JPH06128445A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a thermoplastic resin composition imparted with various properties such as flexibility, processability and low-temperature characteristics while keeping the excellent properties of acrylic resin such as weather resistance, surface hardness and transparent feeling. CONSTITUTION:The resin composition is produced by compounding (A) 100 pts.wt. of a resin composition composed of (i) an acrylic resin and (ii) a saturated thermoplastic elastomer consisting of a hydrogenation product of a thermoplastic block copolymer composed of a block of an aromatic vinyl monomer and a block of isoprene and/or butadiene with (B) 0.2-50 pts.wt. in total of a reactive acrylic resin and a hydrogenation product of a reactive block copolymer at a weight ratio of 10/90 to 90/10.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition which is not only flexible and has a high surface hardness, but also has excellent processability and weather resistance and has a transparent feeling.

[0002]

2. Description of the Related Art Acrylic resins conventionally used as molding materials are used in various materials by taking advantage of their characteristics such as transparency, color development, weather resistance and surface hardness.
In particular, it is often used outdoors as a weather-resistant resin having good color developability, and is also used as a transparent material such as a fluorescent lamp cover. Further, since it decomposes into a monomer when heated, it is also being researched as a recyclable material. However, since acrylic resins generally have poor flexibility and low impact strength, many studies have been conducted for the purpose of improving flexibility.

Olefin resins and olefin elastomers have been used as molding materials because of their advantages such as flexibility and extrusion processability. For example, it is a molding material for automobile bumpers and console panel surfaces, but since it has no polar groups, it is inferior in paintability, printability, and color development during coloring, and the fact is that it is not possible to select the type of color when processing. Is.
In addition, although it has relatively good workability, it is difficult to mold by a molding method with a relatively high shearing force such as injection molding, and it has a problem that the surface hardness is low in contrast to the flexibility and the scratch resistance is poor. is there. However, due to the recent increasing interest in environmental issues, recyclable materials have come to the forefront, and studies on the improvement of olefin polymers have been earnestly studied.

ABS resin, which can satisfy the physical properties of both these resins to some extent,
There are impact resistant acrylic resins and the like, but both are known to have poor weather resistance because the rubber component for imparting impact resistance has a chemically unstable double bond in the main chain. There is. In order to satisfy the weather resistance, AES resin, acrylic resin in which acrylic acid ester rubber is dispersed, and the like have been studied, but the applications to be used are limited due to the balance between physical properties and cost.

On the other hand, vinyl chloride-based polymers are inexpensive and widely used along with olefin-based polymers, and their hardness and mechanical properties can be controlled by the amount of plasticizer, so that they actually have high hardness. , Low hardness from the field that competes with acrylic resin that requires transparency,
It has been used for many materials in the field of polyolefin where flexibility is required, and it has been advantageous due to its low cost. However, vinyl chloride polymers originally have poor processability and require a large amount of plasticizers. The plasticizer has a problem of a phenomenon (bleed-out) of depositing on the surface due to aging. Further, since this polymer produces a halogen-containing decomposition product by heating, and therefore it is practically difficult to recycle it, its replacement is required.

Therefore, if an acrylic resin and an olefin polymer, which are incompatible with each other, can be compatibilized with each other, the weather resistance, surface hardness, and transparency of the acrylic resin can be maintained, while the olefin polymer further has these properties. It should be possible to impart properties such as flexibility, processability and low temperature properties. However, compatibilizing two or more mutually incompatible polymers with a third polymer that is partially compatible with any of these polymers is
Although known for some special types of mixture systems, no examples of successful compatibilization in such resin mixture systems are known so far.

[0007]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to maintain the weather resistance, surface hardness, and transparency of acrylic resin while maintaining the properties such as flexibility, processability, and low temperature characteristics. An object of the present invention is to provide a given novel thermoplastic resin composition having recyclability.

[0008]

As a result of the study by the present inventors, the above-mentioned problem is that a hydrogenated product of a thermoplastic block copolymer is used as an olefin polymer, and a hydrogenated product of this thermoplastic block copolymer is used. It has been found that the problem can be solved by adding a specific reactive resin to a mixture of acrylic resins.

