KR102087151B1 - Thermoplastic resin and method for preparing thereof - Google Patents

Abstract

The present invention relates to a thermoplastic resin and a method for manufacturing the same. According to the present invention, an aromatic vinyl compound such as a styrene monomer is excluded, and a thermoplastic resin having excellent heat resistance and scratch resistance and a transparent thermoplastic resin using a compound having a specific glass transition temperature range in the homopolymer type and also a radical initiator having a specific half life and It has the effect of providing a method for its manufacture.

Description

Thermoplastic resin and its manufacturing method {THERMOPLASTIC RESIN AND METHOD FOR PREPARING THEREOF}

The present invention relates to a thermoplastic resin and a method for manufacturing the same, and more particularly, to an aromatic vinyl compound such as a styrene monomer, excluding the heat resistance and scratch resistance, and a transparent thermoplastic resin having excellent heat resistance and scratch resistance.

Conventional methods for producing transparent resins include emulsion polymerization, turbid polymerization, solution polymerization, and bulk polymerization. Among them, emulsification polymerization and suspension polymerization should use emulsifiers, viscosity enhancers, flocculants, etc. during polymerization, and these additives are not completely removed in the final step and remain as impurities in the final product, which causes deterioration of physical properties. In addition, after the polymerization is completed, the reaction medium has to undergo additional processes such as dehydration and agglomeration or drying to remove water, and the removed water is purified again, which is economically expensive.

On the other hand, solution polymerization or bulk polymerization is difficult to control the heat of reaction or the viscosity of the reaction solution, but there are no additional additives for polymerization, so there are very few impurities remaining in the final product. Since all of them are recovered and reused, they have the advantage of low production cost unlike emulsion polymerization or suspension polymerization.

On the other hand, acrylonitrile-butadiene-styrene (hereinafter referred to as ABS) resins based on styrene have rigidity, chemical resistance, impact resistance, and workability, and have impact strength and mechanical properties, surface gloss, plating, printing, and painting. It has excellent secondary processing characteristics, and has the advantage of being able to produce products of various colors. However, the use of the ABS resin itself is limited to parts requiring transparency, such as parts for automobile interior and exterior materials requiring heat resistance, transparent window washing machines for transparency, dust cups for cleaning, and transparent windows for office equipment.

In order to overcome the above problems, a technique for providing transparency to a plastic material using polycarbonate resin and having excellent transparency and impact resistance at room temperature is known. However, there is a problem in that the chemical resistance is weak and the impact resistance is poor at low temperature, and the processability is insufficient, so there is a limit to apply to large parts.

In addition, U.S. Patent No. 3,787,522 and Japanese Patent Publication No. 63-42940 disclose a method for securing transparency and processability by imparting impact resistance to a transparent PMMA resin. However, the impact resistance is still very weak, which limits its application.

In addition, although European Patent No. 0 703 252 discloses a method of imparting transparency to HIPS (High Impact Polystyrene) resin, there is a problem that chemical resistance and scratch resistance are deteriorated.

Meanwhile, a method of introducing a monomer having excellent heat resistance, such as maleimide or alpha methyl styrene, has been developed in a part of the composition to produce an ABS resin having excellent heat resistance. However, the maleimide monomer has a very high polymerization rate, so it is very difficult to control the reaction temperature, and it is difficult to apply it by increasing its content in the resin. In fact, the more it is contained, the lower the compatibility and impact strength with the ABS resin. In addition, the alphamethyl styrene monomer has a disadvantage in that the polymerization rate is very slow, and thus a long reaction time is required, and the resulting polymer has a low molecular weight and easily decomposes.

In order to solve the transparency problem of the ABS resin, a transparent ABS in which the refractive index of the rubber phase and the continuous phase matrix resin are matched has been developed, wherein the matrix resin is methyl methacrylate-styrene-acrylonitrile copolymer (hereinafter referred to as MSAN). Is usually used. However, there is still a problem that such a transparent ABS is limited to applications requiring both scratch resistance and heat resistance.

