JP6846105B2 - Polymers, resin compositions and resin molded products, and methods for producing polymers - Google Patents

Description

The present invention relates to a polymer having a ring structure in the main chain, a method for producing the same, and a resin composition and a resin molded product containing the polymer.

Resin compositions containing transparent polymers such as acrylic polymers, polycycloolefins, polycarbonates, polystyrenes and polyesters are widely used in applications of optical components such as lenses, prisms, optical fibers and optical films. Among them, the acrylic polymer has features such as high optical transparency, high balance of weather resistance, mechanical strength, molding processability and surface hardness.

Among the transparent polymers, there is a polymer having a ring structure in the main chain. Among the above-mentioned polymers, polycycloolefin, polycarbonate, polyethylene terephthalate (PET), which is a kind of polyester, and the like fall under this category. Acrylic polymers also include polymers having a ring structure in the main chain. For example, Patent Document 1 (Patent No. 4825409) discloses an acrylic polymer having a lactone ring structure in the main chain. Patent Document 2 (Japanese Unexamined Patent Publication No. 2006-328334) discloses an acrylic polymer having a glutarimide structure in the main chain. Patent Document 3 (Japanese Unexamined Patent Publication No. 2007-31537) discloses an acrylic polymer having an N-substituted maleimide structure in the main chain.

Generally, the glass transition temperature (Tg) of an acrylic polymer is around 100 ° C. even if it is high, but these documents show that an acrylic polymer having a ring structure in the main chain has a higher Tg. There is. When the Tg of the polymer is improved, the heat resistance of the resin composition containing the polymer and the resin molded product is improved. When the resin molded body is an optical member, there has been a strong demand in recent years for products equipped with an optical member. This will increase the possibility of meeting design requirements for arranging optical members in the vicinity of heating elements such as batteries and circuit boards.

Patent No. 4825409 Japanese Unexamined Patent Publication No. 2006-328334 Japanese Unexamined Patent Publication No. 2007-31537

On the other hand, when the Tg of the polymer becomes high, the molding temperature required for melt molding the polymer or the resin composition containing the polymer to obtain a resin molded body becomes high. That is, the polymer in which Tg is increased due to the ring structure of the main chain is exposed to a higher temperature at the time of its molding. Considering molding into a resin molded product by melt molding, a polymer having a ring structure in the main chain is required to have heat-resistant decomposition characteristics to a temperature at the time of melt molding, which is forced to rise due to its own ring structure.

One of the objects of the present invention is to provide a polymer having a ring structure in the main chain and having improved heat-resistant decomposition characteristics, particularly heat-resistant decomposition characteristics against high temperatures expected during melt molding, and a method for producing the same. It is in.

The polymer of the present invention has a ring structure represented by the following formula (1) in the main chain, and the 5% heat loss temperature determined by the thermogravimetric analysis method specified in JIS K7120 is 300 ° C. or higher.

In the formula (1), R ¹ is a hydrogen atom, a methyl group or -NHCOR ³ groups, and R ³ is a hydrogen atom, a methyl group, a phenyl group, a linear alkyl group having 2 to 18 carbon atoms, or a carbon number of carbon atoms. It is a cycloalkyl group of 3-18. R ² is a hydrogen atom or -COOR ⁴ group, and R ⁴ is a hydrogen atom, a methyl group, a phenyl group, a linear alkyl group having 2 to 18 carbon atoms, or a cycloalkyl group having 3 to 18 carbon atoms. .. The ring structure represented by the formula (1) may be continuous on the main chain, and in this case, the ring structures adjacent to each other are the carbon atom at the 3-position of one of the ring structures and the other of the ring structures. A spiro ring structure in which the carbon atom at the 5-position is the same carbon atom is formed, ^{and R 1 bonded to the carbon atom at the 3-position and R 2} bonded to the carbon atom at the 5-position do not exist.

The resin composition of the present invention contains the above-mentioned polymer of the present invention.

The resin molded product of the present invention contains the above-mentioned polymer of the present invention.

The method for producing a polymer of the present invention is a precursor polymer formed by polymerization of a group of monomers containing a vinyl monomer, and has an ester group and / or a carboxyl group and an amide group as side chains. And further deacylated the acyl group on the tertiary amide structure constituting the ring structure formed by the cyclization to have a 5-membered ring structure having a secondary amide structure (-NH-CO-). This is a method for obtaining a polymer having the above in the main chain.

According to the present invention, there are provided a polymer having a ring structure in the main chain and having improved thermostable decomposition characteristics, particularly heat-resistant decomposition characteristics with respect to high temperatures expected at the time of melt molding, and a method for producing the same. ..

[Polymer (A)]
The polymer (A) of the present invention has a ring structure represented by the following formula (1) in the main chain. In the formula (1), R ¹ is a hydrogen atom, a methyl group or -NHCOR ³ groups, and R ³ is a hydrogen atom, a methyl group, a phenyl group, a linear alkyl group having 2 to 18 carbon atoms, or a carbon number of carbon atoms. It is a cycloalkyl group of 3-18. R ² is a hydrogen atom or -COOR ⁴ group, and R ⁴ is a hydrogen atom, a methyl group, a phenyl group, a linear alkyl group having 2 to 18 carbon atoms, or a cycloalkyl group having 3 to 18 carbon atoms. .. The polymer (A) is typically a thermoplastic polymer. The polymer (A) is typically an amorphous polymer. The polymer (A) is typically a water-insoluble polymer.

The ring structure represented by the formula (1) has a 5-membered amide ring structure (cyclic amide structure) as a basic skeleton. This cyclic amide structure is also a 5-membered lactam ring structure (γ-lactam structure). As shown in the formula (1), three carbon atoms (3rd, 4th and 5th positions of the ring structure) that do not form the amide structure of the ring structure, more specifically, the secondary amide structure (-NH-CO-). The carbon atom at the position) is located in the main chain of the polymer (A). The ring structure represented by the formula (1) constitutes the main chain of the polymer (A).

The 5% heating weight loss temperature of the polymer (A) (5% heating weight loss temperature determined by the thermogravimetric analysis method specified in JIS K7120, hereinafter the same) is 300 ° C. or higher.

The polymer (A) has a property derived from the ring structure located in the main chain. A typical example of the property is a higher glass transition temperature (Tg) as compared with the case where the ring structure is not provided in the main chain. A high Tg brings about the advantage of improving the heat resistance and thermal stability of the polymer (A) or the resin molded product obtained by molding the resin composition containing the polymer (A). However, a high Tg of the polymer means that a high molding temperature is required when the polymer and the resin composition containing the polymer are melt-molded, in other words, the temperature condition of the melt molding. Means that will be harsh. Severe temperature conditions during molding induce the generation of foaming on the obtained resin molded product, the generation of silver streaks, the precipitation of decomposition products, and the like. At the time of molding the resin molded body, particularly when the optical member is obtained as the resin molded body, it is required to suppress the occurrence of these which may be defects (in the case of the optical member, it may be a serious optical defect) as much as possible. Here, the polymer (A) is excellent in heat-resistant decomposition characteristics, and in particular, the heat-resistant decomposition characteristics with respect to high temperatures expected at the time of melt molding are improved. Therefore, the polymer (A) is a resin molded product having improved heat resistance and thermal stability based on high Tg derived from the ring structure constituting the main chain of the polymer (A), but at the same time. The advantageous effect of achieving a resin molded product in which the occurrence of defects such as foaming is suppressed is realized. As the resin composition containing the polymer (A) and the polymer (A), high Tg derived from the ring structure of the main chain is achieved, and at the same time, defects such as foaming occur during melt molding. The advantageous effect of achieving a suppressed polymer or resin composition is realized.

The polymer (A) may have other properties derived from the ring structure located in the main chain. The property is, for example, an optical property, and a more specific example is a birefringence property. The ring structure of the formula (1) located in the main chain improves the birefringence expression (phase difference expression) of the polymer (A). The ring structure represented by the formula (1) has an action of imparting positive or negative intrinsic birefringence to the polymer (A). More specifically, the ring structure represented by the formula (1) basically has an action of giving positive birefringence to the polymer (A), but the substituent bonded to the basic skeleton of the ring structure is bulky. In some cases, the polymer (A) may be given a negative intrinsic birefringence. The positive or negative of the intrinsic birefringence as the polymer (A) is determined by the balance of the birefringence characteristics exhibited by each structural unit of the polymer (A). For example, even when the ring structure represented by the formula (1) has an action of giving a positive intrinsic birefringence to the polymer (A), the polymer (A) is a structural unit having an action of giving a negative intrinsic birefringence. When further possessed, the intrinsic birefringence as the polymer (A) may be negative.

The polymer (A) can be used for various purposes based on each of these properties. Applications are, for example, optical members. The high Tg and thermal decomposition properties as well as the optical properties of the polymer (A) described above can be advantageous features of the optical member. A high Tg leads to, for example, an improvement in the heat resistance of the optical member containing the polymer (A), and such an optical member improves the degree of freedom in designing a product including the optical member. As a specific example, with respect to an optical film which is a kind of optical member, since the film can be arranged close to a heating element such as a light source, a power supply unit, or a circuit board, a liquid crystal display device (LCD) or the like can be used. The degree of freedom in designing the image display device is improved. The high heat-resistant decomposition property contributes to the suppression of the occurrence of optical defects when molding the optical member and the realization of an optical member having few optical defects. The high birefringence expression leads to an improvement in the retardation value per unit thickness of the optical film, for example, and an optical film that achieves the designed retardation value while being thinner is realized. The birefringence manifestation can be evaluated by, for example, the stress optical coefficient Cr. The larger the absolute value of Cr, the higher the birefringence expression. The action of imparting positive intrinsic birefringence to the polymer (A) leads to, for example, the realization of a positive retardation film in which the retardation Rth in the thickness direction is positive.

The ring structure represented by the formula (1) may be a structural unit (repeating unit) of the polymer (A) or a structure that constitutes a part of the structural unit. In the latter case, the structural unit includes a ring structure represented by the formula (1) as a part of its molecular structure.

In the formula (1), R ¹ is a hydrogen atom, a methyl group or -NHCOR ³ groups, and R ³ is a hydrogen atom, a methyl group, a phenyl group, a linear alkyl group having 2 to 18 carbon atoms, or a carbon number of carbon atoms. It is a cycloalkyl group of 3-18. R ² is a hydrogen atom or -COOR ⁴ group, and R ⁴ is a hydrogen atom, a methyl group, a phenyl group, a linear alkyl group having 2 to 18 carbon atoms, or a cycloalkyl group having 3 to 18 carbon atoms. .. R ³ and R ⁴ may be the same or different from each other.

The linear alkyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 4 carbon atoms. The linear alkyl group is, for example, an ethyl group, a propyl group, or a butyl group. The cycloalkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. The cycloalkyl group is, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.

In one embodiment, R ¹ in formula (1) is the above-NHCOR ³ groups. In this case, R ³ is preferably a hydrogen atom, a methyl group, a phenyl group, an n-butyl group or a t-butyl group.

In yet another embodiment, R ² is the above-mentioned ^four -COOR groups in the formula (1). In this case, R ⁴ is preferably a hydrogen atom, a methyl group, an ethyl group, an n-butyl group or a benzyl group.

In yet another embodiment, in formula (1), R ¹ and R ² are independent of each other, a hydrogen atom or a methyl group.