That is, according to the present invention, (A): 10 to 90% by weight of an acrylic resin, (B): a block (a) composed of an aromatic vinyl monomer and having a number average molecular weight of 3,000 to 80,000, and isoprene. And / or butadiene having a number average molecular weight of 20,000 to 200,000 and composed of a block (b), and the aromatic vinyl monomer component is 10 to 60 weight based on the total weight of (a) and (b). % Average molecular weight of 30000-3
Hydrogenated product of thermoplastic block copolymer of 00000 90-
(C) in a weight ratio range of 10/90 to 90/10 with respect to 100 parts by weight of a resin composition of 10% by weight: a hydroxyl group at the terminal of the molecular chain, or active hydrogen such as a primary or secondary amino group. Group-containing acrylic resin, and (D): Hydrogenation of a thermoplastic block copolymer modified with a carboxyl group, which is composed of a block composed of an aromatic vinyl monomer and a block composed of isoprene and / or butadiene There is provided a thermoplastic resin composition which comprises a total amount of 0.2 to 50 parts by weight.

The present invention will be described in detail below.

In the present invention, the acrylic resin used as the component (A) is a single polymer of methyl methacrylate or a small amount of other copolymerizable monomer containing methyl methacrylate as a main component. It is a copolymer, and its manufacturing method is not particularly limited. As the copolymerizable component that can be used, acrylic acid, acrylic acid metal salt,
Methyl acrylate, ethyl acrylate, acrylic acid n-
Acrylic esters such as butyl, s-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methacrylic acid metal salt, ethyl methacrylate, n-butyl methacrylate, s-butyl methacrylate, T-butyl methacrylate, methacrylic acid 2
-Methacrylic acid esters such as hydroxyethyl, glycidyl methacrylate, cyclohexyl methacrylate,
Acetic acid esters such as vinyl acetate, styrene, aromatic vinyl compounds such as α-methylstyrene, maleic anhydride, maleic acid mono- and dialkyl esters, N-
Examples thereof include maleimides such as phenylmaleimide, and these can be used alone or in any combination in any ratio. It is necessary that the copolymerization ratio with methyl methacrylate does not significantly change the properties of the acrylic resin, and specifically, it can be used at about 0.01 to 30% by weight.

The hydrogenated product of the thermoplastic block copolymer used as the component (B) is composed of a block (a) made of an aromatic vinyl monomer and a block (b) made of isoprene and / or butadiene. It The aromatic vinyl monomer used here is styrene, α-methylstyrene or the like, and these can be used alone or in combination of two or more kinds.

The block (a) made of an aromatic vinyl monomer needs to have a number average molecular weight in the range of 3,000 to 80,000, and the block (a) is based on the total weight of the block (b) and the block (b). It is necessary that the ratio is in the range of 10 to 60% by weight.
The thermoplasticity of the hydrogenated component of the thermoplastic block copolymer as a component is maintained. The number average molecular weight of the block (a) and the ratio of the block (a) to the total weight of the block (b) may be set low, and conversely, when hardness or strength is required, they may be set large.

The number of segments in the block (a) can be arbitrarily determined, but if it is too large, the manufacturing process becomes complicated, so it is preferable to set it to about 1 or 2, and such a small number of segments. Even if it is a number, sufficient performance can be exhibited, and no problem occurs in the physical properties of the product.

The block (b) composed of isoprene and / or butadiene has a number average molecular weight of 20000 to 2000.
Must be in the range of 00, which results in (B)
The thermoplasticity of the hydrogenated component of the thermoplastic block copolymer as a component is maintained. When the number average molecular weight of the block (b) exceeds the above range, the hydrogenated product of the thermoplastic block copolymer as the component (B) impairs fluidity, which is not preferable.

