JP2017039868A - Resin composition, optical film, polarizing plate, and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel resin composition which contains a polymer having a ring structure in the main chain and is applicable even to an optical member.SOLUTION: The resin composition contains a polymer (A) having a lactam ring structure in the main chain and a polymer (B) having an aromatic vinyl compound unit as a constituent unit. The lactam ring structure is, for example, a pyrrolidinone ring structure. The pyrrolidinone ring structure is a five-membered amide ring structure (cyclic amide structure). The polymer (B) may further have a vinyl cyanide unit and/or an N-substituted maleimide unit as a constituent unit.SELECTED DRAWING: None

Description

  The present invention relates to a novel resin composition containing a polymer having a ring structure in the main chain. Further, the present invention includes an optical film comprised of the novel resin composition, and to a polarizing plate and an image display device comprising the optical film.

  Resin compositions containing transparent polymers such as acrylic polymers, polycycloolefins, polycarbonates, polystyrenes, and polyesters are widely used for optical members such as lenses, prisms, optical fibers, and optical films. Among them, the acrylic polymer has characteristics such as high optical transparency and a 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 correspond to this. Acrylic polymers also include polymers having a ring structure in the main chain. For example, Patent Document 1 (Japanese Patent No. 4825409) discloses an acrylic polymer having a lactone ring structure in the main chain. Patent Document 2 (Japanese Patent Laid-Open No. 2006-328334) discloses an acrylic polymer having a glutarimide structure in the main chain. Patent Document 3 (Japanese Patent Laid-Open No. 2007-31537) discloses an acrylic polymer having an N-substituted maleimide structure in the main chain.

  In general, even if the glass transition temperature (Tg) of an acrylic polymer is high, it is around 100 ° C., but these documents indicate that an acrylic polymer having a ring structure in the main chain has a higher Tg. Yes. When the Tg of the polymer is improved, the heat resistance of the resin composition containing the polymer and the resin molded body is improved. When the resin molding is an optical member, a recent strong demand for a product including the optical member, as a specific example, a light source, a power supply unit, and the like from the viewpoint of compactness of the product, high performance, improvement of design flexibility, etc. There is an increased possibility of being able to meet the design requirements for arranging optical members in the vicinity of heating elements such as batteries and circuit boards.

Japanese Patent No. 4825409 JP 2006-328334 A JP 2007-31537 A

  One of the objects of the present invention is to provide a novel resin composition that includes a polymer having a ring structure in the main chain and can be applied to an optical member.

  The resin composition of this invention contains the polymer (A) which has a lactam ring structure in a principal chain, and the polymer (B) which has an aromatic vinyl compound unit as a structural unit.

  The optical film of the present invention is composed of the resin composition of the present invention.

  The polarizing plate of the present invention includes a polarizer, the laminated on at least one major surface of the polarizer, and the optical film of the present invention is a polarizer protective film, a.

  The image display device of the present invention includes an optical film of the present invention.

  According to the present invention comprises a polymer having a ring structure in its main chain, the resin composition can be applied to the optical member is realized.

  The resin composition of the present invention (C) is mainly include chain polymer having a lactam ring structure (A), a polymer having an aromatic vinyl compound unit as a constituent unit and (B).

  Polymer (A), a lactam ring structure has the main chain, the glass transition temperature (Tg) of higher. Therefore, it is possible to increase the Tg of the polymer (A) a resin composition comprising (C). When the Tg of the resin composition (C) is high, the heat resistance of the resin molded body composed of the resin composition (C) and the resin composition (C), for example, an optical member is improved. The optical member heat resistance is improved, for example, in various devices such as image display apparatus including an optical member, a light source, power supply unit, it is possible to arrange in the vicinity of the heating element such as a circuit board, thereby, the The degree of freedom in device design is improved. Improvement of the degree of freedom of design, for example, reduction in size, contains thinner, high performance, such as improvement of the degree of freedom in design.

  A polymer having a lactam ring structure in its main chain (A), a polymer having an aromatic vinyl compound unit as a constituent unit (B) and the high compatibility, the resin composition comprising both polymer (C) securing optical clarity is possible. Therefore, the resin composition (C) is available as an optical member. Further, the polymer (A) and the polymer (B), for example compared to a combination of a polymer having other ring structure as described above in the main chain, a polymer having an aromatic vinyl compound unit as a constituent unit It can be compatible with a wider variety of composition range. This means that in the resin molded article composed of the resin composition (C) and the resin composition (C), the composition range optical clarity can be secured wide, for example, a composition range which can be used as an optical member is wide Means that. Also in this point, the resin composition (C) is suitable for use in an optical member.

  Focusing on the optical properties, for example, the intrinsic birefringence, the intrinsic birefringence of the polymer (A) is basically positive, intrinsic birefringence of the polymer (B) is essentially negative. Therefore, the resin composition (C), it is possible to include positive and negative signs are different from each other two or more polymers of intrinsic birefringence. Here, the polymer (A), (B) together with the fact composition range the compatibility can be ensured between wide, the resin composition (C), the sign of positive or negative intrinsic birefringence as a resin composition (C) , and increases flexibility of the degree of control. Thus, for example, a resin composition from (C), the value of birefringence, and typically from the optical film retardation value is near zero, the phase difference in the thickness direction is negative "negative retardation film it is possible to realize up to. " The former optical film, for example, a polarizer protecting film. The latter negative retardation film is also large demand in the image display areas of the liquid crystal display device (LCD).

  Thus the resin composition (C), while achieving high Tg by including a polymer having a ring structure in its main chain can be secured optical transparency, further, the degree of freedom in controlling the birefringence value It is high, for example, may allow resin composition realized by optical film exhibiting retardation value close to zero to a negative retardation film.

[Polymer (A)]
The polymer (A) has a lactam ring structure in the main chain. 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.

  Lactam ring structure polymer (A) has a main chain, for example, a pyrrolidinone ring structure.

  Pyrrolidinone ring structure has a 5-membered ring of the amide ring structure as a basic skeleton (cyclic amide structure). The cyclic amide structure is also 5-membered ring lactam structure (.gamma.-lactam structure). The polymer has a pyrrolidinone ring structure in its main chain, at least one atom of the five atoms which constitute the basic skeleton of the pyrrolidinone ring is a 5-membered ring, typically amide bond (-NRCO-) configured not three carbon atoms, but located in the main chain of the polymer, which means that constitute the main chain.

  The polymer (A) has a characteristic derived from a lactam ring structure (for example, pyrrolidinone ring structure, the same applies hereinafter) located in the main chain. Properties, for example, thermal properties, optical properties.

  The thermal characteristic is, for example, the glass transition temperature (Tg), and the Tg of the polymer (A) is higher than when the main chain does not have a lactam ring structure.

  The optical characteristic is, for example, a birefringence characteristic. The ring structure located in the main chain, birefringence expression of the polymer (A) (phase difference developability) is improved. The lactam ring structure has an effect of giving intrinsic birefringence to the polymer (A). More specifically, lactam ring structure has the effect of allowing a positive intrinsic birefringence essentially polymer (A), in the case where such substituents are bulky bonded to the basic skeleton of the ring structure, the polymer the substance may have a negative intrinsic birefringence (a). The positive or negative of the intrinsic birefringence as the polymer (A) is determined by the balance between the birefringence characteristics of the respective structural units of the polymer (A). For example, in a case having an effect lactam ring structure gives a positive intrinsic birefringence polymer (A) also, when further has a structural unit having an effect of allowing a negative intrinsic birefringence polymer (A) is a heavy intrinsic birefringence may become negative as a polymer (a).

  Polymer (A), other properties, for example, based on Included (cyclic) amide structure in lactam ring structure, adhesion, hydrolysis resistance, may have such thermal decomposition resistance.

  These properties may be a resin composition comprising a polymer (A) to (C) to an advantageous feature of using as an optical member. High Tg, for example, help improve the heat resistance of the optical member having a portion constituted of a resin composition (C), such optical members, thereby improving the degree of freedom in product design with the optical member . As a specific example, the optical film is a kind of optical members, the film source, the power supply unit, since it is possible to arrange in proximity to the heating element such as a circuit board, an image display device such as LCD Design freedom is improved. High birefringence expression can, for example, an optical film, the value of the birefringence, and typically improve the degree of freedom of control of the phase difference value. At this time, as described above, the high compatibility of the polymer (A) with the polymer (B) greatly contributes to the improvement of the degree of freedom. Birefringence expressing, for example can be evaluated by the stress optical coefficient Cr. The larger the absolute value of Cr, the higher the birefringence expression. Adhesion, also hydrolysis resistance and thermal decomposition resistance of the high, an advantage as an optical member.

The pyrrolidinone ring structure that the polymer (A) may have in the main chain is, for example, a ring structure represented by the following formula (1). In this ring structure, as shown in the formula (1), three carbon atoms that do not constitute the amide structure (—NR ³ —CO—) (carbon atoms at the 3rd, 4th and 5th positions of the ring structure) Located in the main chain of the polymer (A) (constitutes the main chain). The ring structure shown in Formula (1) may be a structural unit (repeating unit) of the polymer (A) or a structure constituting a part of the structural unit. In the latter case, the structural unit includes a pyrrolidinone ring structure represented by the formula (1) as a part of its molecular structure.

In Formula (1), R ¹ is a hydrogen atom, a methyl group, or a —NHCOR 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 carbon number 3 to 18 cycloalkyl groups. R ² is a hydrogen atom or a —COOR ⁵ group, and R 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 ³ is a hydrogen atom or —COR ⁶ group, and R ⁶ 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 ^{4 to} R ⁶ may be the same as or different from each other.

  2-12 are preferable and, as for carbon number of a linear alkyl group, 2-4 are more preferable. The straight chain alkyl group is, for example, an ethyl group, a propyl group, or a butyl group. 3-12 are preferable and, as for carbon number of a cycloalkyl group, 3-6 are more preferable. The cycloalkyl group is, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.

In one embodiment, in formula (1), R ¹ is the —NHCOR ⁴ group. In this case, R ⁴ is preferably a hydrogen atom, a methyl group, a phenyl group, an n-butyl group or a t-butyl group.

In another embodiment, in formula (1), R ² is the —COOR ⁵ group. In this case, R ⁵ is preferably a hydrogen atom, a methyl group, an ethyl group, an n-butyl group or a benzyl group.

In still another embodiment, R ³ in formula (1) is a hydrogen atom. In this case, the Tg of the polymer (A) and the resin composition (C) containing the polymer (A) is particularly high, and the thermal decomposition characteristics of the polymer (A) and the resin composition (C) are particularly improved. .

In still another embodiment, in Formula (1), R ¹ and R ² are each independently a hydrogen atom or a methyl group.

A specific example of the combination of R ¹ and R ^{2 is} a combination in which R ¹ is a hydrogen atom, a methyl group or a —NHCOR ⁴ group, and R ² is a —COOR ⁵ group. At this time, R ⁴ may be a hydrogen atom, a methyl group, a phenyl group, an n-butyl group or a t-butyl group, and independently of this, R ⁵ is a hydrogen atom, a methyl group, an ethyl group, or n-butyl group. Group or benzyl group. An example of a preferable combination of R ¹ and R ² in this range is a combination in which R ¹ is a methyl group or a —NHCOR ⁴ group, and R ² is a —COOR ⁵ group. At this time, R ⁴ may be a methyl group, and independently of this, R ⁵ may 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 group, and R ² is a —COOCH ₃ group.

Another specific example of the combination of R ¹ and R ^{2 is} a combination in which R ¹ is a hydrogen atom or a methyl group, and independently, R ² is a hydrogen atom or a methyl group. An example of a combination of R ¹ and R ² in this range is a combination in which R ¹ is a methyl group and R ² is a hydrogen atom.

Independent of R ¹ and R ² , for example, independent of the combination of R ¹ and R ² , R ³ can take a hydrogen atom or a —COR ⁶ group. In a specific example of the combination with R ¹ and R ² , R ³ is a hydrogen atom. In this case, as described above, the Tg of the polymer (A) and the resin composition (C) is particularly high, and the thermal decomposition characteristics of the polymer (A) and the resin composition (C) are particularly improved.

