JP2011184662A - Resin composition and film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition giving a film suitable for an optical film such as a polarizing plate protective film and a retardation film, and to provide a film formed from the composition. <P>SOLUTION: The resin composition contains an aliphatic polyester resin, an acrylic resin and a compound containing at least a cyclic structure having one carbodiimide group, wherein the first nitrogen and the second nitrogen thereof are bonded by bonding groups. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a resin composition capable of providing a film suitable for an optical film such as a polarizing plate protective film and a retardation film, and a film comprising the same.

  In recent years, biodegradable polymers that are decomposed in a natural environment have attracted attention from the viewpoint of global environmental conservation, and various biodegradable polymers have been developed. Among them, polylactic acid has good transparency, can be melt-molded, can be produced economically by fermentation using biomass as a raw material, and is expected to be used as an optical material.

  Recently, for example, with the expansion of the display market, there is an increasing demand for a clearer image, and there is a demand for a material with higher optical properties in addition to simple transparency.

  In general, a polymer generates birefringence because its refractive index is different between the molecular main chain direction and the direction perpendicular thereto. Depending on the application, it is required to strictly control birefringence, and in the case of a polarizing plate protective film used for a polarizing plate of liquid crystal, low birefringence is required.

  As a polarizing plate protective film, a triacetyl cellulose (TAC) film has been often used so far. In recent years, with the widespread use of various types of displays such as large liquid crystal displays and plasma displays, it has become necessary to increase the size of necessary films and reduce the distribution of fluctuations in birefringence. Therefore, there is a demand for a material that has a small change in birefringence due to an external force, good dimensional stability during heating, and a small change in birefringence due to thermal stress. That is, an optical material having a low photoelastic coefficient and a low thermal shrinkage rate is demanded.

  As optical materials having a low photoelastic coefficient, homopolymers (PMMA) of the aforementioned TAC and methyl methacrylate are known. Further, amorphous polyolefin (APO) is known (Non-Patent Document 1). However, these materials still have a problem that the birefringence change due to external force is large or the polarity is too low.

In order to solve this problem, a material comprising an aliphatic polyester and an acrylic resin has been proposed. The photoelastic coefficient of the film made of this material is more than −13 × 10 ⁻¹² / Pa and less than about 12 × 10 ⁻¹² / Pa (see Patent Document 1).

  However, aliphatic polyester is known to be prone to hydrolysis when used in a hot and humid atmosphere. When used in such an environment, the hydrolysis resistance is reduced by some means. There is a need to improve.

  As a technique for improving the hydrolysis resistance of the aliphatic polyester, it has been proposed to add a carbodiimide compound (Patent Document 2).

  The carbodiimide compound used in this proposal is a linear carbodiimide compound, but when this on-line carbodiimide compound is used as a terminal blocker of a polymer compound, the carbodiimide compound binds to the terminal of the polymer compound. Along with this, there is a problem that the compound having an isocyanate group is liberated, a unique odor of the isocyanate compound is generated, and the working environment is deteriorated.

JP 2006-227090 A JP 2003-003052 A

Chemical Review, No. 39, 1998 (published by Academic Publishing Center)

  The object of the present invention is to eliminate the problems of the prior art, improve the hydrolysis resistance without deteriorating the working environment, and provide a resin composition that can provide a film suitable for optical applications. And a film comprising the same.

As a result of intensive studies, the present inventors have completed the present invention. That is, the object of the present invention is to
Aliphatic polyester resin (component A), acrylic resin (component B), compound having at least a cyclic structure in which one carbodiimide group is bonded to the first nitrogen and the second nitrogen by a bonding group (C Component).
Moreover, the other objective of this invention can be achieved by the film which consists of the said composition.

  According to the present invention, it is possible to provide a resin composition capable of providing a film suitable for optical applications and a film comprising the resin composition, with improved hydrolysis resistance without deteriorating the working environment.