As a generalized method to supplement the scratch resistance of the surface of the ABS resin, a method of blending PMMA with ABS resin has been developed (US Patent No. 7173093, US Patent No. 5489633). In addition, Korean Patent Publication No. 10-2001-0063763 is intended to improve the thermal discoloration of PMMA using a polyfunctional high temperature initiator, and Korean Patent Publication No. 10-2004-0105464 is an acrylate-styrene-acrylonitrile resin (hereinafter referred to as ASA). Invented a method of blending a butadiene-styrene-methylmethacrylate ternary copolymer and an alkyl acrylate copolymer in) to disclose an ASA resin composition having excellent basic properties and excellent appearance properties such as scratch resistance, color, and gloss. do. However, the matrix resins have a technical limitation that cannot simultaneously improve heat resistance and scratch resistance.

In order to overcome the problems of the prior art, the present invention excludes an aromatic vinyl compound such as a styrene monomer, and uses a radical initiator having a specific glass transition temperature and a compound having a specific glass transition temperature range in the homopolymer type, thereby providing heat resistance and resistance. An object of the present invention is to provide a thermoplastic resin having excellent scratch resistance and a method for manufacturing the same.

The above and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention is a copolymer of (meth) acrylic acid alkyl ester compound-alpha methylene gamma butyrolactone-vinyl cyan compound,

The (meth) acrylic acid alkyl ester compound is more than 45% by weight to less than 75% by weight; 15% by weight or more and less than 54% by weight of the alphamethylene gamma-butyrolactone compound; And the vinyl cyan compound provides a thermoplastic resin, characterized in that 1 to 25% by weight.

In addition, the present invention (meth) acrylic acid alkyl ester compound more than 45% by weight to 75% by weight or less; Alpha methylene gamma-butyrolactone compound 15 wt% or more to less than 54 wt%; And vinyl cyan compound 1 to 25% by weight; to prepare a copolymer by reacting,

The reaction provides a method for producing a thermoplastic resin characterized by radical polymerization at a polymerization temperature of 110 to 160 ° C using a radical initiator having a half life of 2 to 30 minutes at 130 to 160 ° C.

In addition, the present invention is (meth) acrylic acid alkyl ester compound 50 to 70% by weight, alpha methylene gamma butyrolactone compound 16 to 32% by weight, vinyl cyanide compound 5 to 10% by weight, and benzene having an alkyl substituent having 2 to 6 carbon atoms A radical initiator and a molecular weight modifier are added to the mixture containing 18 to 23% by weight of the derivative and subjected to polymerization reaction,

The reaction provides a method for producing a thermoplastic resin characterized by radical polymerization at a polymerization temperature of 110 to 160 ° C using a radical initiator having a half life of 2 to 30 minutes at 130 to 160 ° C.

According to the present invention, an aromatic vinyl compound such as a styrene monomer is excluded, and a thermoplastic resin having excellent heat resistance and scratch resistance and a transparent thermoplastic resin is used by using a radical initiator having a specific glass transition temperature range and a specific half-life in the homopolymer type. And it has the effect of providing a method of manufacturing.

Hereinafter, the present invention will be described in detail.

The present inventors have heat resistance and scratch resistance when polymerizing (meth) acrylic acid alkyl ester compounds, alphamethylene gamma-butyrolactone compounds and vinyl cyan compounds with a radical initiator having a specific half-life, except for aromatic vinyl compounds such as styrene monomers. The present invention has been completed based on the confirmation that an excellent and transparent resin is provided.

Looking in detail the thermoplastic resin according to the present invention are as follows.

The thermoplastic resin according to the present invention is a copolymer of (meth) acrylic acid alkyl ester compound-alphamethylene gamma-butyrolactone-vinyl cyan compound, wherein the (meth) acrylic acid alkyl ester compound is greater than 45% by weight to less than 75% by weight; 15% by weight or more and less than 54% by weight of the alphamethylene gamma-butyrolactone compound; And the vinyl cyan compound is characterized in that 1 to 25% by weight.