  Pyrrolidinone ring structure shown in formula (1) may be contiguous on the backbone of the polymer (A). In this case, pyrrolidinone ring successive form a spiro ring structure the ring structure adjacent to. However, if the pyrrolidinone ring structure shown in formula (1) constitutes a part of the structural units of the polymer (A), for example, structural units having the polymer (A) is a ring structure represented by the formula (1) 3-position or the 5-position carbon atoms of an alkylene group such as methylene group is a structural unit having a structure bonded (more specific example, when a structural unit represented by the formula (4) below), heavy continuous of the structural unit in the main chain of the polymer (a), since the alkylene group constituting the main chain of the polymer during the ring (a) is located, continuous pyrrolidinone ring structure in the main chain Not applicable. In this case, between pyrrolidinone ring are not adjacent on the main chain, and can be said.

When the pyrrolidinone ring structure represented by the formula (1) is continuous on the main chain of the polymer (A), the two adjacent ring structures are the carbon atom at the 3-position of one ring structure and the 5 of the other ring structure. A spiro ring structure in which the carbon atom at the position is the same carbon atom is formed. There is no R ¹ bonded to the 3rd carbon atom and R ² bonded to the 5th carbon atom.

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

The structure shown in Formula (2) is a spiro ring structure in which two pyrrolidinone ring structures shown in Formula (1) are continuous on the main chain of the polymer (A). The carbon atom at the 5th position in the left ring structure and the carbon atom at the 3rd position in the right ring structure adjacent to the ring structure are the same carbon atom. In any ring structure, three carbon atoms from the 3rd position to the 5th position constitute the main chain of the polymer (A). R ² bonded to the carbon atom at the 5-position of the left ring structure and R ¹ bonded to the carbon atom at the 3-position of the right ring structure do not exist. It may be R ³ and R ³ of the right ring structure of the left ring structure optionally being the same or different, may be identical to one another.

The structure shown in Formula (3) is a spiro ring structure in which three pyrrolidinone ring structures shown in Formula (1) are continuous on the main chain. 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 any ring structure, three carbon atoms from the 3rd position to the 5th position constitute the main chain of the polymer (A). R ² bonded to the carbon atom at the 5-position of the leftmost ring structure, R ¹ bonded to the carbon atom at the 3-position of the central ring structure and R ² bonded to the carbon atom at the 5-position, and 3 of the ring structure at the right-end. There is no R ¹ attached to the carbon atom at the position. R ^{3 in} each ring structure may be the same as or different from each other, and may be the same as each other.

Thus, when the pyrrolidinone 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 / or R ² are not present, but adjacent to the ring structure together with the bonding hand of the carbon atom to which the group is bonded (the bonding hand to the outside of the ring structure to which the group belongs). It can also be expressed as forming.

  If pyrrolidinone ring structure shown in formula (1) are consecutive on the main chain of the polymer (A), the number of consecutive not limited. In one certain embodiment, the polymer pyrrolidinone ring structure shown in Formula (1) over the entire main chain is continuous (A), in other words, as a constitutional unit pyrrolidinone ring structure shown in formula (1), only the structural unit it is a homopolymer comprising a polymer (a), in can be.

  The polymer (A) has a structural unit P including a lactam ring structure (for example, a pyrrolidinone ring structure represented by the formula (1)). The structural unit P may be composed only of a lactam ring structure, or may be composed of a lactam ring structure and another molecular structure. Other molecular structure, for example, attached to the 3-position and / or 5-position carbon atom of the pyrrolidinone ring, a molecular structure constituting the main chain of the polymer together with the ring structure (A), more specifically an example is an alkylene group such as methylene group as described above.

  An example of a configuration unit P composed of a pyrrolidinone ring structure and other molecular structures are shown in the following equation (4).

The structural unit X shown in Formula (4) is a unit composed of a pyrrolidinone ring structure and a methylene group bonded to the 3-position carbon atom of the ring structure. The carbon atom of the methylene group and the 3rd to 5th carbon atoms of the ring structure constitute the main chain of the polymer (A). The pyrrolidinone ring structure of the structural unit X is a ring structure represented by the formula (1), and a secondary amide structure (R ³ is a hydrogen atom) or a tertiary amide structure (R ³ is a —COR ⁶ group) As part of the molecular structure (including secondary or tertiary amide structures as part of the ring structure).

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

R ¹ to R ³ of formula (4), including the specific example described above, the same as R ¹ to R ³ 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 hydrogen atom, a methyl group or a —NHCOR ⁴ group, and R ² is a —COOR ⁵ group. At this time, R ⁴ may be a hydrogen atom, a methyl group, a phenyl group, an n-butyl group or a t-butyl group, and independently of this, R ⁵ is a hydrogen atom, a methyl group, an ethyl group, or n-butyl group. Group or benzyl group. An example of a preferable combination of R ¹ and R ² in this range is a combination in which R ¹ is a methyl group or a —NHCOR ⁴ group, and R ² is a —COOR ⁵ group. At this time, R ⁴ may be a methyl group, and independently of this, R ⁵ may 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 group and R ² is a —COOCH ₃ group, and the structural unit X having such a combination is, for example, methacrylic acid A copolymer of methyl (MMA) and methyl acetamide acrylate (AcAAM) can be used as a precursor polymer (D) to form a cyclization reaction between adjacent structural units in the polymer (D). When the adjacent structural unit for proceeding the cyclization reaction is a combination of an MMA unit and an AcAAM unit, R ¹ is a methyl group, and when it is a combination of a set of AcAAM units, R ¹ is a —NHCOCH ₃ group. is there. The structural unit X having these combinations has an effect of imparting positive intrinsic birefringence to the polymer (A). In these combinations, R ³ may be a hydrogen atom, and such a polymer (A) is, for example, a tertiary amide constituting the ring structure formed by the cyclization after the cyclization reaction. It can be formed by deacylating structural acyl groups.

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 hydrogen atom or a methyl group, and independently, R ² is a hydrogen atom or a methyl group. An example of the combination of R ¹ and R ² in this range 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, methyl methacrylate ( MMA) and N-vinylacetamide (NVA) as a precursor polymer (D), formed by advancing a cyclization reaction between adjacent MMA units and NVA units in the polymer (D) it can. The structural unit X having these combinations has an effect of imparting positive intrinsic birefringence to the polymer (A). In these combinations, R ³ may be a hydrogen atom, and such a polymer (A) is, for example, a tertiary amide constituting the ring structure formed by the cyclization after the cyclization reaction. It can be formed by deacylating structural acyl groups.

  Polymer (A) may be a homopolymer composed only of the structural unit P including the lactam ring structure, a structural unit P, there in a copolymer composed of the structural units Q other than the structural units P May be. The copolymer may be a random copolymer, a block copolymer, or a graft copolymer.

  The polymer (A) may have two or more kinds of structural units P and may have two or more kinds of 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 further properties depending on the type and content of the structural unit Q. The structural unit Q includes, for example, (meth) acrylic acid ester units, (meth) acrylic acid units, N-substituted maleimide units, aromatic vinyl compound units, unsaturated carboxylic acid compound units, vinyl cyanide compound units, heteroaromatics. An α, β-unsaturated monomer unit having a group.

  The polymer (A) may have at least one selected from a (meth) acrylic acid ester unit and a (meth) acrylic acid unit as the structural unit Q. In this case, such optical clarity of the polymer (A) and the polymer (A) a resin composition comprising (C) becomes higher, the optical characteristics are further improved, for example by use as an optical member Preferred. The polymer (A) which is a copolymer preferably has a (meth) acrylic acid ester unit as the structural unit Q. In other words, the polymer (A) preferably 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-hydroxyacryl It is a structural unit (derived from each of these monomers) formed by polymerization of each (meth) acrylic acid ester of methyl acid and ethyl α-hydroxyacrylate. The (meth) acrylic acid ester unit is preferably a methyl methacrylate (MMA) unit, an ethyl methacrylate unit, an n-butyl methacrylate unit, a cyclohexyl methacrylate unit, an isobornyl methacrylate unit, or a benzyl methacrylate unit, and an MMA unit. 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%. 85 mass% is preferable and 60-80 mass% is more preferable. In these cases, the balance between the high Tg and optical properties of the polymer (A) and the resin composition (C) containing the polymer (A) is further improved. When the polymer (A) has a ring structure represented by the formula (1) in the main chain and R ^{3 of the} ring structure is a hydrogen atom, the resin further includes the polymer (A) and the polymer (A). The balance with the thermal decomposition characteristic of the composition (C) is also improved.

  Including the structural unit X represented by the formula (4), depending on the type of structural unit P, and copolymers of (meth) acrylic acid esters such as MMA as precursor polymer (D), the precursor polymer (D ) the cyclization reaction, in some cases further deacylation, can form a polymer by progress (a), in this case, the polymer (a), as a unit of unreacted (meth) acrylic acid ester It may have a unit.

  When the content rate of the (meth) acrylic acid ester unit in a polymer (A) exceeds 15 mass%, the said polymer (A) is an acrylic polymer. The polymer (A), which is an acrylic polymer, exhibits properties that acrylic polymers generally have, such as high optical transparency, and a high balance of mechanical strength, molding processability and surface hardness. In the polymer (A) which is an acrylic polymer, the total content of (meth) acrylic acid ester units 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, (meth) copolymer is a precursor polymer having the structural unit of the acrylic acid ester unit (D) the cyclization reaction, is allowed to proceed deacylation reaction, further optionally polymer when forming the (a), the polymer (a) can also be considered as derivatives of (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 weight or more, 70% by weight or more, 80% by weight or more, and further 90% by weight or more. Incidentally, as described later, (meth) precursor polymer is a copolymer of acrylic acid ester (D), i.e., the precursor polymer is a copolymer having a constituent unit of (meth) acrylic acid ester units ( in D), the polymer and an ester group and / or carboxyl group and an amide group on the side chain of (D) is present, the polymer (cyclization reaction to D), optionally further deacylation, As long as the polymer (A) having a lactam ring structure in the main chain is obtained by the progress of, the monomer that is a partner for copolymerization with the (meth) acrylic acid ester is not limited. When the lactam ring structure is a pyrrolidinone ring structure, the monomers are, for example, may be an amide of acrylic acid esters, for example, containing amide groups, such as N- vinylformamide, N- vinyl carboxylic acid amides such as N- vinylacetamide It can be a vinyl monomer.

  Polymer (A) has be N- substituted maleimide units as structural units, for example, N- cyclohexyl maleimide, N- phenylmaleimide, N- methyl maleimide, N- ethylmaleimide, N- isopropyl maleimide, N-t- It is a structural unit derived from each monomer of butylmaleimide, N-tribromophenylmaleimide, N-laurylmaleimide, and N-benzylmaleimide. The N-substituted maleimide unit is preferably an N-cyclohexylmaleimide unit or an N-phenylmaleimide unit.

  Polymer (A) is an aromatic vinyl compound unit which may have a structural unit, for example, styrene, alpha-methyl styrene, alpha-chlorostyrene, p-t-butylstyrene, p- methyl styrene, p- chlorostyrene, It is a structural unit derived from each aromatic vinyl compound of o-chlorostyrene, 2,5-dichlorostyrene, 3,4-dichlorostyrene, and divinylbenzene. The aromatic vinyl compound unit is preferably a styrene unit.

  Polymer (A) is an unsaturated carboxylic acid compound unit which may have a structural unit, for example, acid and alkali metal salts thereof, such as crotonic acid, ammonium salt, is a structural unit formed by polymerization of an organic amine salt . In the present specification, the unsaturated carboxylic acid compound unit does not include a (meth) acrylic acid unit.

  Polymer (A) is a vinyl cyanide compound unit which may have a structural unit, for example, a (meth) acrylonitrile units.

  Polymer (A) alpha has a heteroaromatic group which may have a structural unit, beta-unsaturated monomer units, for example, selected vinylcarbazole unit, vinylpyridine units, vinyl imidazole units and vinyl thiophene units it is at least one.

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

  The polymer (A) may or may not have the same type of structural unit as the structural unit of the polymer (B). For example, the polymer (A) may be not have the aromatic vinyl compound unit as a constituent unit, this time, for example, a vinyl cyanide units and / or N- substituted maleimide units as structural units it may not be.

