a barrel temperature of 250
° C, rotation speed 100rpm, decompression degree 10-300mmH
g, a vent-type screw twin-screw extruder having one rear vent and four forevents (Φ = 29.75 mm, L /
D = 30) at a processing rate of 0.7 kg / hour in terms of the amount of resin, a dealcoholation reaction and a devolatilization treatment are performed in the extruder, and the mixture is extruded to obtain transparent pellets (A) of the polymer (A). A-1) was obtained.

The coloring degree YI of the pellet (A-1) is as follows:
The glass transition temperature was 126 ° C. Also,
5% which is an index of heat resistance of the pellet (A-1)
Since the weight loss temperature was 366 ° C., it was found that the pellets had excellent thermal stability in a high temperature region.

On the other hand, apart from the above reaction and treatment, the polymer solution was diluted with tetrahydrofuran, poured into excess hexane to reprecipitate, and the precipitate was dried under vacuum (1 mmHg, 80 ° C., 3 ° C.). Time), a thermal analysis (TG-DTA) of the resulting white solid resin was performed.
The pellet (A-1) obtained by the extruder is 150 to
The measured weight loss rate at 275 ° C. was 0.10% by weight. On the other hand, the theoretical weight loss rate (calculated by calculating the weight loss occurring when all the hydroxyl groups in the polymer composition are removed as methanol) is 5.52% by weight. This calculation method has been described above. Then, the dealcoholization reaction rate in the extruder is 98%. Therefore,
The proportion of the lactone ring structure in the polymer of the pellet (A-1) was 19.6% by weight.

The residual volatile content in the pellet (A-1) was as shown below. Methyl methacrylate: 470 ppm Methyl 2- (hydroxymethyl) acrylate: 50 pp
m Methanol: 280 ppm Toluene: 90 ppm (Production Example 2) Polymer (A) was prepared in the same manner as in Production Example 1 except that methyl 2- (hydroxymethyl) acrylate was changed to 10 parts and methyl methacrylate was changed to 15 parts. (A-2) was obtained. The polymerization reaction rate was 9
3.2%, the ratio of methyl 2- (hydroxymethyl) acrylate unit in the polymer was 40.2%, and the weight average molecular weight of the polymer was 117000.

The coloring degree YI of the pellet (A-2) is as follows.
9, and the glass transition temperature was 141 ° C. Also,
The theoretical weight loss rate of the pellet (A-2) was 11.09% by weight, and was 150 to 27% by thermal analysis (TG-DTA).
Since the weight loss rate at 5 ° C. is 0.34% by weight, the dealcoholization reaction rate is 97%. Therefore, the pellet (A
The proportion of the lactone ring structure in the polymer of -2) is 3
It was 9.0% by weight.

Further, since the pellet (A-2) had a 5% weight loss temperature as an index of heat resistance of 350 ° C., it was found that this pellet was excellent in thermal stability in a high temperature region. Was. In addition, the residual volatile matter in the pellet (A-2) was a value shown below. Methyl methacrylate: 520 ppm Methyl 2- (hydroxymethyl) acrylate: 60 pp
m Methanol: 690 ppm Toluene: 90 ppm [Examples 1 to 5 and Comparative Examples 1 and 2] Using the pellets (A-1) and (A-2) as the polymer (A), as the thermoplastic resin (B) Using vinyl chloride resin and styrene-acrylonitrile resin (AS resin),
These were dissolved in tetrahydrofuran at the compounding ratio (weight ratio) shown in Table 1, the solution was dropped into methanol, and the precipitated white solid was filtered by suction and dried to obtain the thermoplastic resin composition of the present invention. Obtained. Table 1 shows each physical property of the obtained thermoplastic resin composition.

[0057]

[Table 1]

Examples 6 to 9 and Comparative Example 3 The pellet (A-1) was used as the polymer (A), and the acrylonitrile-styrene resin (A) was used as the thermoplastic resin (B).
S resin) and an acrylonitrile-butadiene-styrene resin (ABS resin), which were mixed in an omni-mixer at the compounding ratio (weight ratio) shown in Table 2, and then twin-screw extrusion of 30 mmφ controlled at a cylinder temperature of 240 ° C The mixture was melt-kneaded using a mixer to obtain a thermoplastic resin composition of the present invention. Table 2 shows the physical properties of the obtained thermoplastic resin composition.

[0059]

[Table 2]

[0060]

According to the present invention, a thermoplastic resin composition having excellent heat resistance while retaining the inherent properties of the contained thermoplastic resin, for example, transparency, mechanical strength, moldability and the like. Can be provided.

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Claims (6)

[Claims] 1. A thermoplastic resin composition comprising, as a thermoplastic resin, a polymer (A) having a lactone ring structure in a molecule and a thermoplastic resin (B) other than the polymer (A). 2. The polymer (A) has a glass transition temperature of 10
The thermoplastic resin composition according to claim 1, which is at least 0 ° C. 3. The thermoplastic resin composition according to claim 1, wherein the lactone ring structure is formed by a dealcoholation reaction between a hydroxyl group and an ester group in a molecular chain. 4. The polymer (A) has the general formula (1): ## STR1 ## (Wherein, R ₁ and R ₂ are the same or different groups and represent a hydrogen atom or an organic residue.) A polymer obtained by a dealcoholation reaction of a copolymer containing a monomer unit represented by the formula: The thermoplastic resin composition according to any one of claims 1 to 3, which is a united product. 5. The thermoplastic resin composition according to claim 1, wherein the proportion of the lactone ring structure in the polymer (A) is 10% by weight or more. 6. The thermoplastic resin composition according to claim 1, which has a haze value of 5% or less.