Examples of the (meth) acrylic acid alkyl ester compound include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid decyl ester and ( Meta) acrylic acid may be one or more selected from the group consisting of lauryl ester.

The (meth) acrylic acid alkyl ester compound is, for example, (meth) acrylic acid alkyl ester compound, alpha methylene gamma butyrolactone compound and vinyl cyan compound out of 100% by weight, more than 45% by weight to 75% by weight or less, 50% by weight to It may contain 75% by weight, or 50 to 70% by weight, within this range heat resistance, scratch resistance, haze, transparency, chemical resistance (chemical resistance) and the like can provide improved effects. In particular, the larger the content of the compound, the more scratch resistance can be improved.

The alpha methylene gamma-butyrolactone compound may provide a radical polymerization site for a radical initiator described below, and may also serve to provide heat resistance by increasing the glass transition temperature of the thermoplastic resin. Considering this role, suitable alphamethylene gamma-butyrolactone compounds may have a glass transition temperature of 195 ° C or higher, 205 ° C or higher, or 220 ° C or higher, measured by gel permeation chromatography (GPC) for their homopolymers. For example, the alpha methylene gamma-butyrolactone compound may have a glass transition temperature of 330 ° C or less, 320 ° C or less, or 310 ° C or less measured by gel permeation chromatography (GPC) for the homopolymer.

The alpha methylene gamma butyrolactone compound is, for example, gamma methyl alpha methylene gamma butyrolactone, beta methyl alpha methylene gamma butyrolactone, beta ethyl alpha methylene gamma butyrolactone, and beta butyl alpha methylene gamma butyrolactone. It may be one or more selected from the group.

The alpha methylene gamma-butyrolactone compound is, for example, (meth) acrylic acid alkyl ester compound, alpha methylene gamma-butyrolactone compound and vinyl cyan compound of 100% by weight, more than 15% by weight to less than 54% by weight, 15% by weight to It may contain 45% by weight, or 16 to 32% by weight, and within this range, heat resistance, scratch resistance, haze, transparency, chemical resistance (chemical resistance), and the like may provide improved effects. In particular, the larger the content of the compound, the better the glass transition temperature can be.

The vinyl cyan compound may be, for example, one or more selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile.

The vinyl cyan compound may provide a radical polymerization site for a radical initiator to be described later, for example, (meth) acrylic acid alkyl ester compound, alpha methylene gamma-butyrolactone compound and vinyl cyan compound in total 100% by weight, 1% by weight To 25% by weight, 5% to 20% by weight, 5% to 15% by weight, or 5 to 10% by weight, and within this range, heat resistance, scratch resistance, haze, transparency, chemical resistance ( Chemical resistance) and the like.

The copolymer of the present invention is preferably a polymer with a radical initiator having a half life of 2 to 30 minutes at 130 to 160 ° C.

The radical initiator is, for example, 1,1-bis (t-butylperoxy) -2-methylcyclohexane (1,1-bis (t-butylperoxy) -2-methylcyclohexane), 1,1-bis (t-hex Silperoxy) -3,3,5-trimethylcyclohexane (1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane), 1,1-bis (t-hexylperoxy) cyclohexane (1 , 1-bis (t-hexylperoxy) cyclohexane), 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane (1,1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane), 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-di-t-butylperoxy) Cyclohexane) propane (2,2-bis (4,4-di-t-butylperoxy cyclohexane) propane), t-hexyl peroxy isopropyl monocarbonate, t-butylperoxymaleic acid (t-butyl peroxymaleic acid), t-butyl peroxy-3,5,5-trimethyl hexanoate, t-butyl peroxymaleic acid (t- butyl peroxylaurate), 2,5-dimethyl-2,5-bis (m-toluoyl peroxy) hexane (2,5-dimethyl-2,5-bis (m-toluoyl peroxy) hexane), t-butyl peroxy isopropyl monocarbonate, t- Hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis (benzoyl peroxy) hexane, t- T-butyl peroxyacetate, 2,2-bis (t-butyl peroxy) butane, t-butyl peroxybenzoate (t-butyl peroxybenzoate), n-butyl-4,4-bis (t-butyl peroxy) valerate, α, α'-bis (t-butyl Peroxy) diisopropyl benzene (α, α'-bis (t-butylperoxy) diisopropyl benzene), dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) Hexane (2,5-dimethyl-2,5-bis (t-butyl peroxy) hexane), t-butyl cumyl peroxide, di-t-butyl peroxide ), p-mentan hydroperoxide (p -Menthane hydroperoxide), 2,5-dimethyl-2,5-bis (t-butylperoxy) hexine-3 (2,5-dimethyl-2,5-bis (t-butyl peroxy) hexyne-3), etc. have.