  The polymer (A) may have a structural unit having ultraviolet (UVA) absorption ability. 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 is introduced. In these derivatives, the polymerizable group to be introduced can be appropriately selected, and is, for example, a vinyl group.

  Although the content rate of the structural unit P in a polymer (A) is not limited, in order to acquire the characteristic derived from the structural unit P more reliably, it is 30 mass% or more, for example, 35 mass% or more is preferable, and 40 mass % Or more is more preferable. The upper limit of the content rate of the structural unit P is not specifically limited, 100 mass% or less may be sufficient. When the polymer (A) further includes other structural unit Q, in particular, a (meth) acrylate 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 such as ¹ H nuclear magnetic resonance ( ¹ H-NMR) or infrared spectroscopy (IR).

The lactam ring structure that the polymer (A) has in the main chain can be confirmed by a known method such as ¹ H-NMR or IR. Specific confirmation of example in the lactam ring structure is a pyrrolidinone ring structure, in the infrared absorption spectrum, the following range wavenumber 1690 cm ^-1 or 1710 cm ^-1, is assigned to the stretching vibration of the carbonyl group of pyrrolidinone ring structure Whether or not an absorption peak is observed. In the infrared absorption spectrum, the fact that the absorption peak attributed to the stretching vibration of the carbonyl group of the pyrrolidinone ring structure is in the above-mentioned wave number range is published on September 15, 2006 as an infrared absorption region in a 5-membered lactam ring. It is described in “Identification Method of Organic Compounds by Spectrum, 7th Edition, Tokyo Chemical Doujin”.

Specific structure of the pyrrolidinone 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 Depending on the case, it may be difficult to confirm the absorption peak in the infrared absorption spectrum. However, depending on the structure of the polymer (A), reheating the polymer (A) may cause a cyclization reaction between the remaining structural units without the cyclization reaction proceeding during the formation of the polymer (A). May advance to form the same ring structure as the pyrrolidinone ring structure already present in the polymer (A) (or the pyrrolidinone ring structure before deacylation). At this time, the pyrrolidinone ring structure of the main chain can be confirmed by taking the difference between 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 an observed polymer.

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

  Polymer (A), it shows a high Tg based on the lactam ring structure in the main chain. Tg of the polymer (A) are, for example, 110 ° C. or higher. Specific structure and content of the lactam ring structure, or by the specific structure and content of the constituent unit P comprising a lactam ring structure, Tg of the polymer (A), 120 ° C. or higher, 130 ° C. or higher further it may take a value greater than or equal to 160 ° C..

When the polymer (A) has a ring structure represented by the formula (1) in the main chain and R ³ in the ring structure is a hydrogen atom, the Tg of the polymer (A) is further improved. At this time, the Tg of the polymer (A) is, for example, 120 ° C. or more, and the specific structure and content of the ring structure represented by the formula (1) or the structural unit including the ring structure represented by the formula (1) Depending on the specific structure of P and the content thereof, Tg of the polymer (A) can take values of 130 ° C. or higher, 140 ° C. or higher, 150 ° C. or higher, and 160 ° C. or higher.

When the polymer (A) has a ring structure represented by the formula (1) in the main chain and R ³ in the ring structure is a hydrogen atom, the thermal decomposition characteristics of the polymer (A) are particularly improved. The thermal decomposition characteristics of the polymer (A) are, for example, 5% heat loss temperature (hereinafter simply referred to as “5% heat loss temperature”) determined by the thermogravimetric method defined in JIS K7120. At this time, the 5% heat loss temperature of the polymer (A) is, for example, 300 ° C. or more, and the specific structure and content of the ring structure shown in the formula (1) or the ring shown in the formula (1) Depending on the specific structure of the structural unit P including the structure and the content thereof, the 5% heat loss temperature of the polymer (A) can be 320 ° C. or higher, 340 ° C. or higher, and further 360 ° C. or higher.

  The molecular weight of the polymer (A) is expressed as a weight average molecular weight, for example, 3 to 1,000,000, preferably 5 to 500,000, and more preferably 8 to 250,000.

  The polymer (A) may be crosslinked by a crosslinking agent.

  A polymer (A) can be formed with the manufacturing method of the polymer (A) shown below, for example.

[Production Method of Polymer (A)]
The polymer (A) having a lactam ring structure in the main chain is, for example, a precursor polymer (D) formed by polymerization of a monomer group including a vinyl monomer, and includes an ester group and / or a carboxyl group and an amide. The precursor polymer (D) having a group as a side chain can be formed by cyclization.

When the lactam ring structure is a pyrrolidinone ring structure, in this cyclization, a cyclization condensation reaction is allowed to proceed between the ester group and / or carboxyl group located in the side chain of the precursor polymer (D) and the amide group. Forms a 5-membered amide ring 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 pyrrolidinone ring structure, and the amide group is changed to an amine group containing a nitrogen atom at the 1-position of the pyrrolidinone ring structure. This amine group is, for example, a tertiary amine group having an acyl group (—COR ⁶ ) represented by the formula (5).

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

R ^1, R ² and R ⁶ of formula (5), including the specific examples described above are the same as R ^1, R ² and R ⁶ of formula (1). R ⁷ 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; 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 ⁷ is preferably a linear alkyl group or a cycloalkyl group, and the carbon number thereof is preferably 1 to 12, and more preferably 1 to 4. R ⁷ 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 to the precursor polymer (D) having the molecular structure on the left side to form the polymer (A) having the structural unit P 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 ⁷ OH is eliminated. When R ⁷ is a hydrogen atom, water is eliminated, that is, this reaction is a dehydration cyclocondensation reaction. When R ⁷ is an organic residue, the alcohol is eliminated, that is, this reaction is a dealcoholization cyclocondensation reaction. For example, when R ⁷ is a methyl group, methanol is eliminated. This reaction proceeds within the molecular chain of the precursor polymer (D). The structural unit P on the right side of the formula (5) includes a pyrrolidinone ring structure represented by the formula (1) and a methylene group bonded to the 3-position carbon atom of the ring structure.

The polymer (A) represented by the ring structure represented by the formula (1) and R ³ is a hydrogen atom is, for example, deacylated with respect to the structural unit P (R ³ is —COR ⁶ group) on the right side of the formula (5). It can be formed by further proceeding. An example of such deacylation is shown in the following formula (6). Such deacylation can be similarly applied to the structural unit P (R ³ is —COR ⁶ group) on the right side of each of the reaction formulas shown below, whereby a ring structure in which R ³ is a hydrogen atom. A polymer (A) having a structural unit P containing can be formed. R ⁸ may be the same as a hydrogen atom or R ⁷ . In the former case, the nucleophile that attacks the carbon atom of the carbonyl group during deacylation is water. In the latter case, the nucleophile is, for example, the case of alcohol R ⁷ OH formed during the cyclization reaction described above.

The precursor polymer (D) has an ester group and / or a carboxyl group in its side chain and an amide group. More specifically, the precursor polymer (D) of the formula (5) has a configuration having an ester group (carboxyl ester group: R ⁷ is an organic residue) and / or a carboxyl group (R ⁷ is a hydrogen atom) in the side chain. A copolymer having a unit and a structural unit having an amide group in the side chain. Any structural unit is a unit derived from a vinyl monomer. Thus, the precursor polymer (D) can be formed by polymerization of a monomer group including a vinyl monomer. More specifically, the precursor polymer (D) of the formula (5) is formed by polymerization of a monomer group including a vinyl monomer A having an ester group and / or a carboxyl group and a vinyl monomer B having an amide group. Copolymer. In this precursor polymer (D), the side chain ester group and / or carboxyl group and amide group have one methylene group (one carbon atom) located in the main chain of the precursor polymer (D). I) It is in the inserted positional relationship. In the example shown in Formula (5), by the three carbon atoms located in the main chain of the precursor polymer (D), the carbon atom of the carboxyl group and / or the ester group located in the side chain, and the nitrogen atom of the amide group, A pyrrolidinone ring structure is formed.

An example of vinyl monomer A at this time is shown in the following formula (7), and an example of 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 ⁷ is the same as R ⁷ of formula (5). R ¹ may 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 ⁶ is the same as R ⁶ in the formula (5). R ² may 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 ⁷ is an organic residue) or a (meth) acrylic acid unit (R ¹ Is a hydrogen atom or a methyl group, and R ⁷ is a hydrogen atom. Since the optical transparency of the formed polymer (A) becomes higher, the vinyl monomer A is preferably acrylic acid or methyl methacrylate (MMA), and more preferably MMA.

The vinyl monomer B represented by the formula (8) includes N-vinylformamide (R ² and R ⁶ are hydrogen atoms), N-vinylcarboxylic acid amide (R ² is a hydrogen atom, R ⁶ is a methyl group, a linear alkyl group or It may be an amide group-containing vinyl monomer such as a cycloalkyl group. R ⁶ may be a hydrogen atom, a methyl group or a linear alkyl group, may be a methyl group or a linear alkyl group, or may be a methyl group. When R ² is a hydrogen atom and R ⁶ is a methyl group, the vinyl monomer B shown in Formula (8) is N-vinylacetamide (see Formula (9)).

The vinyl monomer B represented by the formula (8) can be a monomer further having an ester group and / or a carboxyl group together with an amide group. At this time, R ² in formula (8) is a —COOR ⁵ group, which is the same as the —COOR ⁵ group that R ^{2 in} formula (1) can take. An example of such a vinyl monomer B is shown in the following formula (10).

  Monomer B shown in formula (10) may be an amido acrylate ester. Amide acrylate 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) may be an amide acrylate ester. Examples of the amide acrylate ester include methyl acetamidoacrylate (AcAAM), ethyl acetamidoacrylate, and acetamidoacrylic. N-butyl acid, n-d dodecyl acetamidoacrylate, cyclohexyl acetamidoacrylate, and phenyl acetamidoacrylate.

  When precursor polymer (D) is a copolymer of vinyl monomer A and a vinyl monomer B, and the structural unit Y1 derived from a monomer A in the polymer (D), and the structural unit Y2 derived from a monomer B of Although the ratio of the content is not particularly limited, and the weight ratio, for example Y1: Y2 = 95 to 50: 5 to 50, 90 to 50: 10 to 50 is preferable, 85 to 60: 15 to 40 and more preferably . The structural unit Y1 may be a (meth) acrylic acid ester unit, and may be a MMA unit as a more specific example. 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 preferred range, the cyclization reaction between the (meth) acrylic acid ester and the vinyl monomer B A rate can be improved, for example, Tg of the polymer (A) finally obtained can be made higher. When performing until deacylation as described above, for example, the balance of the content of the finally obtained polymer in (A) and (meth) ring structure shown in acrylic acid ester units of formula (1) is improved , heat resisting decomposition characteristic of the polymer (a) can be further improved. The polymer (A) can have unreacted structural units Y1 and / or Y2. For example, when the structural unit Y1 is a (meth) acrylic acid ester unit, the finally obtained polymer (A) can have an unreacted (meth) acrylic acid ester unit as a structural unit.

  Precursor polymer (D) may be a polymer formed by polymerization of a monomer group containing two or more vinyl monomers A and / or two or more vinyl monomers B. That is, the precursor polymer (D) has two or more structural units derived from two or more constituent units Y1 and / or two or more vinyl monomers B from two or more vinyl monomers A Y2 it 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 (D) may be a homopolymer of the same vinyl monomer. As can be understood from the molecular structure shown in 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 (D) may be a polymer formed by polymerization of a monomer group including a vinyl monomer C having an ester group and / or carboxyl group and an amide group. If precursor polymer (D) is such a homopolymer, Tg of the polymer (A) is particularly high. In other words, the polymer (A), increase in the Tg of the precursor polymer (D) becomes particularly large.

  The vinyl monomer C is, for example, an amide acrylate ester.

  Precursor polymer is a homopolymer of vinyl monomer C is an example of a cyclization reaction of (D), shown in the following equation (11). In the example shown in equation (11), and allowed to proceed cyclization reaction precursor polymer is a homopolymer of acrylic acid amide ester (B), the pyrrolidinone ring form a polymer (A) having in the main chain Yes.