Hereinafter, the present invention will be described in detail.
<C component>
First, a compound (C component) that is a characteristic component in the present invention and includes at least a cyclic structure in which one carbodiimide group is included and the first nitrogen and the second nitrogen are bonded by a bonding group will be described. The C component has a cyclic structure (hereinafter, the C component may be abbreviated as a cyclic carbodiimide compound). The cyclic carbodiimide compound may have a plurality of cyclic structures.

  Here, the cyclic structure has one carbodiimide group (—N═C═N—), and the first nitrogen and the second nitrogen are bonded by a bonding group. One cyclic structure has only one carbodiimide group. The number of atoms in the cyclic structure is preferably 8 to 50, more preferably 10 to 30, further preferably 10 to 20, and particularly preferably 10 to 15.

  Here, the number of atoms in the cyclic structure means the number of atoms that directly constitute the cyclic structure. For example, it is 8 for an 8-membered ring and 50 for a 50-membered ring. This is because if the number of atoms in the cyclic structure is smaller than 8, the stability of the cyclic carbodiimide compound is lowered, and it may be difficult to store and use. From the viewpoint of reactivity, there is no particular restriction on the upper limit of the number of ring members, but cyclic carbodiimide compounds having more than 50 atoms are difficult to synthesize, and the cost may increase significantly. From this viewpoint, the number of atoms in the cyclic structure is preferably 10-30, more preferably 10-20, and particularly preferably 10-15.

The cyclic structure is preferably a structure represented by the following formula (1).

  In the formula, Q is a divalent to tetravalent linking group that is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, each of which may contain a hetero atom and a substituent. A heteroatom in this case refers to O, N, S, P. Two of the valences of this linking group are used to form a cyclic structure. When Q is a trivalent or tetravalent linking group, it is bonded to a polymer or other cyclic structure via a single bond, a double bond, an atom, or an atomic group.

  The linking group may include a heteroatom and a substituent, each having a divalent to tetravalent carbon number of 1 to 20 aliphatic group, a divalent to tetravalent carbon number of 3 to 20 alicyclic group, A linking group which is a tetravalent aromatic group having 5 to 15 carbon atoms or a combination thereof and has a necessary number of carbon atoms to form the cyclic structure defined above is selected. Examples of combinations include structures such as an alkylene-arylene group in which an alkylene group and an arylene group are bonded.

The linking group (Q) is preferably a divalent to tetravalent linking group represented by the following formula (1-1), (1-2) or (1-3).

In the formula, Ar ¹ and Ar ² are each independently a 2- to 4-valent aromatic group having 5 to 15 carbon atoms which may contain a hetero atom and a substituent.

  As an aromatic group, each of which contains a hetero atom and may have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, an arenetetra having 5 to 15 carbon atoms Yl group. Examples of the arylene group (divalent) include a phenylene group and a naphthalenediyl group. Examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group. Examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

R ¹ and R ² each independently contain a heteroatom and a substituent, each having 2 to 4 valent aliphatic groups having 1 to 20 carbon atoms and 2 to 4 valent fatty acids having 3 to 20 carbon atoms A cyclic group, and a combination thereof, or a combination of the aliphatic group, the alicyclic group, and a divalent to tetravalent aromatic group having 5 to 15 carbon atoms.

  Examples of the aliphatic group include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, and an alkanetetrayl group having 1 to 20 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and a hexadecylene group. As the alkanetriyl group, methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group, Examples include a hexadecantriyl group. As alkanetetrayl group, methanetetrayl group, ethanetetrayl group, propanetetrayl group, butanetetrayl group, pentanetetrayl group, hexanetetrayl group, heptanetetrayl group, octanetetrayl group, nonanetetrayl group Decanetetrayl group, dodecanetetrayl group, hexadecanetetrayl group and the like. These aliphatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