The radical initiator may include 0.005 to 0.1 parts by weight, 0.01 to 0.1 parts by weight, or 0.005 to 0.01 parts by weight based on 100 parts by weight of the (meth) acrylic acid alkyl ester compound, the alphamethylene gamma-butyrolactone compound, and the vinyl cyan compound. It is possible to perform a sufficient radical polymerization within this range, there is an effect of providing a transparent resin excellent in heat resistance and scratch resistance.

The copolymer of the present invention may include an n-alkyl mercaptans molecular weight modifier.

The molecular weight modifier may be used as an example dodecyl mercaptans, the (meth) acrylic acid alkyl ester compound, alpha methylene gamma butyrolactone compound and vinyl cyan compound total 0.01 to 0.5 parts by weight, based on 100 parts by weight, 0.1 to It may contain 0.5 parts by weight, or 0.1 to 0.3 parts by weight, there is an effect to control the weight average molecular weight of the thermoplastic resin within this range.

The thermoplastic resin may be added with additives commonly used in this field. Examples include antibacterial agents, heat stabilizers, antioxidants, release agents, light stabilizers, inorganic additives, surfactants, coupling agents, plasticizers, compatibilizers, lubricants, antistatic agents, colorants, pigments, dyes, flame retardants, flame retardants, anti-dropping agents, weathering agents , UV absorbers and sunscreens may include one or more selected from the group consisting of.

The copolymer may be, for example, a weight average molecular weight of 80,000 to 300,000 g / mol, 80,000 to 150,000 g / mol, or 90,000 to 100,000 g / mol.

The thermoplastic resin may have a glass transition temperature of 130 ° C or higher, 145 ° C or higher, or 145 to 180 ° C, as measured by gel permeation chromatography (GPC), for example.

The thermoplastic resin may be, for example, pencil hardness according to ASTM D3365 or higher, or H or 2H.

The thermoplastic resin is a (meth) acrylic acid alkyl ester compound is used in excess, so basically to provide a transparent resin, for example, according to ASTM D1003 haze 1.0 and a light transmittance of 90% or more thermoplastic resin, or haze 0.4 or less and The light transmittance may be more than 92% thermoplastic resin.

The method for producing the thermoplastic resin of the present disclosure is, for example, more than 45% by weight to 75% by weight of the (meth) acrylic acid alkyl ester compound; Alpha methylene gamma-butyrolactone compound 15 wt% or more to less than 54 wt%; And vinyl cyan compound 1 to 25% by weight; to prepare a copolymer by reacting,

The reaction is characterized in that radical polymerization is performed at a polymerization temperature of 110 to 160 ° C using a radical initiator having a half life of 2 to 30 minutes at 130 to 160 ° C.

At this time, for the total of 100 parts by weight of the (meth) acrylic acid alkyl ester compound, the alphamethylene gamma-butyrolactone compound, and the vinyl cyan compound, 0.005 to 0.1 parts by weight of the radical initiator may be used.

The method can be performed under a benzene derivative substituted with an alkyl group having 2 to 6 carbon atoms as a solvent.

The benzene derivative substituted with an alkyl group having 2 to 6 carbon atoms may be, for example, one or more selected from the group consisting of ethylbenzene, toluene, and xylene. In this case, when ethylbenzene is used, styrene-based monomers are removed by hydrogen evolution during the reaction. It can further provide the effect provided.