A specific example of a combination of R ¹ and R ^{2 is a combination in which R 1} is a methyl group or -NHCOR ³ groups and R ² is a -COOR ⁴ group. At this time, R ³ can be a methyl group, and independently of this, R ⁴ can be a methyl group. A more specific example of a combination is ^{one in} which R 1 is a methyl group or -NHCOCH ₃ groups and R ² is a -COOCH ₃ group.

Another specific example of a combination of R ¹ and R ^{2 is a combination in which R 1} is a methyl group and R ² is a hydrogen atom.

The ring structure represented by the formula (1) may be continuous on the main chain of the polymer (A). In this case, the continuous ring structure forms a spiro ring structure between adjacent ring structures. However, when the ring structure represented by the formula (1) constitutes a part of the structural unit of the polymer (A), for example, the structural unit of the polymer (A) is 3 of the ring structure represented by the formula (1). When the structural unit has a structure in which an alkylene group such as a methylene group is bonded to the carbon atom at the 5-position or 5-position (more specific example is the structural unit represented by the formula (4) described later), the polymer. The continuity of the structural unit in the main chain of (A) corresponds to the continuity of the ring structure on the main chain because the alkylene group constituting the main chain of the polymer (A) is located between the ring structures. do not do. In this case, it can be said that the ring structures are not adjacent to each other on the main chain.

When the ring structure represented by the formula (1) is continuous on the main chain of the polymer (A), the two ring structures adjacent to each other are the carbon atom at the 3-position of one ring structure and the 5-position of the other ring structure. Form a spiro ring structure in which the carbon atom of the above is the same carbon atom. ^{Then, R 1} bonded to the carbon atom at the 3-position ^{and R 2} bonded to the carbon atom at the 5-position do not exist.

Examples of such a continuous ring structure on the main chain of the polymer (A) are shown in the following formulas (2) and (3).

The structure represented by the formula (2) is a spiro ring structure in which the two ring structures represented by the formula (1) are continuous on the main chain of the polymer (A). The carbon atom at the 5-position of the ring structure on the left side and the carbon atom at the 3-position of the ring structure on the right side adjacent to the ring structure are the same carbon atom. In each ring structure, three carbon atoms at the 3rd to 5th positions form the main chain of the polymer (A). ^{There is no R 2} bonded to the carbon atom at the 5-position of the ring structure on the left side ^{and R 1} bonded to the carbon atom at the 3-position of the ring structure on the right side.

The structure represented by the formula (3) is a spiro ring structure in which the three ring structures represented by the formula (1) are continuous on the main chain of the polymer (A). The carbon atom at the 5-position of the leftmost ring structure and the carbon atom at the 3-position of the central ring structure adjacent to the ring structure are the same carbon atom. The carbon atom at the 5-position of the central ring structure and the carbon atom at the 3-position of the rightmost ring structure adjacent to the ring structure are the same carbon atom. In each ring structure, three carbon atoms at the 3rd to 5th positions form the main chain of the polymer (A). ^{R 2} bonded to the carbon atom at the 5th position of the leftmost ring structure, ^{R 1} bonded to the carbon atom at the 3rd position of the central ring structure, ^{R 2} bonded to the carbon atom at the 5th position, and 3 of the ring structure at the right end. There is no ^{R 1} bonded to the carbon atom at the position.

As described above, when the ring structure represented by the formula (1) is continuous on the main chain of the polymer (A), R ¹ and / or R ² may not be present. At this time, R ¹ and / R ² are not absent, but are adjacent rings together with the bond hand of the carbon atom to which the group is bonded (the bond hand to the outside of the ring structure represented by the formula (1)). It can also be expressed as forming a structure.

When the ring structure represented by the formula (1) is continuous on the main chain of the polymer (A), the number of continuous rings is not limited. In one example, the polymer (A) in which the ring structure represented by the formula (1) is continuous throughout the main chain, in other words, the ring structure represented by the formula (1) is used as a constituent unit, and is composed of only the constituent unit. It can be a polymer (A), which is a homopolymer.

The polymer (A) will have a structural unit P including a ring structure represented by the formula (1). The structural unit P may be composed of only the ring structure represented by the formula (1), or may be composed of the ring structure represented by the formula (1) and another molecular structure. The other molecular structure is, for example, a molecular structure that is bonded to the carbon atom at the 3-position and / or the 5-position of the ring structure represented by the formula (1) to form the main chain of the polymer (A) together with the ring structure. Yes, and more specific examples are alkylene groups such as the methylene group described above.

An example of the structural unit P composed of the ring structure represented by the formula (1) and another molecular structure is shown in the following formula (4).

The structural unit X represented by the formula (4) is a unit composed of the ring structure represented by the formula (1) and a methylene group bonded to the carbon atom at the 3-position of the ring structure. The carbon atom of the methylene group and the carbon atom at the 3- to 5-position of the ring structure constitute the main chain of the polymer (A). The ring structure of the structural unit X contains a secondary amide structure (-NH-CO-) as a molecular structure constituting a part of the ring (including a secondary amide structure as a part of the ring structure). There is).

The structural unit X basically has an action of imparting positive intrinsic birefringence to the polymer (A). However, if the substituent bonded to the basic skeleton of the ring structure is bulky, the polymer (A) may be given a negative intrinsic birefringence. A structural unit having an action of giving a positive (or negative) intrinsic birefringence to a polymer is a unit in which the homopolymer exhibits positive (or negative) intrinsic birefringence when a homopolymer of the unit is formed. Say. The positive or negative of the intrinsic birefringence as the polymer (A) is determined not only by the structural unit X but also by the balance with the birefringence characteristics of the other structural units of the polymer (A).

R ¹ and R ² of formula (4), including the specific example described above, the same as R ¹ and R ² of formula (1).

A specific example of the combination ^{of R 1} and R ² in the formula (4) is ^{a combination in which R 1} is a methyl group or -NHCOR ³ groups and R ² is a -COOR ⁴ group. At this time, R ³ can be a methyl group, and independently of this, R ⁴ can be a methyl group. A more specific example of the combination is a combination in which R ¹ is a methyl group or -NHCOCH ₃ groups and R ² is a -COOCH ₃ group, and the structural unit X having such a combination is, for example, a methacrylic acid. Obtained after a copolymer of methyl (MMA) and methyl acetamide acrylate (AcAAM) is used as a precursor polymer (B) and a cyclization reaction is allowed to proceed between adjacent structural units in the polymer (B). The acyl group on the tertiary amide structure constituting the ring structure (ring structure formed by the cyclization reaction) of the intermediate polymer (C) can be deacylated. If the adjacent building blocks that promote the cyclization reaction are a combination of MMA units and AcAAM units, R ¹ is a methyl group, and if it is a combination of a set of AcAAM units, R ¹ is -NHCOCH ₃ groups. is there. The structural unit X having such a combination has an action of imparting positive intrinsic birefringence to the polymer (A).

Another specific example of the combination ^{of R 1} and R ² in the formula (4) is ^{a combination in which R 1} is a methyl group and R ² is a hydrogen atom, and the structural unit X having such a combination is, for example, , A cyclization reaction between adjacent MMA units and NVA units in the polymer (B) using a copolymer of methyl methacrylate (MMA) and N-vinylacetamide (NVA) as a precursor polymer (B). Can be formed by deacylating the acyl group on the tertiary amide structure constituting the ring structure (ring structure formed by the cyclization reaction) of the obtained intermediate polymer (C). The structural unit X having such a combination has an action of imparting positive intrinsic birefringence to the polymer (A).

Even if the polymer (A) is a homopolymer composed only of the structural unit P containing the ring structure represented by the formula (1), it is composed of the structural unit P and the structural unit Q other than the structural unit P. It may be a copolymer. The copolymer can be a random copolymer, a block copolymer, or a graft copolymer.

The polymer (A) may have two or more structural units P, or may have two or more structural units Q.

When the polymer (A) is a copolymer composed of the structural unit P and the structural unit Q, the polymer (A) exhibits various additional properties depending on the type and content of the structural unit Q. The structural unit Q is, for example, a (meth) acrylic acid ester unit, a (meth) acrylic acid unit, an N-substituted maleimide unit, an aromatic vinyl compound unit, an unsaturated carboxylic acid compound unit, a vinyl cyanide compound unit, or a complex aromatic. It is an α, β-unsaturated monomer unit having a group.

The polymer (A) may have at least one selected from the (meth) acrylic acid ester unit and the (meth) acrylic acid unit as the constituent unit Q. In this case, the optical properties of the polymer (A) and the resin composition containing the polymer (A) are further improved, such as higher optical transparency, and the resin composition is more suitable for use as an optical member, for example. .. The polymer (A), which is a copolymer, preferably has a (meth) acrylic acid ester unit as a constituent unit Q. In other words, it is preferable that the polymer (A) further has a (meth) acrylic acid ester unit as a constituent unit.

The (meth) acrylic acid ester unit is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, α-hydroxyacrylic It is a structural unit (derived from each of these monomers) formed by polymerization of each (meth) acrylic acid ester of methyl acrylate and ethyl α-hydroxyacrylic acid. The (meth) acrylic acid ester unit is preferably methyl methacrylate (MMA) unit, ethyl methacrylate unit, n-butyl methacrylate unit, cyclohexyl methacrylate unit, isobornyl methacrylate unit, or benzyl methacrylate unit, and the MMA unit is preferable. More preferred. At this time, the optical transparency of the polymer (A) is further increased.

When the polymer (A) further has a (meth) acrylic acid ester unit as a constituent unit, the content of the (meth) acrylic acid ester unit in the polymer (A) is, for example, 15 to 90% by mass, and 40 to 40 to 85% by mass is preferable, and 60 to 80% by mass is more preferable. In these cases, the balance between the high Tg, the thermostable decomposition property and the optical property of the polymer (A) and the resin composition containing the polymer (A) is further improved.

Depending on the type of the structural unit P, including the structural unit X represented by the formula (4), a copolymer with a (meth) acrylic acid ester such as MMA is used as the precursor polymer (B), and the precursor polymer (B) is used. ) Can be allowed to proceed with a cyclization reaction and a deacylation reaction to form the polymer (A), in which case the polymer (A) may have a (meth) acrylic acid ester unit as an unreacted unit. ..

When the content of the (meth) acrylic acid ester unit in the polymer (A) exceeds 15% by mass, the polymer (A) is an acrylic polymer. The polymer (A), which is an acrylic polymer, exhibits properties generally possessed by the acrylic polymer, such as high optical transparency, and a high balance of mechanical strength, moldability and surface hardness. In the polymer (A) which is an acrylic polymer, the total content of the (meth) acrylic acid ester unit may be 40% by mass or more, 60% by mass or more, 80% by mass or more, and further 85% by mass or more.

Further, as described above, the polymer (A) is formed by advancing the cyclization reaction and the deacylation reaction on the precursor polymer (B) which is a copolymer having a (meth) acrylic acid ester unit as a constituent unit. If so, the polymer (A) can also be regarded as a derivative of the (meth) acrylic acid ester. In this case, when the total content of the structural unit P and the (meth) acrylic acid ester unit in the polymer (A) exceeds 50% by mass, the polymer (A) is an acrylic polymer. The total content may be 60% by mass or more, 70% by mass or more, 80% by mass or more, and even 90% by mass or more. As will be described later, the precursor polymer (B), which is a copolymer with the (meth) acrylic acid ester, that is, the precursor polymer (B), which is a copolymer having the (meth) acrylic acid ester unit as a constituent unit ( In B), an ester group and / or a carboxyl group and an amide group are present in the side chain of the polymer (B), and the polymer (B) has a tertiary amide structure due to the progress of the cyclization reaction to the polymer (B). As long as a polymer having a 5-membered ring structure in the main chain (intermediate polymer (C)) can be obtained, the monomer to be copolymerized with the (meth) acrylic acid ester is not limited. The monomer can be, for example, an amide acrylic acid ester, or, for example, an amide group-containing vinyl monomer such as N-vinylcarboxylic acid amide such as N-vinylformamide or N-vinylacetamide.

