JP2010013613A - Acrylic block copolymer, thermoplastic copolymer composition, and molded article made of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an acrylic block copolymer and a thermoplastic copolymer composition having excellent heat resistance, molding processability, colorless transparency, and impact resistance, with little foreign substance generation amount under a high temperature detention, in particular, having excellent dimension size stability under a high temperature wet heat. <P>SOLUTION: The acrylic block copolymer (A) includes (a) a polymer block having (i) a ring structure unit represented by general formula (1), (ii) an unsaturated carboxylic acid alkyl ester monomer unit and (iii) another copolymerizable vinyl monomer unit, and (b) a polymer block having an acrylate monomer unit. The acrylic block copolymer (A) satisfies that (I) (iii) the other polymerizable vinyl monomer unit is included by 0.1-20 wt.% with respect to 100 wt.% of (i) the ring structure unit represented by the general formula (1) of the (A) acrylic block copolymer, and that (II) the weight average molecular weight is 50,000-300,000. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention is an acrylic block copolymer that is excellent in heat resistance, molding processing characteristics, colorless transparency, impact resistance, generates a small amount of foreign matter under high temperature residence, and is particularly excellent in dimensional stability under high temperature wet heat and The present invention relates to a thermoplastic copolymer composition.

  Amorphous resins such as polymethyl methacrylate (hereinafter referred to as “PMMA”) and polycarbonate (hereinafter referred to as “PC”) make use of transparency and dimensional stability of optical materials, household electrical appliances, office automation equipment, automobiles, and the like. It is used in a wide range of fields including parts.

  In recent years, these resins have been widely used in higher performance optical materials such as optical lenses, prisms, mirrors, optical disks, optical fibers, liquid crystal display sheets and films, light guide plates, etc. The optical properties, moldability (fluidity), and heat resistance required for the products are also higher.

  At present, these transparent resins are also used as lamp members for automobiles such as tail lamps and head lamps, but in recent years, tail lamp lenses, inner lenses, There is a tendency to reduce the distance between various light sources such as headlamps and shield beams and the light source, and to reduce the thickness of the parts, and there is a demand for excellent moldability (fluidity). Further, since the vehicle is used under severe conditions, it is required to have a small shape change under high temperature and high humidity, and excellent scratch resistance, weather resistance, and oil resistance.

  However, although PMMA resin has excellent transparency and weather resistance, there is a problem that heat resistance is not sufficient. On the other hand, although PC resin is excellent in heat resistance and impact resistance, it has a large birefringence, which is an optical strain, and optical anisotropy occurs in the molded product, molding processability (fluidity), scratch resistance, There was a problem that oil resistance was remarkably inferior.

  Therefore, for the purpose of improving the heat resistance of PMMA, a resin in which a maleimide monomer or a maleic anhydride monomer is introduced as a heat resistance imparting component has been developed. However, maleimide monomers are expensive and have low reactivity, and maleic anhydride has a problem of poor thermal stability.

  As methods for solving these problems, copolymers containing glutaric anhydride units or lactone ring units are disclosed in, for example, Patent Documents 1 and 2, but these copolymers are brittle, resin and The impact resistance of the film was insufficient.

  As methods for improving impact resistance, Patent Documents 3 to 5 disclose methods of adding multilayer organic fine particles having a shell layer compatible with a copolymer and a core layer of a crosslinked elastomer.

  However, the methods disclosed in these patent documents are excellent in colorless transparency and impact resistance, but the moldability (fluidity) and heat resistance are never satisfactory. There was a case to increase. The multilayer organic fine particles tend to generate aggregates under residence, and have a cross-linked structure, so that the aggregates are insoluble and infusible, making it difficult to remove the aggregates.

  Further, although a block copolymer comprising a block containing a glutaric anhydride unit and a block containing an elastomer component is disclosed in Patent Document 6, although it exhibits excellent characteristics regarding colorless transparency and impact resistance, In addition, when introducing a glutaric anhydride unit by intramolecular cyclization reaction, it is heated for a long time at a high temperature. Patent Document 6 discloses a thermoplastic resin composition in which a block copolymer composed of a block containing a glutaric anhydride unit and a block containing an elastomer component is added to another thermoplastic resin. The thermoplastic resin that does not have excellent impact resistance and molding processability, but the transparency of the thermoplastic resin that has transparency is low, the performance as an optical material is not sufficient. Further, in the polymerization method of Patent Document 6, it is very difficult to remove the metal complex used in the polymerization, and it remains in the polymer, and the thermoplastic copolymer composition finally obtained is colored and kept at high temperature. There was a problem that the amount of foreign matter generated increased. Furthermore, in patent document 6, since the intramolecular cyclization reaction at the time of introduce | transducing a glutaric anhydride unit is inadequate, and the ratio of the hydrophilic unsaturated carboxylic acid which is a precursor of glutaric anhydride is high, it is high temperature. There was a problem that the dimensional change due to water absorption under wet heat increased.

In other words, for use in higher performance optical materials such as optical lenses, prisms, mirrors, optical disks, optical fibers, liquid crystal display sheets and films, light guide plates, etc. There has been a demand for an acrylic block copolymer and a thermoplastic copolymer composition that are excellent in impact properties, generate a small amount of foreign matter under high temperature residence, and are particularly excellent in dimensional stability under high temperature wet heat.
JP 2004-51928 A (Page 1-2, Examples) JP 2002-138106 A (page 1-2, Examples) JP 2007-169626 A (page 1-2, Examples) JP-A-7-149994 (Section 1-2, Examples) JP 2007-254727 A (No. 1-2, Example) JP-A-2004-013192 (Section 1-2, Example)

  The present invention is an acrylic block copolymer that is excellent in heat resistance, molding processing characteristics, colorless transparency, impact resistance, generates a small amount of foreign matter under high temperature residence, and is particularly excellent in dimensional stability under high temperature wet heat and It is an object of the present invention to provide a thermoplastic copolymer composition.

  As a result of intensive studies to solve the above problems, the present inventors have found that a polymer comprising a specific ring structure unit, an unsaturated carboxylic acid alkyl ester monomer unit, and other copolymerizable vinyl monomer units. Acrylic block copolymer (A) comprising a block (a) and a polymer block (b) having an acrylate monomer unit alone or an acrylic having a glass transition temperature of 120 ° C. or higher having a specific ring structure unit By blending the copolymer (B), the amount of foreign matter generated is low even under high temperature retention, molding processability (fluidity), colorless transparency, heat resistance, which could not be achieved with conventional knowledge. The present inventors have found that an acrylic block copolymer and a thermoplastic copolymer composition excellent in impact resistance, particularly dimensional stability under high-temperature wet heat, can be obtained, and the present invention has been achieved.

That is, the present invention
[1] having (i) a ring structural unit represented by the following general formula (1), (ii) an unsaturated carboxylic acid alkyl ester monomer unit, and (iii) other copolymerizable vinyl monomer units An acrylic block copolymer (A) comprising a polymer block (a) and a polymer block (b) having an acrylate monomer unit satisfies the following (I) to (III): Acrylic block copolymer.
(I) Acrylic block copolymer (A) (i) The ring structural unit represented by the following general formula (1) is 100% by weight, and (iii) Other copolymerizable vinyl monomer units are 0. .1-20% by weight.
(II) The weight average molecular weight is 50,000 to 300,000.

(However, R ¹ and R ² are the same or different and represent any one selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms and an alkyl ester group, and R ³ represents a ketone group and a carbon number. And any one selected from alkyl groups having 1 to 20; R ⁴ represents an oxygen atom or NR ⁵ ; and R ⁵ represents any one selected from a hydrogen atom and an organic residue having 1 to 20 carbon atoms)
[2] The acrylic block copolymer according to [1], wherein the ring structural unit represented by the general formula (1) is a glutaric anhydride represented by the following general formula (2). Polymer.

(However, R ⁶ and R ⁷ are the same or different and represent any one selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms.)
[3] In the acrylic block copolymer (A), the acrylic block copolymer (A) is 100% by weight, the polymer block (a) is 20 to 80% by weight, and the polymer block (b) ) Is contained in an amount of 20 to 80% by weight. The acrylic block copolymer according to [1] or [2].
[4] The acrylic block copolymer (A) is represented by the general formula ab or the general formula (ab) _n -a (n is an integer of 1 or more, and a is (i) the above general formula. The polymer block (a) having a ring structural unit represented by (1) and b represents a polymer block (b) having an acrylate unit)) [1] -The acrylic block copolymer in any one of [3].
[5] The polymer block (a) of the acrylic block copolymer (A), wherein the polymer block (a) is 100% by weight, (i) a ring structure represented by the general formula (1) 5 to 50% by weight unit, (ii) 50 to 95% by weight of unsaturated carboxylic acid alkyl ester monomer unit, and (iii) 0.05 to 10% by weight of other copolymerizable vinyl monomer units. The acrylic block copolymer according to any one of the above [1] to [4].
[6] The polymer block (b) of the acrylic block copolymer (A) is composed of 100% by weight of the polymer block (b), and (iv) 70 to 100% by weight of acrylate monomer units. And (v) the acrylic block copolymer according to any one of [1] to [5] above, which contains 0 to 30% by weight of an aromatic vinyl monomer unit.
[7] The above (1) to [6], wherein (iv) the acrylate ester monomer unit of the polymer block (b) is n-butyl acrylate and / or ethyl acrylate. The acrylic block copolymer according to any one of the above.
[8] The acrylic block copolymer as described in any one of [1] to [7], wherein the acrylic block copolymer (A) satisfies the following (III) and / or (IV): Coalescence.
(III) The content of insoluble matter in a 5% by weight solution of tetrahydrofuran is 1% by weight or less.
(IV) The total light transmittance per 2 mm thickness of the thermoplastic copolymer composition is 90% or more.
[9] Acrylic block copolymer (A) according to any one of [1] to [8] and (i) the same ring structural unit as the polymer block (a) represented by the general formula (1) A thermoplastic copolymer composition comprising an acrylic copolymer (B) having a glass transition temperature of 120 ° C. or higher.
[10] The acrylic block copolymer (A) and the acrylic copolymer (B) are 100% by weight in total, the acrylic block copolymer (A) is 5 to 50% by weight, and the acrylic copolymer. The thermoplastic copolymer composition as described in [9] above, wherein (B) is blended in an amount of 50 to 95% by weight.
[11] Acrylic block copolymer (A) and acrylic copolymer (B) (i) where the total of the cyclic structural units represented by the general formula (1) is 100% by weight, the acrylic block copolymer The above [9], wherein the total of (iii) other copolymerizable vinyl monomer units of the polymer (A) and the acrylic copolymer (B) is 0.1 to 20% by weight [10] The thermoplastic resin composition according to [10].
[12] The cyclic structural unit represented by the general formula (1) of the acrylic copolymer (B) is a glutaric anhydride represented by the general formula (2). [9] The thermoplastic copolymer composition according to any one of [11].
[13] The thermoplastic copolymer composition as described in any one of [9] to [12] above, wherein the acrylic copolymer (B) has a weight average molecular weight of 30,000 to 150,000. object.
[14] The acrylic copolymer (B) comprises 100% by weight of the acrylic copolymer (B), and (i) 5 to 50% by weight of the ring structural unit represented by the general formula (1). (Ii) containing 50 to 95% by weight of unsaturated carboxylic acid alkyl ester units, and (iii) 0.05 to 10% by weight of other copolymerizable vinyl monomer units. [13] The thermoplastic copolymer composition according to any one of the above.
[15] A thermoplastic copolymer composition comprising an acrylic block copolymer (A) and an acrylic copolymer (B) satisfies the above (III) and / or (IV) The thermoplastic copolymer composition according to any one of [9] to [14].
[16] A molded article comprising the acrylic block copolymer according to any one of [1] to [8] or the thermoplastic copolymer composition according to any one of [9] to [15]. .
[17] The molded product according to [16], wherein the molded product is a film.

  According to the present invention, an acrylic block copolymer having excellent heat resistance, molding processing characteristics, colorless transparency, impact resistance, a small amount of foreign matter generated even under high temperature residence, and particularly excellent in dimensional stability under high temperature wet heat and It has become possible to provide a thermoplastic copolymer composition.

  Hereinafter, the thermoplastic copolymer composition of the present invention will be specifically described.

<Acrylic block copolymer (A)>
The acrylic block copolymer (A) of the present invention includes (i) a ring structural unit represented by the following general formula (1), (ii) an unsaturated carboxylic acid alkyl ester monomer unit, and (iii) It is an acrylic block copolymer comprising a polymer block (a) having a copolymerizable vinyl monomer unit and a polymer block (b) having an acrylate monomer unit.

(However, R ¹ and R ² are the same or different and represent any one selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms and an alkyl ester group, and R ³ represents a ketone group and a carbon number. And any one selected from alkyl groups having 1 to 20; R ⁴ represents an oxygen atom or NR ⁵ ; and R ⁵ represents any one selected from a hydrogen atom and an organic residue having 1 to 20 carbon atoms)

In the acrylic block copolymer (A) of the present invention, (i) as the ring structural unit represented by the general formula (1), R ¹ and R ² are the same or different, and a hydrogen atom and Any one selected from alkyl groups having 1 to 20 carbon atoms, R ³ is a ketone group, R ⁴ is an oxygen atom, and R ¹ and R ² are the same or different. , A hydrogen atom and an alkyl group having 1 to 5 carbon atoms, R ³ is a ketone group, R ⁴ is represented by NR ⁵ , R ⁵ is hydrogen and an organic residue having 1 to 20 carbon atoms. A glutarimide unit selected from a group, R ¹ is an alkyl group having 1 to 20 carbon atoms, R ² is an alkyl ester group having 1 to 20 carbon atoms, and R ³ is an alkyl group having 1 to 20 carbon atoms. Examples include lactone ring units. The organic residue having 1 to 20 carbon atoms is not particularly limited, and may be linear, branched or cyclic, and may contain a hetero atom in the structure. R ⁵ is preferably a hydrogen atom, an unsubstituted or halogen-substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic group having 5 to 20 carbon atoms with halogen or an aliphatic hydrocarbon group It is preferably a group selected from a group, unsubstituted or substituted with a halogen or an aliphatic hydrocarbon group, a C3-C20 alicyclic hydrocarbon group, or a C1-C20 hydroxyalkyl group. Is a hydrogen atom, an unsubstituted or halogenated alkyl group having 1 to 6 carbon atoms, an unsubstituted or phenyl group substituted with a halogen or an alkyl group, an unsubstituted or substituted naphthyl group with a halogen or an alkyl group, an Substituted or substituted benzyl group with halogen or alkyl group, unsubstituted or substituted cycloalkyl group with halogen or alkyl group A group selected from an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom, a cyclohexyl group, an unsubstituted or halogen-substituted alkyl group having 1 to 6 carbon atoms. Particularly preferred are a hydrogen atom or a methyl group. For example, a hydrogen atom is most preferred from the viewpoint of improving heat resistance with a small content of a ring structural unit.