The benzene derivative substituted with the alkyl group having 2 to 6 carbon atoms is 15 to 40 parts by weight, 20 to 35 parts by weight based on 100 parts by weight of the (meth) acrylic acid alkyl ester compound, alpha methylene gamma butyrolactone compound, and vinyl cyan compound Parts, or 20 to 30 parts by weight.

Other examples of the method for producing the thermoplastic resin of the present disclosure include (meth) acrylic acid alkyl ester compound 50 to 70% by weight, alpha methylene gamma butyrolactone compound 16 to 32% by weight, vinyl cyanide compound 5 to 10% by weight, and carbon number 2 A radical initiator and a molecular weight modifier are added to a mixture containing 18 to 23% by weight of a benzene compound having an alkyl substituent of 6 to 6, and polymerization reaction is performed.

The reaction is characterized in that radical polymerization is performed at a polymerization temperature of 110 to 160 ° C using a radical initiator having a half life of 2 to 30 minutes at 130 to 160 ° C.

At this time, with respect to the total 100 parts by weight of the mixture, as described above, a radical initiator 0.005-0.1 parts by weight, and a molecular weight modifier 0.01-0.5 parts by weight may be used.

Further, the manufacturing method of the present disclosure further includes the step of removing the unreacted compound by extruding the obtained polymerization product by extruding it for devolatilization while maintaining the polymerization temperature of 200 to 220 ° C; and further providing trace amounts of residual components. .

The reaction is, for example, to sufficiently perform a radical polymerization reaction, for example, polymerization for 2 to 8 hours at 110 to 160 ° C, or polymerization for 2 to 4 hours at 110 to 140 ° C, and then additionally 2 to 4 at 120 to 160 ° C. It can polymerize for an hour.

The thermoplastic resin according to the present invention can provide improved scratch resistance and heat resistance to the composition of the ABS resin composition when used as a matrix resin for a universal grade ABS resin. For example, the thermoplastic resin of the present invention may be in the range of 10 to 90% by weight of the total 100% by weight of the desired ABS resin composition.

Hereinafter, preferred embodiments are provided to help understanding of the present invention, but the following examples are merely illustrative of the present invention, and it is obvious to a person skilled in the art that various changes and modifications are possible within the scope and technical scope of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.

[Example]

Example 1

50 parts by weight of methyl methacrylate, 40 parts by weight of beta-methyl-alphamethylene-gamma butyrolactone, 10 parts by weight of acrylonitrile, a benzene derivative substituted with an alkyl group having 2 to 6 carbon atoms, and molecular weight modifier for 25 parts by weight of ethylbenzene As a raw material mixed with 0.15 parts by weight of dietary dodecyl mercaptan, the reaction temperature was maintained at 148 ° C. by continuously introducing the reaction material to an average reaction time of 3 hours.

1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane (1,1-bis (t-hexylperoxy)) as a radical initiator having a half-life of 2 to 30 minutes at 130 to 160 ° C in the reaction tank -3,3,5-trimethylcyclohexane) 0.01 parts by weight was added and polymerized at 110 to 140 ° C for 2 to 4 hours, followed by radical polymerization at 120 to 160 ° C for 2 to 4 hours.

The polymerization solution discharged from the reaction tank was heated in a preliminary heating tank, unreacted compounds were volatilized in a volatilization tank, and the polymer temperature was maintained at 210 ° C, so that the copolymer was processed into pellets using a polymer transfer pump extrusion processor. The weight average molecular weight of the produced copolymer was about 100,000 g / mol.

Example 2

In Example 1, the same process as in Example 1 was repeated except that methyl methacrylate was used in 60 parts by weight, and beta-methyl-alphamethylene-gamma butyrolactone was used in 30 parts by weight. Processed. The weight average molecular weight of the produced copolymer was about 90,000 g / mol.

Example 3

In Example 1, the same process as in Example 1 was repeated except that methyl methacrylate was used in 70 parts by weight and beta-methyl-alphamethylene-gamma butyrolactone was used in 20 parts by weight. Processed. The weight average molecular weight of the produced copolymer was about 100,000 g / mol.