The N-substituted maleimide units are, for example, N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, Nt-butylmaleimide, N-tribromophenylmaleimide, N-. It is a structural unit derived from each monomer of laurylmaleimide and N-benzylmaleimide. The N-substituted maleimide unit is preferably an N-cyclohexylmaleimide unit or an N-phenylmaleimide unit.

The aromatic vinyl compound unit is, for example, styrene, α-methylstyrene, α-chlorostyrene, pt-butylstyrene, p-methylstyrene, p-chlorostyrene, o-chlorostyrene, 2,5-dichlorostyrene, It is a structural unit derived from each aromatic vinyl compound of 3,4-dichlorostyrene and divinylbenzene. The aromatic vinyl compound unit is preferably a styrene unit.

The unsaturated carboxylic acid compound unit is a structural unit formed by polymerization of an acid such as crotonic acid and an alkali metal salt, an ammonium salt, or an organic amine salt thereof. In the present specification, the unsaturated carboxylic acid compound unit does not include the (meth) acrylic acid unit.

The vinyl cyanide compound unit is, for example, a (meth) acrylonitrile unit.

The α, β-unsaturated monomer unit having a complex aromatic group is at least one selected from, for example, vinyl carbazole unit, vinyl pyridine unit, vinyl imidazole unit and vinyl thiophene unit.

The structural unit Q is a vinyl compound unit other than the above-mentioned units, for example, vinyl acetate, vinyl chloride, vinylidene chloride, ethylene, propylene, butene, isoprene, N-vinyl-2-pyrrolidone; divinyl adipate, divinyl sebacate, etc. Divinyl esters; sulfonic acids such as vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamide-2-phenylpropane sulfonic acid, 2-acrylamide-2-methylpropane sulfonic acid and alkali metal salts, ammonium salts and organic amine salts thereof. Can be a structural unit formed by the polymerization of;

The polymer (A) may have a structural unit capable of absorbing ultraviolet (UVA). The structural unit is, for example, a structural unit formed by polymerization of a benzotriazole derivative, a triazine derivative or a benzophenone derivative into which a polymerizable group has been introduced. In these derivatives, the polymerizable group to be introduced can be appropriately selected, for example, a vinyl group.

The content of the structural unit P in the polymer (A) is not limited, but in order to more reliably obtain the characteristics derived from the structural unit P, for example, it is 30% by mass or more, preferably 35% by mass or more, preferably 40% by mass. % Or more is more preferable. The upper limit of the content of the structural unit P is not particularly limited, and may be 100% by mass or less. When the polymer (A) further has another structural unit Q, particularly (meth) acrylic acid ester unit, the upper limit of the structural unit P is, for example, 90% by mass or less, 85% by mass or less, and 82% by mass or less. sell.

The content of each structural unit in the polymer (A) ^{can be determined by a known method, for example, 1} H nuclear magnetic resonance ( ¹ H-NMR) or infrared spectroscopic analysis (IR).

The ring structure represented by the formula (1) contained in the main chain of the polymer (A) ^{can be confirmed by a known method, for example, 1 1} H-NMR or IR. Examples of specific confirmation, in the infrared absorption spectrum, the range of wave number 1690 cm ^-1 or 1710 cm ^-1, the absorption peak attributed to the stretching vibration of the carbonyl group of the ring structure shown in formula (1) is observed It is a confirmation of whether or not it is possible. The fact that the absorption peak attributed to the expansion and contraction vibration of the carbonyl group of the ring structure represented by the formula (1) in the infrared absorption spectrum is in the above wavenumber range is defined as the infrared absorption region in the 5-membered lactam ring in 2006. It is described in "" Spectrum-based identification method for organic compounds, 7th edition, "Tokyo Kagaku Dojin," published on September 15.

Depending on the specific structure of the ring structure, the content of the ring structure in the polymer (A), and the type and content of the structural unit Q when the polymer (A) is a copolymer further having the structural unit Q. May be difficult to confirm the absorption peak in the infrared absorption spectrum. However, depending on the composition of the polymer (A), by reheating the polymer (A), the cyclization reaction does not proceed during the formation of the polymer (A), and the cyclization reaction is performed again between the remaining structural units. The same ring structure as the ring structure existing in the intermediate polymer (C) when the polymer (A) is formed from the precursor polymer (B), and in some cases, the polymer (A) has already been formed. It may be possible to form the same ring structure as the ring structure shown in the formula (1) existing in. At this time, these ring structures can be confirmed by taking the difference in the infrared absorption spectra before and after the reheating of the polymer (A). In other words, this time the polymer (A), upon heating the polymer at 200 ° C. or higher, the difference between the infrared absorption spectra before and after heating, the absorption peak in the range of less wave numbers 1690 cm ^-1 or 1710 cm ^-1 It can be the polymer observed.

When the polymer (A) is formed through the dealcohol cycloaddition reaction described later, the alcohol produced during the cyclization reaction may remain in the polymer (A). At this time, the content of the residual alcohol in the polymer (A) is, for example, 10 to 3000 ppm.

The polymer (A) exhibits a high Tg based on the ring structure represented by the formula (1) constituting the main chain. The Tg of the polymer (A) is, for example, 120 ° C. or higher. Depending on the specific structure of the ring structure represented by the formula (1) and its content, or the specific structure of the structural unit P including the ring structure represented by the formula (1) and its content, the polymer (A) may be used. Tg can take a value of 130 ° C. or higher, 140 ° C. or higher, 150 ° C. or higher, and further 160 ° C. or higher.

The 5% heating weight loss temperature of the polymer (A) is 300 ° C. or higher. Depending on the specific structure of the ring structure represented by the formula (1) and its content, or the specific structure of the structural unit P including the ring structure represented by the formula (1) and its content, the polymer (A) may have a specific structure. The 5% heating weight loss temperature can take a value of 320 ° C. or higher, 340 ° C. or higher, and further 360 ° C. or higher.

The polymer (A) may be crosslinked with a crosslinking agent or the like.

The polymer (A) can be formed, for example, by the following method for producing the polymer (A).

[Method for producing polymer (A)]
In the production method of the present invention, it is a precursor polymer (B) formed by polymerization of a group of monomers containing a vinyl monomer, and is an ester group and / or a carboxyl group and an amide group (secondary amide group: -NHCOR). ) As a side chain, and the intermediate polymer (C) having a ring structure (ring structure having a tertiary amide structure) formed by the cyclization in the main chain is obtained. obtain. Then, the acyl group on the tertiary amide structure constituting the ring structure in the intermediate polymer (C) is further deacylated to form a 5-membered ring structure having a secondary amide structure (-NH-CO-). Obtain a polymer having a main chain. The polymer is, for example, the polymer (A), and the 5-membered ring structure having the secondary amide structure is, for example, the ring structure represented by the formula (1).

In the cyclization of the precursor polymer (B), a cyclization condensation reaction is allowed between the ester group and / or the carboxyl group located in the side chain of the polymer (B) and the amide group to proceed with the tertiary amide. It forms a 5-membered amide ring structure with a structure. At this time, the ester group and / or the carboxyl group is changed to a carbonyl group containing a carbon atom at the 2-position of the ring structure, and the amide group is an amide group containing a nitrogen atom at the 1-position of the ring structure (tertiary amide group). ). This tertiary amide group can also be regarded as a tertiary amine group having an acyl group (-COR). The carbonyl group containing a carbon atom at the 2-position and the amine group containing a nitrogen atom at the 1-position form a tertiary amide structure, and the intermediate polymer (C) thus formed is the first. It has a 5-membered ring structure with a tertiary amide structure in the main chain. Three carbon atoms at the 3- to 5-positions of the ring structure are located in the main chain of the intermediate polymer (C).

An example of such a cyclization reaction is shown in the following formula (5).

R ¹ and R ² of formula (5), including the specific example described above, the same as R ¹ and R ² of formula (1). ^{R 5} of the formula (5) is a hydrogen atom, a methyl group, a phenyl group, a linear alkyl group having 2 to 18 carbon atoms, or a cycloalkyl group having 3 to 18 carbon atoms. R ⁵ is independent of ^{R 1} and R ^{2. R 6} of the formula (5) is a hydrogen atom or an organic residue having 1 to 18 carbon atoms. The organic residue is, for example, an alkyl group such as a methyl group, an ethyl group or a propyl group; an unsaturated aliphatic hydrocarbon group such as an ethenyl group or a propenyl group; an aromatic hydrocarbon group such as a phenyl group or a naphthyl group; the above alkyl. In the group, the unsaturated aliphatic hydrocarbon group and the aromatic hydrocarbon group, one or more hydrogen atoms are substituted with at least one group selected from a hydroxyl group, a carboxyl group, an ether group and an ester group. ;. R ⁶ is preferably a linear alkyl group or a cycloalkyl group, and the carbon number thereof is preferably 1 to 12, more preferably 1 to 4. R ⁶ can be a linear alkyl group or a cycloalkyl group.

In the reaction represented by the formula (5), the cyclization reaction is allowed to proceed on the precursor polymer (B) having the molecular structure on the left side to form the intermediate polymer (C) having the structural unit shown on the left side on the right side. This cyclization reaction is a condensation reaction in which the broken line portion shown on the left side is bonded and R ^{6 OH is eliminated.} Water is desorbed when R ⁶ is a hydrogen atom, that is, this reaction is a dehydration cyclization condensation reaction. Alcohol is eliminated when R ⁶ is an organic residue, i.e., this reaction is a dealcohol cyclization condensation reaction. For example, when R ⁶ is a methyl group, methanol is eliminated. This reaction proceeds within the molecular chain of the precursor polymer (B). The structural unit shown on the right side of the formula (5) includes a 5-membered ring structure and a methylene group bonded to a carbon atom at the 3-position of the ring structure.

The deacyllation of the structural unit shown on the right side of the formula (5) is shown in the following formula (6). The structural unit shown on the left side of the right side of the equation (6) is an example of the above-mentioned structural unit P. That is, a polymer (A) is formed from the precursor polymer (B) via the intermediate polymer (C) by a reaction including a cyclization reaction represented by the formula (5) and a deacylation reaction represented by the formula (6). be able to. R ⁷ can be identical to a hydrogen atom or R ^6. In the former case, the nucleophile that attacks the carbon atom of the carbonyl group during deacyllation is the case of water. In the latter case, the nucleophile is, for example, the case of ^{alcohol R 6 OH formed during the cyclization reaction described above.}

The precursor polymer (B) has an ester group and / or a carboxyl group in its side chain and also has an amide group. More specifically, the precursor polymer (B) of the formula (5) has an ester group (carboxyl ester group: R ⁶ is an organic residue) and / or a carboxyl group (R ⁶ is a hydrogen atom) in the side chain. It is a copolymer having a unit and a constituent unit having an amide group (secondary amide group: -NHCOR ^{5) in the side chain.} Each structural unit is a unit derived from a vinyl monomer. As described above, the precursor polymer (B) can be formed by polymerizing a group of monomers containing a vinyl monomer. More specifically, the precursor polymer (B) of the formula (5) is formed by polymerization of a monomer group containing a vinyl monomer A having an ester group and / or a carboxyl group and a vinyl monomer B having an amide group. It is a copolymer. In this precursor polymer (B), the ester group and / or carboxyl group of the side chain and the amide group have one methylene group (one carbon atom) located in the main chain of the precursor polymer (B) between them. One) It is in the inserted positional relationship. In the example shown in the formula (5), the three carbon atoms located in the main chain of the precursor polymer (B), the carbon atoms of the carboxyl group and / or the ester group located in the side chain, and the nitrogen atom of the amide group are used. A 5-membered ring structure with a tertiary amide structure is formed.