R ⁵ of formula (11) is the same as R ⁵ in the formula (1), R ⁶ of formula (11) is the same as R ⁶ in the formula (5). In the cyclization reaction shown in Formula (11), a polymer (A) having a structural unit P shown on the left side of the right side of Formula (11) is formed. The cyclization reaction shown in Formula (11) is a cyclization condensation reaction in which a broken line part between adjacent structural units in the precursor polymer (B) is bonded and R ⁵ OH is eliminated. Note that when the deacylation further proceeds with respect to the structural unit P represented by the formula (11), the structural unit P has two acyl groups that can be eliminated by deacylation. An acyl group may be eliminated.

  Precursor polymer is a homopolymer of vinyl monomer C another example of the cyclization reaction of (D), shown in the following equation (12). In the example shown in equation (12), and allowed to proceed cyclization reaction precursor polymer is a homopolymer of acrylic acid amide ester (B), to form a polymer having a spiro ring structure pyrrolidinone rings (A) Yes.

R ⁵ of formula (12) is the same as R ⁵ in the formula (1), R ⁶ of formula (12) is the same as R ⁶ in the formula (5). In the cyclization reaction shown in Formula (12), a polymer (A) having the structural unit P shown on the left side of the right side of Formula (12) is formed. The structural unit P includes a spiro ring structure in which two pyrrolidinone ring structures are continuous on the main chain. In the formula (12), a cyclization reaction (bonding a broken line portion in the molecular structure on the left side and R ⁵ OH between the left and center vinyl monomers C adjacent to each other and between the vinyl monomers C adjacent to the center and right ends. (Desorption reaction) is in progress. As can be understood from this, by proceeding the cyclization condensation reaction between all the adjacent vinyl monomers C, a polymer that is a homopolymer having only a structural unit composed of the ring structure represented by the formula (1) ( It is also possible to form A). Further, in the precursor polymer (D) which is a copolymer of vinyl monomers A and B, depending on the type of vinyl monomer B, in a region where the structural units derived from monomer B are continuous, a cyclization reaction causes a ring. A spiro ring structure having a continuous structure can be formed. That is, a polymer (A) having a spiro ring structure with a continuous ring structure can be formed. Note that when the deacylation further proceeds with respect to the structural unit P represented by the formula (12), there are three acyl groups in the structural unit P that can be eliminated by deacylation. An acyl group may be eliminated. The fact that at least one acyl group is eliminated in the deacylation is the same regardless of the number of consecutive ring structures. Of course, all acyl groups may be eliminated.

  Polymer spiro ring structure is formed (A), in particular a polymer is the homopolymer (A), it is expected that characteristic based on the ring structure of the main chain is particularly remarkable. The characteristic is, for example, a very high Tg. Such a polymer (A) having a very high Tg is expected to be used for applications requiring extremely high heat resistance.

  If precursor polymer (D) is a copolymer, the polymer (D) is a random copolymer may be an alternating copolymer.

  Precursor polymer (D) may be a copolymer of two or more amide acrylate.

  Precursor polymer (D) is, if a copolymer formed by polymerization of a monomer group including a vinyl monomer A and a vinyl monomer B, the monomer group is further contain a vinyl monomer C Good. Precursor polymer (D) is, if a polymer formed by polymerization of a monomer group including a vinyl monomer C, the monomer group is further contain a vinyl monomer A and / or vinyl monomers B Also good.

  Precursor polymer (D) may, for example, may further have a constitutional unit derived from a monomer other than the vinyl monomer A through C. In this case, the polymer further including the structural units (A) can be formed. The said structural unit is structural unit Q other than the structural unit P mentioned above in description of a polymer (A), for example.

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

  The monomer group includes, for example, a vinyl monomer. 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 the vinyl monomer A is at least one selected from (meth) acrylic acid esters and (meth) acrylic acid. Examples of the vinyl monomer B are amide group-containing vinyl monomers such as N-vinylformamide and N-vinylcarboxylic amide. The vinyl monomer B may be at least one selected from N-vinylformamide and N-vinylacetamide. Another example of vinyl monomer B and an example of vinyl monomer C are amidoacrylates.

  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. 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-containing hydrocarbons; alcohols such as methanol and ethanol; water, dimethyl sulfoxide (DMSO), and tetrahydrofuran.

  In the polymerization precursor polymer (D), if necessary, a polymerization initiator, a chain transfer agent and the like can be used. The polymerization initiator is not particularly limited, and examples thereof include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and t-amyl peroxide. 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 is not particularly limited as long as it is appropriately set according to the combination of monomers included in the monomer group or the polymerization conditions.

  The polymerization conditions such as the polymerization temperature can be appropriately set.

  If there is a polymerization rate differences between monomers contained in the monomer group, as compared with the content of each monomer included in the monomer group to be subjected to polymerization, in the monomers in the precursor polymer (D) formed by polymerization the content of derived from each of the structural units, there is a tendency that the content of the constituent unit polymerization rate is derived from the fast monomer is relatively large. Therefore, a precursor polymer is a copolymer (D), a polymer having a value desire for content and / or content ratio of the structural units that constitute the polymer (D) with (D) to obtain, or note the content of each monomer in the monomer group subjected to polymerization, or control the polymerization process (e.g., supplied to the polymerization system dropwise some or all of the fast monomer of polymerization rate) to, the content of each constituent unit in the formed precursor polymer (D) can be appropriately adjusted.

(Cyclization reaction)
The method for cyclizing the precursor polymer (D) is not limited. For example, by heating the precursor polymer (D), a cyclization condensation reaction that is an amide cyclization reaction can proceed in the molecular chain of the polymer (D) to form the polymer (A).

  If allowed to proceed cyclization reaction by heating of the precursor polymer (D), the heating temperature is, for example, 70 ° C. or higher, preferably at least 100 ° C., 0.99 ° C. or higher, more preferably in the order of more than 200 ° C.. The heating of the precursor polymer (D) can be performed in any state such as a state where the precursor polymer (D) is in a solid state or a state in which the precursor polymer (D) is dissolved in a solvent. When heating in the solid state, due to rapid progression of the cyclization reaction, the powder is preferably set to precursor polymers having high form the surface area of such particles (D). Moreover, in order to advance cyclization reaction rapidly by removing the alcohol or water produced | generated by cyclization reaction described in the right side of Formula (5), (11), (12), it is under reduced pressure. Heating is preferred. The degree of decompression is, for example, 26.6 kPa or less in absolute pressure. That may be allowed to proceed cyclization reaction by heating precursor polymer (D) under a pressure of less than 26.6 kPa. The degree of decompression is preferably 13.3 kPa or less, and more preferably 2.7 kPa or less.

  When the cyclization reaction proceeds, a catalyst that promotes the reaction may be used as necessary. When using a catalyst, for a uniform reaction, heating is preferably in a state where the precursor polymer (D) is dissolved in a solvent.

  As the catalyst, for example, at least one selected from acids, bases and salts thereof, metal complexes, and metal oxides can be used. Kinds of acids, bases and salts thereof, metal complexes, and metal oxides are not particularly limited. Polymers formed (A), or if the polymer resin composition comprising (A) (C) or the resin molded article is used in applications where importance is attached to transparency, catalyst, these transparency It is preferable to use it in a range that does not decrease and does not cause adverse effects such as coloring.

  The acid is not limited, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and phosphorous acid, and organic acids such as p-toluenesulfonic acid, phenylphosphonic acid, organic carboxylic acid, and phosphoric acid ester. The base is not limited, and examples thereof include metal hydroxides, amines, imines, alkali metal derivatives, alkoxides, and ammonium hydroxide salts. Acid and base salts are not limited, for example, metal organic acid salts and metal inorganic acid salts. Specific examples of metal organic acid salts are metal carboxylates, and specific examples of metal inorganic acid salts are metals. Carbonate. A metal complex is not limited, For example, the example of the organic component is acetylacetone. The metal oxide is not limited, and examples thereof include zinc oxide, calcium oxide, and magnesium oxide. Among these exemplified catalysts, acid and base salts are preferable, metal organic acid salts are more preferable, and metal carboxylates are particularly preferable. Metal organic acid salts, for example, the metal of the metal carboxylate, the finally obtained polymer (A), does not inhibit the characteristics of the resin composition (C) or the resin molded article, and the environmental pollution when these waste not limited unless causing, for example, lithium, sodium, potassium alkali metals such as; a; zinc; magnesium, calcium, strontium, alkaline earth metals such as barium zirconium. Of these, zinc is preferable. The carboxylic acid constituting the metal carboxylate is not limited. For example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, octylic acid, nonanoic acid, decanoic acid, lauric acid, myristic Acid, palmitic acid, stearic acid, behenic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, lactic acid, malic acid, citric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid and adipic acid. As a specific metal carboxylate, zinc acetate, zinc propionate, zinc octylate, or zinc stearate is preferable.

(Deacylation reaction)
As described above, the deacylation reaction can proceed to the polymer after the cyclization reaction.

  When deacylation proceeds by heating, the heating temperature is, for example, 100 ° C. or higher, preferably 200 ° C. or higher, and more preferably in the order of 240 ° C. or higher, 280 ° C. or higher. Heating for deacylation can polymer is carried out in any state, such as state dissolved solid state, in a solvent. In the case of heating in a solid state, it is preferable to use a polymer having a large surface area such as powder and particles in order to quickly proceed with deacylation. Also, heating under reduced pressure is preferred in order to rapidly proceed with the deacylation by removing the produced carboxylic acid or carboxylic acid ester. The degree of pressure reduction may be the same as the reduced pressure at the time of the cyclization reaction to precursor polymer (D).

  When the deacylation proceeds, a catalyst that promotes the reaction may be used as necessary. When using a catalyst, for a uniform reaction, heating is preferably in a state where the polymer is dissolved in a solvent.

  As the catalyst, for example, at least one selected from acids, bases and salts thereof, metal complexes, and metal oxides can be used. Kinds of acids, bases and salts thereof, metal complexes, and metal oxides are not particularly limited. Specific examples of each catalyst may be the same as the catalyst examples described above in the description of the cyclization reaction. If the polymer (A), or the polymer (A) a resin composition comprising (C) or the resin molded article is used in applications where importance is attached to transparency, the catalyst is lowered these transparency not, it is preferably used in a range of adverse effects such as coloring does not occur.

  Salt of the acid is not limited, for example, a metal organic acid salt. Specific examples of the metal organic acid salt is a metal carboxylate. Metal organic acid salts, for example, the metal of the metal carboxylate, the polymer (A), does not inhibit the characteristics of the resin composition (C) or resin molded product, and unless causing environmental pollution when these waste limited without, for example, lithium, sodium, potassium alkali metals such as; a; zinc; magnesium, calcium, strontium, alkaline earth metals such as barium zirconium. Of these, zinc is preferable. The carboxylic acid constituting the metal carboxylate is not limited. For example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, octylic acid, nonanoic acid, decanoic acid, lauric acid, myristic Acid, palmitic acid, stearic acid, behenic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, lactic acid, malic acid, citric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid and adipic acid. As a specific metal carboxylate, zinc acetate, zinc propionate, zinc octylate, or zinc stearate is preferable.

  And cyclization reaction to precursor polymer (D), the deacylation reaction for the polymer which is formed through the cyclization reaction, (for example separately) stepwise be carried, even if carried out continuously Good. When it carries out continuously, a common catalyst can also be used depending on the kind of catalyst. For example, may be used cyclization and subsequent catalyst metal organic acid salt of deacylation of the precursor polymer (D), this time, the metal organic acid salt of zinc organic acid salts are preferred. By using the zinc organic acid salt, the cyclization reaction and the deacylation reaction for the precursor polymer (D) can proceed more stably and reliably.

  If you use a common catalyst for the cyclization and subsequent deacylation of the precursor polymer (D), a catalytic amount necessary to promote the reaction, separately after the start of the time or the reaction to initiate each reaction The catalyst added at the start of the cyclization reaction may be left as it is, and the deacylation may be promoted by the remaining catalyst.