In the block (b), isoprene and butadiene can be used alone, or both can be copolymerized in an arbitrary ratio. In this case, both random and block structures can be used depending on the purpose. can do. Since isoprene has a higher degree of molecular mobility than that of butadiene because it has a methyl group branch compared to butadiene, those with a high ratio of isoprene are more flexible, and those with a high ratio of butadiene are as harder elastomers. Since it has properties, it is possible to determine the properties of the elastomer by any choice. Further, hydrogenation is performed to improve the heat resistance and weather resistance of the block segment, but since the glass transition temperature hardly changes, the properties of the thermoplastic elastomer can be retained. To obtain the desired heat resistance and weather resistance,
The hydrogenation rate is preferably 70% or more.

The method for synthesizing the hydrogenated product of the thermoplastic block copolymer can be obtained by obtaining a polymer by anionic living polymerization which usually uses an organic alkali metal catalyst, and then hydrogenating the polymer. For example, n
-Saturated aliphatic hydrocarbon compounds such as hexane, heptane, and cyclohexane, or benzene, using an anionic polymerization initiator such as -butyllithium and s-butyllithium
A living polymer is produced by anionically polymerizing an aromatic vinyl monomer under a temperature condition of 30 to 60 ° C. using an aromatic hydrocarbon compound such as toluene or xylene as a solvent, and subsequently producing a living polymer such as isoprene or butadiene. A block copolymer is prepared by dropping a conjugated diene-based monomer into the system to carry out block copolymerization, and then again dropping an aromatic vinyl monomer into the system. By repeating this operation, a multi-element block polymer can be produced. The living polymer thus obtained may also be subjected to coupling treatment with a dihalogen compound such as 1,2-dibromoethane, 1,4-dibromobutane, or 1,4-dichlorobenzene, or a tin compound such as tin tetrachloride to obtain a multi-component compound. A block polymer can be obtained. Alternatively, when a bifunctional anionic polymerization initiator such as 1,4-dilithiobutane or dilithionaphthalene is used as a polymerization initiator, a conjugated diene monomer and then an aromatic vinyl monomer are sequentially added to form a ternary compound. A block copolymer is produced. Moreover, a multi-element block polymer can be manufactured by repeating this operation. When carrying out polymerization, dimethyl ether, diethyl ether, tetrahydrofuran, as a cocatalyst,
Ethers such as dioxane, glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, triethylamine, N,
N, N ', N'-tetramethylethylenediamine, N-
A Lewis base such as amines such as methylmorpholine is used in an amount of about 0.1 to 10 relative to the number of moles of the metal cation of the polymerization catalyst.
When it is used in the range of 00 times, the microstructure of the block segment composed of isoprene and / or butadiene is changed to contain a vinyl bond. When this vinyl structural unit is 40% or more, it has a glass transition temperature near room temperature, and vibration damping performance near room temperature can be imparted (JP-A-2-102212). Then, when the desired molecular weight is reached, active hydrogen compounds such as alcohols, carboxylic acids and water are added to terminate the polymerization.

Subsequently, the copolymer thus obtained is hydrogenated to produce a hydrogenated product of the thermoplastic block copolymer. A homogeneous catalyst or a heterogeneous catalyst can be used as the hydrogenation catalyst. When a homogeneous catalyst is used, an organic transition metal catalyst (for example, nickel acetylacetonate, cobalt acetylacetonate, nickel naphthenate, cobalt naphthenate, etc.) and an alkyl compound of a metal such as aluminum, an alkali metal or an alkaline earth metal is used. A Ziegler catalyst or the like depending on the combination is used in an amount of about 0.01 to 0.1 mol% per double bond of the polymer to be hydrogenated. The hydrogenation reaction is carried out at room temperature to 150 ° C. and normal pressure to 50 kg / cm ² of hydrogen pressure, and is completed in about 1 to 50 hours. After completion of the reaction, acidic water is added to the vessel and vigorously stirred to dissolve the hydrogenation catalyst in water. By removing the aqueous phase of the two phases that have been phase-separated and further distilling off the solvent, the hydrogenated product of the desired thermoplastic block copolymer is obtained.