  Examples of the alicyclic group include a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkanetriyl group having 3 to 20 carbon atoms, and a cycloalkanetetrayl group having 3 to 20 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclododecylene group, and a cyclohexadecylene group. As the alkanetriyl group, cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group , Cyclododecanetriyl group, cyclohexadecanetriyl group and the like. As the alkanetetrayl group, cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group Group, cyclododecanetetrayl group, cyclohexadecanetetrayl group and the like. These alicyclic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

  As an aromatic group, each of which contains a hetero atom and may have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, an arenetetra having 5 to 15 carbon atoms Yl group. Examples of the arylene group include a phenylene group and a naphthalenediyl group. Examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group. Examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

In the above formulas (1-1) and (1-2), X ¹ and X ² are each independently a divalent to tetravalent C 1-20 aliphatic optionally containing a hetero atom and a substituent. Group, a C2-C20 alicyclic group having 2 to 4 carbon atoms, a C2-C15 aromatic group having 2 to 4 carbon atoms, or a combination thereof.

  Examples of the aliphatic group include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, and an alkanetetrayl group having 1 to 20 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and a hexadecylene group. As the alkanetriyl group, methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group, Examples include a hexadecantriyl group. As alkanetetrayl group, methanetetrayl group, ethanetetrayl group, propanetetrayl group, butanetetrayl group, pentanetetrayl group, hexanetetrayl group, heptanetetrayl group, octanetetrayl group, nonanetetrayl group Decanetetrayl group, dodecanetetrayl group, hexadecanetetrayl group and the like. These aliphatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

  Examples of the alicyclic group include a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkanetriyl group having 3 to 20 carbon atoms, and a cycloalkanetetrayl group having 3 to 20 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclododecylene group, and a cyclohexadecylene group. As the alkanetriyl group, cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group , Cyclododecanetriyl group, cyclohexadecanetriyl group and the like. As the alkanetetrayl group, cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group Group, cyclododecanetetrayl group, cyclohexadecanetetrayl group and the like. These alicyclic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

  As an aromatic group, each of which contains a hetero atom and may have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, an arenetetra having 5 to 15 carbon atoms Yl group. Examples of the arylene group include a phenylene group and a naphthalenediyl group. Examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group. Examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

In the above formulas (1-1) and (1-2), s and k are integers of 0 to 10, preferably 0 to 3, more preferably 0 to 1. This is because if s and k exceed 10, the cyclic carbodiimide compound is difficult to synthesize, and the cost may increase significantly. From this viewpoint, the integer is preferably selected in the range of 0 to 3. When s or k is 2 or more, X ¹ or X ² as a repeating unit may be different from other X ¹ or X ² .

In the above formula (1-3), X ³ may contain a heteroatom and a substituent, respectively, a divalent to tetravalent aliphatic group having 1 to 20 carbon atoms, and a divalent to tetravalent carbon number of 3 to 20 Are alicyclic groups, divalent to tetravalent aromatic groups having 5 to 15 carbon atoms, or combinations thereof.

  Examples of the aliphatic group include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, and an alkanetetrayl group having 1 to 20 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and a hexadecylene group. As the alkanetriyl group, methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group, Examples include a hexadecantriyl group. As alkanetetrayl group, methanetetrayl group, ethanetetrayl group, propanetetrayl group, butanetetrayl group, pentanetetrayl group, hexanetetrayl group, heptanetetrayl group, octanetetrayl group, nonanetetrayl group Decanetetrayl group, dodecanetetrayl group, hexadecanetetrayl group and the like. These aliphatic groups may contain a substituent, such as an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, or an ester group. , Ether group, aldehyde group and the like.

  Examples of the alicyclic group include a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkanetriyl group having 3 to 20 carbon atoms, and a cycloalkanetetrayl group having 3 to 20 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclododecylene group, and a cyclohexadecylene group. As the alkanetriyl group, cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group , Cyclododecanetriyl group, cyclohexadecanetriyl group and the like. As the alkanetetrayl group, cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group Group, cyclododecanetetrayl group, cyclohexadecanetetrayl group and the like. These alicyclic groups may contain a substituent, such as an alkyl group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, and an ester. Group, ether group, aldehyde group and the like.