  The acrylic block copolymer (A) of the present invention is composed of (i) 100% by weight of the ring structural unit represented by the general formula (1), and (iii) other copolymerizable vinyl monomer units. Is preferably 0.1 to 20% by weight. (Iii) When the copolymerizable vinyl monomer unit is higher than 20% by weight, the dimensional stability under high-temperature wet heat is poor, and in order to make it lower than 0.1% by weight, an intramolecular cyclization step Since it is necessary to increase the heat history at, transparency tends to decrease. More preferably, the ring structural unit is 100% by weight, and (iii) other copolymerizable vinyl monomer units are 0.1 to 15% by weight, especially (iii) other copolymerizable vinyl monomers. More preferably, the unit is 0.1 to 10% by weight.

  The acrylic block copolymer (A) of the present invention is composed of (i) a polymer block (a) having a ring structural unit represented by the above general formula (1) and a polymer having an acrylate monomer unit. The ratio of the combined block (b) is such that the acrylic block copolymer (A) is 100% by weight, the polymer block (a) is 20 to 90% by weight, and the polymer block (b) is 10 to 80% by weight. Preferably there is. When the polymer block (a) is higher than 90% by weight, the impact resistance is poor, and when it is lower than 20% by weight, the colorless transparency tends to be lowered. When the acrylic block copolymer (A) is used alone, it is preferably 20 to 90% by weight of the polymer block (a) and 10 to 80% by weight of the polymer block (b). It is more preferable that a) is 30 to 90% by weight and the polymer block (b) is 10 to 70% by weight. In addition, when the acrylic block copolymer (A) is used by blending with an acrylic copolymer having the same ring structure unit as the polymer block (a) and having a glass transition temperature of 120 ° C. or higher, the polymer block ( a) 20 to 80% by weight, polymer block (b) 20 to 80% by weight, especially polymer block (a) 30 to 70% by weight, polymer block (b) 30 to 70% by weight It is more preferable that

  When the polymer block (a) constituting the acrylic block copolymer (A) of the present invention is 100% by weight, (i) / (ii) / (iii) = 5-50 / 95-50 / 0.05 When 10% by weight is preferred, and (i) exceeds 50% by weight, there is a problem that molding processability (fluidity) is inferior due to a significant increase in viscosity accompanying an increase in glass transition temperature (Tg). When i) is lower than 5% by weight, there is a problem that heat resistance is lowered. More preferably (i) / (ii) / (iii) = 10-40 / 90-60 / 0.05-5% by weight, especially (i) / (ii) / (iii) = 10-40 / 90-60 / 0.05-3 weight% is preferable.

  In addition, (i) is a ring structural unit represented by the above general formula (1), (ii) is an unsaturated carboxylic acid alkyl ester unit, and (iii) is a copolymerizable vinyl unit.

  The polymer block (b) constituting the acrylic block copolymer (A) of the present invention is defined as 100% by weight, and (iv) 70 to 100% by weight of an acrylate monomer unit, (v) an aromatic vinyl unit It is preferable to contain 0 to 30% by weight of monomer units. From the viewpoint of impact resistance, (iv) 75% by weight or more of an acrylate monomer unit is more preferable.

  (Iv) Preferable specific examples of the monomer used as a raw material for the acrylate ester unit include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, and n-acrylate. -Hexyl, cyclohexyl acrylate, chloromethyl acrylate, 2-chloroethyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2,3,4,5,6-pentahydroxyhexyl acrylate, acrylic Examples include acid 2,3,4,5-tetrahydroxypentyl and benzyl acrylate, and n-butyl acrylate is most preferably used. These can be used alone or in combination of two or more thereof.

  (V) Preferable specific examples of the monomer used as the raw material for the aromatic vinyl monomer unit include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, and p-ethyl. Examples thereof include aromatic vinyl monomers such as styrene and pt-butylstyrene, and one or more of them can be used.

The structure of the acrylic block copolymer (A) of the present invention is preferably a general formula ab or a general formula (ab) _n -a (n is an integer of 1 or more). Among these, from the viewpoint of colorless transparency and impact resistance, it is preferable to include a block copolymer represented by the general formula a-b-a (a in the general formula is (i) the following general formula (1) And b represents a polymer block having an acrylate unit).

  The method for producing the acrylic block copolymer (A) of the present invention is not particularly limited, but is preferably radical polymerization, and more preferably living radical polymerization.

  Living radical polymerization has been actively studied in recent years, and various methods have been proposed. In any case, the reversible generation of carbon radicals is controlled, radical polymerization proceeds when carbon radicals are generated, and the polymerization is stopped when the carbon radicals are captured by a scavenger. By controlling the generation of this irreversible radical, it is possible to suppress the termination reaction between radicals, that is, the termination reaction between radicals and chain transfer reaction to initiators, solvents, monomers, etc., and production of block copolymers, etc. Is possible.

  Examples of living radical polymerization methods include cobalt as a radical scavenger, a method for controlling the reversible generation of radicals with a cobalt-porphyrin complex, and a stable radical such as a nitroxide compound as a scavenger, and the reversibility of radicals by heat. Reversible radicals in redox reactions of metal complexes using halogens as scavengers, such as NMP (Nitroxide Mediated Liying Radical Polymerization) and Atom Transfer Radical Polymerization (ATRP). A method for controlling the formation, a method for controlling the reversible generation of radicals using a chain transfer agent such as a dithioester as a scavenger (reversible addition-fragmentation chain transfer: Reversib) e Addition Fragmentation Chain Transfer Radical Polymerization), etc. In the present invention, from the viewpoint of control of polymerization and ease of impurity removal, a stable radical such as a nitroxide compound that does not use a metal complex is used as a scavenger. The method used as is preferred.

  Although it does not specifically limit as a nitroxide compound which is a radical scavenger of NMP, TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxy), 4-oxo-TEMPO, tetramethyl-isoindoline- 1-oxyl, tetraethyl-isoindoline-1-oxyl, N-tert-butyl-N- [1-diethylphosphono- (2,2-dimethylpropyl)] nitroxide (hereinafter abbreviated as DEPN), 2,2, Examples thereof include 5-trimethyl-4-phenyl-3-azahexane-3-nitroxide (hereinafter abbreviated as TIPNO), and DEPN and TIPNO can be preferably used because of easy control of the polymerization rate and molecular weight.

  The diblock copolymer represented by the general formula a-b can be synthesized by performing living radical polymerization using a nitroxide compound of the radical scavenger and a radical initiator. A radical initiator can be used. The radical initiator is not particularly limited. Among them, 2,2′-azobisisobutyronitrile, 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, 2,2′-azobis Organic peroxides such as azo compounds such as −2,4-dimethylvaleronitrile and 2,2′-azobis-2-methylbutyronitrile, lauroyl peroxide and benzoyl peroxide can be preferably used. . The triblock copolymer represented by the general formula a-b-a is obtained by polymerizing the diblock copolymer represented by the general formula a-b and subsequently adding the raw material of the block polymer (a). Can be synthesized.

In addition, living radical polymerization is also possible in an alkoxyamine in which a nitroxide compound that is a radical scavenger and a carbon radical are paired. The alkoxyamine is not particularly limited, but when synthesizing a diblock copolymer represented by the general formula ab and a triblock copolymer represented by the general formula aba, for example,
X—CH (CH ₃ ) —COOH
_{X-CH (CH 3) -C} 6 H 5
_{X-C (CH 3) 2} -C 6 C 5
X—CH ₂ —COOCH ₃
X-C ₆ H ₅
The alkoxyamine shown by these is preferable.
However, X in the formula represents DEPN or TIPNO.

Moreover, when synthesizing the triblock copolymer represented by the general formula aba, an alkoxyamine having two nitroxide compounds is more preferable and not particularly limited.
_{X-CH (CH 3) -C} 6 H 4 -CH (CH 3) -X,
_{X-CH (CH 3) COO} (CH 2) n OCOCH (CH 3) -X
The alkoxyamine shown by these is preferable.
However, X in a formula represents DEPN or TIPNO, and n represents the integer of 1-10.

  The acrylic block copolymer (A) of the present invention can be basically produced by the following method by using the living radical polymerization. That is, in the presence of a radical scavenger and a radical initiator or dormant species, (iv) an acrylate monomer and (v) an aromatic vinyl monomer are copolymerized to synthesize a polymer block (b). And (i) a polymer block containing a ring structural unit represented by the general formula (1), (ii) an unsaturated carboxylic acid alkyl ester unit, and (iii) other copolymerizable vinyl units (a) To obtain a block copolymer (C) which is a precursor of the acrylic block copolymer (A).

  For example, when the ring structural unit represented by the general formula (1) contained in the polymer block (a) is a glutaric anhydride unit, (iii) other copolymerizable vinyl monomers The unit is an unsaturated carboxylic acid, an unsaturated carboxylic acid which gives a glutaric anhydride unit and an unsaturated carboxylic acid monomer unit by a subsequent heating step, and (ii) an unsaturated carboxylic acid alkyl ester unit after copolymerization To obtain a block copolymer (C1). At that time, the block copolymer (C1) thus obtained is heated in the presence or absence of a suitable catalyst to cause intramolecular cyclization reaction by dehydration and / or dealcoholization reaction, thereby allowing glutaric acid. An acrylic block copolymer (A) containing an anhydride unit can be produced. In this case, typically, the block copolymer (C1) is heated to cause a dehydration reaction between the carboxyl groups of two adjacent unsaturated carboxylic acid units, or to the adjacent unsaturated carboxylic acid unit. The dealcoholization reaction between the monomer unit and the (ii) unsaturated carboxylic acid alkyl ester unit produces one unit of the glutaric anhydride unit.

  For example, when the ring structural unit represented by the general formula (1) contained in the polymer block (a) is a glutarimide unit, (iii) other copolymerizable vinyl monomers The unit is an amide group-containing vinyl monomer, and an amide group-containing vinyl monomer that gives a glutarimide unit and an amide group-containing vinyl monomer unit by a subsequent heating step, and (ii) after copolymerization An unsaturated carboxylic acid alkyl ester monomer giving an unsaturated carboxylic acid alkyl ester unit is copolymerized to obtain a block copolymer (C2). At that time, the obtained block copolymer (C2) is heated in the presence or absence of a suitable catalyst, and intramolecular cyclization by deammonification reaction and / or deprimary amine and / or dealcoholization reaction. By carrying out the reaction, an acrylic block copolymer (A) containing a glutarimide unit can be produced. In this case, typically, the block copolymer (C2) is heated to remove ammonia and / or remove primary amine between two adjacent amide group-containing vinyl monomer units. Alternatively, one unit of the glutarimide unit is generated by a dealcoholization reaction between an adjacent amide group-containing vinyl monomer unit and (ii) an unsaturated carboxylic acid alkyl ester unit.

  Further, for example, when (i) the ring structural unit represented by the general formula (1) contained in the polymer block (a) is a lactone ring unit, (iii) other copolymerizable vinyl monomers The unit is an α-hydroxymethyl acrylate monomer unit, and an α-hydroxymethyl acrylate monomer that gives a lactone ring unit and an α-hydroxymethyl acrylate monomer unit by a subsequent heating step, And (ii) an unsaturated carboxylic acid alkyl ester monomer which gives an unsaturated carboxylic acid alkyl ester unit after copolymerization is copolymerized to obtain a block copolymer (C3).

  Preferred specific examples of the unsaturated carboxylic acid alkyl ester monomer include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, and methacrylic acid. n-hexyl, cyclohexyl methacrylate, chloromethyl methacrylate, 2-chloroethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2,3,4,5,6-pentahydroxyhexyl methacrylate Examples include acid 2,3,4,5-tetrahydroxypentyl and benzyl methacrylate, and methyl methacrylate is most preferably used. These can be used alone or in combination of two or more thereof.

  In the acrylic block copolymer (A) of the present invention, when the ring structural unit represented by (i) the general formula (1) is a glutaric anhydride unit, the copolymer block (C1) Examples of the copolymer component include the unsaturated carboxylic acid monomer. There is no particular limitation as long as it is a copolymerizable unsaturated carboxylic acid monomer, but preferred unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, maleic acid, and a hydrolyzate of maleic anhydride. It is done. In particular, acrylic acid or methacrylic acid is preferable from the viewpoint of excellent thermal stability, and methacrylic acid is more preferable. These can be used alone or in combination of two or more thereof. The unsaturated carboxylic acid monomer gives an unsaturated carboxylic acid unit when copolymerized.