An example of the vinyl monomer A at this time is shown in the following formula (7), and an example of the vinyl monomer B is shown in the following formula (8). R ¹ of formula (7), including the specific examples are the same as R ¹ of formula (1), R ⁶ is the same as R ⁶ in the formula (5). R ¹ can be a hydrogen atom or a methyl group. R ² of formula (8), including the specific examples are the same as R ² of formula (1), R ⁵ is the same as R ⁵ in formula (5). R ² can be a hydrogen atom or a methyl group. The vinyl monomer A represented by the formula (7) is a (meth) acrylic acid ester unit (R ¹ is a hydrogen atom or a methyl group and R ⁶ is an organic residue), or a (meth) acrylic acid unit (R ^1). Is a hydrogen atom or a methyl group, and R ⁶ is a hydrogen atom). As the vinyl monomer A, acrylic acid or methyl methacrylate (MMA) is preferable, and MMA is more preferable, because the formed polymer (A) has higher optical transparency.

The vinyl monomer B represented by the formula (8) is N-vinylformamide (R ² and R ⁵ are hydrogen atoms), N-vinylcarboxylic acid amide (R ² is a hydrogen atom, R ⁵ is a methyl group, a linear alkyl group or It can be an amide group-containing vinyl monomer (cycloalkyl group). R ⁵ can be a hydrogen atom, a methyl group or a linear alkyl group, a methyl group or a linear alkyl group, or a methyl group. When R ² is a hydrogen atom and R ⁵ is a methyl group, the vinyl monomer B represented by the formula (8) is N-vinylacetamide (see formula (9)).

The vinyl monomer B represented by the formula (8) can be a monomer having an ester group and / or a carboxyl group as well as an amide group. At this time, R ² of the formula (8) is −COOR ⁴ groups, which is the same as the ^{−COOR 4 groups that R 2} of the formula (1) can take. An example of such a vinyl monomer B is shown in the following formula (10).

The monomer B represented by the formula (10) can be an amidoacrylic acid ester. The amide acrylic acid ester is a vinyl monomer having both an ester group and / or a carboxyl group and an amide group.

The vinyl monomer B represented by the formula (8) and the formula (10) can be an amide acrylic acid ester, and the amide acrylic acid ester is, for example, methyl acetamidoacrylate (AcAAM), ethyl acetamidoacrylate, or acetamidoacrylic acid. Acid n-butyl, acetamide acrylate nd dodecyl, acetamide acrylate cyclohexyl, acetamide acrylate phenyl.

When the precursor polymer (B) is a copolymer of vinyl monomer A and vinyl monomer B, the structural unit Y1 derived from the monomer A and the structural unit Y2 derived from the monomer B in the polymer (B) are used. The content ratio is not particularly limited, but the mass ratio is, for example, Y1: Y2 = 95 to 50: 5 to 50, preferably 90 to 50: 10 to 50, and more preferably 85 to 60: 15 to 40. .. The structural unit Y1 may be a (meth) acrylic acid ester unit, or, as a more specific example, an MMA unit. When the structural unit Y1 is a (meth) acrylic acid ester unit and the mass ratio of the structural units Y1 and Y2 is in the above-mentioned preferable range, the cyclization reaction between the (meth) acrylic acid ester and the vinyl monomer B The ratio can be improved, and for example, the Tg of the finally obtained polymer (A) can be made higher. Further, at this time, in the finally obtained polymer (A), the balance between the content of the (meth) acrylic acid ester unit and the ring structure represented by the formula (1) is improved, and the heat resistance of the polymer (A) is improved. Decomposition characteristics can be further improved. The finally obtained polymer (A) may have unreacted building blocks Y1 and / or Y2. For example, when the structural unit Y1 is a (meth) acrylic acid ester unit, the finally obtained polymer (A) may have an unreacted (meth) acrylic acid ester unit as a structural unit.

The precursor polymer (B) may be a polymer formed by polymerizing a group of monomers containing two or more kinds of vinyl monomer A and / or two or more kinds of vinyl monomer B. That is, the precursor polymer (B) has two or more structural units Y1 derived from two or more vinyl monomers A and / or two or more structural units Y2 derived from two or more vinyl monomers B. May be.

The vinyl monomer A represented by the formula (7) and the vinyl monomer B represented by the formula (8) may be the same vinyl monomer depending on the type of the substituent. That is, the precursor polymer (B) may be a homopolymer of the same vinyl monomer. As can be understood from the molecular structure represented by each formula, this vinyl monomer is a vinyl monomer C having both an ester group and / or a carboxyl group and an amide group. That is, the precursor polymer (B) may be a polymer formed by polymerizing a group of monomers containing a vinyl monomer C having an ester group and / or a carboxyl group and an amide group. When the precursor polymer (B) is such a homopolymer, the Tg of the finally obtained polymer (A) is particularly high. In other words, for the polymer (A), the increase in Tg from the precursor polymer (B) is particularly large.

The vinyl monomer C is, for example, an amidoacrylic acid ester.

An example of a cyclization reaction for forming an intermediate polymer (C) from a precursor polymer (B) which is a homopolymer of vinyl monomer C is shown in the following formula (11). In the example shown in the formula (11), the intermediate polymer (C) is formed by advancing the cyclization reaction on the precursor polymer (B) which is a homopolymer of the amidoacrylic acid ester.

R ⁴ of formula (11) is the same as R ⁴ of formula (1), R ⁵ of formula (11) is the same as R ⁵ in formula (5). By advancing deacyllation to the structural unit having a ring structure in the main chain shown on the right side of the formula (11), R ¹ is -NHCOR ⁵ groups (-NHCOR ³ groups) and R ² is -COOR ⁴ A structural unit P including a ring structure represented by the basic formula (1) is formed. That is, the polymer (A) having the structural unit P is formed. The cyclization reaction represented by the formula (11) is a cycloaddition reaction in which the broken line portion between adjacent structural units in the precursor polymer (B) is bonded and R ⁴ OH is eliminated.

Another example of the cyclization reaction for forming the intermediate polymer (C) from the precursor polymer (B) which is a homopolymer of the vinyl monomer C is shown in the following formula (12). In the example shown in the formula (12), the intermediate polymer (C) is formed by advancing the cyclization reaction on the precursor polymer (B) which is a homopolymer of the amidoacrylic acid ester.

R ⁴ of formula (12) is the same as R ⁴ of formula (1), R ⁵ of formula (12) is the same as R ⁵ in formula (5). By advancing deacyllation to the structural unit having a ring structure in the main chain shown on the right side of the formula (12), a structural unit P containing a spiro ring structure in which two ring structures are continuous on the main chain is formed. To. That is, the polymer (A) having the structural unit P is formed. ^{In formula (12), a cyclization reaction (bonding the broken line portion in the molecular structure on the left side and R 4} OH) is performed between the left-end and central vinyl monomers C adjacent to each other and between the central and right-end vinyl monomers C adjacent to each other. The desorption reaction) is in progress. As can be understood from this, the cyclization condensation reaction is allowed to proceed between all the adjacent vinyl monomers C to form the intermediate polymer (C), and the formed intermediate polymer (C) is further deacylated. By advancing, it is also possible to form a polymer (A) which is a homopolymer having only a structural unit composed of a ring structure represented by the formula (1). Further, also in the precursor polymer (B) which is a copolymer of vinyl monomers A and B, depending on the type of vinyl monomer B, a ring is formed by a cyclization reaction in a region where the structural units derived from the monomer B are continuous. The structure can form a continuous spiro ring structure. That is, a polymer (A) having a continuous spiro ring structure can be formed.

The polymer (A) on which the spiro ring structure is formed, particularly the polymer (A) which is the homopolymer, is expected to have particularly remarkable characteristics based on the ring structure represented by the formula (1). The property is, for example, a very high Tg. Such a polymer (A) having a very high Tg is expected to be used in applications requiring extremely high heat resistance.

When the precursor polymer (B) is a copolymer, the polymer (B) can be a random copolymer or an alternating copolymer.

The precursor polymer (B) can be a copolymer of two or more kinds of amidacrylic acid esters.

When the precursor polymer (B) is a copolymer formed by polymerization of a monomer group containing vinyl monomer A and vinyl monomer B, the monomer group may further contain vinyl monomer C. Good. When the precursor polymer (B) is a polymer formed by polymerizing a group of monomers containing vinyl monomer C, the group of monomers further contains vinyl monomer A and / or vinyl monomer B. May be good.

The precursor polymer (B) may further have a structural unit derived from a monomer other than the vinyl monomers A to C, for example. In this case, the intermediate polymer (C) and the polymer (A) further having the structural unit can be formed. The structural unit is, for example, a structural unit Q other than the structural unit P described above in the description of the polymer (A).

(Formation of precursor polymer (B))
The method for forming the precursor polymer (B) is not particularly limited. The monomer may be selected so that the formed precursor polymer (B) has an ester group and / or a carboxyl group and an amide group as side chains, and the monomer group containing the monomer may be polymerized. The monomer group may contain a monomer other than the monomer essential for the formation of the polymer (B), if necessary. The monomer is, for example, a monomer that becomes a constituent unit Q by polymerization.

The monomer group includes, for example, vinyl monomers. As a more specific example, the monomer group includes a vinyl monomer A having an ester group and / or a carboxyl group, and a vinyl monomer B having an amide group. The monomer group includes, as another specific example, a vinyl monomer C having an ester group and / or a carboxyl group and an amide group. An example of vinyl monomer A is at least one selected from (meth) acrylic acid ester and (meth) acrylic acid. An example of vinyl monomer B is an amide group-containing vinyl monomer such as N-vinylformamide and N-vinylcarboxylic acid amide. The vinyl monomer B can be at least one selected from N-vinylformamide and N-vinylacetamide. Another example of vinyl monomer B and example of vinyl monomer C is an amidacrylic acid ester.

The polymerization method of the monomer group is not particularly limited, and a known polymerization method such as solution polymerization can be applied. When solution polymerization is selected, the polymerization solvent is not particularly limited, and for example, aromatic hydrocarbons such as toluene, xylene and ethylbenzene; ketones such as methyl ethyl ketone and methyl isobutyl ketone; chloroform, methylene chloride, 1,2-dichloroethane and the like. Halogen hydrocarbons; alcohols such as methanol and ethanol; water, dimethylsulfoxide (DMSO), tetrahydrofuran.

In the polymerization of the precursor polymer (B), a polymerization initiator, a chain transfer agent, or the like can be used, if necessary. The polymerization initiator is not particularly limited, but for example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and t-amylper. Organic peroxides such as oxy-2-ethylhexanoate and t-amylperoxyisononanoate; azo compounds such as azobisisobutyronitrile (AIBN); These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator used may be appropriately set according to the combination of the monomers contained in the monomer group, the polymerization conditions, and the like, and is not particularly limited.