When a heterogeneous catalyst is used, nickel, cobalt, palladium, rhodium, ruthenium, platinum or the like may be used alone or in combination with silica, diatomaceous earth, alumina,
It is used by supporting it on activated carbon or the like, and its amount is suitably 0.5 to 10% by weight based on the weight of the polymer. This is added to the polymerization reaction liquid. At this time, ethers such as diethyl ether, tetrahydrofuran and dioxane, and alcohols such as ethanol and isopropanol can also be used as a mixed solvent. The hydrogenation reaction is from room temperature to 250 ° C,
It is carried out under a hydrogen pressure of atmospheric pressure to 200 kg / cm ² , and about 1 to
It ends in 50 hours. After completion of the reaction, the reaction product is taken out from the container, the catalyst is filtered off, and the solvent is distilled off from the obtained filtrate to obtain a hydrogenated product of the desired thermoplastic block copolymer.

An acrylic resin having an active hydrogen group at the molecular chain terminal as the component (C) with respect to the components (A) and (B) thus obtained, and an aromatic vinyl monomer as the component (D). A thermoplastic resin composition is obtained by blending a hydrogenated product of a thermoplastic block copolymer, which is composed of a block of a polymer and a block of isoprene and / or butadiene and is modified with a carboxyl group. In the component (C) and the component (D), the acrylic resin (C) having an active hydrogen group at the terminal of the molecular chain has a high affinity for the component (A), and a block composed of an aromatic vinyl monomer, isoprene and The hydrogenated product (D) of the thermoplastic block copolymer, which is composed of a block composed of // butadiene and is modified with a carboxyl group, has a high affinity for the component (B), and the components (C) and (D) Since each of them has reactivity with each other, it has a compatibilizing effect by forming a compatibilizer during kneading.

The component (C) is basically the same polymer as that described for the component (A). It is a homopolymer of methyl methacrylate or methyl methacrylate as a main component. It is a copolymer obtained by copolymerizing a small amount of monomers having the same copolymerizability as that used. The monomer copolymerized with this methyl methacrylate is
One or more of them can be used in any combination and in any ratio, but it is preferable that the composition is as close as possible to the component (A). Saturated carbonyl compounds such as ethyl acetate, butyl acetate, acetone, methyl ethyl ketone,
Using a hydrocarbon compound such as toluene or xylene as a solvent as necessary, methyl methacrylate alone, or methyl methacrylate and a monomer copolymerizable therewith, a thiol compound (because a hydroxyl group is introduced at the terminal, In the presence of a hydroxyl group-containing thiol compound such as 2-hydroxyethanethiol and an amino group-containing thiol compound such as 2-aminoethanethiol when introducing an amino group), a normal radical polymerization initiator, for example, 2 , 2'-azobisisobutyronitrile, 2,2 '
-Introducing an active hydrogen group at the end of the molecular chain of the component (C) by polymerizing at room temperature to 100 ° C for 3 to 30 hours using an organic azo compound such as azobis (2-methylbutyronitrile). To do. The molecular weight of the acrylic resin having a hydroxyl group or a primary or secondary amino group at the terminal of the thus obtained molecular chain is not limited in a strict sense, but if this is unnecessarily too large, it may be due to the carboxyl group of the component (D). Since the reactivity with the modified thermoplastic resin composition is lowered and the desired compatibilizing effect may not be exhibited in some cases, the number average molecular weight is preferably in the range of 10,000 to 80,000.

The functional group to be introduced at the end of the molecular chain may be a hydroxyl group or a primary or secondary amino group, but in the thermoplastic resin composition, the functional group concentration is very high. It is important to select functional groups that are lower and thus more reactive with carboxyl groups. Therefore, in order to enhance the reactivity with the carboxyl group in the component (D) and clarify the effect, the functional group to be introduced at the terminal of the component (C) is most preferably a primary amino group.