  When (i) the ring structural unit represented by the general formula (1) in the acrylic block copolymer (A) of the present invention is a glutarimide unit, the copolymer in the copolymer block (C2) Examples of the polymerization component include the amide group-containing vinyl monomers. There is no particular limitation as long as it is a copolymerizable amide group-containing vinyl monomer, but preferred amide group-containing vinyl monomers include acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, and butoxymethyl. Acrylamide, butoxymethylmethacrylamide, Nn-propylacrylamide, Nn-propylmethacrylamide, N-isopropylacrylamide, N-isopropylmethacrylamide, Nn-butylacrylamide, Nn-butylmethacrylamide, N- Isobutylacrylamide, N-isobutylmethacrylamide, N-tert-butylacrylamide, N-tert-butylmethacrylamide, Nn-pentylacrylamide, Nn-pentylmethacrylamide, Nn-hexyl Acrylamide, Nn-hexylmethacrylamide, N-cyclohexylacrylamide, N-cyclohexylmethacrylamide, N-phenylacrylamide, N-phenylmethacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N-chlorophenylacrylamide, N- Examples thereof include chlorophenyl methacrylamide, N-dichlorophenyl acrylamide, N-dichlorophenyl methacrylamide, N-trichlorophenyl acrylamide, N-trichlorophenyl methacrylamide, N-methylol acrylamide, N-methylol methacrylamide and the like. N-methyl methacrylamide and methacrylamide are preferred, and most preferred is meta- Is Riruamido. These can be used alone or in combination of two or more thereof. The amide group-containing vinyl monomer gives an amide group-containing vinyl monomer unit when copolymerized.

  When the ring structural unit represented by (i) the general formula (1) in the acrylic block copolymer (A) of the present invention is a lactone ring unit, the copolymer in the copolymer block (C3) Examples of the polymerization component include the α-hydroxymethyl acrylate monomer. There is no particular limitation as long as it is a copolymerizable α-hydroxymethyl acrylate monomer, but preferable α-hydroxymethyl acrylate monomers include methyl α-hydroxymethyl acrylate and α-hydroxymethyl acrylate. Examples include ethyl, isopropyl α-hydroxymethyl acrylate, normal butyl α-hydroxymethyl acrylate, and tert-butyl α-hydroxymethyl acrylate. In particular, methyl α-hydroxymethyl acrylate and ethyl α-hydroxymethyl acrylate are preferable, and methyl α-hydroxymethyl acrylate is more preferable in terms of excellent thermal stability. These can be used alone or in combination of two or more thereof. In addition, the α-hydroxymethyl acrylate monomer gives an α-hydroxymethyl acrylate alkyl unit when copolymerized.

In general, for determination of each component unit in the acrylic block copolymer (A), an infrared spectrophotometer, a proton nuclear magnetic resonance ( ¹ H-NMR) measuring machine, a carbon nuclear magnetic resonance ( ¹³ C-NMR) measuring machine. Is used. For example, (i) cyclic structural unit represented by the general formula (1) is, if a glutaric anhydride unit, in the infrared spectroscopy, glutaric anhydride units of 1800 cm ^-1 and 1760 cm ^-1 Absorption is characteristic and can be distinguished from unsaturated carboxylic acid units, (ii) unsaturated carboxylic acid alkyl ester units, (iii) acrylic acid ester units, and (iv) aromatic vinyl units. In the ¹ H-NMR method, the copolymer composition can be determined from the integral ratio of the spectrum. For example, in the case of an acrylic copolymer block composed of a glutaric anhydride unit, a methacrylic acid unit, a methyl methacrylate unit and an n-butyl acrylate unit, the spectral assignment measured in chloroform heavy solvent is 0.5 The peak at ˜1.5 ppm is the hydrogen of the α-methyl group of methacrylic acid, methyl methacrylate, n-butyl acrylate and glutaric anhydride units, and the peak at 1.6 to 2.1 ppm is the methylene group of the polymer main chain. Hydrogen, 3.5 ppm peak is methyl methacrylate carboxylate (-COOCH ₃ ) hydrogen, 4.2 ppm peak is n-butyl acrylate carboxylate ester (-COOCH _2- ) hydrogen, 12.4 ppm The peak of is the hydrogen of carboxylic acid of methacrylic acid, and the composition of each can be determined from these integral values. .

In the ¹³ C-NMR spectrum of the acrylic block copolymer (A), for example, in the case of a copolymer comprising a glutaric anhydride unit, a methacrylic acid unit, a methyl methacrylate unit and an n-butyl acrylate unit, glutaric acid The peak of the carbonyl group of the acid anhydride of the anhydride-containing unit was observed with a chemical shift splitting in the range of 170.50 to 174.40 ppm, and the peak of the carbonyl group of the methyl methacrylate unit and the n-butyl acrylate unit was Depending on the sequence and tacticity, a chemical shift was observed in the range of 174.60 to 179.43 ppm, and the peak of the carbonyl group of the methacrylic acid unit was changed to a chemical shift of 179.15 to 182. Observed to split into the range of 00 ppm, these Each composition can be determined from the integrated value.

  The block copolymer (C1), (C2), and (C3), which are precursors of the acrylic block copolymer (A), are polymerized by bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, precipitation. A known polymerization method such as polymerization can be used. Solution polymerization and precipitation polymerization are particularly preferred in terms of fewer impurities.

  When the copolymer (C1), (C2), or (C3) is produced by solution polymerization, the solvent used is not particularly limited as long as it is a solvent in which the monomer and copolymer are dissolved. , Ketones, ethers, amides, alcohols, and the like can be preferably used. Specific examples include acetone, methyl ethyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, diethyl ether, tetrahydrofuran, Dioxane, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, N-methylpyrrolidone, ethylene glycol, propylene glycol, 2-methoxy-2-propanol, tetraglyme, methanol, ethanol, 2-propanol, 2- Ethanol, iso-butyl alcohol, tert- butyl alcohol, it may be used known solvents, such as tert- pentyl alcohol. From the viewpoint of the solubility and recoverability of the copolymer, methyl ethyl ketone and a mixed solvent containing them are preferred.

  The polymerization temperature is not particularly limited as long as the polymerization proceeds, but is preferably 80 ° C. or higher, more preferably 100 ° C. or higher from the viewpoint of productivity considering the polymerization rate. For the purpose of improving the polymerization yield or polymerization rate, the polymerization temperature can be raised as the polymerization proceeds. The polymerization time is not particularly limited as long as it is a sufficient time to obtain the required degree of polymerization, but is preferably in the range of 180 to 1200 minutes, particularly preferably in the range of 360 to 800 minutes from the viewpoint of production efficiency.

  The proportion of the monomer mixture used in the production of the block copolymer (C1), (C2), or (C3) is particularly preferably the proportion of each copolymer unit of the acrylic block copolymer (A). Although there is no limitation, the monomer mixture of the polymer block (a) is preferably 20 to 80% by weight, more preferably 25 to 80% by weight, most preferably 30 to 100% by weight based on the whole monomer mixture. 80% by weight of the monomer mixture of polymer block (b) is preferably 20-80% by weight, more preferably 20-75% by weight, most preferably 20-70% by weight, and polymer block (a) Preferably, the unsaturated carboxylic acid alkyl ester monomer that gives (ii) an unsaturated carboxylic acid alkyl ester unit after copolymerization is preferably 50 to 95% by weight based on 100% by weight of the total monomer mixture of More preferably 60 to 95% by weight, most preferably 70 to 95% by weight, any one of unsaturated carboxylic acid monomer, amide group-containing vinyl monomer, and α-hydroxymethyl acrylate is preferably It is 5 to 50% by weight, more preferably 5 to 40% by weight, and most preferably 5 to 30% by weight.

  The acrylic block copolymer (A) of the present invention preferably has a weight average molecular weight of 50,000 to 300,000. The weight average molecular weight is preferably 50,000 to 300,000, more preferably 60,000 to 250,000, and particularly preferably 70,000 to 200,000. When the weight average molecular weight is within this range, both colorless transparency and impact resistance of the molded product and the film can be achieved. The acrylic block copolymer (A) having such a molecular weight is produced when the block copolymer (C1), (C2) or (C3) is produced. This can be achieved by previously controlling C3) to a weight average molecular weight of 50,000 to 300,000. In addition, the weight average molecular weight as used in the field of this invention shows the weight average molecular weight in the absolute molecular weight measured by multi-angle light scattering gel permeation chromatography (GPC-MALLS).

  The block copolymer (C1) in the present invention is heated and subjected to an intramolecular cyclization reaction by dehydration reaction and / or dealcoholization reaction to produce an acrylic polymer block (a) containing glutaric anhydride units. An acrylic block containing a glutarimide unit by heat-treating the block copolymer (C2), performing an intramolecular cyclization reaction by a deammonification reaction and / or a deprimary amine and / or a dealcoholization reaction A method for producing the copolymer (A), and an acrylic polymer block (a) containing a lactone ring unit by heat-treating the block copolymer (C3) and carrying out an intramolecular cyclization reaction by a dealcoholization reaction There is no particular limitation on the method for producing the block copolymer, but the block copolymer (C1), (C2), or (C3) was heated with a vent. Method of heating devolatilized under way or an inert gas atmosphere or vacuum through the extruder is preferable. When the intramolecular cyclization reaction by heating in the presence of oxygen tends to deteriorate the YI value, it is preferable to sufficiently substitute the inside of the system with an inert gas such as nitrogen. Particularly preferable heat treatment apparatuses include, for example, a single screw extruder equipped with a “unimelt” type screw, a twin screw extruder, a twin / single screw combined continuous kneading extruder, a triaxial extruder and other extruders, a continuous machine. A kneader of a type or batch type kneader can be used, and a biaxial / single-axis composite type continuous kneading extrusion apparatus can be preferably used from the viewpoint of color tone. As the biaxial / uniaxial continuous kneading and extruding apparatus, for example, “HTM50”, “HTM38”, and “HTM78” manufactured by CTE can be preferably used.

  An apparatus having a structure capable of introducing an inert gas such as nitrogen is more preferable. For example, as a method for introducing an inert gas such as nitrogen into a twin-screw extruder, a method of connecting a pipe of an inert gas stream of about 10 to 100 liters / minute from the upper part and / or the lower part of the hopper can be mentioned. .

  In addition, the temperature for heating and devolatilization by the above method is not particularly limited as long as the intramolecular cyclization reaction occurs, but is preferably in the range of 180 to 370 ° C, particularly preferably in the range of 200 to 360 ° C.

  In addition, the time for heating and devolatilization in this case can be appropriately set according to the desired copolymer composition, but is usually preferably 1 minute to 60 minutes, more preferably 2 minutes to 30 minutes, and particularly preferably 3 The range is ~ 20 minutes. In order to secure a heating time for a sufficient intramolecular cyclization reaction to proceed using an extruder, L / D is 40 or more and 110 or less, where L is the length of the extruder screw and D is the diameter. It is preferable. When an extruder with a short L / D is used, a large amount of unreacted unsaturated carboxylic acid units, amide group-containing vinyl monomer units, or α-hydroxymethyl acrylate units remain, so that heat forming processing Sometimes the reaction proceeds again and there is a tendency for silver and bubbles to be seen in the molded product and for the color tone to deteriorate when the molding stays. When the L / D of the extruder is larger than 110, it is not preferable because practical advantages are reduced due to mechanical strength and structural problems of the extruder.

  Furthermore, when the block copolymer (C1), (C2), or (C3) is heated by the above method or the like, a catalyst that promotes an intramolecular cyclization reaction to a glutaric anhydride, glutarimide, or lactone ring As an additive, at least one selected from acids, alkalis and salt compounds can be added. The addition amount is preferably about 0.01 to 1 part by weight with respect to 100 parts by weight of the block copolymer (C1), (C2), or (C3). Examples of the acid catalyst include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, phosphoric acid, phosphorous acid, phenylphosphonic acid, and methyl phosphate. Examples of the basic catalyst include metal hydroxides, amines, imines, alkali metal derivatives, alkoxides, ammonium hydroxide and the like. Furthermore, examples of the salt-based catalyst include acetic acid metal salts, stearic acid metal salts, metal carbonate salts, and ammonium salts including various alkyl ammonium salts. However, it is preferable to add the catalyst in such a range that the color of the catalyst does not adversely affect the coloring of the thermoplastic polymer and the transparency is not lowered. Among them, the compound containing an alkali metal can be preferably used because it exhibits an excellent reaction promoting effect with a relatively small addition amount. Specifically, hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, alkoxide compounds such as sodium methoxide, sodium ethoxide, sodium phenoxide, potassium methoxide, potassium ethoxide, and potassium phenoxide, lithium acetate And organic carboxylates such as sodium acetate, potassium acetate and sodium stearate. In particular, sodium hydroxide, sodium methoxide, lithium acetate, and sodium acetate can be preferably used.

  The block copolymer (C) preferably has a weight average molecular weight of 50,000 to 300,000, more preferably 60,000 to 250,000, and particularly preferably 70,000 to 200,000. When the weight average molecular weight is within this range, both colorless transparency and impact resistance of the molded product and the film can be achieved. On the other hand, when the weight average molecular weight is more than 300,000, the polymerization becomes difficult, and the intended block copolymer cannot be obtained.

  Further, when the acrylic block copolymer (A) is produced, hindered phenol-based, benzotriazole-based, benzophenone-based, benzoate-based, and cyanoacrylate-based UV absorbers and antioxidants are used within the range not impairing the object of the present invention. Agents, higher fatty acids, acid esters and acid amides, lubricants and plasticizers such as higher alcohols, montanic acid and salts thereof, esters thereof, half esters thereof, stearyl alcohol, stearamide and ethylene wax, Anti-coloring agents such as phosphates and hypophosphites, halogen flame retardants, phosphorous and silicone non-halogen flame retardants, nucleating agents, amines, sulfonic acids, polyethers, etc. In addition, additives such as colorants such as pigments may be optionally contained. However, it is necessary to add in a range where the color of the additive does not adversely affect the thermoplastic copolymer of the present invention and the transparency is not lowered.