Polymerization conditions such as polymerization temperature can be set as appropriate.

When there is a difference in polymerization rate between the monomers contained in the monomer group, the monomer in the precursor polymer (B) formed by the polymerization has a higher content ratio than the content of each monomer contained in the monomer group to be polymerized. Regarding the content of each of the derived structural units, the content of the structural units derived from the monomer having a high polymerization rate tends to be relatively large. Therefore, a precursor polymer (B) which is a copolymer and a polymer (B) having a desired value for the content rate and / or the content rate ratio of each structural unit constituting the polymer (B). In order to obtain the polymer, attention should be paid to the content of each monomer in the monomer group to be polymerized, and the polymerization method may be controlled (for example, a part or all of the monomers having a high polymerization rate may be supplied to the polymerization system by dropping). Therefore, the content of each structural unit in the formed precursor polymer (B) can be appropriately adjusted.

(Cyclic reaction)
The method for cyclizing the precursor polymer (B) is not limited. For example, by heating the precursor polymer (B), the cycloaddition reaction, which is an amide cyclization reaction, is allowed to proceed in the molecular chain of the polymer (B) to form the intermediate polymer (C).

When the cyclization reaction is allowed to proceed by heating the precursor polymer (B), the heating temperature is, for example, 70 ° C. or higher, preferably 100 ° C. or higher, and more preferably 150 ° C. or higher and 200 ° C. or higher. The heating of the precursor polymer (B) can be carried out in any state such as a state in which the precursor polymer (B) is in a solid state or a state in which the precursor polymer (B) is dissolved in a solvent. When heating in a solid state, it is preferable to use a precursor polymer (B) having a large surface area such as powder or particles for the rapid progress of the cyclization reaction. Further, in order to rapidly proceed the cyclization reaction by removing the alcohol or water generated by the cyclization reaction described on the right side of the formulas (5), (11) and (12), the pressure is reduced. Heating is preferred. The degree of decompression is, for example, 26.6 kPa or less in terms of absolute pressure. That is, the cyclization reaction may proceed by heating the precursor polymer (B) under a pressure of 26.6 kPa or less. The degree of depressurization is preferably 13.3 kPa or less, and more preferably 2.7 kPa or less.

When proceeding with the cyclization reaction, a catalyst that promotes the reaction may be used, if necessary. When a catalyst is used, heating in a state where the precursor polymer (B) is dissolved in a solvent is preferable for a uniform reaction.

As the catalyst, for example, at least one selected from acids, bases and salts thereof, metal complexes, and metal oxides can be used. The types of acids, bases and salts thereof, metal complexes, and metal oxides are not particularly limited. When the finally obtained polymer (A), or the resin composition (D) or resin molded product containing the polymer (A) is used in applications where transparency is important, the catalyst is a catalyst for these. It is preferable to use the product within a range in which the transparency is not deteriorated and adverse effects such as coloring do not occur.

The acid is not limited, and is, for example, an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, and phosphite, and an organic acid such as p-toluenesulfonic acid, phenylphosphonic acid, organic carboxylic acid, and phosphoric acid ester. The base is not limited, and includes, for example, metal hydroxides, amines, imines, alkali metal derivatives, alkoxides, and ammonium hydroxide salts. Acids and base salts are not limited, for example, metal organic acid salts, metal inorganic acid salts, specific examples of metal organic acid salts are metal carboxylates, specific examples of metal inorganic acid salts are metals. It is a carbonate. The metal complex is not limited, and an example of its organic component is acetylacetone. The metal oxide is not limited, for example, zinc oxide, calcium oxide, magnesium oxide. Among these exemplified catalysts, salts of acids and bases are preferable, metal organic acid salts are more preferable, and metal carboxylates are particularly preferable. The metal of the metal organic acid salt, for example, the metal carboxylate, does not impair the properties of the finally obtained polymer (A), resin composition (D) or resin molded product, and pollutes the environment at the time of disposal thereof. Unless inviting, for example, alkali metals such as lithium, sodium, potassium; alkaline earth metals such as magnesium, calcium, strontium, barium; zinc; zirconium; Of these, zinc is preferable. The carboxylic acids that make up the metal carboxylate are not limited, for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanic acid, octanoic acid, octyl acid, nonanoic acid, decanoic acid, lauric acid, myristine Acids, palmitic acid, stearic acid, bechenic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, lactic acid, malic acid, citric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, adipic acid. As the specific metal carboxylate, zinc acetate, zinc propionate, zinc octylate, or zinc stearate is preferable.

An intermediate polymer (C) is formed from the precursor polymer (B) through a cyclization reaction. The molecular structure of the intermediate polymer (C) can be understood from the above description. For example, the intermediate polymer (C) has a 5-membered ring structure having a tertiary amide structure in the main chain.

(Deacylation reaction)
Deacylation reaction on the intermediate polymer (C), more specifically, the acyl group on the tertiary amide structure forming the ring structure of the intermediate polymer (C) in the main chain is deacylated to obtain the first. The method for advancing the reaction for forming the polymer (A) having a 5-membered ring structure having a secondary amide structure in the main chain is not limited. For example, the deacyllation reaction is allowed to proceed by heating the intermediate polymer (C) to form the polymer (A).

When deacylated by heating the intermediate polymer (C), the heating temperature is, for example, 100 ° C. or higher, preferably 200 ° C. or higher, and more preferably 240 ° C. or higher and 280 ° C. or higher. The heating of the intermediate polymer (C) can be carried out in any state such as a state in which the intermediate polymer (C) is in a solid state or a state in which the intermediate polymer (C) is dissolved in a solvent. When heating in a solid state, it is preferable to use an intermediate polymer (C) having a large surface area such as powder or particles for rapid deacylation. In addition, heating under reduced pressure is preferable in order to rapidly proceed with deacylation by removing the carboxylic acid or carboxylic acid ester produced. The degree of depressurization can be the same as that of the depressurization during the cyclization reaction on the precursor polymer (B).

When proceeding with deacylation, a catalyst that promotes the reaction may be used, if necessary. When a catalyst is used, heating in a state where the intermediate polymer (C) is dissolved in a solvent is preferable for a uniform reaction.

As the catalyst, for example, at least one selected from acids, bases and salts thereof, metal complexes, and metal oxides can be used. The types of acids, bases and salts thereof, metal complexes, and metal oxides are not particularly limited. Specific examples of each catalyst can be the same as those of the catalysts described above in the description of the cyclization reaction. When the finally obtained polymer (A), or the resin composition (D) or resin molded product containing the polymer (A) is used in applications where transparency is important, the catalyst is a catalyst for these. It is preferable to use the product within a range in which the transparency is not deteriorated and adverse effects such as coloring do not occur.

The salt of the acid is not limited, for example, a metal organic acid salt. A specific example of a metal organic acid salt is a metal carboxylate. The metal of the metal organic acid salt, for example, the metal carboxylate, does not impair the properties of the finally obtained polymer (A), resin composition (D) or resin molded product, and pollutes the environment at the time of disposal thereof. Unless inviting, for example, alkali metals such as lithium, sodium, potassium; alkaline earth metals such as magnesium, calcium, strontium, barium; zinc; zirconium; Of these, zinc is preferable. The carboxylic acids that make up the metal carboxylate are not limited, for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanic acid, octanoic acid, octyl acid, nonanoic acid, decanoic acid, lauric acid, myristine. Acids, palmitic acid, stearic acid, bechenic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, lactic acid, malic acid, citric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, adipic acid. As a specific metal carboxylate, zinc acetate, zinc propionate, zinc octylate, or zinc stearate is preferable. After deacylation, the intermediate polymer (C) is mainly composed of the ring structure represented by the formula (1). The polymer (A) contained in the chain is formed.

The cyclization reaction on the precursor polymer (B) and the deacylation reaction on the intermediate polymer (C) formed through the cyclization reaction can be carried out stepwise (for example, separately) or continuously. It may be carried out. In the case of continuous implementation, a common catalyst can be used depending on the type of catalyst. For example, a metal organic acid salt may be used as a catalyst for the cyclization of the precursor polymer (B) and the subsequent deacylation of the intermediate polymer (C), in which case the metal organic acid salt is a zinc organic acid salt. Is preferable. By using the zinc organic acid salt, the cyclization reaction for the precursor polymer (B) and the deacylation reaction for the intermediate polymer (C) can proceed more stably and reliably.

When a common catalyst is used for the cyclization of the precursor polymer (B) and the subsequent deacylation of the intermediate polymer (C), the amount of catalyst required to promote each reaction is used when starting each reaction or. It may be added to the system individually after the start of each reaction, or the catalyst added at the start of the cyclization reaction is left as it is in the intermediate polymer (C), and the residual catalyst deacylates the intermediate polymer (C). It may promote the conversion.

The reaction rate of deacyllation with respect to the intermediate polymer (C) is not always 100%. Further, the deacyllation of the intermediate polymer (C) is partially promoted, and more specifically, the intermediate polymer (C) has a plurality of 5-membered ring structures (tertiary amide structure) in the main chain. It is also possible to proceed with deacylation only for a part of the ring structure). In this case, the polymer (A) formed by deacylated to the intermediate polymer (C) was formed by a cyclization reaction to the precursor polymer (B) in addition to the ring structure represented by the formula (1). , The intermediate polymer (C) may further have the above-mentioned ring structure or a structural unit containing the above-mentioned ring structure.

The production method of the present invention can include any step other than the above-mentioned steps as long as the polymer (A) is formed.

The polymer (A) of the present invention viewed from the aspect of such a production method is a precursor polymer (B) formed by polymerization of a group of monomers containing a vinyl monomer, and is an ester group and / or a carboxyl. A precursor polymer (B) having a group and an amide group (secondary amide group) as a side chain is cyclized, and an acyl group on the tertiary amide structure constituting the ring structure formed by the cyclization is further formed. It is a deacylated polymer.

As described above, the precursor polymer (B) has a copolymer weight formed by, for example, polymerization of a monomer group containing a vinyl monomer A having an ester group and / or a carboxyl group and a vinyl monomer B having an amide group. Can be coalesced. Further, the precursor polymer (B) can be, for example, a polymer formed by polymerization of a monomer group containing a vinyl monomer C having an ester group and / or a carboxyl group and an amide group, and can be a polymer of the vinyl monomer C. It can also be a homopolymer. Examples of vinyl monomers A, B and C are as described above.

[Resin composition (D)]
The resin composition (D) of the present invention contains a polymer (A). The resin composition (D) is typically a thermoplastic resin composition. The resin composition (D) is typically amorphous. The resin composition (D) is typically water insoluble. The resin composition (D) may contain two or more polymers (A).

The resin composition (D) exhibits various properties derived from the polymer (A). The characteristics are, for example, thermal characteristics and optical characteristics. The thermal property is, for example, Tg, and the Tg of the resin composition (D) is increased due to the polymer (A). The Tg of the resin composition (D) is, for example, 120 ° C. or higher, and depending on the structure and content of the polymer (A), the Tg may be 130 ° C. or higher, 140 ° C. or higher, 150 ° C. or higher, and further 160 ° C. or higher. It can be taken.