  As long as a polymer (A) is formed, the manufacturing method of this invention can include arbitrary processes other than the process mentioned above.

  Such polymers of the present invention as viewed from the side of the production method (A) is a precursor polymer formed by polymerization of a monomer group including a vinyl monomer (D), an ester group and / or carboxyl cyclizing the precursor polymer (D) having an acid group and an amide group as a side chain, furthermore, the tertiary amide structural acyl group constituting the ring structure formed by the cyclization optionally deacylated It is a polymer formed.

  Precursor polymer as described above (D), for example, the copolymerization formed by polymerization of a monomer group including a vinyl monomer A having an ester group and / or carboxyl group, and a vinyl monomer B having an amide group It may be combined. Further, the precursor polymer (D) may, for example, be a polymer formed by polymerization of a monomer group including a vinyl monomer C having an ester group and / or carboxyl group and an amide group, vinyl monomers C It can also be a homopolymer. Examples of vinyl monomers A, B and C are as described above.

[Polymer (B)]
The polymer (B) has an aromatic vinyl compound unit as a structural unit. The polymer (B) is typically a thermoplastic polymer. The polymer (B) is typically an amorphous polymer.

The aromatic vinyl compound unit is a structural unit represented by the following formula (13), and is formed by polymerization of an aromatic vinyl monomer. In the formula (13), R ¹¹ is an aromatic group, R ¹² is a hydrogen atom, and R ¹³ and R ¹⁴ are each independently a hydrogen atom or a methyl group. R ¹¹ is, for example, an aryl group which may have a substituent, and may be a heteroaromatic group.

  Aromatic vinyl compound units, for example, styrene, alpha-methyl styrene, methoxy styrene, a structural unit formed by polymerization of vinyl toluene, each monomer of the halogenated styrene. Especially, since the polymer (B), resin composition (C), and resin molding which show high optical transparency are obtained, a styrene unit is preferable.

  Aromatic vinyl compound units may be in unit heteroaromatic vinyl compounds, for example, vinyl carbazole, vinyl pyridine, vinyl imidazole, or may be a constituent unit derived from each monomer of vinyl thiophene.

  Polymer having a lactam ring structure in its main chain and (A), a resin composition containing a polymer having an aromatic vinyl compound unit as a constituent unit (B) and the high compatibility, the polymer (A) and (B) securing optical transparency of the object (C) are possible. Further, the polymer having a lactam ring structure in its main chain and (A), a polymer having an aromatic vinyl compound unit as a constituent unit and (B), for example, a polymer having other ring structure in its main chain an aromatic compared to a combination of a polymer having a group vinyl compound unit as a constituent unit, it is possible compatible with a wider variety of composition range.

  Aromatic vinyl compound unit has the effect of giving a negative intrinsic birefringence of polymer (B). Polymer (B) is basically a polymer having a negative intrinsic birefringence. If the sign of the intrinsic birefringence of the polymer (A) and (B) are reversed, for example, a polymer A polymer (A) is a positive intrinsic birefringence, intrinsic polymer (B) is negative If a polymer exhibits birefringence, the resin composition (C), the polymer (a), the birefringence values indicating the composition (C) is the differ sign of the intrinsic birefringence of the (B) The degree of freedom of control can be increased. Thus, for example, a resin composition capable of realizing an optical film exhibiting retardation value close to zero to a negative retardation film becomes (C).

  The polymer (B) may have a structural unit other than the aromatic vinyl compound unit. If the polymer (B) has a structural unit other than the aromatic vinyl compound unit, the content of the structural unit in the polymer (B), for example 70 wt% or less, preferably 55 wt% or less, more preferably 35 or less by mass%.

  May have the polymer (B), another structural unit other than aromatic vinyl compound units, for example, vinyl cyanide compound unit, N- substituted maleimide units, (meth) acrylic acid ester units, vinyl ester units, and Maleic anhydride units. Transparency of the polymer (B), and polymer resin compositions based on the height of the compatibility with (A) (C) of the transparency can be more reliably ensured, and negative intrinsic to the polymer (B) since it has an effect of giving a birefringence, other structural units of the vinyl cyanide compound unit and N- substituted maleimide units are preferred. Polymer (B) may further comprise a vinyl cyanide compound unit and / or N- substituted maleimide units as structural units.

  The vinyl cyanide compound unit is formed by polymerization of a vinyl cyanide monomer. The vinyl cyanide compound unit is not limited, and is, for example, a structural unit derived from each monomer of acrylonitrile and methacrylonitrile.

The N-substituted maleimide unit is a structural unit represented by the following formula (14). N-substituted maleimide units are formed by polymerization of N-substituted maleimide monomers. In the formula (14), R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 14 carbon atoms, and X has a substituent. An optionally substituted chain alkyl group having 1 to 12 carbon atoms, an optionally substituted cycloalkyl group having 3 to 12 carbon atoms, or an optionally substituted aryl having 6 to 14 carbon atoms It is a group.

R ¹⁵ and R ¹⁶ are each independently preferably a hydrogen atom, a methyl group, a benzyl group or a phenyl group, more preferably a hydrogen atom. X is a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, phenyl group, chlorophenyl group, methylphenyl group, naphthylphenyl group, hydroxyphenyl group, methoxyphenyl group, nitrophenyl group, A carboxylphenyl group and a tribromophenyl group are preferable, and a cyclohexyl group, a phenyl group, and a benzyl group are more preferable.

  N- substituted maleimide units has a function of improving the Tg of the polymer (B), thereby, as compared with the case where the polymer (B) has no a constituent unit N- substituted maleimide units, the polymer It can be improved Tg and heat resistance of the resin composition (C) comprising (B) and polymer (B).

  (Meth) acrylic acid ester unit is formed by polymerization of (meth) acrylic acid ester monomer. The (meth) acrylic acid ester unit that the polymer (B) may have as a structural unit is not limited, and is, for example, the unit exemplified in the description of the polymer (A). (Meth) acrylic acid ester units, since the optical transparency of the polymer (B) is high, MMA units are preferred.

  Vinyl ester units, e.g., vinyl acetate unit, vinyl propionate unit.

The maleic anhydride unit is a structural unit represented by the following formula (15). Maleic anhydride units are formed by polymerization of maleic anhydride monomers. In the formula (15), R ¹⁷ and R ¹⁸ are independently of each other preferably a hydrogen atom, a methyl group, a benzyl group or a phenyl group, and more preferably a hydrogen atom.

  Maleic anhydride unit has a function of improving the Tg of the polymer (B), thereby, as compared with the case where the polymer (B) has no maleic anhydride units as structural units, the polymer (B ) and it can be improved Tg and heat resistance of the resin composition (C) comprising polymer (B).

  A case where the polymer (B) further has a structural unit of the vinyl cyanide compound unit content of the polymer (B) a vinyl cyanide compound unit in is, for example, 1 to 35 wt%, preferably 5 to 20 mass %, more preferably from 7 to 13 mass%.

  A case where the polymer (B) further has a structural unit of N- substituted maleimide units, the content of N- substituted maleimide units in the polymer (B) is, for example, 1 to 60 wt%, preferably from 15 to 50 weight %, more preferably 35 to 45 wt%.

  A case where the polymer (B) further has a structural unit of the vinyl cyanide compound unit and N- substituted maleimide units, an example of its composition, the aromatic vinyl compound unit 30 to 65 wt%, vinyl cyanide compound unit 5-20 wt%, 15 to 50 wt% N-substituted maleimide unit. While ensuring the compatibility with the polymer (A), it is possible to widen the composition range of the polymer (B) in this way.

The content of each structural unit in the polymer (B) can be determined by a known method such as ¹ H nuclear magnetic resonance ( ¹ H-NMR) or infrared spectroscopy (IR).

  The weight average molecular weight of the polymer (B) is, for example, 100,000 to 300,000, preferably 150,000 to 250,000, and more preferably 150,000 to 200,000.

  Polymer (B) can be produced by a known method. For example, an aromatic vinyl monomer, and optionally by polymerizing a monomer group including other monomer (the vinyl cyanide monomer and / or N- substituted maleimide monomer as an example) heavy A coalescence (B) can be formed.

  The polymerization of the monomer group, suspension polymerization, emulsion polymerization, can be applied a variety of polymerization methods such as solution polymerization. When forming a polymer further having a N- substituted maleimide units (B), since it can reduce the residual amount of N- substituted maleimide monomer in the obtained polymer (B), the solution polymerization is preferred.

  Solution polymerization may be performed according to a known method. Polymerization solvent used in the solution polymerization, for example, toluene, xylene, ethylbenzene, isopropylbenzene, methyl isobutyl ketone, butyl cellosolve, dimethylformamide, 2-methylpyrrolidone, be appropriately selected and used general polymerization solvent such as methyl ethyl ketone .

[Resin composition (C)]
The resin composition (C) of the present invention includes a polymer (A) and a polymer (B). The resin composition (C) includes a polymer having a ring structure in the main chain and is a novel resin composition applicable to an optical member; composed of the resin composition (C) and the resin composition (C) In the molded resin product, it is possible to ensure optical transparency while achieving high Tg (high heat resistance) by including a polymer having a ring structure in the main chain; and the resin composition (C ), Depending on the configuration of the polymer (A) and the polymer (B), the degree of birefringence can be controlled more freely, for example, from an optical film showing a retardation value near zero to a negative retardation film. That it is a possible resin composition is as described above.

  Resin composition (C) is typically a thermoplastic resin composition. Resin composition (C) is typically amorphous. Resin composition (C) is typically non-water soluble. Resin composition (C) may comprise two or more polymers (A) and / or two or more of the polymer (B).

  Resin composition (C) show various characteristics derived from the polymer (A) and / or polymer (B). The characteristic is, for example, a thermal characteristic or an optical characteristic.

  Thermal properties, for example, a Tg, Tg of the resin composition (C) increases derived from the polymer (A). Further, the polymer (B) also, depending on its configuration contributes to a high Tg can take of the resin composition (C). For example, since the N-substituted maleimide unit increases the Tg of the polymer having the unit, the Tg of the resin composition (C) is increased by the polymer (B) further having the N-substituted maleimide unit as a constituent unit. Conceivable. Tg of the resin composition (C) is, for example, 110 ° C. or higher, depending on the specific structure of the polymer (A) and the polymer (B), 120 ° C. or higher, 130 ° C. or higher, 140 ° C. or higher, 0.99 ° C. or more, further it can take a value of more than 160 ° C.. Incidentally, the polymer when compatibility between the polymer (A) (B) is low, or the resin composition (C) the polymer (A) and (B) and compatibility further lower other polymers the such as when containing, there are cases where the resin composition for (C) a plurality of Tg are measured, essentially from that compatibility with the polymer (a) and polymer (B) is high, the resin composition Tg the object (C) can be measured only one point.

Another example of thermal characteristics is thermal decomposition characteristics, and the thermal decomposition characteristics of the resin composition (C) are increased due to the polymer (A). The 5% heat loss temperature of the resin composition (C) is, for example, 250 ° C. or more, and the specific configuration of the polymer (A) and the composition of the resin composition (C), for example, the weight in the resin composition (C). Depending on the content of the coalesced (A), the 5% heat loss temperature of the resin composition (C) can take a value of 300 ° C. or higher, 320 ° C. or higher, 340 ° C. or higher, or 360 ° C. or higher. From the viewpoint of the specific configuration of the polymer (A), for example, the specific structure of the ring structure of the polymer (A) in the main chain, for example, when R ³ shown in the formula (1) is a hydrogen atom, Further, the thermal decomposition characteristics (5% heat loss temperature) of the polymer (A) and the resin composition (C) containing the polymer (A) are particularly high.

  An example of the optical property is transparency (optical transparency) based on the high compatibility between the polymer (A) and the polymer (B). This property, the resin composition (C) becomes applicable to an optical member. However, in all of the compositions in which the resin composition (C) can take, the resin composition (C) is not necessarily transparent. Resin composition (C) can only be optically transparent.