The acrylic block copolymer (A) of the present invention has a very small amount of foreign matter generated under high temperature residence, and the tetrahydrofuran insoluble matter after residence is 1% by weight or less, preferably 0.5% by weight or less. In particular, 0.3% by weight or less is more preferable. The term “tetrahydrofuran insoluble” as used herein means that the acrylic block copolymer (A) of the present invention is retained for 20 minutes at the time of injection molding at 260 ° C., and is then dissolved in tetrahydrofuran to obtain a 5 wt% solution. 20 g is produced. After standing for 24 hours in a stationary state at room temperature, the mixture is filtered through a 400 mesh stainless steel wire mesh, dried, the weight of the residue on the wire mesh is measured, and the content of tetrahydrofuran insoluble matter is calculated from the following formula.
Insoluble content (wt%) = α / β
Each symbol indicates the following numerical value.
α = residue on wire mesh β = Acrylic block copolymer charged (A)

  The acrylic block copolymer (A) of the present invention has a total light transmittance of 90% or more, preferably 92% or more. Thereby, it has extremely excellent transparency. The upper limit of the total light transmittance is usually about 94%.

  Further, the acrylic block copolymer (A) of the present invention preferably has a haze value (turbidity), which is one of the indices representing transparency, of 3% or less, more preferably 1% or less. Thereby, it has high transparency. Further, the lower limit of the haze value is usually about 0.5%.

  The total light transmittance and haze of the acrylic block copolymer (A) are values obtained by measuring a molded product having a thickness of 2 mm obtained by injection molding in accordance with JIS-K7361 and JIS-K7136.

  The acrylic block copolymer (A) of the present invention preferably has a heat distortion temperature of 100 ° C. or higher, more preferably 110 ° C. or higher, and particularly preferably 115 ° C. or higher. Thereby, it has extremely excellent heat resistance. The upper limit of the heat distortion temperature is usually about 140 ° C. In addition, the heat distortion temperature said here shows the value which measured the thickness 6.4mm molded article obtained by injection molding according to ASTM D648.

  The acrylic block copolymer (A) used in the present invention preferably has a YI value (Yellowness Index) of 5 or less, more preferably 4 or less, and most preferably 3 or less. Thereby, since the molded article and film which have the very outstanding colorlessness can be obtained, it is preferable. Here, the YI value (Yellowness Index) is an injection molding of the acrylic block copolymer (A), and the resulting 1 mm-thick molded product is SM color computer (Suga Test Instruments Co., Ltd.) according to JIS-K7103. It is the value measured using the product.

In a preferred embodiment, the acrylic block copolymer (A) of the present invention has a value of dimensional change under high-temperature wet heat of 0.8% or less, and in a more preferred embodiment, 0.5% or less. Has dimensional stability. In the above, the dimensional change was made by melting at 260 ° C., and a film having a thickness of 40 μm and a side of 3 cm was produced by a press machine. The film was treated for 500 hr in a constant temperature and humidity apparatus adjusted to a temperature of 60 ° C. and a humidity of 90% RH, the dimensional change rate of each side was calculated from the following formula, and the average value was calculated as the dimensional change rate (%).
Dimensional change rate (%) = {(L1-L0) / L0} × 100
Each symbol indicates the following numerical value.
L0 = Dimension before treatment (cm)
L1 = Dimension after treatment (cm)

  The acrylic block copolymer (A) of the present invention is also excellent in molding processability (fluidity) and can be melt-molded, and thus can be subjected to extrusion molding, injection molding, press molding, and the like. Sheets, tubes, rods, and other molded articles having any desired shape and size can be used.

  A well-known method can be used for the manufacturing method of the film which consists of an acryl-type block copolymer (A) of this invention. That is, production methods such as an inflation method, a T-die method, a calendar method, a cutting method, a casting method, an emulsion method, and a hot press method can be used. Preferably, an inflation method, a T-die method, a cast method or a hot press method can be used. In the case of a production method using an inflation method or a T-die method, an extruder type melt extrusion apparatus equipped with a single screw or twin screw can be used. The melt extrusion temperature for producing the film of the present invention is preferably 150 to 350 ° C, more preferably 200 to 300 ° C. Moreover, when melt-kneading using a melt-extrusion apparatus, it is preferable to perform the melt-kneading under reduced pressure or the melt-kneading under nitrogen stream from a viewpoint of coloring suppression. When the film of the present invention is produced by the casting method, solvents such as tetrahydrofuran, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone can be used. Preferred solvents are acetone, methyl ethyl ketone, N-methylpyrrolidone and the like. The film is prepared by dissolving the acrylic block copolymer (A) of the present invention in one or more of the above-mentioned solvents, and using the bar coater, T die, T die with bar, die coat, etc. It can be produced by casting on a heat-resistant film such as terephthalate, a steel belt, a flat plate such as a metal foil or a curved plate (roll), and using a dry method in which the solvent is removed by evaporation or a wet method in which the solution is solidified with a coagulating liquid .

  The molded product or film thus obtained makes use of its excellent heat resistance, and various applications such as electrical and electronic parts, automobile parts, mechanical mechanism parts, OA equipment, home appliances and other housings and their parts, general miscellaneous goods, etc. Can be used.

  In particular, because of its excellent transparency and heat resistance, various imaging equipment-related parts such as cameras, IVTR, projection TIV and other imaging lenses, viewfinders, filters, prisms, Fresnel lenses, etc. Information equipment related parts such as optical disc (IVD, CD, DIVD, MD, LD, etc.) substrate, various disc substrate protective films, optical disc player pickup lens, optical fiber, optical switch, optical connector, etc., liquid crystal display, flat panel display, plasma display Light guide plate, Fresnel lens, polarizing plate, polarizing plate protective film, retardation film, light diffusion film, viewing angle widening film, reflection film, antireflection film, antiglare film, brightness enhancement film, prism sheet, picker Prens, conductive films for touch panels, covers, etc. as transportation equipment related parts such as automobiles, tail lamp lenses, head lamp lenses, inner lenses, amber caps, reflectors, extensions, side mirrors, room mirrors, side visors, instrument needles, instrument covers, As medical equipment-related parts such as glazing typified by window glass, spectacle lenses, spectacle frames, contact lenses, endoscopes, optical cells for analysis, etc., as building material-related parts, lighting windows, road translucent plates, lighting covers, It is extremely useful for applications such as signs, translucent sound insulation walls, and bathtub materials.

<Acrylic copolymer B>
The glass transition temperature of the acrylic copolymer (B) of the present invention is preferably 120 ° C. or higher, and more preferably 125 ° C. or higher from the viewpoint of heat resistance. In addition, the glass transition temperature here is a glass transition temperature (Tg) measured at a heating rate of 20 ° C./min using a differential scanning calorimeter (DSC-7 manufactured by Perkin Elmer).

In the acrylic copolymer (B) of the present invention, (i) the ring structural units represented by the above general formula (1) are the same or different from each other in R ¹ and R ² , hydrogen atoms and carbon A glutaric anhydride unit in which R ³ is a ketone group, R ⁴ is an oxygen atom, R ¹ and R ² are the same or different from each other, selected from alkyl groups of 1 to 20; Any one selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms; R ³ is a ketone group; R ⁴ is represented by NR ⁵ ; and R ⁵ is hydrogen and an organic residue having 1 to 20 carbon atoms. A lactone having a glutarimide unit selected from: R ¹ is an alkyl group having 1 to 20 carbon atoms, R ² is an alkyl ester group having 1 to 20 carbon atoms, and R ³ is an alkyl group having 1 to 20 carbon atoms A ring unit is mentioned. The organic residue having 1 to 20 carbon atoms is not particularly limited, and may be linear, branched or cyclic, and may contain a hetero atom in the structure. R ⁵ is preferably a hydrogen atom, an unsubstituted or halogen-substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic group having 5 to 20 carbon atoms with halogen or an aliphatic hydrocarbon group It is preferably a group selected from a group, unsubstituted or substituted with a halogen or an aliphatic hydrocarbon group, a C3-C20 alicyclic hydrocarbon group, or a C1-C20 hydroxyalkyl group. Is a hydrogen atom, an unsubstituted or halogenated alkyl group having 1 to 6 carbon atoms, an unsubstituted or phenyl group substituted with a halogen or an alkyl group, an unsubstituted or substituted naphthyl group with a halogen or an alkyl group, an Substituted or substituted benzyl group with halogen or alkyl group, unsubstituted or substituted cycloalkyl group with halogen or alkyl group A group selected from an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom, a cyclohexyl group, an unsubstituted or halogen-substituted alkyl group having 1 to 6 carbon atoms. Particularly preferred is a hydrogen atom or a methyl group. For example, hydrogen is most preferred from the viewpoint of improving heat resistance with a small content of a ring structural unit.

  (I) / (ii) / (iii) = 5 to 50/95 to 50 / 0.05 to 10% by weight based on 100% by weight of the acrylic copolymer (B) of the present invention, (i) Is more than 50% by weight, there is a problem that molding processability (fluidity) is inferior due to a significant increase in viscosity accompanying an increase in glass transition temperature (Tg), and when (i) is lower than 5% by weight, There exists a subject that heat resistance falls. More preferably (i) / (ii) / (iii) = 10-40 / 90-60 / 0.05-5% by weight, especially (i) / (ii) / (iii) = 10-40 / 90-60 / 0.05-3 weight% is preferable.

  In addition, (i) is a ring structural unit represented by the above general formula (1), (ii) is an unsaturated carboxylic acid alkyl ester unit, and (iii) is a copolymerizable vinyl unit.

  (Ii) Preferable specific examples of the unsaturated carboxylic acid alkyl ester unit include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, methacryl N-hexyl acid, cyclohexyl methacrylate, chloromethyl methacrylate, 2-chloroethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2,3,4,5,6-pentahydroxyhexyl methacrylate Examples thereof include 2,3,4,5-tetrahydroxypentyl methacrylate and benzyl methacrylate. Among them, methyl methacrylate is most preferably used. These may include one or more thereof.

  (Iii) Other preferred specific examples of monomers that can be used as a raw material for copolymerizable vinyl monomers include acrylic acid, methacrylic acid, maleic acid, hydrolyzed maleic anhydride, acrylamide, methacrylamide, N- Methyl acrylamide, N-methyl methacrylamide, butoxymethyl acrylamide, butoxymethyl methacrylamide, Nn-propyl acrylamide, Nn-propyl methacrylamide, N-isopropyl acrylamide, N-isopropyl methacrylamide, Nn-butyl acrylamide N-butylmethacrylamide, N-isobutylacrylamide, N-isobutylmethacrylamide, N-tert-butylacrylamide, N-tert-butylmethacrylamide, Nn-pentylacrylamide, N- -Pentylmethacrylamide, Nn-hexylacrylamide, Nn-hexylmethacrylamide, N-cyclohexylacrylamide, N-cyclohexylmethacrylamide, N-phenylacrylamide, N-phenylmethacrylamide, N-benzylacrylamide, N- Benzylmethacrylamide, N-chlorophenylacrylamide, N-chlorophenylmethacrylamide, N-dichlorophenylacrylamide, N-dichlorophenylmethacrylamide, N-trichlorophenylacrylamide, N-trichlorophenylmethacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, α-hydroxymethyl acrylate, α-hydroxymethyl acrylate, α-hydroxymethyl acrylate Isopropyl acid, normal butyl α-hydroxymethyl acrylate, tert-butyl α-hydroxymethyl acrylate, styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, o-ethyl styrene, p-ethyl styrene, p-t-butylstyrene etc. are mentioned, These can contain the 1 type (s) or 2 or more types.

  For example, when (i) the ring structural unit represented by the general formula (1) contained in the acrylic copolymer (B) is a glutaric anhydride unit, a glutaric anhydride may be formed by a subsequent heating step. An unsaturated carboxylic acid monomer giving a unit and (ii) an unsaturated carboxylic acid alkyl ester monomer giving an unsaturated carboxylic acid alkyl ester unit after copolymerization are copolymerized to obtain a copolymer (D1). At that time, the obtained copolymer (D1) is heated in the presence or absence of a suitable catalyst to cause intramolecular cyclization reaction by dehydration reaction and / or dealcoholization reaction, thereby allowing glutaric anhydride. An acrylic copolymer (B) containing a physical unit can be produced. In this case, typically, by heating the copolymer (D1), by a dehydration reaction between the carboxyl groups of two adjacent unsaturated carboxylic acid units, or by an adjacent unsaturated carboxylic acid monomer. One unit of the glutaric anhydride unit is generated by a dealcoholization reaction between the body unit and the (ii) unsaturated carboxylic acid alkyl ester unit.

  For example, when the ring structural unit represented by the general formula (1) contained in the acrylic copolymer (B) is a glutarimide unit, the glutarimide unit is converted by a subsequent heating step. An amide group-containing vinyl monomer to be provided and (ii) an unsaturated carboxylic acid alkyl ester monomer to give an unsaturated carboxylic acid alkyl ester unit after copolymerization are copolymerized to obtain a copolymer (D2). At that time, the obtained copolymer (D2) is heated in the presence or absence of a suitable catalyst, and deammonia reaction and / or intramolecular cyclization reaction by deprimary amine and / or dealcoholization reaction. By carrying out the process, an acrylic copolymer (B) containing a glutarimide unit can be produced. In this case, typically, by heating the copolymer (D2), a deammonia reaction and / or a deprimary amine reaction between two adjacent amide group-containing vinyl monomer units. Alternatively, one unit of the glutarimide unit is generated by a dealcoholization reaction between an adjacent amide group-containing vinyl monomer unit and (ii) an unsaturated carboxylic acid alkyl ester unit.

  Further, for example, when the ring structural unit represented by (i) the general formula (1) contained in the acrylic copolymer (B) is a lactone ring unit, the lactone ring unit is converted by a subsequent heating step. The α-hydroxymethylacrylic acid ester monomer to be fed and (ii) the unsaturated carboxylic acid alkyl ester monomer to give the unsaturated carboxylic acid alkyl ester unit after copolymerization are copolymerized to obtain a copolymer (D3). At that time, the obtained copolymer (D3) is heated in the presence or absence of a suitable catalyst to cause an intramolecular cyclization reaction by a dealcoholization reaction, whereby an acryl type containing a lactone ring unit. A copolymer (B) can be manufactured. In this case, typically, by heating the copolymer (D3), by a dealcoholization reaction of two adjacent α-hydroxymethyl acrylate units or by adjacent α-hydroxymethyl acrylate esters. The dealcoholization reaction between the unit and (ii) the unsaturated carboxylic acid alkyl ester unit produces one unit of the lactone ring unit.