Further, since the resin composition (D) contains the polymer (A), its heat-resistant decomposition characteristics, particularly the heat-resistant decomposition characteristics against high temperature expected at the time of melt molding of the resin composition, are improved. The 5% heating weight loss temperature of the resin composition (D) is, for example, 300 ° C. or higher, and depending on the structure of the polymer (A) and the content of the polymer (A) in the resin composition (D), the resin composition The 5% heating weight loss temperature of (D) can take a value of 320 ° C. or higher, 340 ° C. or higher, and further 360 ° C. or higher.

The optical property is, for example, birefringence property, and the resin composition (D) exhibits high birefringence expression (phase difference expression) derived from the polymer (A). The high retardation property can be evaluated by, for example, the absolute value of the high stress optical coefficient Cr. Depending on the structure and content of the polymer (A), the resin composition (D) exhibits positive birefringence, and at this time, the resin composition (D) can form, for example, a positive retardation film. The intrinsic birefringence as the resin composition (D) is determined by the balance with the intrinsic birefringence exhibited not only by the polymer (A) but also by other polymers contained in the resin composition (D).

The resin composition (D) may have various other properties derived from the polymer (A). Based on these characteristics, the resin composition (D) can be used for the same purposes as the polymer (A), including the optical member.

The resin composition (D) may contain a polymer other than the polymer (A). When the resin composition (D) is used for the optical member, it is preferable that the other polymer is compatible with the polymer (A) in order to ensure the optical transparency. The other polymer can be a water-insoluble polymer.

The other polymer is, for example, an olefin polymer such as polyethylene, polypropylene, ethylene-propylene polymer, poly (4-methyl-1-pentene); a halogen-containing polymer such as vinyl chloride or vinyl chlorinated resin. Acrylic polymers such as polymethylmethacrylate; polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; polyamides such as nylon 6, nylon 66, nylon 610; polyacetal; polycarbonate; polyphenylene oxide; polyphenylene sulfide; polyether ether Ketone; polysulfone; polyether sulfone; polyoxypendylene; polyamideimide; rubbery polymer. The resin composition (D) may contain two or more of these polymers.

The content of the polymer (A) in the resin composition (D) is usually 50% by mass or more, preferably 70% by mass or more, and more preferably 80% by mass or more. The resin composition (D) may contain only the polymer (A) as the polymer.

The resin composition (D) can contain a material other than the polymer, for example, an additive. Additives include, for example, stabilizers such as antioxidants, light-resistant stabilizers, weather-resistant stabilizers, and heat-stabilizing agents; retardation modifiers such as retardation enhancers, retardation reducing agents, and retardation stabilizers; glass fiber, Reinforcing materials such as carbon fiber; UV absorbers; Near infrared absorbers; Flame retardants such as tris (dibromopropyl) phosphates, triallyl phosphates, antimony oxides; Antistatic agents containing anionic, cationic and nonionic surfactants Agents; colorants such as inorganic pigments, organic pigments, dyes; organic fillers, inorganic fillers, resin modifiers, plasticizers, lubricants. The content of the additive in the resin composition (D) is preferably less than 7% by mass, more preferably 2% by mass or less, still more preferably 1% by mass or less.

The method for forming the resin composition (D) is not particularly limited. If the resin composition (D) is made of the polymer (A), the polymer (A) may be used as it is as the resin composition (D), and the resin composition (D) may be used with the above-mentioned other polymers. When / or an additive is contained, the polymer (A) can be formed by mixing the other polymer and / or the additive by a known mixing method. Mixing can be carried out by pre-blending with a mixer such as an omni mixer and then kneading the obtained mixture. The kneader is not particularly limited, and for example, a known kneader such as an extruder such as a single-screw extruder or a twin-screw extruder or a pressure kneader can be used.

[Resin molded product]
The resin molded product of the present invention contains the polymer (A). The resin molded product of the present invention is composed of, for example, a thermoplastic resin composition (D) containing the polymer (A). The use of the resin molded product is not limited, depending on the properties obtained from the polymer (A) and the properties obtained from other polymers and / or additives contained in the resin composition (D). Can be selected. The resin molded product of the present invention is, for example, an optical member used for optical applications.

The optical member is, for example, a lens, a prism, an optical fiber, or an optical film. The optical film includes, for example, a protective film for the substrate of various optical disks (VD, CD, DVD, MD, LD, etc.), a retardation film and a polarizer protective film included in an image display device such as a liquid crystal display (LCD), and It is a viewing angle compensating film, a light diffusing film, a reflective film, an antireflection film, an antiglare film, a brightness improving film, and a conductive film for a touch panel.

The resin molded product of the present invention may have heat resistance derived from the high Tg of the polymer (A). Therefore, the degree of freedom of use of the resin molded product of the present invention is high, and various effects can be obtained by using the resin molded product of the present invention. For example, the use of the resin molded product of the present invention, which is an optical film, improves the degree of freedom in designing an image display device such as an LCD.

The resin molded product of the present invention contains the polymer (A), so that its heat-resistant decomposition characteristics are improved. As an application of the resin molded product of the present invention, an application utilizing this high heat-resistant decomposition property is expected.

The resin molded product of the present invention may have high optical transparency. For example, the total light transmittance determined in accordance with the provisions of JIS K7361 can be a resin molded product of 85% or more, 90% or more, and further 91% or more, typically a film. ..

The resin molded article of the present invention may have a low surface haze. For example, the haze obtained in accordance with the provisions of JIS K7136 can be a resin molded product having a haze of 5% or less, 3% or less, and further 2% or less, typically a film. ..

The resin molded product of the present invention can be a retardation film. The retardation film is, for example, a positive retardation film in which the retardation Rth in the thickness direction is positive. The retardation film can be, for example, a λ / 4 plate or an elliptical polarizing plate.

The resin molded product of the present invention may be an optical film that does not exhibit birefringence (isotropic with respect to birefringence). This optical film is typically a stretched film, more specifically a biaxially stretched film. Such an optical film can be used, for example, as a polarizer protective film.

The resin molded product of the present invention can be combined with other members. For example, the resin molded product of the present invention, which is an optical film, may be combined with other optical members.

Various functional coating layers may be formed on the surface of the resin molded product of the present invention, if necessary. The functional coating layer includes, for example, an antistatic layer, an adhesive layer, an adhesive layer, an easy-adhesion layer, an antiglare layer, an antifouling layer such as a photocatalyst layer, an antireflection layer, a hard coat layer, and an ultraviolet shield. It is a layer, a heat ray shielding layer, an electromagnetic wave shielding layer, and a gas barrier layer.

The method for forming the resin molded product of the present invention is not particularly limited. The resin composition (D) can be molded by a known molding method such as a melt extrusion method, a casting method, or a press molding method to form the resin molded product of the present invention. If necessary, a molding method and another known method, for example, a stretching method, may be combined. In order to obtain a retardation film, it is necessary to stretch the film (raw film) obtained by molding the resin composition. A method that particularly utilizes the high heat-resistant decomposition characteristics of the polymer (A) is a melt molding method such as a melt extrusion method.

The product including the resin molded product of the present invention is not particularly limited, and is, for example, an image display device. The image display device includes, for example, the resin molded product of the present invention, which is an optical film. The image display device is not particularly limited, and for example, a reflective, transmissive, semi-transmissive LCD; an LCD of various drive systems such as TN, STN, OCB, HAN, VA, and IPS; A liquid crystal display (EL) display; a plasma display (PD); a field emission display (FED).

Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to the examples shown below.

In this example, MMA, NVA and AcAAM are abbreviations for methyl methacrylate, N-vinylacetamido and methyl 2-acetamidoacrylate, respectively.

First, the evaluation method of the polymer produced in this example will be shown.

[Structure of structural unit]
About what structural units was produced polymer has what molecular structures were evaluated by infrared spectroscopy (IR) and ¹ H- nuclear magnetic resonance (NMR). The evaluation of IR was carried out by the total reflection measurement method (ATR method) using an infrared spectroscopic analyzer (manufactured by Varian, Excalibur Series). The measurement conditions were a scan speed of 5 kHz and a resolution of 4 cm ^-1 . ^{1 1} H-NMR evaluation was carried out using a nuclear magnetic resonance spectrometer (BRUKER, AV300M). Deuterated chloroform (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the measurement solvent.

[Content rate of structural units in polymer]
The contents of AcAAM units and NVA units in the prepared precursor polymer were calculated from the amount of unreacted monomers remaining in the polymerization solution obtained during the polymerization reaction. The amount of unreacted monomer was determined by gas chromatography (manufactured by Shimadzu Corporation, GC2010).

[Glass transition temperature (Tg)]
The Tg of the produced polymer (including the precursor polymer and the intermediate polymer) was determined in accordance with the provisions of JIS K7121. Specifically, it was obtained by using a differential scanning calorimeter (manufactured by Rigaku, DSC-8230) to raise the temperature of a sample of about 10 mg from room temperature to 300 ° C (heating rate 20 ° C / min) in a nitrogen gas atmosphere. The DSC curve was evaluated by the starting point method. As a reference, α-alumina was used.

[5% heating weight loss temperature]
The 5% heating weight loss temperature (the temperature at which the weight of the polymer decreases by 5% when the temperature of the polymer is raised at a constant rate) of the produced polymer (including the precursor polymer and the intermediate polymer) is JIS K7120. The evaluation was carried out under the conditions of a sample mass of 5 mg, a heating rate of 10 ° C./min, and a nitrogen atmosphere using a differential calorimetry balance (manufactured by Rigaku, TG-8120) in accordance with the above-mentioned regulations. As a sample, a polymer that had been previously dried in a hot air dryer at 80 ° C. for 12 hours was used.

[Stress optical coefficient Cr]
The stress optical coefficient Cr (measurement wavelength 590 nm) of the produced polymer was determined as follows.

First, the produced polymer was formed into a film by a hot press at 210 ° C. to obtain an unstretched film (thickness 150 μm) of the polymer. Next, the produced unstretched film was cut out to a size of 20 mm × 60 mm to obtain a test piece for Cr evaluation. ^{Next, a weight having a weight of 1 N / mm 2} or less applied to the test piece at the time of stretching was selected and attached to one short side of the test piece, and then dried at a constant temperature held at Tg + 20 ° C. of the polymer. It was housed in a machine (manufactured by AS ONE, DOV-450A) and left for 1 hour. When the test piece is housed in a constant temperature dryer, the other short side of the test piece is fixed by a chuck, and the stress applied to the test piece by the weight causes the test piece to move in the long side direction (vertical direction). It was made to be stretched. Further, when accommodating, the distance between the chuck and the weight of the test piece was set to 40 mm.

After heating and stretching for 1 hour, the heater of the dryer was turned off, and the test piece was allowed to slowly cool in the dryer as it was. When the temperature in the oven reached Tg-40 ° C of the polymer, the test piece (uniaxially stretched film) was taken out, and the thickness of the taken out test piece and the in-plane retardation Re with respect to light having a wavelength of 590 nm were measured. The in-plane birefringence Δn of the test piece was calculated. Separately from this, the cross-sectional area of the test piece after being stretched by the load of the weight was obtained, and the stress σ (Pa) applied to the film was calculated from the cross-sectional area and the load of the weight. While changing the weight of the weight, Δn and σ were obtained for each load, and the slope of Δn with respect to the obtained σ was obtained by the least squares method, and this was defined as the stress optical coefficient Cr (Pa ^-1 ). When the orientation angle when measuring the in-plane retardation Re is close to 0 ° with respect to the stretching direction (load application direction), the sign of the stress optical coefficient Cr is positive. In this case, the intrinsic birefringence of the polymer is positive. On the other hand, when the orientation angle is close to 90 ° with respect to the stretching direction, the sign of the stress optical coefficient Cr becomes negative. In this case, the intrinsic birefringence of the polymer is negative. The larger the absolute value of Cr, the higher the expression of birefringence due to stretching.