  Another example of the optical properties is a birefringent properties. As described above, the resin composition (C) has a high degree of freedom in controlling the birefringence value, and the resin composition (C) changes, for example, from an optical film showing a retardation value near zero to a negative retardation film. to be realized. Although the positive / negative of the intrinsic birefringence of the resin composition (C) is not limited, for example, it can be from zero or near zero or near zero to negative above a certain value. The intrinsic birefringence as the resin composition (C) is a balance between the intrinsic birefringence exhibited by the polymer (A) and the polymer (B), and when the resin composition (C) further contains another polymer, determined by further consideration of the intrinsic birefringence other polymers shown.

In the example of the resin composition (C) focusing on the birefringence characteristics, the absolute value of the stress optical coefficient (Cr) is 13 × 10 ⁻¹¹ Pa ⁻¹ or less. With such a resin composition (C), an optical film showing a retardation value near zero can be realized. Another example of the resin composition (C) focusing on the birefringence characteristics shows negative intrinsic birefringence, and the absolute value of the stress optical coefficient (Cr) is 100 × 10 ⁻¹¹ Pa ⁻¹ or more. With such a resin composition (C), a negative retardation film can be realized. In addition, it becomes possible to enlarge the absolute value of the phase difference which the optical film comprised from the said composition can show, so that the absolute value of Cr of a resin composition is large. The actual retardation value depends on the thickness of the optical film and the state of stretching of the optical film.

  Resin composition (C) may have various other properties derived from the polymer (A) and / or polymer (B). Based on these characteristics, the resin composition (C) may be used in a variety of applications including optical members.

  The content of polymer in the resin composition (C) (A) and (B), the polymer (A), for example, 40 to 95 wt%, may be 60 to 80 mass%. For the polymer (B), for example, 5 to 60% by weight, it may be 20 to 40 mass%. The range for the content of the polymer in the range of the content of these polymers (A) (B), can be arbitrarily combined.

  Resin composition (C), the polymer as the polymer (A), in which only may contain (B), the polymer (A), may contain other polymers other than (B) . When using the resin composition (C) to the optical member, in order to ensure optical clarity, other polymer is preferably compatible with the polymer (A) and the polymer (B).

  Examples of the other polymer include olefin polymers such as polyethylene, polypropylene, ethylene-propylene polymer, and poly (4-methyl-1-pentene); halogen-containing polymers such as vinyl chloride and chlorinated vinyl resins. Acrylic polymers such as polymethyl methacrylate; polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; polyamides such as nylon 6, nylon 66 and nylon 610; polyacetals; polycarbonates; polyphenylene oxides; polyphenylene sulfides; Ketone; Polysulfone; Polyethersulfone; Polyoxypentylene; Polyamideimide; Rubbery polymer. Resin composition (C) may comprise two or more of these polymers.

  Resin composition (C), materials other than polymers, for example additives may include. Additives include, for example, antioxidants, light stabilizers, weather stabilizers, heat stabilizers and other stabilizers; phase difference adjusting agents such as phase difference increasing agents, phase difference reducing agents, phase difference stabilizers; glass fibers, Reinforcing materials such as carbon fibers; UV absorbers; near infrared absorbers; flame retardants such as tris (dibromopropyl) phosphate, triallyl phosphate, antimony oxide; antistatic agents including 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 (C) is preferably less than 7% by mass, more preferably 2% by mass or less, and further preferably 1% by mass or less.

  Method of forming the resin composition (C) is not particularly limited. If it is a resin composition (C) containing only the polymers (A) and (B), the polymers (A) and (B) can be mixed by a known mixing method. When the resin composition (C) comprises the other polymers and / or additives, mixed with the polymer (A) and (B) with the other polymers and / or additives and the known mixing methods and it can be formed. Mixing can be carried out, for example, by pre-blending with a mixer such as an omni mixer and then kneading the resulting mixture. A kneading machine is not specifically limited, For example, well-known kneading machines, such as extruders, such as a single screw extruder and a twin screw extruder, and a pressure kneader, can be used.

  The resin composition of (C) to form a resin molded body. The resin molded body includes a polymer (A) and the polymer (B), composed of the resin composition (C). Application of the resin molded body is not limited, the polymer (A) and / or polymer (B), and the resin composition (C) on the properties obtained derived from other polymers and / or additives contained in the in response can be selected. Resin molding, for example, an optical member for use in optical applications.

  The optical member is, for example, a lens, a prism, an optical fiber, or an optical film. Optical films include, for example, protective films for substrates of various optical disks (VD, CD, DVD, MD, LD, etc.), retardation films and polarizer protective films provided in image display devices such as liquid crystal display devices (LCD), and A viewing angle compensation film, a light diffusion film, a reflection film, an antireflection film, an antiglare film, a brightness enhancement film, and a conductive film for a touch panel.

  Resin composition (C) from constructed resin molding may have a heat resistance derived from high polymer (A) Tg. Therefore, flexibility of the resin composition (C) from the constructed resin molding applications is high, various effect by the use of the resin molded article is obtained. For example, the use of the resin molded article is an optical film, the degree of freedom in designing the image display device such as an LCD is improved.

  The resin molded body composed of the resin composition (C) can have high heat decomposition characteristics derived from the polymer (A). At this time, for example, even when a resin molded body is obtained by melt molding of the resin composition (C), defects such as foaming due to decomposition of components contained in the resin composition (C) (optical defects as an optical member) Can be suppressed.

  The resin molded body composed of the resin composition (C) can have high optical transparency. For example, the total light transmittance obtained in accordance with the provisions of JIS K7361 can be 85% or more, 90% or more, and further 91% or more of a resin molded body, typically a film. .

  The resin molding comprised from the resin composition (C) may have a haze with a low surface. For example, it is possible to obtain a resin molded body having a haze of 5% or less, 3% or less, and further 2% or less, typically a film, as a haze determined in accordance with the provisions of JIS K7136. .

  Composed of the resin composition (C) the resin molded body may be a phase difference film. The retardation film is, for example, a negative retardation film in which the thickness direction retardation Rth is negative.

  The resin molded body composed of the resin composition (C) can be an optical film that exhibits a retardation value near zero, that is, substantially 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 a polarizer protective film, for example.

  The resin molded body composed of the resin composition (C) can be combined with other members. For example, the resin molded article is an optical film may be combined with other optical members. One example is a polarizing plate. Polarizing plate comprises a polarizer and a polarizer protective film disposed on at least one major surface of the polarizer. As a polarizer protective film, an optical film composed of the resin composition (C) can be used.

  The optical member may be, for example, a structure having a layer composed of the resin composition (C).

  The surface of the resin molded article, various functional coating layer may be formed as needed. Functional coating layers include, for example, antistatic layers, adhesive layers, adhesive layers, easy adhesion layers, antiglare (non-glare) layers, antifouling layers such as photocatalyst layers, antireflection layers, hard coat layers, and UV shielding layers. A layer, a heat ray shielding layer, an electromagnetic wave shielding layer, and a gas barrier layer.

  The method for forming the resin molded body from the resin composition is not particularly limited. A resin molded body can be formed by molding the resin composition (C) by a known molding technique such as a melt extrusion method, a casting method, or a press molding method. As needed, you may combine a shaping | molding method and other well-known methods, for example, the extending | stretching method. In order to obtain a retardation film, it is necessary to stretch a film (original film) obtained by molding a resin composition.

  A product provided with the resin molded body comprised from the resin composition (C) is not specifically limited, For example, it is an image display apparatus provided with the said resin molded body which is an optical film. The image display device is not particularly limited. For example, reflective, transmissive, and transflective LCDs; TN, STN, OCB, HAN, VA, IPS, and other driving LCDs; electro A luminescence (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-vinylacetamide and methyl 2-acetamidoacrylate, respectively. PMI, AN and St are abbreviations for phenylmaleimide, acrylonitrile and styrene, respectively.

  Initially, the evaluation method of the polymer produced in the present Example is shown.

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

[Content of constituent unit 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 resin composition was determined in accordance with the provisions of JIS K7121. Specifically, a differential scanning calorimeter (manufactured by Rigaku, DSC-8230) is used, and a sample of about 10 mg is heated from normal temperature to 200 ° C. (temperature increase rate 20 ° C./min) in a nitrogen gas atmosphere. The DSC curve was evaluated by the starting point method. Α-alumina was used as a reference.

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

First, the produced polymer or resin composition was formed into a film by hot pressing to obtain an unstretched film (thickness 150 μm) of the polymer or composition. Next, the produced unstretched film was cut out with a size of 20 mm × 60 mm to obtain a test piece for Cr evaluation. Next, on one short side of the test piece, a polymer or resin composition to be evaluated is selected after attaching a weight having a weight that applies a stress of 1 N / mm ² or less to the test piece during stretching. Was kept in a constant temperature drier (manufactured by ASONE, DOV-450A) kept at Tg + 20 ° C. for 1 hour. When the test piece is stored in a constant temperature dryer, the other short side of the test piece is fixed with a chuck, and the test piece is uniaxially free in the long side direction (vertical direction) due to the stress applied to the test piece by the weight. It was made to extend | stretch. Moreover, when accommodating, the distance between the chuck and the weight in 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 cool slowly in the dryer. When the temperature in the oven reaches Tg−40 ° C. of the polymer or the resin composition, the test piece (uniaxially stretched film) is taken out, and the thickness of the taken out test piece and the in-plane retardation Re with respect to light with a wavelength of 590 nm are calculated. Measurement was performed to calculate the in-plane birefringence Δn of the test piece. Separately from this, the cross-sectional area of the test piece after being stretched by the weight load was obtained, and the stress σ (Pa) applied to the film was calculated from the cross-sectional area and the weight load. While changing the weight of the weight, Δn and σ were obtained for each load, the slope of Δn with respect to the obtained σ was obtained by the least square 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 near 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 or resin composition to be evaluated is positive. On the other hand, when the orientation angle is near 90 ° with respect to the stretching direction, the sign of the stress optical coefficient Cr is negative. In this case, the intrinsic birefringence of the polymer or resin composition to be evaluated is negative. The larger the absolute value of Cr, the higher the expression of birefringence by stretching.

  The in-plane phase difference Re (nm) of the test piece was determined using a phase difference measuring device (manufactured by Oji Scientific Instruments, KOBRA-WR). The in-plane phase difference Re is the refractive index nx in the slow axis direction (direction showing the maximum refractive index in the film plane) in the test piece (film) plane, and the fast axis direction (slow axis direction in the same plane). 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.

(Production Example 1)
0.45 parts by mass of AcAAM, 14.55 parts by mass of MMA, 15.00 parts by mass of methyl ethyl ketone, and 0.03 parts by mass of azobisisobutyronitrile (AIBN) were placed 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, after the formed polymerization solution is poured into excess methanol and reprecipitated, the resulting precipitate is vacuum-dried for 1 hour under conditions of a pressure of 0.13 kPa and a temperature of 100 ° C. to remove volatile components. As a result, a solid polymer (1-1) as a precursor polymer was obtained. The Tg of the polymer (1-1) was 110 ° C. Moreover, the content rate of the AcAAM unit in a polymer (1-1) was 17.9 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 changed 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, thereby obtaining a solid polymer (1-2). The Tg of the polymer (1-2) was 138 ° C. According to the ¹ H-NMR evaluation of the polymers (1-1) and (1-2), the peak attributed to the secondary amide structure of the AcAAM unit observed in the NMR spectrum of the polymer (1-1) Disappeared in the NMR spectrum of the polymer (1-2), and in the latter NMR spectrum, a large peak attributed to the acetylamide group constituting the ring structure was newly generated at 2.49 ppm.

Next, deacylation proceeds by heating the produced polymer (1-2) in a solid state at a temperature of 240 ° C. for 2 hours under a reduced pressure of 0.13 kPa at a temperature higher than that at the time of the cyclization reaction. A solid polymer (1-3) was obtained. The Tg of the polymer (1-3) was 140 ° C. According to the IR evaluation of the polymers (1-1) to (1-3), the carbonyl group of the secondary amide ring structure that does not exist in the IR spectra of the polymers (1-1) and (1-2) The absorption peak (wave number 1780 cm ⁻¹ ) attributed to the stretching vibration of the polymer was confirmed in the IR spectrum of the polymer (1-3). That is, a pyrrolidinone ring structure having an acetylamide group as a part of the structure is formed in the main chain of the polymer by the previous heating of the polymer (1-1), and the polymer (1 -2) to form a polymer (1-3) having a deacylated pyrrolidinone ring structure (R ³ is a hydrogen atom ring structure in the structure shown in Formula (1)) in the main chain. It was confirmed that Cr of the polymer (1-3) was + 60 × 10 ⁻¹¹ Pa ⁻¹ and the polymer (1-3) had a positive intrinsic birefringence.