  As an aromatic group, each of which contains a hetero atom and may have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, an arenetetra having 5 to 15 carbon atoms Yl group. Examples of the arylene group include a phenylene group and a naphthalenediyl group. Examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group. Examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ may contain a hetero atom, and when Q is a divalent linking group, Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ are all divalent groups. When Q is a trivalent linking group, one of Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ is a trivalent group. When Q is a tetravalent linking group, one of Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ is a tetravalent group or two are trivalent It is a group.

Examples of the cyclic carbodiimide compound used in the present invention include compounds represented by (a) to (c) below.
<Cyclic carbodiimide compound (a)>
Examples of the cyclic carbodiimide compound used in the present invention include a compound represented by the following formula (2) (hereinafter sometimes referred to as “cyclic carbodiimide compound (a)”).

Wherein, Q _a is an aliphatic group, an alicyclic group, an aromatic group or a divalent linking group which is a combination of these, it may contain a heteroatom. The aliphatic group, alicyclic group, and aromatic group are the same as those described in Formula (1). However, in the compound of formula (2), the aliphatic group, alicyclic group, and aromatic group are all divalent. Q _a is preferably a divalent linking group represented by the following formula (2-1), (2-2) or (2-3).

In the formula, Ar _a ¹ , Ar _a ² , R _a ¹ , R _a ² , X _a ¹ , X _a ² , X _a ³ , s and k are represented by formulas (1-1) to (1-3), respectively. Are the same as Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s and k. However, these are all divalent.

  Examples of the cyclic carbodiimide compound (a) include the following compounds.

<Cyclic carbodiimide compound (b)>
Furthermore, examples of the cyclic carbodiimide compound used in the present invention include a compound represented by the following formula (3) (hereinafter sometimes referred to as “cyclic carbodiimide compound (b)”).

Wherein, Q _b is an aliphatic group, an alicyclic group, an aromatic group or a trivalent linking group combinations thereof, and may contain a hetero atom. Y is a carrier supporting a cyclic structure. Aliphatic group in Q _b, alicyclic group, aromatic group are the same as those described in formula (1). However, in the compound of formula (3), the inner one of the group constituting the Q _b is trivalent.
Q _b is preferably a trivalent linking group represented by the following formula (3-1), (3-2) or (3-3).

In the formula, Ar _b ¹ , Ar _b ² , R _b ¹ , R _b ² , X _b ¹ , X _b ² , X _b ³ , s and k are respectively represented by the formulas (1-1) to (1-3). The same as Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s and k. However, one of these is a trivalent group.

  Y is preferably a single bond, a double bond, an atom, an atomic group or a polymer. Y is a bonding portion, and a plurality of cyclic structures are bonded via Y to form a structure represented by the formula (3).

  Examples of the cyclic carbodiimide compound (b) include the following compounds.

<Cyclic carbodiimide compound (c)>
Examples of the cyclic carbodiimide compound used in the present invention include a compound represented by the following formula (4) (hereinafter sometimes referred to as “cyclic carbodiimide compound (c)”).

In the formula, Q _c is a tetravalent linking group which is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may have a hetero atom. Z ¹ and Z ² are carriers that support a cyclic structure. Z ¹ and Z ² may be bonded to each other to form a cyclic structure.

Aliphatic group in Q _c, alicyclic group, aromatic group are the same as those described in formula (1). However, in the compound of formula (4), Q _c is tetravalent. Accordingly, one of these groups is a tetravalent group or two are trivalent groups.

Q _c is preferably a tetravalent linking group represented by the following formula (4-1), (4-2) or (4-3).