  Preferred specific examples of the unsaturated carboxylic acid alkyl ester monomer include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, and methacrylic acid. n-hexyl, cyclohexyl methacrylate, chloromethyl methacrylate, 2-chloroethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2,3,4,5,6-pentahydroxyhexyl methacrylate Examples include acid 2,3,4,5-tetrahydroxypentyl and benzyl methacrylate, and methyl methacrylate is most preferably used. These can be used alone or in combination of two or more thereof.

  When (i) the ring structural unit represented by the general formula (1) in the acrylic copolymer (B) of the present invention is a glutaric anhydride unit, the copolymer in the copolymer (D1) Examples of the polymerization component include the unsaturated carboxylic acid monomer. There is no particular limitation as long as it is a copolymerizable unsaturated carboxylic acid monomer, but preferred unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, maleic acid, and a hydrolyzate of maleic anhydride. It is done. In particular, acrylic acid or methacrylic acid is preferable from the viewpoint of excellent thermal stability, and methacrylic acid is more preferable. These can be used alone or in combination of two or more thereof. The unsaturated carboxylic acid monomer gives an unsaturated carboxylic acid unit when copolymerized.

  In the acrylic copolymer (B) of the present invention, when the ring structural unit represented by (i) the general formula (1) is a glutarimide unit, a copolymer component in the copolymer (D2) Examples of the amide group-containing vinyl monomer. There is no particular limitation as long as it is a copolymerizable amide group-containing vinyl monomer, but preferred amide group-containing vinyl monomers include acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, and butoxymethyl. Acrylamide, butoxymethylmethacrylamide, Nn-propylacrylamide, Nn-propylmethacrylamide, N-isopropylacrylamide, N-isopropylmethacrylamide, Nn-butylacrylamide, Nn-butylmethacrylamide, N- Isobutylacrylamide, N-isobutylmethacrylamide, N-tert-butylacrylamide, N-tert-butylmethacrylamide, Nn-pentylacrylamide, Nn-pentylmethacrylamide, Nn-hexyl Acrylamide, Nn-hexylmethacrylamide, N-cyclohexylacrylamide, N-cyclohexylmethacrylamide, N-phenylacrylamide, N-phenylmethacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N-chlorophenylacrylamide, N- Examples thereof include chlorophenyl methacrylamide, N-dichlorophenyl acrylamide, N-dichlorophenyl methacrylamide, N-trichlorophenyl acrylamide, N-trichlorophenyl methacrylamide, N-methylol acrylamide, N-methylol methacrylamide and the like. N-methyl methacrylamide and methacrylamide are preferred, and most preferred is meta- Is Riruamido. These can be used alone or in combination of two or more thereof. The amide group-containing vinyl monomer gives an amide group-containing vinyl monomer unit when copolymerized.

  When (i) the ring structural unit represented by the general formula (1) in the acrylic copolymer (B) of the present invention is a lactone ring unit, the copolymer component in the copolymer (D3) As the above-mentioned α-hydroxymethyl acrylate monomer. There is no particular limitation as long as it is a copolymerizable α-hydroxymethyl acrylate monomer, but preferable α-hydroxymethyl acrylate monomers include methyl α-hydroxymethyl acrylate and α-hydroxymethyl acrylate. Examples include ethyl, isopropyl α-hydroxymethyl acrylate, normal butyl α-hydroxymethyl acrylate, and tert-butyl α-hydroxymethyl acrylate. In particular, methyl α-hydroxymethyl acrylate and ethyl α-hydroxymethyl acrylate are preferable, and methyl α-hydroxymethyl acrylate is more preferable in terms of excellent thermal stability. These can be used alone or in combination of two or more thereof. In addition, the α-hydroxymethyl acrylate monomer gives an α-hydroxymethyl acrylate alkyl unit when copolymerized.

In general, for determination of each component unit in the acrylic copolymer (B), an infrared spectrophotometer, a proton nuclear magnetic resonance ( ¹ H-NMR) measuring machine, or a carbon nuclear magnetic resonance ( ¹³ C-NMR) measuring machine is used. Used. For example, (i) cyclic structural unit represented by the general formula (1) is, if a glutaric anhydride unit, in the infrared spectroscopy, glutaric anhydride units of 1800 cm ^-1 and 1760 cm ^-1 Absorption is characteristic and can be distinguished from unsaturated carboxylic acid units and (ii) unsaturated carboxylic acid alkyl ester units. In the ¹ H-NMR method, the copolymer composition can be determined from the integral ratio of the spectrum. For example, in the case of a copolymer consisting of a glutaric anhydride unit, a methacrylic acid unit and a methyl methacrylate unit, the attribution of the spectrum measured in dimethyl sulfoxide heavy solvent is 0.5 to 1.5 ppm peak. , Methyl methacrylate, and hydrogen of α-methyl group of glutaric anhydride unit, peak of 1.6 to 2.1 ppm is hydrogen of methylene group of polymer main chain, peak of 3.5 ppm is carboxylic acid of methyl methacrylate The hydrogen of ester (—COOCH ₃ ), the peak at 12.4 ppm is the hydrogen of carboxylic acid of methacrylic acid.

In the ¹³ C-NMR spectrum of the acrylic copolymer (B), for example, in the case of a copolymer comprising a glutaric anhydride unit, a methacrylic acid unit, and a methyl methacrylate unit, an acid anhydride of a glutaric anhydride-containing unit is used. The peak of the carbonyl group of the product was observed to split into a chemical shift range of 170.50 to 174.40 ppm, and the peak of the carbonyl group of the methyl methacrylate unit was changed to a chemical shift of 174.60 to 179 depending on the sequence and tacticity. The peak of the carbonyl group of the methacrylic acid unit is observed by splitting into the chemical shift range of 179.43 to 182.00 ppm depending on the sequence and tacticity, and the integral value thereof is observed. Each composition can be determined from

  Regarding the polymerization method of the copolymer (D1), (D2) or (D3), polymerization methods such as suspension polymerization, emulsion polymerization, bulk polymerization, solution polymerization, precipitation polymerization, etc., and bulk suspension by radical polymerization. A combination of known polymerization methods such as polymerization is preferably used. In particular, the solution is reduced from the viewpoint of reducing foreign matters in the copolymer of the present invention, particularly unmelted polymer, etc., and achieving low foreign matters required for film applications. Polymerization, precipitation polymerization and a combination of these polymerization methods are more preferred, and solution polymerization is most preferred.

  When the copolymer (D1), (D2), or (D3) is produced by solution polymerization, the solvent used is not particularly limited as long as it is a solvent in which the monomer and copolymer are dissolved. , Ketones, ethers, amides, alcohols, and the like can be preferably used. Specific examples include acetone, methyl ethyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, diethyl ether, tetrahydrofuran, Dioxane, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, N-methylpyrrolidone, ethylene glycol, propylene glycol, 2-methoxy-2-propanol, tetraglyme, methanol, ethanol, 2-propanol, 2- Ethanol, iso-butyl alcohol, tert- butyl alcohol, it may be used known solvents, such as tert- pentyl alcohol. From the viewpoint of the remarkable improvement in the heat and humidity resistance which is an effect of the present invention, alcohol and a mixed solvent containing alcohol are preferred, and methanol, 2-propanol and a mixed solvent containing these are particularly preferred.

  The polymerization temperature of the copolymer (D1), (D2), or (D3) can be arbitrarily set, but is preferably in the range of 60 ° C to 160 ° C. By controlling the polymerization temperature within the above range, it is possible to suppress the acceleration phenomenon of the polymerization rate due to the gel effect, and to suppress the formation of a dimer generated at the time of high-temperature polymerization, so that an acrylic copolymer having excellent thermal stability ( B) can be produced efficiently.

  The polymerization time of the copolymer (D1), (D2), or (D3) is determined by the target polymerization rate, polymerization temperature, type and amount of initiator used, and ranges from 60 to 420 hours. Preferably, it is 60 to 360 hours. By setting it in this range, the polymerization control is stabilized and a high-quality acrylic copolymer (B) can be produced. When the residence time is shorter than 1 hour, it is necessary to increase the amount of the radical polymerization initiator used, and the control of the polymerization reaction tends to be difficult, and preferably 2 hours or longer. Since productivity will fall when it exceeds 7 hours, More preferably, it is 6 hours or less.

  The ratio of the monomer mixture used in the production of the copolymer (D1), (D2), or (D3) is not particularly limited as long as it is the ratio of each copolymer unit of the acrylic copolymer (B). Although the total monomer mixture is 100% by weight, the unsaturated carboxylic acid monomer, the amide group-containing vinyl monomer, or the α-hydroxymethyl acrylate monomer is preferably 5 to 50% by weight. More preferably 5 to 40% by weight, most preferably 5 to 30% by weight, preferably (ii) an unsaturated carboxylic acid alkyl ester monomer which gives an unsaturated carboxylic acid alkyl ester unit after copolymerization, preferably 50 to 95% by weight. %, More preferably 60 to 95% by weight, most preferably 70 to 95% by weight.

  The acrylic copolymer (B) preferably has a weight average molecular weight of 30,000 to 150,000, more preferably 50,000 to 150,000, and particularly preferably 70,000 to 150,000. When the weight average molecular weight is within this range, coloring during heat deaeration in the subsequent step can be reduced, a polymer having a small YI value can be obtained, and the mechanical strength of the molded product can be increased. . The acrylic copolymer (B) having such a molecular weight is produced when the copolymer (D1), (D2), or (D3) is produced during the production of the copolymer (D1), (D2), or (D3). This can be achieved by previously controlling D3) to a weight average molecular weight of 30,000 to 150,000. In addition, the weight average molecular weight as used in the field of this invention shows the weight average molecular weight in the absolute molecular weight measured by multi-angle light scattering gel permeation chromatography (GPC-MALLS).

  Regarding the molecular weight control method of the copolymer (D1), (D2), or (D3), for example, the addition amount of radical polymerization initiators such as azo compounds and peroxides, or alkyl mercaptan, carbon tetrachloride, tetraodor. It can be controlled by the addition amount of a chain transfer agent such as carbonized carbon, dimethylacetamide, dimethylformamide, triethylamine or the like. In particular, a method of controlling the amount of alkyl mercaptan added as a chain transfer agent can be preferably used from the viewpoint of stability of polymerization, ease of handling, and the like.

  Examples of the alkyl mercaptan include n-octyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan, 2-ethylhexyl 3-mercaptopropionate, among others. -Dodecyl mercaptan or n-dodecyl mercaptan, 2-ethylhexyl 3-mercaptopropionate is preferably used.

  The amount of the alkyl mercaptan added is preferably 0.2 to 5.0 parts by weight, more preferably 0.3 to 4 parts by weight based on 100 parts by weight of the total amount of the monomer mixture in order to control the molecular weight to be preferable. 0.0 part by weight, more preferably 0.4 to 3.0 parts by weight.

  The copolymer (D1) in the present invention is subjected to a heat treatment and subjected to an intramolecular cyclization reaction by a dehydration reaction and / or a dealcoholization reaction to produce an acrylic copolymer (B) containing a glutaric anhydride unit. Process, copolymer (D2) is subjected to a heat treatment, an intramolecular cyclization reaction is carried out by a deammonification reaction and / or a deprimary amine and / or a dealcoholization reaction, and an acrylic polymer containing a glutarimide unit ( A method for producing B), and a method for producing an acrylic copolymer (B) containing a lactone ring unit by subjecting the copolymer (D3) to a heat treatment and carrying out an intramolecular cyclization reaction by a dealcoholization reaction. Although there is no restriction | limiting in particular, The method which passes a copolymer (D1), (D2), or (D3) through the heated extruder which has a vent, an inert gas atmosphere, or heat devolatilization under vacuum That process is preferred. When the intramolecular cyclization reaction by heating in the presence of oxygen tends to deteriorate the YI value, it is preferable to sufficiently substitute the inside of the system with an inert gas such as nitrogen. Particularly preferable heat treatment apparatuses include, for example, a single screw extruder equipped with a “unimelt” type screw, a twin screw extruder, a twin / single screw combined continuous kneading extruder, a triaxial extruder and other extruders, a continuous machine. A kneader of a type or batch type kneader can be used, and a biaxial / single-axis composite type continuous kneading extrusion apparatus can be preferably used from the viewpoint of color tone. As the biaxial / uniaxial continuous kneading and extruding apparatus, for example, “HTM50”, “HTM38”, and “HTM78” manufactured by CTE can be preferably used.

  An apparatus having a structure capable of introducing an inert gas such as nitrogen is more preferable. For example, as a method for introducing an inert gas such as nitrogen into a twin-screw extruder, a method of connecting a pipe of an inert gas stream of about 10 to 100 liters / minute from the upper part and / or the lower part of the hopper can be mentioned. .

  In addition, the temperature for heating and devolatilization by the above method is not particularly limited as long as the intramolecular cyclization reaction occurs, but is preferably in the range of 180 to 370 ° C, particularly preferably in the range of 200 to 360 ° C.

  In addition, the time for heating and devolatilization in this case can be appropriately set according to the desired copolymer composition, but is usually preferably 1 minute to 60 minutes, more preferably 2 minutes to 30 minutes, and particularly preferably 3 The range is ~ 20 minutes. In order to secure a heating time for a sufficient intramolecular cyclization reaction to proceed using an extruder, L / D is 40 or more and 110 or less, where L is the length of the extruder screw and D is the diameter. It is preferable. When an extruder with a short L / D is used, a large amount of unreacted unsaturated carboxylic acid units, amide group-containing vinyl monomer units, or α-hydroxymethyl acrylate units remain, so that heat forming processing Sometimes the reaction proceeds again and there is a tendency for silver and bubbles to be seen in the molded product and for the color tone to deteriorate when the molding stays. When the L / D of the extruder is larger than 110, it is not preferable because practical advantages are reduced due to mechanical strength and structural problems of the extruder.