(Production Example 2)
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 amyl peroxyisononanoate (manufactured by Atofina Yoshitomi, trade name: Luperox 570) The reaction vessel was accommodated and the inside of the vessel was purged with nitrogen. Next, the container was heated in an oil bath at 80 ° C. for 4 hours to proceed solution polymerization of NVA and MMA. Next, after the formed polymerization solution is poured into excess methanol and reprecipitated, the resulting precipitate is vacuum-dried for 1 hour under conditions of a pressure of 0.13 kPa and a temperature of 100 ° C. to remove volatile components. As a result, a solid polymer (2-1) as a precursor polymer was obtained. The Tg of the polymer (2-1) was 114 ° C. Moreover, the content rate of the NVA unit in a polymer (2-1) was 13.1 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 changed to 0. The cyclization reaction was allowed to proceed while removing volatile components by heating at 180 ° C. for 2 hours under a reduced pressure of 13 kPa, thereby obtaining a solid polymer (2-2). The Tg of the polymer (2-2) was 131 ° C. According to ¹ H-NMR evaluation on the polymers (2-1) and (2-2), peaks attributed to the secondary amide structure of NVA units observed in the NMR spectrum of the polymer (2-1) Disappeared in the NMR spectrum of the polymer (2-2), and in the latter NMR spectrum, a large peak attributed to the acetylamide group constituting the ring structure was newly generated at 2.49 ppm.

Next, deacylation is allowed to proceed by heating the produced polymer (2-2) in a solid state at a temperature of 240 ° C. for 2 hours under a reduced pressure of 0.13 kPa at a temperature higher than that at the time of the cyclization reaction. A solid polymer (2-3) was obtained. Tg of the polymer (2-3) was 144 ° C. According to the IR evaluation for the polymers (2-1) to (2-3), the carbonyl group of the secondary amide ring structure that does not exist in the IR spectra of the polymers (2-1) and (2-2) The absorption peak (wave number 1780 cm ⁻¹ ) attributed to the stretching vibration of the polymer was confirmed in the IR spectrum of the polymer (2-3). That is, a pyrrolidinone ring structure having an acetylamide group as a part of the structure is formed in the main chain of the polymer by the previous heating of the polymer (2-1), and the polymer (2 It was confirmed that the polymer (2-3) having a deacylated pyrrolidinone ring structure in the main chain was formed by the subsequent heating with respect to -2. The polymer (2-3) had a Cr of + 75 × 10 ⁻¹¹ Pa ⁻¹ and the polymer (2-3) had a positive intrinsic birefringence.

(Production Example 3)
3.20 parts by weight of NVA, 4.80 parts by weight of MMA, 12.00 parts by weight of methyl ethyl ketone and 0.016 parts by weight of tertiary amyl peroxyisonononanoate (manufactured by Atofina Yoshitomi, trade name: Luperox 570) The reaction vessel was accommodated and the inside of the vessel was purged with nitrogen. Next, the container was heated in an oil bath at 80 ° C. for 4 hours to proceed solution polymerization of NVA and MMA. Next, after the formed polymerization solution is poured into excess methanol and reprecipitated, the resulting precipitate is vacuum-dried for 1 hour under conditions of a pressure of 0.13 kPa and a temperature of 100 ° C. to remove volatile components. As a result, a solid polymer (3-1) as a precursor polymer was obtained. The Tg of the polymer (3-1) was 114 ° C. Moreover, the content rate of the NVA unit in a polymer (3-1) was 18.7 mass%.

Next, 10.00 parts by mass of the produced polymer (3-1), 0.02 parts by mass of zinc octylate as a cyclization and deacylation catalyst, 72.00 parts by mass of acetone and 18.00 parts by mass of methanol. The polymer was dissolved in a part of the mixed solvent and heated at 180 ° C. for 2 hours under a reduced pressure of 0.13 kPa to allow the cyclization reaction to proceed while removing the volatile component, so that a solid polymer (3-2) Got. The Tg of the polymer (3-2) was 137 ° C. According to ¹ H-NMR evaluation on the polymers (3-1) and (3-2), a peak attributed to the secondary amide structure of NVA unit observed in the NMR spectrum of the polymer (3-1) Disappeared in the NMR spectrum of the polymer (3-2), and in the latter NMR spectrum, a large peak attributed to the acetylamide group constituting the ring structure was newly generated at 2.49 ppm.

Next, deacylation is allowed to proceed by heating the produced polymer (3-2) in a solid state at a temperature of 240 ° C. for 2 hours under a reduced pressure of 0.13 kPa at a temperature higher than that at the time of the cyclization reaction. A solid polymer (3-3) was obtained. The Tg of the polymer (3-3) was 165 ° C. According to the IR evaluation for the polymers (3-1) to (3-3), the carbonyl group of the secondary amide ring structure that does not exist in the IR spectra of the polymers (3-1) and (3-2) The absorption peak (wave number 1780 cm ⁻¹ ) attributed to the stretching vibration of the polymer was confirmed in the IR spectrum of the polymer (3-3). That is, a pyrrolidinone ring structure having an acetylamide group as a part of the structure is formed in the main chain of the polymer by the previous heating of the polymer (3-1), and the polymer (3 It was confirmed that the polymer (3-3) having a deacylated pyrrolidinone ring structure in the main chain was formed by the subsequent heating with respect to 2). Cr of the polymer (3-3) was + 116 × 10 ⁻¹¹ Pa ⁻¹ and the polymer (3-3) had positive intrinsic birefringence.

(Production 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 amyl peroxyisononanoate (manufactured by Atofina Yoshitomi, trade name: Luperox 570) The reaction vessel was accommodated and the inside of the vessel was purged with nitrogen. Next, the container was heated in an oil bath at 80 ° C. for 4 hours to proceed solution polymerization of NVA and MMA. Next, after the formed polymerization solution is poured into excess methanol and reprecipitated, the resulting precipitate is vacuum-dried for 1 hour under conditions of a pressure of 0.13 kPa and a temperature of 100 ° C. to remove volatile components. As a result, a solid polymer (4-1) as a precursor polymer was obtained. The Tg of the polymer (4-1) was 113 ° C. Moreover, the content rate of the NVA unit in a polymer (4-1) was 8.0 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 changed 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, thereby obtaining a solid polymer (4-2). The Tg of the polymer (4-2) was 128 ° C. According to ¹ H-NMR evaluation on the polymers (4-1) and (4-2), the peak attributed to the secondary amide structure of NVA unit observed in the NMR spectrum of the polymer (4-1) Disappeared in the NMR spectrum of the polymer (4-2), and in the latter NMR spectrum, a large peak attributed to the acetylamide group constituting the ring structure was newly generated at 2.49 ppm.

Next, deacylation proceeds by heating the produced polymer (4-2) in a solid state at a temperature of 240 ° C. for 2 hours under a reduced pressure of 0.13 kPa at a temperature higher than that at the time of the cyclization reaction. A solid polymer (4-3) was obtained. The Tg of the polymer (4-3) was 137 ° C. According to the IR evaluation of the polymers (4-1) to (4-3), the carbonyl group of the secondary amide ring structure that does not exist in the IR spectra of the polymers (4-1) and (4-2) The absorption peak (wave number 1780 cm ⁻¹ ) attributed to the stretching vibration of the polymer was confirmed in the IR spectrum of the polymer (4-3). That is, a pyrrolidinone ring structure having an acetylamide group as a part of the structure is formed in the main chain of the polymer by the previous heating of the polymer (4-1), and the polymer (4 It was confirmed that the polymer (4-3) having a deacylated pyrrolidinone ring structure in the main chain was formed by the subsequent heating with respect to -2. The polymer (4-3) had a Cr of + 39 × 10 ⁻¹¹ Pa ⁻¹ and the polymer (4-3) had a positive intrinsic birefringence.

(Production Example 5)
MMA 40 mass parts, 2- (hydroxymethyl) methyl acrylate (MHMA) 10 mass parts, toluene 50 mass parts as a polymerization solvent in a 1000 L internal reaction vessel equipped with a stirrer, temperature sensor, cooling pipe and nitrogen introduction pipe And 0.025 mass part of antioxidant (Adeka Stub 2112, made by ADEKA) was prepared, and it heated up to 105 degreeC, supplying nitrogen to this. When the reflux accompanying the temperature increase started, 0.05 parts by mass of t-amylperoxyisononanoate (manufactured by Arkema Yoshitomi, trade name: Luperox 570) was added as a polymerization initiator, and the above-mentioned t-amylperoxyisononoate was added. While 0.10 parts by mass of nanoate was added dropwise over 3 hours, solution polymerization was allowed to proceed under reflux at about 105 to 110 ° C., followed by further aging for 4 hours.

  Next, 0.05 parts by mass of 2-ethylhexyl phosphate (Phoslex A-8, manufactured by Sakai Chemical Industry Co., Ltd.) as a catalyst is added to the resulting polymerization solution, and the lactone ring is refluxed at about 90 to 110 ° C. for 2 hours. The cyclized condensation reaction to form the structure was allowed to proceed. Next, the obtained polymerization solution was heated to 240 ° C. using an autoclave, and the cyclization condensation reaction was further advanced at the temperature.

  Next, the obtained polymerization solution was subjected to a barrel temperature of 240 ° C., a rotation speed of 100 rpm, a degree of vacuum of 13.3 to 400 hPa (10 to 300 mmHg), a rear vent number of 1 and a forevent number of 4 (first and 2 and 3rd and 4th vents) are introduced into a vent type screw twin screw extruder (φ = 50.0 mm, L / D = 30) at a processing rate of 45 kg / hr (resin amount conversion) Volatilization was performed. At that time, a separately prepared mixed solution of antioxidant / lactone cyclization catalyst deactivator was charged at a rate of 0.68 kg / hr after the first vent, and then ion-exchanged water was 0.22 kg / hr. After the second and third vents, the charging was performed at the charging speed. In the mixed solution of the antioxidant / lactone cyclization catalyst deactivator, 50 parts by mass of an antioxidant (manufactured by Ciba Specialty Chemicals, Irganox 1010) and 35 parts by mass of zinc octylate (Nippon Chemical Co., Ltd.) A solution prepared by dissolving Nikka octix zinc (manufactured by Industrial Co., Ltd., 3.6% by mass) in 200 parts by mass of toluene was used.

  After completion of devolatilization, the resin in the molten state remaining in the extruder is discharged from the tip of the extruder, pelletized by a pelletizer, and (meth) acrylic polymer pellets having a lactone ring structure in the main chain Obtained.

Example 1
As a polymer (A), 8.40 parts by mass of the polymer (1-3) produced in Production Example 1 was dissolved in 75.60 parts by mass of acetone. This solution and a styrene-acrylonitrile copolymer which is a polymer (B-1) having an aromatic vinyl compound unit as a structural unit (styrene / acrylonitrile ratio is 73 mass% / 27 mass%, weight average molecular weight 220,000) A solution obtained by dissolving 1.60 parts by mass in 14.40 parts by mass of acetone was mixed. Next, the obtained mixed solution was heated for 1 hour under conditions of a pressure of 0.13 kPa and a temperature of 240 ° C. to remove volatile components, and a transparent and solid resin composition (C-1) was obtained. The resin composition (C-1) includes a polymer (1-3) and a styrene-acrylonitrile copolymer (B-1). Only one point of Tg of 136 ° C. was confirmed for the Tg of the resin composition (C-1), that is, the polymer (1-3) and the styrene-acrylonitrile copolymer (B-1) were compatible in the composition. It was confirmed that it was in a state. The Cr of the resin composition (C-1) was + 2 × 10 ⁻¹¹ Pa ^−1, that is, the intrinsic birefringence of the resin composition (C-1) was near zero.