The component (D) is produced by a method similar to the method described in detail for the method for producing the component (B), and is synthesized by anion living polymerization using an organic alkali metal catalyst which is usually performed (B). It is obtained by hydrogenating a polymer similar to the component. The structure is such that the block (D) of the aromatic vinyl monomer is a block (a) of the aromatic vinyl monomer of the component (B), and the block of (D) isoprene and / or butadiene. Preferably has the same or similar molecular weight as the block (b) consisting of isoprene and / or butadiene as the component (B). Further, by hydrogenating at 70% or more, the heat resistance and weather resistance are excellent, and the compatibilizing effect is excellent by having a molecular structure similar to that of the component (B). Further, when the constitution of each block segment of the component (D) is binary or ternary, it is most effective in terms of compatibilization and production cost. The component (D) thus obtained and a dibasic unsaturated acid anhydride such as maleic anhydride, itaconic anhydride or citraconic anhydride are, if necessary, hydrocarbons such as toluene, xylene and cyclohexane. In a system solvent, 0.01 to 1% by weight of a peroxide catalyst such as benzoyl peroxide, dicumyl peroxide, and di (t-butyl) peroxide is added to the component (C2), if necessary. Room temperature to 200 ° C, 1 to 1
By reacting with stirring for 00 hours, a thermoplastic block copolymer (D) modified with a carboxyl group is obtained.

The ratio of the components (C) and (D) to be used can be arbitrarily determined, but in order to further clarify the effect as a compatibilizer, a ratio closer to the composition of both components (A) and (B). Is good, and specifically (C) / (D) (weight ratio) is 1
In the range of 0/90 to 90/10, more preferably 25 /
Used in the range of 75 to 75/25.

The components (C) and (D) thus obtained are blended with the components (A) and (B), and the mixture is reacted while being mixed, whereby the compatibilizing effect is exerted and the objective is obtained. A thermoplastic resin composition can be obtained.

The total amount of the component (C) and the component (D) to be used may be an amount capable of exerting a sufficient function as a compatibilizing agent, but if the amount is too large, the components (A) and (B) will be used. Since the production cost of each component (C) and (D) is higher than that of each component, it is used in the range of 0.2 to 50 parts by weight based on 100 parts by weight of the composition of both (A) and (B). .

The thermoplastic resin composition of the present invention comprises a filler,
Various additives such as pigments can be optionally contained.
For example, alumina, talc, carbon black, mica, zeolite, glass fiber, carbon fiber, ferrite, calcium carbonate, aluminum hydroxide and other general fillers, dyes, pigments, flame retardants, ultraviolet absorbers, etc. , Other organic or inorganic additives used as functional additives. The addition amount thereof is in the range of the amount generally used, and for example, 0.001 to 50 parts by weight, or in some cases, a larger amount can be used based on 100 parts by weight of the total resin composition. Further, the resin composition of the present invention may contain polyolefins such as polyethylene and polypropylene, olefin plasticizers such as polybutene, polyisobutylene and process oil to an extent that the physical properties are not impaired.

The method of mixing the components constituting the composition can be carried out by a conventional method, and is not particularly limited. For example, it can be carried out by a method of mixing in a molten state with a melt kneader such as an ordinary extruder or kneader. At that time, (A), (B), (C), and (D)
The respective components may be melt-kneaded at the same time, or the remaining components may be melt-kneaded with a product obtained by melt-kneading two or three members in advance by arbitrary selection. The kneading conditions are
It is necessary to carry out kneading at a temperature and a shearing state in which the raw material resins are melted and fluidized, and a temperature and a shearing state at which a sufficient reaction can occur are realized and further deterioration does not occur. The conditions for achieving a good shearing state differ depending on the kneading machine, so it cannot be unequivocally exemplified, but the temperature is specifically in the range of 150 to 300 ° C, and more preferably 180 to 280 ° C.

[0029]

EXAMPLES Next, the present invention will be specifically described with reference to examples. In addition, the part in each Example represents a weight part. Moreover, each physical property was calculated | required by the method shown below. (1) Acid value: 0.1N-potassium hydroxide was directly titrated with an ethanol solution. (2) Amino value: Titrated directly with 0.01 N-hydrochloric acid methanol solution. (3) Tensile physical property test: In accordance with JISK-7113,
The dumbbell No. 2 test piece was used for measurement and evaluation. (4) Hardness: ASTMD-2240 or JISK-
It was measured and evaluated according to 6301. (5) Oil resistance test: 120 in JIS No. 2 oil at room temperature
After immersion for a period of time, the change in appearance was visually evaluated. (6) Pencil scratch resistance: The scratch resistance was evaluated by a method and an apparatus based on JISK-5400.