Ar _c ¹ , Ar _c ² , R _c ¹ , R _c ² , X _c ¹ , X _c ² , X _c ³ , s and k are each Ar ^{1 in} formulas (1-1) to (1-3). , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s and k are the same. Provided that Ar _c ¹ , Ar _c ² , R _c ¹ , R _c ² , X _c ¹ , X _c ² and X _c ³ are one of which is a tetravalent group or two of which are trivalent It is a group. Z ¹ and Z ² are preferably each independently a single bond, a double bond, an atom, an atomic group or a polymer. Z ¹ and Z ² are bonding portions, and a plurality of cyclic structures are bonded via Z ¹ and Z ² to form a structure represented by the formula (4).

Examples of the cyclic carbodiimide compound (c) include the following compounds.

  In the present invention, the production method of the cyclic carbodiimide compound is not particularly limited and can be produced by a conventionally known method. For example, a method for producing an amine body via an isocyanate body, a method for producing an amine body via an isothiocyanate body, a method for producing an amine body via a triphenylphosphine body, a urea body from an amine body The method of manufacturing via a thiourea body, the method of manufacturing via a thiourea body, the method of manufacturing from a carboxylic acid body via an isocyanate body, the method of manufacturing a lactam body, etc. are mentioned.

  Moreover, the cyclic carbodiimide compound of this invention can be manufactured by combining the method described in the following literature, or changing or combining suitably according to the target compound.

Tetrahedron Letters, Vol. 34, no. 32, 515-5158, 1993.
Medium- and Large-Membered Rings from Bis (iminophosphoranes): An Efficient Preparation of Cyclic Carbidiimides, Pedro Molina et al.
Journal of Organic Chemistry, Vol. 61, no. 13, 4289-4299, 1996.
New Models for the Study of the Racemization Mechanism of Carbodiimides. Synthesis and Structure (X-ray Crystallography and 1H NMR) of Cyclic Carbodiimides, Pedro Molina et al.
Journal of Organic Chemistry, Vol. 43, No8, 1944-1946, 1978.
Macrocyclic Ureas As Masked Isocynates, Henri Ulrich et al.
Journal of Organic Chemistry, Vol. 48, no. 10, 1694-1700, 1983.
Synthesis and Reactions of Cyclic Carbodiimides, R.A. Richter et al.
Journal of Organic Chemistry, Vol. 59, no. 24, 7306-7315, 1994.
A New and Efficient Preparation of Cyclic Carboxidimids from Bis (iminophosphoranea) and the System Boc2O / DMAP, Pedro Molina et al.

  Depending on the compound to be produced, an appropriate production method may be employed. For example, (1) nitrophenols represented by the following formula (a-1), nitrophenols represented by the following formula (a-2) And a compound represented by the following formula (b) to obtain a nitro compound represented by the following formula (c),

（３）得られたアミン体とトリフェニルホスフィンジブロミドを反応させ下記式（ｅ）で表されるトリフェニルホスフィン体を得る工程、および (2) A step of reducing the obtained nitro body to obtain an amine body represented by the following formula (d);

(3) a step of reacting the obtained amine body with triphenylphosphine dibromide to obtain a triphenylphosphine body represented by the following formula (e); and

（４）得られたトリフェニルホスフィン体を反応系中でイソシアネート化した後、直接脱炭酸させることによって製造したものは、本願発明に用いる環状カルボジイミド化合物として好適に用いることができる。
（上記式中、Ａｒ^１およびＡｒ^２は各々独立に、炭素数１〜６のアルキル基またはフェニル基で置換されていてもよい芳香族基である。Ｅ^１およびＥ^２は各々独立に、ハロゲン原子、トルエンスルホニルオキシ基およびメタンスルホニルオキシ基、ベンゼンスルホニルオキシ基、ｐ−ブロモベンゼンスルホニルオキシ基からなる群から選ばれる基である。Ａｒ^ａは、フェニル基である。Ｘは、下記式（ｉ−１）から（ｉ−３）の結合基である。）

(4) After the obtained triphenylphosphine body is isocyanated in the reaction system and then directly decarboxylated, it can be suitably used as the cyclic carbodiimide compound used in the present invention.
(In the above formula, Ar ¹ and Ar ² are each independently an aromatic group optionally substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group. E ¹ and E ² are each independently a halogen atom. A group selected from the group consisting of an atom, a toluenesulfonyloxy group, a methanesulfonyloxy group, a benzenesulfonyloxy group, and a p-bromobenzenesulfonyloxy group, Ar ^a is a phenyl group, X is represented by the following formula (i -1) to (i-3).