(Example 2)
As a polymer (A), 8.10 parts by mass of the polymer (2-3) produced in Production Example 2 was dissolved in 72.90 parts by mass of acetone. This solution was mixed with a solution obtained by dissolving 1.90 parts by mass of polymer (B-1) having an aromatic vinyl compound unit as a constituent unit in 17.10 parts by mass of acetone. Next, the obtained mixed solution was heated for 1 hour under conditions of a pressure of 0.13 kPa and a temperature of 240 ° C. to remove volatile components, thereby obtaining a transparent and solid resin composition (C-2). The resin composition (C-2) contains a polymer (2-3) and a styrene-acrylonitrile copolymer (B-1). Only one point of Tg of 136 ° C. was confirmed for the Tg of the resin composition (C-2), that is, the polymer (2-3) and the styrene-acrylonitrile copolymer (B-1) were compatible in the composition. It was confirmed that it was in a state. Cr of the resin composition (C-2) was −4 × 10 ⁻¹¹ Pa ^−1, that is, the intrinsic birefringence of the resin composition (C-2) was in the vicinity of zero.

(Example 3)
As a polymer (A), 7.90 parts by mass of the polymer (2-3) produced in Production Example 2 was dissolved in 71.10 parts by mass of cyclopentanone. This solution and a styrene-acrylonitrile-phenylmaleimide copolymer (styrene / acrylonitrile / phenylmaleimide ratio is 54% by mass / 14% by mass /%) which is a polymer (B-2) having an aromatic vinyl compound unit as a constituent unit. 32 mass%, weight average molecular weight 190,000) A solution in which 2.10 mass parts was dissolved in 18.90 mass parts of cyclopentanone was mixed. Next, the obtained mixed solution was heated for 1 hour under conditions of a pressure of 0.13 kPa and a temperature of 240 ° C. to remove volatile components, thereby obtaining a transparent and solid resin composition (C-3). The resin composition (C-3) includes a polymer (2-3) and a styrene-acrylonitrile-phenylmaleimide copolymer (B-2). As for Tg of the resin composition (C-3), only one point of 144 ° C. was confirmed, that is, in the composition, the polymer (2-3) and the styrene-acrylonitrile-phenylmaleimide copolymer (B-2) were It was confirmed that they were in a compatible state. Cr of the resin composition (C-3) was + 11 × 10 ⁻¹¹ Pa ^−1, that is, the intrinsic birefringence of the resin composition (C-3) was in the vicinity of zero.

Example 4
As a polymer (A), 6.80 parts by mass of the polymer (3-3) prepared in Production Example 3 was dissolved in 61.20 parts by mass of cyclopentanone. This solution and a styrene-acrylonitrile-phenylmaleimide copolymer (the ratio of styrene / acrylonitrile / phenylmaleimide is 50% by mass / 10% by mass / a) which is a polymer (B-3) having an aromatic vinyl compound unit as a constituent unit. 40% by mass, weight average molecular weight 190,000) 3.20 parts by mass of cyclopentanone dissolved in 28.80 parts by mass was mixed. Next, the obtained mixed solution was heated under the conditions of a pressure of 0.13 kPa and a temperature of 240 ° C. for 1 hour to remove volatile components, thereby obtaining a transparent and solid resin composition (C-4). The resin composition (C-4) contains a polymer (3-3) and a styrene-acrylonitrile-phenylmaleimide copolymer (B-3). Only one point of Tg of the resin composition (C-4) was confirmed at 165 ° C., that is, in the composition, the polymer (3-3) and the styrene-acrylonitrile-phenylmaleimide copolymer (B-3) were It was confirmed that they were in a compatible state. The Cr of the resin composition (C-4) was + 11 × 10 ⁻¹¹ Pa ^−1, that is, the intrinsic birefringence of the resin composition (C-4) was near zero.

(Example 5)
As a polymer (A), 5.00 parts by mass of the polymer (1-3) produced in Production Example 1 was dissolved in 45.00 parts by mass of acetone. This solution was mixed with a solution obtained by dissolving 5.00 parts by mass of polymer (B-1) having an aromatic vinyl compound unit as a structural unit in 45.00 parts by mass of acetone. Next, the obtained mixed solution was heated under the conditions of a pressure of 0.13 kPa and a temperature of 240 ° C. for 1 hour to remove volatile components, thereby obtaining a transparent and solid resin composition (C-5). The resin composition (C-5) includes a polymer (1-3) and a styrene-acrylonitrile copolymer (B-1). Only one point of Tg of the resin composition (C-5) was confirmed at 124 ° C., that is, the polymer (1-3) and the styrene-acrylonitrile copolymer (B-1) were compatible in the composition. It was confirmed that it was in a state. The Cr of the resin composition (C-5) is −111 × 10 ⁻¹¹ Pa ^−1, that is, the intrinsic birefringence of the resin composition (C-5) is sufficiently negative to form a negative retardation film. there were.

(Example 6)
As a polymer (A), 5.00 parts by mass of the polymer (4-3) produced in Production Example 4 was dissolved in 45.00 parts by mass of acetone. This solution was mixed with a solution obtained by dissolving 5.00 parts by mass of polymer (B-1) having an aromatic vinyl compound unit as a structural unit in 45.00 parts by mass of acetone. Next, the obtained mixed solution was heated for 1 hour under conditions of a pressure of 0.13 kPa and a temperature of 240 ° C. to remove volatile components, thereby obtaining a transparent and solid resin composition (C-6). The resin composition (C-6) includes a polymer (4-3) and a styrene-acrylonitrile copolymer (B-1). As for Tg of the resin composition (C-6), only one point at 121 ° C. was confirmed, that is, the polymer (4-3) and the styrene-acrylonitrile copolymer (B-1) were compatible in the composition. It was confirmed that it was in a state. The Cr of the resin composition (C-6) is −136 × 10 ⁻¹¹ Pa ^−1, that is, the intrinsic birefringence of the resin composition (C-6) is sufficiently negative to form a negative retardation film. there were.

(Comparative Example 1)
5.00 parts by mass of commercially available polymethyl methacrylate (PMMA, Sumipex EX manufactured by Sumitomo Chemical Co., Ltd.) was dissolved in 45.00 parts by mass of cyclopentanone. This solution was mixed with a solution obtained by dissolving 5.00 parts by mass of polymer (B-2) having an aromatic vinyl compound unit as a structural unit in 45.00 parts by mass of cyclopentanone. Next, the obtained mixed solution was heated for 1 hour under conditions of a pressure of 0.13 kPa and a temperature of 240 ° C. to remove volatile components to obtain a solid resin composition (E-1). The thing (E-1) was cloudy. Moreover, since two Tg was measured, it was judged that the compatibility between PMMA and a polymer (B-2) was not able to be ensured.

(Comparative Example 2)
Commercially available PMMA (Sumitomo Chemical Sumipex EX) (5.00 parts by mass) was dissolved in cyclopentanone (45.00 parts by mass). This solution was mixed with a solution obtained by dissolving 5.00 parts by mass of polymer (B-3) having an aromatic vinyl compound unit as a structural unit in 45.00 parts by mass of cyclopentanone. Next, the obtained mixed solution was heated for 1 hour under conditions of a pressure of 0.13 kPa and a temperature of 240 ° C. to remove volatile components, and a solid resin composition (E-2) was obtained. Product (E-2) was cloudy. Moreover, since two Tg was measured, it was judged that the compatibility between PMMA and a polymer (B-3) was not able to be ensured.

(Comparative Example 3)
5.00 parts by mass of the (meth) acrylic polymer having a lactone ring structure in the main chain, prepared in Production Example 5, was dissolved in 45.00 parts by mass of cyclopentanone. This solution was mixed with a solution obtained by dissolving 5.00 parts by mass of polymer (B-3) having an aromatic vinyl compound unit as a structural unit in 45.00 parts by mass of cyclopentanone. Next, the obtained mixed solution was heated for 1 hour under conditions of a pressure of 0.13 kPa and a temperature of 240 ° C. to remove volatile components, and a solid resin composition (E-3) was obtained. The thing (E-3) was cloudy. Moreover, since two Tg were measured, it was judged that the compatibility between the (meth) acrylic polymer having a lactone ring structure in the main chain and the polymer (B-3) could not be secured.

  The compositions and properties of the respective polymers and resin compositions prepared in Production Examples, Examples and Comparative Examples are summarized in Table 1 and Table 2 below. Note that “-” in Table 2 indicates that measurement is impossible.

  As shown in Tables 1 and 2, the resin compositions of Examples 1 to 6 ensured optical transparency while achieving a high Tg of 120 ° C. or higher. In addition, by changing the content (mixing ratio, composition) of the polymer (A) and the polymer (B), Cr can be realized from an optical film showing a retardation value near zero to a negative retardation film. It was confirmed that the value could be taken. On the other hand, in the resin composition of Comparative Examples 1-3, the compatibility between polymers was not securable. Further, from the viewpoint of the composition of the polymer (B), even in the composition of the polymer (B) in which compatibility could not be ensured with the resin composition of the comparative example, the resin compositions of Examples 1 to 6 were in phase. It was confirmed that the solubility was ensured.

  The resin composition of this invention can be used for the use of an optical member, for example. The optical member is, for example, a lens, a prism, an optical fiber, or an optical film.

Claims (20)

A polymer (A) having a lactam ring structure in the main chain;
And a polymer (B) having an aromatic vinyl compound unit as a constituent unit.   The resin composition according to claim 1, wherein the lactam ring structure is a pyrrolidinone ring structure. The resin composition according to claim 2, wherein the pyrrolidinone ring structure is a ring structure represented by the following formula (1).

In Formula (1), R ¹ is a hydrogen atom, a methyl group, or a —NHCOR 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 carbon number 3 to 18 cycloalkyl groups. R ² is a hydrogen atom or a —COOR ⁵ group, and R 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 ³ is a hydrogen atom or —COR ⁶ group, and R ⁶ 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 include the carbon atom at the 3-position of one of the ring structures and the other ring structure. A spiro ring structure in which the carbon atom at the 5th position is the same carbon atom is formed, and R ¹ bonded to the carbon atom at the 3rd position and R ² bonded to the carbon atom at the 5th position do not exist. The resin composition according to claim 3, wherein, in the formula (1), R ² is the —COOR ⁵ group. The resin composition according to claim 3, wherein, in the formula (1), R ¹ is a methyl group or a —NHCOCH ₃ group, and R ² is a —COOCH ₃ group. The resin composition according to claim 3, wherein, in the formula (1), R ¹ is a methyl group and R ² is a hydrogen atom. In the formula (1), the resin composition according to any one of claims 3 to 6 R ³ is a hydrogen atom.   The resin composition according to any one of claims 1 to 7, wherein the polymer (A) further comprises a (meth) acrylic acid ester unit as a constituent unit.   The resin composition according to claim 8, wherein the (meth) acrylic acid ester unit is a methyl methacrylic acid (MMA) unit.   The resin composition according to any one of claims 1 to 9, wherein the polymer (B) further has a vinyl cyanide unit as a constituent unit.   The resin composition according to any one of claims 1 to 10, wherein the polymer (B) further has an N-substituted maleimide unit as a constituent unit.   The resin composition according to claim 1, which has a glass transition temperature of 110 ° C. or higher.   The resin composition according to any one of claims 1 to 12, wherein a 5% heat loss temperature obtained by a thermogravimetric method defined in JIS K7120 is 250 ° C or higher. The resin composition according to claim 1, wherein the absolute value of the stress optical coefficient (Cr) is 13 × 10 ⁻¹¹ Pa ⁻¹ or less. Has negative intrinsic birefringence,
The resin composition according to claim 1, wherein the absolute value of the stress optical coefficient (Cr) is 100 × 10 ⁻¹¹ Pa ⁻¹ or more.   The optical film comprised from the resin composition in any one of Claims 1-15.   The optical film according to claim 16, which is a negative retardation film.   The optical film according to claim 16, which is a polarizer protective film. A polarizer,
A polarizing plate comprising: an optical film which is a polarizer protective film according to claim 18 and is laminated on at least one main surface of the polarizer. An image display apparatus provided with the optical film in any one of Claims 16-18.