A hydrogenated product of a thermoplastic block copolymer composed of a block composed of an aromatic vinyl monomer and a block composed of isoprene and / or butadiene used in the present invention was produced as follows.

Production of Hydrogenated Product (1) of Thermoplastic Block Copolymer A pressure resistant reaction vessel equipped with a stirrer and a dropping funnel was charged with 500 parts of cyclohexane and 11 parts of s-butyllithium and heated to 50 ° C. From the dropping funnel, 60 parts of styrene was continuously charged, then 280 parts of isoprene was continuously charged, and then 60 parts of styrene was continuously charged to obtain 8 parts.
Polymerization was carried out for a time. After that, the reaction system was replaced with hydrogen, and 25 parts of diatomaceous earth-supported nickel catalyst was added to obtain 15 kg / cm.
^The mixture was reacted at 150 ° C. for 10 hours under a hydrogen pressure of ² . The reaction product was diluted with cyclohexane, the catalyst was filtered off, and the filtrate was concentrated and dried under reduced pressure to obtain a hydrogenated product (1) of a thermoplastic block copolymer. Styrene-
An isoprene-styrene ternary block copolymer,
It was confirmed that the styrene content was 30.3%. From the GPC analysis, the number average molecular weight of the styrene block was 8,300, and the number average molecular weight of the isoprene block was 3
The total number average molecular weight was 8,500. The hydrogenation rate according to iodine value was 95.6%, and the hydrogenation rate for the benzene ring by NMR was 1.2%.

Production of Hydrogenated Product (2) of Thermoplastic Block Copolymer 500 parts of cyclohexane and 9 parts of s-butyllithium were charged in a pressure resistant reaction vessel equipped with a stirrer and a dropping funnel,
The temperature was raised to 50 ° C., 120 parts of styrene was continuously charged from the dropping funnel, 160 parts of isoprene was continuously charged, and then 120 parts of styrene was continuously charged, and
Polymerization was carried out for a time. After that, the reaction system was replaced with hydrogen, and 20 parts of a diatomaceous earth-supported nickel catalyst was added to obtain 15 kg / cm.
^The mixture was reacted at 150 ° C. for 7 hours under a hydrogen pressure of ² . The reaction product was diluted with cyclohexane, the catalyst was filtered off, and the filtrate was concentrated and dried under reduced pressure to obtain a hydrogenated product (2) of a thermoplastic block copolymer. By NMR analysis, styrene-
An isoprene-styrene ternary block copolymer,
It was confirmed that the styrene content was 61.1%. From the GPC analysis, the number average molecular weight of the styrene block was 21,400, the number average molecular weight of the isoprene block was 27,200, and the number average molecular weight of the whole was 70,000. The hydrogenation rate according to the iodine value was 93.2%, and the hydrogenation rate for the benzene ring by NMR was 3.2%.

Production of Hydrogenated Product (3) of Thermoplastic Block Copolymer 500 parts of cyclohexane and 9 parts of s-butyllithium were charged into a pressure resistant reaction vessel equipped with a stirrer and a dropping funnel,
The temperature was raised to 50 ° C., 60 parts of styrene was continuously charged from a dropping funnel, 280 parts of isoprene was continuously charged, and then 60 parts of styrene was continuously charged to carry out polymerization for 10 hours. After that, the reaction system was replaced with hydrogen, and 30 parts of a diatomaceous earth-supported nickel catalyst was added to obtain 15 kg / cm ^2.
The reaction was performed at 150 ° C. for 10 hours under hydrogen pressure. The reaction product was diluted with cyclohexane, the catalyst was filtered off, and the filtrate was concentrated and dried under reduced pressure to obtain a hydrogenated product (3) of a thermoplastic block copolymer. By NMR analysis, styrene-
An isoprene-styrene ternary block copolymer,
It was confirmed that the styrene content was 31.5%. From the GPC analysis, the number average molecular weight of the styrene block was 10,900, the number average molecular weight of the isoprene block was 47,300, and the number average molecular weight of the whole was 69,100. The hydrogenation rate according to the iodine value was 98.0%, and the hydrogenation rate for the benzene ring by NMR was 0.8%.