  Further, when the copolymer (D1), (D2), or (D3) is heated by the above method or the like, an acid, an alkali, or the like is used as a catalyst for promoting an intramolecular cyclization reaction to glutaric anhydride or glutarimide. And one or more selected from salt compounds can be added. The amount added is preferably about 0.01 to 1 part by weight per 100 parts by weight of the copolymer (D1), (D2), or (D3). Examples of the acid catalyst include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, phosphoric acid, phosphorous acid, phenylphosphonic acid, and methyl phosphate. Examples of the basic catalyst include metal hydroxides, amines, imines, alkali metal derivatives, alkoxides, ammonium hydroxide and the like. Furthermore, examples of the salt-based catalyst include acetic acid metal salts, stearic acid metal salts, metal carbonate salts, and ammonium salts including various alkyl ammonium salts. However, it is preferable to add the catalyst in such a range that the color of the catalyst does not adversely affect the coloring of the thermoplastic polymer and the transparency is not lowered. Among them, the compound containing an alkali metal can be preferably used because it exhibits an excellent reaction promoting effect with a relatively small addition amount. Specifically, hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, alkoxide compounds such as sodium methoxide, sodium ethoxide, sodium phenoxide, potassium methoxide, potassium ethoxide, and potassium phenoxide, lithium acetate And organic carboxylates such as sodium acetate, potassium acetate and sodium stearate. In particular, sodium hydroxide, sodium methoxide, lithium acetate, and sodium acetate can be preferably used.

  In view of heat resistance, the acrylic copolymer (B) preferably has a glass transition temperature (Tg) of 120 ° C. or higher. The glass transition temperature is more preferably 125 ° C. or higher, and particularly preferably 130 ° C. or higher. Moreover, as an upper limit, it is about 170 degreeC normally. Moreover, there is only one glass transition region. In addition, the glass transition temperature here is a glass transition measured at a heating rate of 20 ° C./min (−100 ° C. to 300 ° C.) using a differential scanning calorimeter (DSC-7 type manufactured by Perkin Elmer). Temperature (Tg).

  The YI value (Yellowness Index) of the acrylic copolymer (B) used in the present invention is preferably 5 or less, more preferably 4 or less, and most preferably 3 or less. Thereby, since the molded article and film which have the very outstanding colorlessness can be obtained, it is preferable. Here, the YI value (Yellowness Index) is an injection molding of the acrylic copolymer (B), and the obtained 1 mm-thick molded product is SM color computer (manufactured by Suga Test Instruments Co., Ltd.) according to JIS-K7103. ).

  Further, at the time of producing the acrylic copolymer (B) of the present invention, hindered phenol-based, benzotriazole-based, benzophenone-based, benzoate-based and cyanoacrylate-based ultraviolet absorbers and Antioxidants, higher fatty acids, acid esters and acid amides, lubricants and plasticizers such as higher alcohols, release agents such as montanic acid and salts thereof, esters thereof, half esters, stearyl alcohol, stearamide and ethylene wax , Anti-coloring agents such as phosphites and hypophosphites, halogen flame retardants, phosphorous and silicone non-halogen flame retardants, nucleating agents, amines, sulfonic acids, polyethers, etc. Additives such as colorants such as inhibitors and pigments may be optionally added. However, it is necessary to add in a range where the color of the additive does not adversely affect the thermoplastic copolymer of the present invention and the transparency is not lowered.

<Thermoplastic copolymer composition>
The thermoplastic copolymer composition of the present invention includes (i) a polymer block (a) having a ring structural unit represented by the general formula (1) and a polymer block having an acrylate monomer unit. (B) an acrylic block copolymer (A), and an acrylic copolymer (B) having a glutaric anhydride unit represented by the following general formula (1) and having a glass transition temperature of 120 ° C. or higher. It is a thermoplastic copolymer composition.

  In the acrylic block copolymer (A) and the acrylic copolymer (B) of the present invention, the total of the ring structural units represented by (i) the general formula (1) is 100% by weight, and the acrylic block copolymer. The total of (iii) other copolymerizable vinyl monomer units of the polymer (A) and the acrylic copolymer (B) is preferably 0.1 to 20% by weight. (Iii) When the copolymerizable vinyl monomer unit is higher than 20% by weight, the dimensional stability under high-temperature wet heat is poor, and in order to make it lower than 0.1% by weight, an intramolecular cyclization step Since it is necessary to increase the heat history at, transparency tends to decrease. More preferably, the ring structural unit is 100% by weight, and (iii) other copolymerizable vinyl monomer units are 0.1 to 15% by weight, especially (iii) other copolymerizable vinyl monomers. More preferably, the unit is 0.1 to 10% by weight.

  The composition ratio of the thermoplastic copolymer composition of the present invention is such that the thermoplastic copolymer composition is 100% by weight, the acrylic block copolymer (A) is 5 to 50% by weight, the acrylic copolymer ( B) is preferably contained in an amount of 50 to 95% by weight, more preferably 10 to 40% by weight of the acrylic block copolymer (A) and 60 to 90% by weight of the acrylic copolymer (B). When the acrylic block copolymer (A) is higher than 50% by weight, the colorless transparency is lowered, and when it is 5% by weight or less, the impact resistance tends to be lowered.

The thermoplastic copolymer composition of the present invention has a very small amount of foreign matter generated under high temperature residence, and the tetrahydrofuran insoluble matter after residence is 1% by weight or less, preferably 0.5% by weight or less. More preferably, it is 0.3% by weight or less. The term “tetrahydrofuran insoluble matter” as used herein means that the thermoplastic copolymer composition of the present invention is retained for 20 minutes at the time of injection molding at 260 ° C., and then dissolved in tetrahydrofuran to give 20 g of a 5 wt% solution. Make it. After standing for 24 hours in a stationary state at room temperature, the mixture is filtered through a 400 mesh stainless steel wire mesh, dried, the weight of the residue on the wire mesh is measured, and the content of tetrahydrofuran insoluble matter is calculated from the following formula.
Insoluble content (wt%) = α / β
Each symbol indicates the following numerical value.
α = residue on wire mesh β = thermoplastic copolymer composition charged

  The thermoplastic copolymer composition of the present invention has a total light transmittance of 90% or more, preferably 92% or more. Thereby, it has extremely excellent transparency. The upper limit of the total light transmittance is usually about 94%.

  The thermoplastic copolymer composition of the present invention preferably has a haze value (turbidity) of 3% or less, more preferably 1% or less, which is one of the indices representing transparency. Thereby, it has high transparency. Further, the lower limit of the haze value is usually about 0.5%.

  The total light transmittance and haze of the thermoplastic copolymer composition are values obtained by measuring a 2 mm-thick molded product obtained by injection molding in accordance with JIS-K7361 and JIS-K7136.

  The thermoplastic copolymer composition of the present invention preferably has a heat distortion temperature of 100 ° C. or higher, more preferably 110 ° C. or higher, and particularly preferably 115 ° C. or higher. Thereby, it has extremely excellent heat resistance. The upper limit of the heat distortion temperature is usually about 140 ° C. In addition, the heat distortion temperature said here shows the value which measured the thickness 6.4mm molded article obtained by injection molding according to ASTM D648.

  The thermoplastic copolymer composition used in the present invention preferably has a YI value (Yellowness Index) of 5 or less, more preferably 4 or less, and most preferably 3 or less. Thereby, since the molded article and film which have the very outstanding colorlessness can be obtained, it is preferable. Here, the YI value (Yellowness Index) is an injection molding of the acrylic copolymer (B), and the obtained 1 mm-thick molded product is SM color computer (manufactured by Suga Test Instruments Co., Ltd.) according to JIS-K7103. ).

In a preferred embodiment, the thermoplastic copolymer composition of the present invention has an extremely high dimensional stability with a value of dimensional change under high-temperature wet heat of 0.8% or less, and in a more preferred embodiment 0.5% or less. Have sex. In the above, the dimensional change was made by melting at 260 ° C., and a film having a thickness of 40 μm and a side of 3 cm was produced by a press machine. The film was treated for 500 hr in a constant temperature and humidity apparatus adjusted to a temperature of 60 ° C. and a humidity of 90% RH, the dimensional change rate of each side was calculated from the following formula, and the average value was calculated as the dimensional change rate (%).
Dimensional change rate (%) = {(L1-L0) / L0} × 100
Each symbol indicates the following numerical value.
L0 = Dimension before treatment (cm)
L1 = Dimension after treatment (cm)

  As a method of blending the acrylic block copolymer (A) and the acrylic copolymer (B), a method of blending in advance and then melt-kneading uniformly with a single-screw or twin-screw extruder usually at 200 to 350 ° C. Is preferably used. Moreover, the method of removing a solvent after mixing in the solution of the solvent which melt | dissolves both (A) and (B) component can also be used. Moreover, as a manufacturing method of the thermoplastic copolymer composition of this invention, after previously blending the above-mentioned acrylic copolymer (B) and the said block copolymer (C), normally at 200-350 degreeC, it is uniaxial. Alternatively, by uniformly melt-kneading with a twin-screw extruder, the block copolymer (C) is converted into the acrylic block copolymer (A) by the cyclization reaction described above, and at the same time, the component (B) Formulation can be performed. At this time, a cyclization reaction can be simultaneously performed in the case where a part of the component (B) includes a copolymer composed of an unsaturated carboxylic acid monomer unit and an unsaturated carboxylic acid alkyl ester monomer unit. . In this case, since the heat history to the acrylic block copolymer (A) is greatly reduced, coloring due to thermal decomposition can be suppressed.

  The thermoplastic copolymer composition of the present invention is excellent in moldability (fluidity) and can be melt-molded, and thus can be extruded, injection-molded, press-molded, etc. It can be used after being formed into a tube, a rod, or other molded article having any desired shape and size.

  A well-known method can be used for the manufacturing method of the film which consists of the thermoplastic copolymer composition of this invention. That is, production methods such as an inflation method, a T-die method, a calendar method, a cutting method, a casting method, an emulsion method, and a hot press method can be used. Preferably, an inflation method, a T-die method, a cast method or a hot press method can be used. In the case of a production method using an inflation method or a T-die method, an extruder type melt extrusion apparatus equipped with a single screw or twin screw can be used. The melt extrusion temperature for producing the film of the present invention is preferably 150 to 350 ° C, more preferably 200 to 300 ° C. Moreover, when melt-kneading using a melt-extrusion apparatus, it is preferable to perform the melt-kneading under reduced pressure or the melt-kneading under nitrogen stream from a viewpoint of coloring suppression. When the film of the present invention is produced by the casting method, solvents such as tetrahydrofuran, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone can be used. Preferred solvents are acetone, methyl ethyl ketone, N-methylpyrrolidone and the like. The film is prepared by dissolving the thermoplastic copolymer composition of the present invention in one or more of the above-mentioned solvents, and using the solution as a bar coater, T die, T die with a bar, die coating, or the like. The film can be cast on a flat plate or curved plate (roll) such as a heat-resistant film, a steel belt or a metal foil, and a dry method in which the solvent is removed by evaporation or a wet method in which the solution is solidified with a coagulating liquid.

  The molded product or film thus obtained makes use of its excellent heat resistance, and various applications such as electrical and electronic parts, automobile parts, mechanical mechanism parts, OA equipment, home appliances and other housings and their parts, general miscellaneous goods, etc. Can be used.

  In particular, because of its excellent transparency and heat resistance, various imaging equipment-related parts such as cameras, IVTR, projection TIV and other imaging lenses, viewfinders, filters, prisms, Fresnel lenses, etc. Information equipment related parts such as optical disc (IVD, CD, DIVD, MD, LD, etc.) substrate, various disc substrate protective films, optical disc player pickup lens, optical fiber, optical switch, optical connector, etc., liquid crystal display, flat panel display, plasma display Light guide plate, Fresnel lens, polarizing plate, polarizing plate protective film, retardation film, light diffusion film, viewing angle widening film, reflection film, antireflection film, antiglare film, brightness enhancement film, prism sheet, picker Prens, conductive films for touch panels, covers, etc. as transportation equipment related parts such as automobiles, tail lamp lenses, head lamp lenses, inner lenses, amber caps, reflectors, extensions, side mirrors, room mirrors, side visors, instrument needles, instrument covers, As medical equipment-related parts such as glazing typified by window glass, spectacle lenses, spectacle frames, contact lenses, endoscopes, optical cells for analysis, etc., as building material-related parts, lighting windows, road translucent plates, lighting covers, It is extremely useful for applications such as signs, translucent sound insulation walls, and bathtub materials.

  Hereinafter, the configuration and effects of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. Prior to the description of each example, a method for measuring various physical properties used in the example will be described.

(1) Weight average molecular weight 10 mg of acrylic block copolymer (A) and acrylic copolymer (B) were dissolved in 2 g of tetrahydrofuran to prepare a measurement sample. Gel permeation chromatograph equipped with a DAWN-DSP type multi-angle light scattering photometer (manufactured by Wyatt Technology) using tetrahydrofuran as a solvent (pump: model 515, manufactured by Waters, column: TSK-gel-GMHXL, manufactured by Tosoh Corporation) ) Was used to measure the weight average molecular weight (absolute molecular weight).

(2) Glass transition temperature (Tg)
The acrylic copolymer (B) of the present invention was measured using a differential scanning calorimeter (DSC-7 type manufactured by Perkin Elmer) at a temperature increase rate of 20 ° C./min in a nitrogen atmosphere (−100 ° C. to 300 ° C).