Comparative Example 1

In Example 1, methyl methacrylate was used in 70 parts by weight, and styrene (Tg: ~ 90 ° C of homopolymer) instead of beta-methyl-alphamethylene-gamma butyrolactone was used in an amount of 20 parts by weight. The same process as in Example 1 was repeated to process the copolymer into pellet form. The copolymer had a weight average molecular weight of about 110,000 g / mol.

Comparative Example 2

In Example 1, 70 parts by weight of styrene (Tg of homopolymer: ~ 90 ° C) was used instead of methyl methacrylate (Tg: 115 ° C of syndiotic type homopolymer), and beta-methyl-alphamethylene-gamma The same process as in Example 1 was repeated except that 20 parts by weight of butyrolactone was used to process the copolymer into pellets. The weight average molecular weight of the produced copolymer was about 100,000 g / mol.

Comparative Example 3

In Example 1, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane (1,1-bis (t-) as a radical initiator having a half-life of 2 to 30 minutes at 130 to 160 ° C. hexylperoxy) -3,3,5-trimethylcyclohexane) The same process as Example 1, except that 0.01 part by weight of lauryl peroxide having a half-life of 0.5 seconds to 10 minutes at 80 to 120 ° C was replaced with 0.01 part by weight. Was repeated to process the copolymer into pellet form. The weight average molecular weight of the produced copolymer was about 80,000 g / mol.

Comparative Example 4

In Example 1, the same process as in Example 1 was used except that methyl methacrylate was used in 55 parts by weight, beta-methyl-alphamethylene-gamma butyrolactone was used in 45 parts by weight, and acrylonitrile was not used. The copolymer was repeatedly processed into pellets. The copolymer had a weight average molecular weight of about 98,000 g / mol.

Reference Example 1

In Example 1, the same process as in Example 1 was repeated except that methyl methacrylate was used in 35 parts by weight and beta-methyl-alphamethylene-gamma butyrolactone was used in 55 parts by weight. And processed. The copolymer had a weight average molecular weight of about 110,000 g / mol.

Reference Example 2

In Example 1, the same process as in Example 1 was repeated except that methyl methacrylate was used in 80 parts by weight and beta-methyl-alphamethylene-gamma butyrolactone was used in 10 parts by weight. And processed. The copolymer had a weight average molecular weight of about 98,000 g / mol.

[Test Example]

The properties of the specimens obtained in Examples 1 to 3 and Comparative Examples 1 to 4 and Reference Examples 1 to 2 were measured by the following methods, and the results are shown in Tables 1 and 2 below.

Method of measuring properties

<Weight average molecular weight>

The sample was dissolved in THF (tetrahydrofuran) and measured using gel permeation chromatography (GPC).

<Glass transition temperature>

Samples were measured using a differential scanning calorimeter (DSC, PERKIN ELMER).

<Pencil hardness>

Samples were measured according to ASTM D3365.

<Haze and light transmittance>

Samples were measured according to ASTM D1003.

<Chemical resistance test-ESCR measurement>

The specimen for measurement was prepared by injection of the sample, and after setting it on a jig of strain 0.5, a 70% solution of isopropyl alcohol was dropped to visually compare and observe the presence or absence of surface cracks. For reference, it was evaluated as good if no crack occurred, normal when fine crack occurred, and defective when broken.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Glass transition temperature (℃) 176 162 145 110 142 140 147 Pencil hardness H 2H 2H 2H HB H 2H Haze 0.4 0.4 0.3 0.5 1.0 1.5 0.4 Light transmittance (%) 92 92 92 92 91 87 92 Chemical resistance (chemical resistance) Good Good usually Bad Good Bad Bad

division Reference Example 1 Reference Example 2 Glass transition temperature (℃) 200 125 Pencil hardness HB 2H Haze 0.6 0.4 Light transmittance (%) 91 92 Chemical resistance (chemical resistance) Good Bad

As shown in Table 1, the thermoplastic resins of Examples 1 to 3 prepared according to the present invention were confirmed to provide pencil hardness H or higher, heat resistance, haze, light transmittance, and chemical resistance (chemical resistance).