Next, the acrylic resin having an amino group at the terminal of the molecular chain and the hydrogenated product of the thermoplastic block copolymer modified with a carboxyl group used in the present invention were produced as follows.

Production of Acrylic Polymer Having Amino Group at Terminal of Molecular Chain 300 parts of ethyl acetate was charged into a pressure-resistant reaction vessel equipped with a stirrer and a dropping funnel, and then 6.2 parts of 2-aminoethanethiol and 200 parts of methyl methacrylate. Parts and 9.9 parts of azobisisobutyronitrile were sequentially charged, and the temperature was raised to 70 ° C.
Polymerization was performed for 10 hours. The obtained polymerization liquid was dropped into n-hexane, the precipitate was filtered off and dried under reduced pressure to obtain polymethyl methacrylate having an amino group at the end of the molecular chain. G
The molecular weight by PC was 38,400, and the amino group content by the amino value was 1.21 per molecule.

Production of hydrogenated products (1) to (3) of a carboxyl group-modified thermoplastic block copolymer 30 parts of xylene and a hydrogenated product of a thermoplastic block copolymer (1) in a pressure-resistant reaction vessel equipped with a stirrer. )-(3), 300 parts, and 8 parts of maleic anhydride were charged, and it was made to react at 230 degreeC for 20 hours. The obtained reaction product was dried under reduced pressure at 120 ° C. for 24 hours to remove the solvent and unreacted maleic anhydride to obtain a hydrogenated product of a carboxyl group-modified thermoplastic block copolymer. Table 1 shows the respective acid values.

[0037]

[Table 1] [Examples 1 to 5 and Comparative Examples 1 to 3] An acrylic resin, a hydrogenated product of a thermoplastic block copolymer, and in Examples 1 to 5, an acrylic resin having an amino group at a molecular chain terminal and a carboxyl group. The hydrogenated product of the modified thermoplastic block copolymer was mixed in a mixer with the composition shown in Table 2, and under a nitrogen atmosphere at 200 ° C. and 200 rp.
m into a twin-screw extruder and melt mixed. Table 2 shows the physical properties measured by molding the obtained mixture into various test pieces with an injection molding machine.

[0038]

[Table 2]

[0039]

INDUSTRIAL APPLICABILITY According to the present invention, a reactive acrylic resin and a reactive thermoplastic block copolymer having reactivity with each other with respect to a hydrogenated product of the acrylic resin and the thermoplastic block copolymer, respectively. By blending a hydrogenated product and kneading at the same time, a thermoplastic resin composition which is not only flexible and has high surface hardness but also excellent in processability and weather resistance and having a transparent feeling is provided.

Claims (1)

[Claims] 1. A number-average molecular weight of (A): 10 to 90% by weight of an acrylic resin, and (B): an aromatic vinyl monomer.
000 to 80,000 block (a) and isoprene and / or butadiene having a number average molecular weight of 20,000
To 200,000 blocks (b) and the aromatic vinyl monomer component is contained in a proportion of 10 to 60% by weight based on the total weight of (a) and (b). The weight ratio is 10/90 to 90/1 with respect to 100 parts by weight of a resin composition consisting of 90 to 10% by weight of a hydrogenated product of a thermoplastic block copolymer of 30,000 to 300,000.
(C) in the range of 0: an acrylic resin having a hydroxyl group or an active hydrogen group such as a primary or secondary amino group at the end of the molecular chain,
And (D): a total amount of hydrogenated products of a thermoplastic block copolymer composed of a block composed of an aromatic vinyl monomer and a block composed of isoprene and / or butadiene and modified with a carboxyl group. A thermoplastic resin composition containing 2 to 50 parts by weight.