The in-plane phase difference Re (nm) of the test piece was determined using a phase difference measuring device (KOBRA-WR, manufactured by Oji Measuring Instruments). The in-plane phase difference Re is the refractive index nx in the slow-phase axial direction (the direction showing the maximum refractive index in the film plane) in the test piece (film) plane, and the phase-advancing axial direction (slow-phase axial direction) in the same plane. It is a value represented by the formula (nx−ny) × d using the refractive index ny in the direction orthogonal to) and the thickness d (nm) of the film. The value of nx−ny corresponds to the in-plane birefringence Δn.

(Example 1)
0.45 parts by mass of AcAAM, 14.55 parts by mass of MMA, 14.50 parts by mass of methyl ethyl ketone and 0.03 parts by mass of azobisisobutyronitrile (AIBN) were contained in a reaction vessel, and the inside of the vessel was filled with nitrogen. Replaced. Next, the container was heated in an oil bath at 65 ° C. for 2 hours to allow solution polymerization of AcAAM and MMA to proceed. Next, the formed polymerization solution was poured into excess methanol for reprecipitation, and then the obtained precipitate was vacuum dried for 1 hour under the conditions of a pressure of 0.13 kPa and a temperature of 100 ° C. to remove volatile components. Then, a solid polymer (1-1), which is a precursor polymer, was obtained. The Tg of the polymer (1-1) was 110 ° C., and the 5% heat loss temperature was 203 ° C. The content of AcAAM units in the polymer (1-1) was 17.9% by mass.

Next, 10.00 parts by mass of the produced polymer (1-1) and 0.02 parts by mass of zinc octylate as a cyclization and deacylation catalyst were dissolved in 90.00 parts by mass of acetone, and the pressure was reduced to 0. The cyclization reaction was allowed to proceed while removing volatile components by heating at a temperature of 180 ° C. for 2 hours under a reduced pressure of 13 kPa to obtain a solid polymer (1-2) as an intermediate polymer. The Tg of the polymer (1-2) was 138 ° C., and the 5% heat loss temperature was 264 ° C. ^{According to 1} H-NMR evaluation for polymers (1-1) and (1-2), peaks attributed to the secondary amide structure of AcAAM units observed in the NMR spectrum of polymer (1-1). Disappeared in the NMR spectrum of the polymer (1-2), and in the latter NMR spectrum, a large peak attributable to the acetylamide group constituting the ring structure was newly generated at 2.49 ppm.

Next, the produced polymer (1-2) was heated in a solid state under a reduced pressure of 0.13 kPa at a temperature of 240 ° C. higher than that at the time of the cyclization reaction for 2 hours to promote deacylation. , Solid polymer (1-3) was obtained. The Tg of the polymer (1-3) was 140 ° C., and the 5% heat loss temperature was 373 ° C. According to the IR evaluation for the polymers (1-1) to (1-3), a carbonyl group having a secondary amide ring structure which is not present in the IR spectra of the polymers (1-1) and (1-2). ^{The absorption peak (wave number 1780 cm -1} ) attributed to the expansion and contraction vibration of the polymer (1-3) was confirmed in the IR spectrum of the polymer (1-3). That is, by the previous heating of the polymer (1-1), a ring structure having an acetylamide group as a part of the structure is formed in the main chain of the polymer, and the polymer (1-) in which the ring structure is formed is formed. It was confirmed that the polymer (1-3) having the ring structure represented by the formula (1) in the main chain was formed by the subsequent heating with respect to 2). The Cr of the polymer (1-3) was +60 × 10 ^-11 Pa ^-1 , and the polymer (1-3) had a positive intrinsic birefringence.

(Example 2)
0.60 parts by mass of AcAAM, 14.40 parts by mass of MMA, 15.00 parts by mass of methyl ethyl ketone and 0.03 parts by mass of AIBN were placed in a reaction vessel, and the inside of the vessel was replaced with nitrogen. Next, the container was heated in an oil bath at 65 ° C. for 2 hours to allow solution polymerization of AcAAM and MMA to proceed. Next, the formed polymerization solution was poured into excess methanol for reprecipitation, and then the obtained precipitate was vacuum dried for 1 hour under the conditions of a pressure of 0.13 kPa and a temperature of 100 ° C. to remove volatile components. Then, a solid polymer (2-1) which was a precursor polymer was obtained. The Tg of the polymer (2-1) was 117 ° C., and the 5% heat loss temperature was 196 ° C. The content of AcAAM units in the polymer (2-1) was 25.4% by mass.

Next, 10.00 parts by mass of the produced polymer (2-1) and 0.02 parts by mass of zinc octylate as a cyclization and deacylation catalyst were dissolved in 90.00 parts by mass of acetone, and the pressure was reduced to 0. The cyclization reaction was allowed to proceed while removing volatile components by heating at a temperature of 180 ° C. for 2 hours under a reduced pressure of 13 kPa to obtain a solid polymer (2-2) as an intermediate polymer. The Tg of the polymer (2-2) was 143 ° C., and the 5% heat loss temperature was 273 ° C. ^{According to 1} H-NMR evaluation for polymers (2-1) and (2-2), peaks attributed to the secondary amide structure of AcAAM units observed in the NMR spectrum of polymer (2-1). Disappeared in the NMR spectrum of the polymer (2-2), and in the latter NMR spectrum, a large peak attributable to the acetylamide group constituting the ring structure was newly generated at 2.49 ppm.

Next, the produced polymer (2-2) was heated in a solid state under a reduced pressure of 0.13 kPa at a temperature of 240 ° C. higher than that at the time of the cyclization reaction for 2 hours to promote deacylation. , Solid polymer (2-3) was obtained. The Tg of the polymer (2-3) was 154 ° C., and the 5% heat loss temperature was 349 ° C. According to the IR evaluation for the polymers (2-1) to (2-3), a carbonyl group having a secondary amide ring structure, which is not present in the IR spectra of the polymers (2-1) and (2-2). ^{The absorption peak (wave number 1780 cm -1} ) attributed to the expansion and contraction vibration of the polymer (2-3) was confirmed in the IR spectrum of the polymer (2-3). That is, by the previous heating of the polymer (2-1), a ring structure having an acetylamide group as a part of the structure is formed in the main chain of the polymer, and the polymer (2-) in which the ring structure is formed is formed. It was confirmed that the polymer (2-3) having the ring structure represented by the formula (1) in the main chain was formed by the subsequent heating with respect to 2). The Cr of the polymer (2-3) was +87 × 10 ^-11 Pa ^-1 , and the polymer (2-3) had a positive intrinsic birefringence.

(Example 3)
1.35 parts by mass of AcAAM, 13.65 parts by mass of MMA, 15.00 parts by mass of methyl ethyl ketone and 0.03 parts by mass of AIBN were placed in a reaction vessel, and the inside of the vessel was replaced with nitrogen. Next, the container was heated in an oil bath at 65 ° C. for 2 hours to allow solution polymerization of AcAAM and MMA to proceed. Next, the formed polymerization solution was poured into excess 2-propanol for reprecipitation, and then the obtained precipitate was vacuum dried for 1 hour under the conditions of a pressure of 0.13 kPa and a temperature of 100 ° C. to volatile components. Was removed to obtain a solid polymer (3-1) which was a precursor polymer. The Tg of the polymer (3-1) was 119 ° C, and the 5% heat loss temperature was 198 ° C. The content of AcAAM units in the polymer (3-1) was 46.8% by mass.

Next, 10.00 parts by mass of the produced polymer (3-1) and 0.02 parts by mass of zinc octylate as a cyclization and deacylation catalyst were dissolved in 90.00 parts by mass of acetone, and the pressure was reduced to 0. The cyclization reaction was allowed to proceed while removing volatile components by heating at a temperature of 180 ° C. for 2 hours under a reduced pressure of 13 kPa to obtain a solid polymer (3-2) which is an intermediate polymer. The Tg of the polymer (3-2) was 151 ° C., and the 5% heat loss temperature was 250 ° C. ^{According to 1} H-NMR evaluation for polymers (3-1) and (3-2), peaks attributed to the secondary amide structure of AcAAM units observed in the NMR spectrum of polymer (3-1). Disappeared in the NMR spectrum of the polymer (3-2), and in the latter NMR spectrum, a large peak attributable to the acetylamide group constituting the ring structure was newly generated at 2.49 ppm.

Next, the produced polymer (3-2) was heated in a solid state at a temperature of 240 ° C., which is higher than that during the cyclization reaction, under a reduced pressure of 0.13 kPa for 2 hours to allow deacylation to proceed. , A solid polymer (3-3) was obtained. The Tg of the polymer (3-3) was 181 ° C., and the 5% heat loss temperature was 304 ° C. According to the IR evaluation for the polymers (3-1) to (3-3), a carbonyl group having a secondary amide ring structure, which is not present in the IR spectra of the polymers (3-1) and (3-2). ^{The absorption peak (wave number 1780 cm -1} ) attributed to the expansion and contraction vibration of the polymer (3-3) was confirmed in the IR spectrum of the polymer (3-3). That is, by the previous heating of the polymer (3-1), a ring structure having an acetylamide group as a part of the structure is formed in the main chain of the polymer, and the polymer (3-) in which the ring structure is formed is formed. It was confirmed that the polymer (3-3) having the ring structure represented by the formula (1) in the main chain was formed by the subsequent heating with respect to 2).

(Example 4)
1.20 parts by mass of NVA, 6.80 parts by mass of MMA, 12.00 parts by mass of methyl ethyl ketone and 0.016 parts by mass of tertiary amylperoxyisononanoate (manufactured by Atofina Yoshitomi, trade name: Luperox 570). The mixture was placed in a reaction vessel, and the inside of the vessel was replaced with nitrogen. Next, the container was heated in an oil bath at 80 ° C. for 4 hours to allow solution polymerization of NVA and MMA to proceed. Next, the formed polymerization solution was poured into excess methanol for reprecipitation, and then the obtained precipitate was vacuum dried for 1 hour under the conditions of a pressure of 0.13 kPa and a temperature of 100 ° C. to remove volatile components. Then, a solid polymer (4-1) which was a precursor polymer was obtained. The Tg of the polymer (4-1) was 113 ° C., and the 5% heat loss temperature was 231 ° C. The content of NVA units in the polymer (4-1) was 8.0% by mass.

Next, 10.00 parts by mass of the produced polymer (4-1) and 0.02 parts by mass of zinc octylate as a cyclization and deacylation catalyst were dissolved in 90.00 parts by mass of acetone, and the pressure was reduced to 0. The cyclization reaction was allowed to proceed while removing volatile components by heating at a temperature of 180 ° C. for 2 hours under a reduced pressure of 13 kPa to obtain a solid polymer (4-2) as an intermediate polymer. The Tg of the polymer (4-2) was 128 ° C., and the 5% heat loss temperature was 285 ° C. ^{According to 1} H-NMR evaluation for polymers (4-1) and (4-2), peaks attributed to the secondary amide structure of NVA units observed in the NMR spectrum of polymer (4-1). Disappeared in the NMR spectrum of the polymer (4-2), and in the latter NMR spectrum, a large peak attributable to the acetylamide group constituting the ring structure was newly generated at 2.49 ppm.