（式中、ｎは１〜６の整数である。）

(In the formula, n is an integer of 1 to 6.)

（式中、ｍおよびｎは各々独立に０〜３の整数である。）

(In the formula, m and n are each independently an integer of 0 to 3.)

（式中、Ｒ^１およびＲ^２は各々独立に、炭素数１〜６のアルキル基、フェニル基を表す。）

(In the formula, R ¹ and R ² each independently represents an alkyl group having 1 to 6 carbon atoms or a phenyl group.)

  In addition, the cyclic carbodiimide compound can effectively seal the acidic group of the polymer compound. However, as long as it does not contradict the gist of the present invention, for example, a conventionally known polymer carboxyl group sealing agent may be used. Can be used together. Examples of such conventionally known carboxyl group-capping agents include agents described in JP-A-2005-2174, such as epoxy compounds, oxazoline compounds, and oxazine compounds.

<Aliphatic polyester resin (component A)>
In the present invention, the aliphatic polyester-based resin (component A) is mainly composed of a polymer mainly composed of an aliphatic hydroxycarboxylic acid, an aliphatic polycarboxylic acid or an ester-forming derivative thereof, and an aliphatic polyhydric alcohol. Examples thereof include polymers formed by polycondensation as a component and copolymers thereof.

  Examples of the polymer having aliphatic hydroxycarboxylic acid as a main constituent component include polycondensates such as glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, and copolymers. Among them, polyglycolic acid, polylactic acid, poly-3-hydroxycarboxylic butyric acid, poly-4-polyhydroxybutyric acid, poly-3-hydroxyhexanoic acid or polycaprolactone, and copolymers thereof may be mentioned. It can be suitably used for lactic acid, poly-D-lactic acid, stereocomplex polylactic acid forming a stereocomplex crystal, and racemic polylactic acid.

  The polylactic acid may be one having L-lactic acid and / or D-lactic acid as the main repeating unit, and particularly preferably has a melting point of 150 ° C. or higher (here, the main is Means that the component occupies 50% or more). When the melting point is lower than 150 ° C., the dimensional stability, high temperature mechanical properties, etc. of the film cannot be improved.

  Poly L monolactic acid and poly D-lactic acid can be produced by a conventionally known method. For example, L- or D-lactide can be heated in the presence of a metal-containing catalyst and produced by ring-opening polymerization. In addition, after crystallizing a low molecular weight polylactic acid containing a metal-containing catalyst, it is heated under reduced pressure or pressure, in the presence or absence of an inert gas stream. It can also be produced by solid phase polymerization. Further, it can be produced by a direct polymerization method in which lactic acid is subjected to dehydration condensation in the presence / absence of an organic solvent.

  The polymerization reaction can be carried out in a conventionally known reaction vessel. For example, a vertical reactor or a horizontal reactor having a high-viscosity stirring blade such as a helical ribbon blade can be used alone or in parallel. . Moreover, any of a batch type, a continuous type, a semibatch type may be sufficient, and these may be combined.

  Alcohol may be used as a polymerization initiator. Such alcohol is preferably non-volatile without inhibiting the polymerization of polylactic acid. For example, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol and the like can be suitably used.