(3) Thermal deformation temperature Acrylic block copolymer (A) and a thermoplastic copolymer composition of the present invention were injection-molded at 280 ° C., and a 127 mm × 12.7 mm × 6.4 mm plate test piece. Got. Using the obtained plate-like test piece, the deflection temperature under load was measured according to ASTM D648 (load: 1.82 MPa), and the heat resistance was evaluated.

(4) Transparency (total light transmittance, haze)
The acrylic block copolymer (A) and thermoplastic copolymer composition of the present invention were injection molded at 280 ° C. to obtain a molded product of 70 mm × 70 mm × 2 mm. Using a direct reading haze meter manufactured by Toyo Seiki Co., Ltd., the total light transmittance (%) and haze (cloudiness) (%) at 23 ° C. of the obtained molded product were measured to evaluate transparency.

  When measuring a molded product having a thickness not 2 mm, the molded product is once pulverized, and a molded product of 70 mm × 70 mm × 2 mm is molded and measured under the above conditions.

(5) Izod impact strength (Izod impact value)
The acrylic block copolymer (A) and the thermoplastic copolymer composition of the present invention were injection molded at 280 ° C. to obtain a notched test piece having a thickness of 12.7 mm in accordance with ASTM D-256. Using the obtained test piece, Izod impact strength was measured at 23 ° C. according to ASTM D-256, and the impact characteristics were evaluated.

(6) Elongation at break The acrylic block copolymer (A) and thermoplastic copolymer composition of the present invention were applied to a 40 mm diameter vented single screw extruder equipped with a T-die for film production having a width of 200 mm. And extruded at a speed of 10 kg / h at 280 ° C. to obtain a film having a thickness of 0.1 mm. ASTM-1 dumbbells were punched from the obtained film to prepare test pieces, and the tensile elongation at break was measured according to JIS K-7113.

(7) Moldability (fluidity)
With respect to the thermoplastic copolymer composition of the present invention, the melt index (MI value) at a temperature of 280 ° C. and a load of 37.3 N was measured according to the ISO-R1133 method.

(8) Aggregate generation amount under high temperature residence (tetrahydrofuran insoluble matter content)
When the acrylic block copolymer (A) and the thermoplastic copolymer composition of the present invention are injection molded at 260 ° C., the acrylic block copolymer (A) and the thermoplastic copolymer composition are retained for 20 minutes and then dissolved in tetrahydrofuran to prepare 20 g of a 5 wt% solution. To do. After standing at room temperature for 24 hours, the mixture was filtered through a 400 mesh stainless wire mesh, dried, the weight of the residue on the wire mesh was measured, and the tetrahydrofuran insoluble matter content was calculated from the following formula.
Insoluble content (wt%) = α / β
Each symbol indicates the following numerical value.
α = residue on wire mesh β = thermoplastic copolymer composition charged

(9) Degree of coloring (YI value (Yellowness Index))
The acrylic block copolymer (A) and the thermoplastic copolymer composition of the present invention are injection molded at the glass transition temperature of the acrylic copolymer (B) + 150 ° C., and the resulting 1 mm-thick molded product is obtained. It is the value measured using SM color computer (made by Suga Test Instruments Co., Ltd.) according to JIS-K7103.

(10) Dimensional change rate under high temperature and humidity (%)
The acrylic block copolymer (A) and the thermoplastic copolymer composition of the present invention were melted at 260 ° C., and a film having a thickness of 40 μm and a side of 3 cm was prepared using a press machine. The film was treated for 500 hr in a constant temperature and humidity apparatus adjusted to a temperature of 60 ° C. and a humidity of 90% RH, the dimensional change rate of each side was calculated from the following formula, and the average value was calculated as the dimensional change rate (%).
Dimensional change rate (%) = {(L1-L0) / L0} × 100
Each symbol indicates the following numerical value.
L0 = Dimension before treatment (cm)
L1 = Dimension after treatment (cm)

(11) Composition analysis method Each of the obtained acrylic block copolymer (A) and acrylic copolymer (B) was dissolved in deuterated pyridine at a concentration of 600 mg / 3 g, and manufactured by Varian, UNITY. Using an INOVA500 type NMR measuring instrument, measurement was performed at a temperature of 15 ° C. using a measurement nucleus 13C, TMS as a reference, an observation frequency of 125.7 MHz, and an integration number of 30000 times. In the 13C-NMR spectrum, the peak of the carbonyl group of glutaric anhydride was observed with a chemical shift splitting in the range of 170.50 to 174.40 ppm, and the peak of the carbonyl group of methyl methacrylate and n-butyl acrylate units was The chemical shift is observed in the range of 174.60 to 179.43 ppm depending on the sequence and tacticity, and the peak of the carbonyl group of methacrylic acid depends on the chemical shift of 179.43 to 182.182 depending on the sequence and tacticity. The ratio of glutaric anhydride / methyl methacrylate and n-butyl acrylate / methacrylic acid in the acryl acrylic block copolymer (A) is determined from the integral value. Glutaric anhydride / methacrylic acid of polymer (B) The ratio of methyl / methacrylate was calculated. In addition, the acrylic block copolymer (A) was dissolved in deuterated chloroform at a concentration of 20 mg / 0.75 g, and a unity INOVA500 NMR measuring machine manufactured by Varian was used. Using the measurement nucleus 1H, TMS as a reference, and 16 times of integration, each measurement was performed at a temperature of 15 ° C. In the 1H-NMR spectrum, the hydrogen peak of methyl methacrylate carboxylate (—COOCH ₃ ) is observed at a chemical shift of 3.5 ppm, and the hydrogen peak of n-butyl acrylate carboxylate ester (—COOCH _{2 —} ) is observed. The peak is observed at 4.2 ppm, the ratio of methyl methacrylate and n-butyl acrylate is calculated from these integral values, and the composition of the acrylic block copolymer (A) is the composition from the 13C-NMR spectrum and 1H-spectrum. It was determined.

<Example 1 Acrylic block copolymer (A-1)>
After supplying a monomer mixture of the following formulation to a stainless steel autoclave having a capacity of 20 liters and equipped with a double helical stirring blade, and stirring at 50 rpm for 15 minutes with nitrogen gas at 20 L / min, The temperature is controlled at 110 ° C., alkoxyamine (E) having two nitroxide compounds represented by the following general formula (3) and DEPN are added, solution polymerization is performed for 6 hours, and a copolymer block (b- 1) A solution was obtained. The polymerization conversion of n-butyl acrylate was 52% by weight and the weight average molecular weight was 31,000.
N-butyl acrylate 100 parts by weight methyl ethyl ketone 66.7 parts by weight alkoxyamine (E) 1.20 parts by weight DEPN 0.10 parts by weight

  Subsequently, unreacted n-butyl acrylate was removed with a vacuum dryer equipped with a cooling trap over 60 ° C. for 24 hours to obtain a copolymer block (b-1).

Using the obtained copolymer block (b-1), supplying a monomer mixture of the following formulation to the stainless steel autoclave and bubbling with nitrogen gas of 20 L / min for 15 minutes while stirring at 50 rpm The block copolymer (c-1) having a copolymer block (a-1) and a copolymer block (b-1) by controlling the internal temperature at 110 ° C. and performing solution polymerization for 8 hours A solution was obtained. The polymerization conversion of methacrylic acid was 54% by weight, and the polymerization conversion of methyl methacrylate was 51% by weight. Moreover, the weight average molecular weight was 161000.
b-1 100 parts by weight Methacrylic acid 160 parts by weight Methyl methacrylate 640 parts by weight Methyl ethyl ketone 200 parts by weight

  Next, unreacted methacrylic acid and methyl methacrylate were removed with a vacuum dryer equipped with a cooling trap over 60 ° C. for 24 hours to obtain a copolymer block (c-1).

  The obtained block copolymer (c-1) is a non-meshing different direction rotating biaxial / uniaxial composite continuous kneading extruder equipped with a flow control valve HTM38 (cylinder diameter 38 mm, biaxial portion L / D = 34, uniaxial part L / D = 14, manufactured by CTE), 0.05 parts of lithium acetate was added, the raw material supply rate was 10 kg / h, the screw rotation speed was 100 rpm, and the cylinder temperature was 300 ° C. A cyclization reaction was performed to obtain a pellet-like acrylic block copolymer (A-1). The reaction was performed while purging nitrogen from the hopper at a rate of 10 L / min.

  As a result of the composition analysis of the acrylic block copolymer (A-1), the weight average molecular weight was as shown in Table 1.

<Example 2 acrylic block copolymer (A-2)>
A block copolymer (c-2) was synthesized in the same manner as in Reference Example (1) except that the amount of methacrylic acid was changed to 216 parts by weight and the amount of methyl methacrylate was changed to 584 parts by weight. A system block copolymer (A-2) was obtained. As a result of the composition analysis of the acrylic block copolymer (A-2), the weight average molecular weight was as shown in Table 1.

<Comparative Example 1 Acrylic Block Copolymer (A-3)>
A block was prepared in the same manner as in Reference Example (1) except that the amount of methacrylic acid was changed to 400 parts by weight, the amount of methyl methacrylate was changed to 400 parts by weight, and the intramolecular cyclization reaction was carried out at a cylinder temperature of 170 ° C. A copolymer (c-3) was synthesized to obtain an acrylic block copolymer (A-3). As a result of the composition analysis of the acrylic block copolymer (A-3), the weight average molecular weight was as shown in Table 1.

<Comparative Example 2 Acrylic Block Copolymer (A-4)>
A block copolymer (c-4) was synthesized in the same manner as in Reference Example (1) except that the amount of methacrylic acid was changed to 0 part by weight and the amount of methyl methacrylate was changed to 800 parts by weight. A system block copolymer (A-4) was obtained. As a result of the composition analysis of the acrylic block copolymer (A-4), the weight average molecular weight was as shown in Table 1.

<Comparative Example 3 Acrylic Block Copolymer (A-5)>
A block copolymer (c-5) was prepared in the same manner as in Reference Example (1) except that the amount of alkoxyamine (E) was changed to 4.8 parts by weight and the amount of DEPN was changed to 0.3 parts by weight. Was synthesized to obtain an acrylic block copolymer (A-5). As a result of composition analysis by ¹ H-NMR and infrared spectrophotometer of the acrylic block copolymer (A-5), the weight average molecular weight by GPC measurement was as shown in Table 1.

<Example 3 Acrylic block copolymer (A-6)>
After supplying a monomer mixture of the following formulation to a stainless steel autoclave having a capacity of 20 liters and equipped with a double helical stirring blade, and stirring at 50 rpm for 15 minutes with nitrogen gas at 20 L / min, The temperature is controlled at 110 ° C., alkoxyamine (E) having two nitroxide compounds represented by the following general formula (3) and DEPN are added, solution polymerization is performed for 6 hours, and a copolymer block (b- 6) A solution was obtained. The polymerization conversion of n-butyl acrylate was 60% by weight, and the weight average molecular weight was 52,000.
N-butyl acrylate 100 parts by weight methyl ethyl ketone 66.7 parts by weight alkoxyamine (E) 1.0 part by weight DEPN 0.07 part by weight

  Subsequently, unreacted n-butyl acrylate was removed with a vacuum dryer equipped with a cooling trap over 60 ° C. for 24 hours to obtain a copolymer block (b-6).

Using the obtained copolymer block (b-6), supplying a monomer mixture of the following formulation to the stainless steel autoclave and bubbling with nitrogen gas of 20 L / min for 15 minutes while stirring at 50 rpm The block copolymer (c-6) having a copolymer block (a-6) and a copolymer block (b-6) by controlling the internal temperature at 110 ° C. and performing solution polymerization for 6 hours A solution was obtained. The polymerization conversion of methacrylic acid was 80% by weight, and the polymerization conversion of methyl methacrylate was 78% by weight. The weight average molecular weight was 108,000.
b-6 100 parts by weight Methacrylic acid 24 parts by weight Methyl methacrylate 96 parts by weight Methyl ethyl ketone 200 parts by weight

  Next, unreacted methacrylic acid and methyl methacrylate were removed with a vacuum dryer equipped with a cooling trap at 60 ° C. for 24 hours to obtain a copolymer block (c-6).

  The obtained block copolymer (c-6) is a non-meshing bi-directional / single-axis combined continuous kneading and extruding device equipped with a flow control valve, and is HTM38 (cylinder diameter 38 mm, biaxial portion L / D = 34, uniaxial part L / D = 14, manufactured by CTE), 0.05 parts of lithium acetate was added, the raw material supply rate was 10 kg / h, the screw rotation speed was 100 rpm, and the cylinder temperature was 300 ° C. A cyclization reaction was performed to obtain a pellet-shaped acrylic block copolymer (A-6). The reaction was performed while purging nitrogen from the hopper at a rate of 10 L / min.

  As a result of the composition analysis of the acrylic block copolymer (A-6), the weight average molecular weight was as shown in Table 1.

<Example 4 acrylic block copolymer (A-7)>
A block copolymer (c-7) was synthesized in the same manner as in Reference Example (6) except that the amount of methacrylic acid was changed to 27 parts by weight and the amount of methyl methacrylate was changed to 73 parts by weight. A system block copolymer (A-7) was obtained. As a result of the composition analysis of the acrylic block copolymer (A-7), the weight average molecular weight was as shown in Table 1.

<Example 5 acrylic block copolymer (A-8)>
After supplying a monomer mixture of the following formulation to a stainless steel autoclave having a capacity of 20 liters and equipped with a double helical stirring blade, and stirring at 50 rpm for 15 minutes with nitrogen gas at 20 L / min, The temperature is controlled at 110 ° C., alkoxyamine (E) having two nitroxide compounds represented by the above general formula (3) and DEPN are added, solution polymerization is performed for 6 hours, and a copolymer block (b- 8) A solution was obtained. The polymerization conversion of n-butyl acrylate was 65% by weight, the polymerization conversion of styrene was 66% by weight, and the weight average molecular weight was 53,000.
N-butyl acrylate 90 parts by weight Styrene 10 parts by weight Methyl ethyl ketone 66.7 parts by weight Alkoxyamine (E) 1.0 part by weight DEPN 0.07 part by weight

  Otherwise, in the same manner as in Reference Example (6), a block copolymer (c-8) was synthesized to obtain an acrylic block copolymer (A-8). As a result of the composition analysis of the acrylic block copolymer (A-8), the weight average molecular weight was as shown in Table 1.