Next, the produced polymer (4-2) was heated in a solid state under a reduced pressure of 0.13 kPa at a temperature of 240 ° C., which is higher than that during the cyclization reaction, for 2 hours to allow deacylation to proceed. , A solid polymer (4-3) was obtained. The Tg of the polymer (4-3) was 137 ° C., and the 5% heat loss temperature was 375 ° C. According to the IR evaluation for the polymers (4-1) to (4-3), a carbonyl group having a secondary amide ring structure, which is not present in the IR spectra of the polymers (4-1) and (4-2). ^{The absorption peak (wave number 1780 cm -1} ) attributed to the expansion and contraction vibration of the polymer (4-3) was confirmed in the IR spectrum of the polymer (4-3). That is, by the previous heating of the polymer (4-1), a ring structure having an acetylamide group as a part of the structure is formed in the main chain of the polymer, and the polymer (4-1) in which the ring structure is formed is formed. It was confirmed that the polymer (4-3) having the ring structure represented by the formula (1) in the main chain was formed by the subsequent heating with respect to 2). The Cr of the polymer (4-3) was + 39 × 10 ^-11 Pa ^-1 , and the polymer (4-3) had a positive intrinsic birefringence.

(Example 5)
2.00 parts by mass of NVA, 6.00 parts by mass of MMA, 12.00 parts by mass of methyl ethyl ketone and 0.016 parts by mass of tertiary amylperoxyisononanoate (manufactured by Atofina Yoshitomi, trade name: Luperox 570). The mixture was placed in a reaction vessel, and the inside of the vessel was replaced with nitrogen. Next, the container was heated in an oil bath at 80 ° C. for 4 hours to allow solution polymerization of NVA and MMA to proceed. Next, the formed polymerization solution was poured into excess methanol for reprecipitation, and then the obtained precipitate was vacuum dried for 1 hour under the conditions of a pressure of 0.13 kPa and a temperature of 100 ° C. to remove volatile components. Then, a solid polymer (5-1), which is a precursor polymer, was obtained. The Tg of the polymer (5-1) was 114 ° C., and the 5% heat loss temperature was 208 ° C. The content of NVA units in the polymer (5-1) was 13.1% by mass.

Next, 10.00 parts by mass of the produced polymer (5-1) and 0.02 parts by mass of zinc octylate as a cyclization and deacylation catalyst were dissolved in 90.00 parts by mass of acetone, and the pressure was reduced to 0. The cyclization reaction was allowed to proceed while removing volatile components by heating at a temperature of 180 ° C. for 2 hours under a reduced pressure of 13 kPa to obtain a solid polymer (5-2) as an intermediate polymer. The Tg of the polymer (5-2) was 131 ° C., and the 5% heat loss temperature was 289 ° C. ^{According to 1} H-NMR evaluation for polymers (5-1) and (5-2), peaks attributed to the secondary amide structure of NVA units observed in the NMR spectrum of polymer (5-1). Disappeared in the NMR spectrum of the polymer (5-2), and in the latter NMR spectrum, a large peak attributable to the acetylamide group constituting the ring structure was newly generated at 2.49 ppm.

Next, the produced polymer (5-2) was heated in a solid state under a reduced pressure of 0.13 kPa at a temperature of 240 ° C. higher than that at the time of the cyclization reaction for 2 hours to promote deacylation. , A solid polymer (5-3) was obtained. The Tg of the polymer (5-3) was 144 ° C., and the 5% heat loss temperature was 357 ° C. According to the IR evaluation for the polymers (5-1) to (5-3), a carbonyl group having a secondary amide ring structure, which is not present in the IR spectra of the polymers (5-1) and (5-2). ^{The absorption peak (wave number 1780 cm -1} ) attributed to the expansion and contraction vibration of the polymer (5-3) was confirmed in the IR spectrum of the polymer (5-3). That is, by the previous heating of the polymer (5-1), a ring structure having an acetylamide group as a part of the structure is formed in the main chain of the polymer, and the polymer (5-) in which the ring structure is formed is formed. It was confirmed that the polymer (5-3) having the ring structure represented by the formula (1) in the main chain was formed by the subsequent heating with respect to 2). The Cr of the polymer (5-3) was + 75 × 10 ^-11 Pa ^-1 , and the polymer (5-3) had a positive intrinsic birefringence.

The composition and properties of the precursor polymers prepared in Examples 1 to 5, and the properties of the intermediate polymer and the polymer finally obtained through deacyllation are summarized in Table 1 below.

As shown in Table 1, the intermediate polymer and the final polymer having a ring structure in the main chain had a higher Tg than the precursor polymer. The final polymer obtained through deacylation exhibits a 5% heat loss temperature that is significantly improved as compared with the intermediate polymer as well as the precursor polymer, that is, has greatly improved thermostable decomposition characteristics. Was. Regarding the 5% heat loss temperature of the final polymer, the degree of increase from the intermediate polymer reached 50 ° C. or higher, 100 ° C. or higher in Example 1, and 90 ° C. or higher in Example 4.

The polymer of the present invention can be used, for example, for applications of optical members. The optical member is, for example, a lens, a prism, an optical fiber, or an optical film.

Claims (23)

It has a ring structure shown in the following formula (1) in the main chain.
It also has a (meth) acrylic ester unit as a constituent unit.
A polymer having a 5% heat loss temperature of 300 ° C. or higher determined by the thermogravimetric analysis method specified in JIS K7120.

In the formula (1), R ¹ is a hydrogen atom, a methyl group or -NHCOR ³ groups, and R ³ is a hydrogen atom, a methyl group, a phenyl group, a linear alkyl group having 2 to 18 carbon atoms, or a carbon number of carbon atoms. It is a cycloalkyl group of 3-18. R ² is a hydrogen atom or -COOR ⁴ group, and R ⁴ is a hydrogen atom, a methyl group, a phenyl group, a linear alkyl group having 2 to 18 carbon atoms, or a cycloalkyl group having 3 to 18 carbon atoms. ..
The ring structure represented by the formula (1) may be continuous on the main chain, and in this case, the ring structures adjacent to each other are the carbon atom at the 3-position of one of the ring structures and the other of the ring structures. A spiro ring structure in which the carbon atom at the 5-position is the same carbon atom is formed, ^{and R 1 bonded to the carbon atom at the 3-position and R 2} bonded to the carbon atom at the 5-position do not exist. The polymer according to claim 1, wherein in the formula (1), R ² is the −COOR ^{4 group.} The polymer according to claim 1, wherein in the formula (1), R ¹ is a methyl group or -NHCOCH ₃ groups, and R ² is -COOCH _{3 groups.} The polymer according to claim 1, wherein in the formula (1), R ¹ is a methyl group and R ^{2 is a hydrogen atom.} The polymer according to claim 1 , wherein the (meth) acrylic acid ester unit is a methyl methacrylate (MMA) unit. The polymer according to claim 1 , wherein the content of the (meth) acrylic acid ester unit is 15 to 90% by mass. The polymer according to any one of claims 1 to 6 , wherein the glass transition temperature is 120 ° C. or higher. It has a structural unit P including a ring structure represented by the above formula (1), and has a structural unit P.
Ri der content of more than 30 wt% of the structural unit P,
The structural unit P is a polymer according to any one of the ring structure only units composed of claims 1-7 which or Ru units der shown in Equation (4) below.

In formula (4), R ¹ is a hydrogen atom, a methyl group or -NHCOR ³ groups, and R ³ is a hydrogen atom, a methyl group, a phenyl group, a linear alkyl group having 2 to 18 carbon atoms, or a carbon number of carbon atoms. It is a cycloalkyl group of 3-18. R ² is a hydrogen atom or -COOR ⁴ group, and R ⁴ is a hydrogen atom, a methyl group, a phenyl group, a linear alkyl group having 2 to 18 carbon atoms, or a cycloalkyl group having 3 to 18 carbon atoms. .. The polymer according to any one of claims 1 to 8, which is a thermoplastic polymer. A resin composition containing the polymer according to any one of claims 1 to 9. The resin composition of claim 1 0 is a thermoplastic resin composition. A resin molded product containing the polymer according to any one of claims 1 to 9. Resin molded article according to claim 1 2 is an optical member. A precursor polymer formed by polymerization of a group of monomers containing a vinyl monomer, in which a precursor polymer having an ester group and / or a carboxyl group and an amide group as a side chain is cyclized, and further formed by the cyclization. The acyl group on the tertiary amide structure constituting the ring structure is deacylated to obtain a polymer having a 5-membered ring structure having a secondary amide structure (-NH-CO-) in the main chain. Method for producing polymer. The precursor polymer cyclization and subsequent the use of metal organic acid salt in the catalyst of the deacylation method of the polymer according to claim 1 4. The method for producing a polymer according to claim 15 , wherein the metal organic acid salt is a zinc organic acid salt. Method for producing a polymer according to any one of claims 1 4 to 1 6 wherein the 5-membered ring structure is a ring structure represented by the formula (1) below.

In the formula (1), R ¹ is a hydrogen atom, a methyl group or -NHCOR ³ groups, and R ³ is a hydrogen atom, a methyl group, a phenyl group, a linear alkyl group having 2 to 18 carbon atoms, or a carbon number of carbon atoms. It is a cycloalkyl group of 3-18. R ² is a hydrogen atom or -COOR ⁴ group, and R ⁴ is a hydrogen atom, a methyl group, a phenyl group, a linear alkyl group having 2 to 18 carbon atoms, or a cycloalkyl group having 3 to 18 carbon atoms. ..
The ring structure represented by the formula (1) may be continuous on the main chain, and in this case, the ring structures adjacent to each other are the carbon atom at the 3-position of one of the ring structures and the other of the ring structures. A spiro ring structure in which the carbon atom at the 5-position is the same carbon atom is formed, ^{and R 1 bonded to the carbon atom at the 3-position and R 2} bonded to the carbon atom at the 5-position do not exist. The polymer having the structural unit P containing the ring structure represented by the formula (1) and having a content of the structural unit P of 30% by mass or more was obtained .
The structural unit P is, the ring structure only units composed of or Ru units der shown in Equation (4) below, method for producing a polymer according to claim 1 7.

In formula (4), R ¹ is a hydrogen atom, a methyl group or -NHCOR ³ groups, and R ³ is a hydrogen atom, a methyl group, a phenyl group, a linear alkyl group having 2 to 18 carbon atoms, or a carbon number of carbon atoms. It is a cycloalkyl group of 3-18. R ² is a hydrogen atom or -COOR ⁴ group, and R ⁴ is a hydrogen atom, a methyl group, a phenyl group, a linear alkyl group having 2 to 18 carbon atoms, or a cycloalkyl group having 3 to 18 carbon atoms. .. Obtaining the polymer is a thermoplastic polymer, polymer production method according to any of claims 1 4 to 18. The cyclization of the precursor polymer is allowed to proceed under heating,
Method for producing a polymer according to any one of claims 1 4-19 heating temperature at the time of the cyclization is 0.99 ° C. or higher. The method for producing a polymer according to claim 20 , wherein the cyclization of the precursor polymer is allowed to proceed under reduced pressure. The deacylation is allowed to proceed under heating.
The polymer production process as claimed in any one heating temperature during deacylation of claim 1 4-2 1 is 200 ° C. or higher. Polymer production method of claim 2 2 for advancing the deacylation under reduced pressure.