  In the solid phase polymerization method, polylactic acid having a relatively low molecular weight (about 15 to 200) obtained by the above-described ring-opening polymerization method or direct polymerization method of lactic acid is used as a prepolymer. The prepolymer is preferably crystallized in advance in the temperature range of the glass transition temperature or higher and lower than the melting point from the viewpoint of preventing resin pellet fusion. The crystallized prepolymer is filled in a fixed vertical or horizontal reaction vessel, or a reaction vessel (such as a rotary kiln) in which the vessel itself rotates, such as a tumbler or kiln. Heated to a temperature range. There is no problem even if the polymerization temperature is increased in stages as the polymerization proceeds. In addition, for the purpose of efficiently removing water generated during solid phase polymerization, a method of reducing the pressure inside the reaction vessels or circulating a heated inert gas stream is also preferably used.

It is preferable to inactivate the metal-containing catalyst used during the polymerization of polylactic acid with a conventionally known deactivator prior to use, because the stability of polylactic acid and the resin composition to heat and moisture can be improved.
Examples of such a deactivator include an organic ligand having a group of chelate ligands having an imino group and capable of coordinating with a polymerized metal catalyst.

  Also, dihydridooxoline (I) acid, dihydridotetraoxodiphosphorus (II, II) acid, hydridotrioxoline (III) acid, dihydridopentaoxodiphosphoric acid (III), hydridopentaoxodi (II, IV) Acid, dodecaoxohexaphosphoric acid (III), hydridooctaoxotriphosphoric acid (III, IV, IV) acid, octaoxotriphosphoric acid (IV, III, IV) acid, hydridohexaoxodiphosphoric acid (III, V) acid, hexaoxodiacid Low oxidation number phosphoric acid having an acid number of 5 or less, such as phosphoric acid (IV), decaoxotetraphosphoric acid (IV), hedecaoxotetraphosphoric acid (IV), and eneoxooxophosphoric acid (V, IV, IV). .

Further, orthophosphoric acid represented by the formula xH ₂ O · yP ₂ O ₅ , x / y = 3, 2> x / y> 1, and diphosphoric acid, triphosphoric acid, tetraphosphoric acid, five Examples thereof include polyphosphoric acid called phosphoric acid and a mixture thereof.

Further, metaphosphoric acid represented by x / y = 1, in particular, trimetaphosphoric acid, tetrametaphosphoric acid, 1> x / y> 0, and ultralin having a network structure in which a part of the phosphorus pentoxide structure is left. Acid (these may be collectively referred to as metaphosphoric acid compounds).
Moreover, acidic salts of these acids, monovalent and polyhydric alcohols, partial esters of polyalkylene glycols, complete esters, phosphono-substituted lower aliphatic carboxylic acid derivatives and the like can be mentioned.

  Metaphosphoric acid compounds include cyclic metaphosphoric acid condensed with about 3 to 200 phosphoric acid units, ultra-regional metaphosphoric acid having a three-dimensional network structure, or their (alkal metal salt, alkaline earth metal salt, onium salt). Include. Of these, cyclic sodium metaphosphate, ultra-region sodium metaphosphate, phosphono-substituted lower aliphatic carboxylic acid derivative dihexylphosphonoethyl acetate (hereinafter sometimes abbreviated as DHPA) and the like are preferably used.

  Preferably, the melting point of polylactic acid is 170 ° C. or higher, more preferably 200 ° C. or higher. Here, the melting point means the peak temperature of the melting peak obtained by DSC measurement. In particular, in order to impart heat resistance, it is preferable that polylactic acid forms a stereocomplex phase crystal.

  Here, the stereocomplex polylactic acid is a eutectic formed by a poly L lactic acid segment and a poly D lactic acid segment.

  Stereocomplex phase crystals usually have a higher melting point than homophase crystals formed solely by poly L lactic acid or poly D lactic acid, so that even if they are contained in a slight amount, the effect of increasing heat resistance can be expected. This is remarkably exhibited when the amount of stereocomplex phase crystals is large relative to the amount of crystals. The stereocomplex crystallinity (S) according to the following formula is preferably 95% or more, and more preferably 100%.