<Comparative Example 4 Acrylic Block Copolymer (A-9)>
A block copolymer (c-9) was synthesized in the same manner as in Reference Example (6) except that methyl methacrylate was added instead of methacrylic acid to obtain an acrylic block copolymer (A-9). It was. As a result of the composition analysis of the acrylic block copolymer (A-9), the weight average molecular weight was as shown in Table 1.

<Reference Example (1) Acrylic Copolymer (B-1)>
After supplying a monomer mixture of the following formulation to a stainless steel autoclave having a capacity of 20 liters and equipped with a double helical stirring blade, and stirring at 50 rpm for 15 minutes with nitrogen gas at 20 L / min, The temperature was controlled at 80 ° C., and solution polymerization was performed for 5 hours. Thereafter, the obtained copolymer solution was reprecipitated with n-hexane, and the precipitated copolymer was vacuum-dried at 80 ° C. for 12 hours to obtain a copolymer (d-1).
Methacrylic acid 20 parts by weight Methyl methacrylate 80 parts by weight 2-propanol 100 parts by weight Lauryl peroxide 0.64 parts by weight n-dodecyl mercaptan 0.3 parts by weight

Next, the obtained copolymer (d-1) is a non-meshing different direction rotating biaxial / uniaxial composite type continuous kneading extruder equipped with a flow control valve HTM38 (cylinder diameter 38 mm, biaxial portion L / D = 34, uniaxial part L / D = 14, manufactured by CTE), 0.05 parts of lithium acetate was added, the raw material supply speed was 10 kg / h, the screw rotation speed was 100 rpm, and the cylinder temperature was 300 ° C. An internal cyclization reaction was performed to obtain a pellet-shaped acrylic copolymer (B-1). The reaction was performed while purging nitrogen from the hopper at a rate of 10 L / min.
The composition analysis results, weight average molecular weight, and glass transition temperature of the acrylic copolymer (B-1) were as shown in Table 2.

<Reference Example (2) Acrylic Copolymer (B-2)>
A copolymer (d-2) was synthesized in the same manner as in Reference Example (10) except that the amount of methacrylic acid was changed to 27 parts by weight and the amount of methyl methacrylate was changed to 73 parts by weight. A copolymer (B-2) was obtained.
The composition analysis results, weight average molecular weight, and glass transition temperature of the acrylic copolymer (B-2) were as shown in Table 2.

[Examples 1-12, Comparative Examples 1-7]
After drying the pellet-like acrylic block copolymer (A) obtained in Examples 1 and 2 and Comparative Examples 1 to 3 at 100 ° C. for 3 hours, an injection molding machine (M, manufactured by Meiki Seisakusho Co., Ltd.) -50AII-SJ), each test piece was molded. Molding conditions are molding temperature: 280 ° C., mold temperature: 80 ° C., injection speed: 90 cm ³ / second, injection time: 10 seconds, cooling time: 30 seconds, molding pressure: pressure at which the mold is filled with all the resin ( Molding lower limit pressure) +1 MPa.

In addition, the acrylic block copolymer (A) obtained in Examples 3 to 5 and Comparative Example 4 and the acrylic copolymer (B) obtained in Reference Examples (1) and (2) are shown. 3 and blended using a twin screw extruder (TEX30 (manufactured by Nippon Steel Co., Ltd., L / D = 44.5)) at a screw rotation speed of 150 rpm and a cylinder temperature of 260 ° C. Then, a plastic copolymer composition was obtained, and the pellets dried at 100 ° C. for 3 hours were subjected to an injection molding machine (M-50AII-SJ manufactured by Meiki Seisakusho Co., Ltd.) to mold each test piece. Molding temperature: 280 ° C., mold temperature: 80 ° C., injection speed: 90 cm ³ / second, injection time: 10 seconds, cooling time: 30 seconds, molding pressure: pressure at which the resin is filled in the mold (molding lower limit pressure) ) +1 MPa.

  In Example 12, instead of the acrylic block copolymer (A), the block copolymer (C) before the intramolecular cyclization reaction was used.

  In Comparative Examples 5 and 7, PMMA ("Delpet (registered trademark) 80N" (manufactured by Asahi Kasei Co., Ltd.)) was used instead of the acrylic copolymer (B). A multilayer organic material comprising a shell layer having a glutaric anhydride unit and a core layer of a crosslinked elastomer synthesized according to the method disclosed in Patent Document 3 and Reference Example 1 instead of the acrylic block copolymer (A) Table 4 shows the evaluation results of test pieces obtained by injection molding using the fine particles under the same molding conditions as described above. Table 5 shows the results of evaluation of test pieces obtained by injection molding under the same molding conditions as described above except that the injection time is 20 minutes.

  From the results of Examples 1 to 12 and Comparative Examples 1 to 7, the acrylic block copolymer (A) of the present invention, the acrylic block copolymer (A) having the same ring structural unit, and the acrylic copolymer are used. It can be seen that the thermoplastic copolymer composition in which the blend (B) is blended has mechanical properties such as high heat resistance and impact resistance, and at the same time, is excellent in colorless transparency. Further, it can be seen that, under high temperature residence, almost no foreign matter is generated, and colorless transparency and impact resistance can be maintained at a high level. Above all, by setting the ring structural unit to 100% by weight and (iii) other copolymerizable vinyl monomer units to 0.1 to 20% by weight, it is possible to highly suppress dimensional changes under high temperature and humidity. I understand that there is.

  In the acrylic block copolymer (A) and the thermoplastic copolymer composition of the present invention, the ring structural unit is 100% by weight, and (iii) other copolymerizable vinyl monomer units are larger than 20% by weight. In the case (Comparative Example 1), it can be seen that the decrease in dimensional stability under high-temperature wet heat is significant.

  When the weight average molecular weight of the acrylic block copolymer (A) of the present invention is smaller than 50,000 (Comparative Example 3), it is understood that although the colorless transparency is excellent, the impact resistance and the heat resistance tend to decrease. .

  When the acrylic block copolymer (A) and the acrylic copolymer (B) do not have the same ring structure (Comparative Examples 4 and 5), the decrease in colorless transparency is remarkable, and the mechanical properties and heat resistance are also improved. It is greatly reduced, and it can be seen that the physical properties are further lowered under high temperature residence.

  When multilayer organic fine particles are used instead of the acrylic block copolymer (A) (Comparative Example 6), the thermoplastic copolymer composition is excellent in colorless transparency and impact resistance, but moldability (fluidity). It can also be seen that the amount of foreign matter generated under high temperature residence is greatly deteriorated, and the impact resistance is greatly reduced as the foreign matter is generated.

  The acrylic block copolymer (A) and the thermoplastic copolymer composition of the present invention have a high degree of colorless transparency and excellent heat resistance even when compared with PMMA (Comparative Examples 2 and 7). It can be seen that it can be a material having both impact resistance.

In the thermoplastic copolymer composition of the present invention, instead of the acrylic block copolymer (A), the block copolymer (C) was used (Example 12), and the block copolymer (C) was mixed during kneading. By converting into the acrylic block copolymer (A) and at the same time blending with the acrylic copolymer (B), it has high heat resistance, impact resistance and transparency, and at the same time, colored It turns out that suppression becomes possible. In addition, the thermoplastic copolymer composition of Example 12 was prepared by dissolving the acrylic block copolymer (A) and the acrylic block copolymer (A) in chloroform that does not dissolve the acrylic copolymer (B). extracts a), a result of composition analysis by infrared spectrophotometer, is absorbed from glutaric anhydride unit (1800 cm ^-1 and 1760 cm ^-1) are observed, also extracted acrylic block copolymerization The coalescence (A) was 100% by weight of glutar anhydride and 10% by weight of methacrylic acid. This shows that the block copolymer (C) undergoes an intramolecular cyclization reaction during kneading with the acrylic copolymer (B) and is converted to the acrylic block copolymer (A).

  According to the present invention, it has high heat resistance and mechanical properties, and at the same time has high colorless transparency, molding processability (fluidity) and impact resistance that have been required in recent years. An acrylic block copolymer and a thermoplastic copolymer composition having a small amount, particularly excellent in dimensional stability under high-temperature wet heat, can be obtained.

  In addition, molded articles and films containing the acrylic block copolymer or thermoplastic copolymer composition of the present invention are excellent in transparency and heat resistance, and are therefore related to video equipment-related parts, optical recording or optical communication-related. It is extremely useful for applications such as parts, information equipment-related parts, transportation equipment-related parts such as automobiles, medical equipment-related parts, building material-related parts.

Claims (17)

(I) a polymer block having a ring structural unit represented by the following general formula (1), (ii) an unsaturated carboxylic acid alkyl ester monomer unit, and (iii) other copolymerizable vinyl monomer units An acrylic block copolymer (A) comprising (a) and a polymer block (b) having an acrylate monomer unit satisfies the following (I) to (III): Block copolymer.
(I) Acrylic block copolymer (A) (i) The ring structural unit represented by the following general formula (1) is 100% by weight, and (iii) Other copolymerizable vinyl monomer units are 0. .1-20% by weight.
(II) The weight average molecular weight is 50,000 to 300,000.

(However, R ¹ and R ² are the same or different and represent any one selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms and an alkyl ester group, and R ³ represents a ketone group and a carbon number. And any one selected from alkyl groups having 1 to 20; R ⁴ represents an oxygen atom or NR ⁵ ; and R ⁵ represents any one selected from a hydrogen atom and an organic residue having 1 to 20 carbon atoms) 2. The acrylic block copolymer according to claim 1, wherein the ring structural unit represented by the general formula (1) is a glutaric anhydride represented by the following general formula (2).

(However, R ⁶ and R ⁷ are the same or different and represent any one selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms.) In the acrylic block copolymer (A), the acrylic block copolymer (A) is 100% by weight, the polymer block (a) is 20 to 90% by weight, and the polymer block (b) is 10%. The acrylic block copolymer according to Example 1 or 2, which is contained in an amount of ˜80% by weight. The acrylic block copolymer (A) has the general formula ab or the general formula (ab) _n -a (n is an integer of 1 or more, and a is (i) the above general formula (1). Any one of Examples 1 to 3, wherein the polymer block (a) having a ring structural unit represented by the formula (b) represents a polymer block (b) having an acrylate unit) An acrylic block copolymer according to any one of the above. In the acrylic block copolymer (A), the polymer block (a) is composed of 100% by weight of the polymer block (a), and (i) a ring structural unit 5 to 5 represented by the general formula (1). 50% by weight, (ii) 50 to 95% by weight of unsaturated carboxylic acid alkyl ester monomer units, and (iii) 0.05 to 10% by weight of other copolymerizable vinyl monomer units. The acrylic block copolymer according to any one of claims 1 to 4. The polymer block (b) of the acrylic block copolymer (A) comprises (iv) 70 to 100% by weight of acrylic acid ester monomer units and 100% by weight of the polymer block (b). The acrylic block copolymer according to any one of claims 1 to 5, which comprises 0 to 30% by weight of an aromatic vinyl monomer unit. The acrylic polymer according to any one of claims 1 to 6, wherein (iv) the acrylate monomer unit of the polymer block (b) is n-butyl acrylate and / or ethyl acrylate. Block copolymer. The acrylic block copolymer according to any one of claims 1 to 7, wherein the acrylic block copolymer (A) satisfies the following (III) and / or (IV).
(III) The content of insoluble matter in a 5 wt% solution of tetrahydrofuran is 1 wt% or less.
(IV) The total light transmittance per 2 mm thickness is 90% or more. The acrylic block copolymer (A) according to any one of claims 1 to 8 and (i) a glass transition temperature 120 having the same ring structural unit as the polymer block (a) represented by the general formula (1). A thermoplastic copolymer composition obtained by blending an acrylic copolymer (B) having a temperature of at least ° C. The total of the acrylic block copolymer (A) and the acrylic copolymer (B) is 100% by weight, the acrylic block copolymer (A) is 5 to 50% by weight, and the acrylic copolymer (B). The thermoplastic copolymer composition according to claim 9, wherein 50 to 95% by weight is blended. Acrylic block copolymer (A) and acrylic copolymer (B) (i) with the total of the ring structural units represented by the general formula (1) being 100% by weight, the acrylic block copolymer ( The total of (iii) other copolymerizable vinyl monomer units of A) and the acrylic copolymer (B) is 0.1 to 20% by weight, according to claim 9 or 10. Thermoplastic resin composition. The cyclic structural unit represented by the general formula (1) of the acrylic copolymer (B) is a glutaric anhydride represented by the general formula (2). The thermoplastic copolymer composition according to any one of the above. The thermoplastic copolymer composition according to any one of claims 9 to 12, wherein the acrylic copolymer (B) has a weight average molecular weight of 30,000 to 150,000. The acrylic copolymer (B) comprises 100% by weight of the acrylic copolymer (B), and (i) 5 to 50% by weight of the ring structural unit represented by the general formula (1), (ii) 14. An unsaturated carboxylic acid alkyl ester unit of 50 to 95% by weight, and (iii) 0.05 to 10% by weight of other copolymerizable vinyl monomer units. The thermoplastic copolymer composition described in 1. The thermoplastic copolymer composition comprising the acrylic block copolymer (A) and the acrylic copolymer (B) satisfies the above (III) and / or (IV). The thermoplastic copolymer composition according to any one of 9 to 14. A molded article comprising the acrylic block copolymer according to any one of claims 1 to 8 or the thermoplastic copolymer composition according to any one of claims 9 to 15. The molded article according to claim 16, wherein the molded article is a film.