On the other hand, in Comparative Example 1, it was confirmed that the glass transition temperature was poor, in Comparative Example 2, it was confirmed that the pencil hardness was poor, and in Comparative Example 3, haze, light transparency, and chemical resistance were also poor. In the case of Comparative Example 4, it was possible to confirm the result of poor chemical resistance.

Furthermore, as shown in Table 2, in the case of Reference Example 1, the pencil hardness was not good, and in the case of Reference Example 2, it was confirmed that the glass transition temperature was not high.

Heat resistance when radical polymerization of a (meth) acrylic acid alkyl ester compound or the like using a radical initiator having a specific glass transition temperature and a specific half-life in a homopolymer type, except for an aromatic vinyl compound such as a styrene monomer from this And a scratch-resistant and transparent resin.

Claims (11)

As a copolymer of (meth) acrylic acid alkyl ester compound-alpha methylene gamma butyrolactone-vinyl cyan compound,
The (meth) acrylic acid alkyl ester compound is more than 45% by weight to less than 75% by weight; 15% by weight or more and less than 54% by weight of the alphamethylene gamma-butyrolactone compound; And the vinyl cyan compound is 1 to 25% by weight,
The copolymer is 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane (1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane) as a radical initiator. Including polymerization,
Thermoplastic resin characterized in that the glass transition temperature measured by differential scanning calorimeter (DSC) is 145 to 180 ° C. delete According to claim 1,
The copolymer is a thermoplastic resin, characterized in that it further comprises an n-alkyl mercaptans molecular weight modifier. delete According to claim 1,
The thermoplastic resin is a thermoplastic resin, characterized in that the pencil hardness according to ASTM D3365 H or more. According to claim 1,
The copolymer is a thermoplastic resin, characterized in that the weight average molecular weight of 80,000 to 300,000 g / mol. (Meth) acrylic acid alkyl ester compound more than 45% by weight to 75% by weight or less; Alpha methylene gamma-butyrolactone compound 15 wt% or more to less than 54 wt%; And vinyl cyan compound 1 to 25% by weight; to prepare a copolymer by reacting,
The reaction is radical polymerization using 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane as a radical initiator at a polymerization temperature of 110 to 160 ° C,
Method for producing a thermoplastic resin, characterized in that the glass transition temperature measured by differential scanning calorimeter (DSC) is 145 to 180 ℃. The method of claim 7,
The (meth) acrylic acid alkyl ester compound, alpha methylene gamma-butyrolactone compound, and vinyl cyanide compound A method for producing a thermoplastic resin, characterized in that 0.005-0.1 parts by weight of a radical initiator is used with respect to 100 parts by weight. (Meth) acrylic acid alkyl ester compound 50 to 70% by weight, alphamethylene gamma butyrolactone compound 16 to 32% by weight, vinyl cyanide compound 5 to 10% by weight, and benzene derivatives having 2 to 6 alkyl substituents 18 to 23 A radical initiator and a molecular weight modifier are added to the mixture containing weight% and subjected to polymerization reaction,
The reaction is radical polymerization using 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane as a radical initiator at a polymerization temperature of 110 to 160 ° C,
Method for producing a thermoplastic resin, characterized in that the glass transition temperature measured by differential scanning calorimeter (DSC) is 145 to 180 ℃. The method of claim 9,
A method for producing a thermoplastic resin, characterized in that 0.005-0.1 parts by weight of a radical initiator and 0.01-0.5 parts by weight of a molecular weight modifier are used with respect to 100 parts by weight of the total mixture. The method of claim 7 or 9,
A method of manufacturing a thermoplastic resin, further comprising the step of extruding by removing the unreacted compound by introducing the obtained polymerization product into an extruder for devolatilization while maintaining a polymerization temperature of 200 to 220 ° C.