S = [ΔHms / (ΔHmh + ΔHms)] × 100
(However, ΔHms is the melting enthalpy of stereocomplex phase crystals, and ΔHmh is the melting enthalpy of homophase polylactic acid crystals.)
In order to stably and highly advance the formation of stereocomplex polylactic acid crystals, a method of blending specific additives is preferably applied.

That is, for example, a technique of adding a metal phosphate metal salt represented by the following formula as a stereocomplex crystallization accelerator can be mentioned.

In the formula, R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹² and R ¹³ each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and M ₁ represents Represents an alkali metal atom, alkaline earth metal atom, zinc atom or aluminum atom, t represents 1 or 2, u represents 0 when M ₁ is an alkali metal atom, alkaline earth metal atom or zinc atom; When it is an atom, it represents 1 or 2.

In the formula, each of R ¹⁴ , R ¹⁵ and R ¹⁶ independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and M ₂ represents an alkali metal atom, an alkaline earth metal atom, a zinc atom or an aluminum atom. , T represents 1 or 2, u represents 0 when M ₂ is an alkali metal atom, alkaline earth metal atom, or zinc atom, and represents 1 or 2 when M ₂ is an aluminum atom.

M ₁ and M ₂ of the metal phosphate represented by the above two formulas are preferably Na, K, Al, Mg, Ca and Li, and in particular, Li, Al is the most among K, Na, Al and Li. It can be used suitably.

  As these metal phosphates, trade names manufactured by ADEKA Corporation, “ADEKA STAB” NA-11, NA-71 and the like are exemplified as suitable agents.

  The metal phosphate is used in an amount of 0.001 to 2 wt%, preferably 0.005 to 1 wt%, more preferably 0.01 to 0.5 wt%, still more preferably 0.02 to 0.3 wt% with respect to polylactic acid. It is preferable. When the amount is too small, the effect of improving the stereocomplex crystallinity (S) is small, and when too large, the stereocomplex crystal melting point is lowered, which is not preferable.

  Further, if desired, a known crystallization nucleating agent can be used in combination to enhance the action of the metal phosphate. Of these, calcium silicate, talc, kaolinite, and montmorillonite are preferably selected.

  The amount of the crystallization nucleating agent used is selected in the range of 0.05 to 5 wt%, more preferably 0.06 to 2 wt%, and still more preferably 0.06 to 1 wt% with respect to polylactic acid.

  Polylactic acid may be obtained by any manufacturing method. For example, a polylactic acid production method includes a two-stage lactide method in which L-lactic acid and / or D-lactic acid is used as a raw material to form lactide, which is a cyclic dimer, and then ring-opening polymerization is performed. In addition, it can be suitably obtained by a generally known polymerization method such as a one-step direct polymerization method in which dehydration condensation is directly performed in a solvent using D-lactic acid as a raw material.

  In the production of polylactic acid, carboxylic acid groups may be contained, but the smaller the amount of carboxylic acid groups contained, the better. For these reasons, it is preferable to use, for example, ring-opened polymerization from lactide using an initiator other than water, or a polymer that has been chemically treated after polymerization to reduce carboxylic acid groups.

  The weight average molecular weight of polylactic acid is usually at least 50,000, preferably at least 100,000, preferably 100,000 to 300,000. When the average molecular weight is lower than 50,000, the strength properties of the film are lowered, which is not preferable. If it exceeds 300,000, the melt viscosity becomes too high and melt film formation may be difficult.

  The polylactic acid in the present invention may be a copolymerized polylactic acid obtained by copolymerizing other components having ester forming ability in addition to L-lactic acid and D-lactic acid. The copolymerizable component includes glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, hydroxycarboxylic acids such as 6-hydroxycaproic acid, ethylene glycol, propylene glycol, butanediol, neo Compounds containing a plurality of hydroxyl groups in the molecule such as pentyl glycol, polyethylene glycol, glycerin and pentaerythritol or derivatives thereof, compounds containing a plurality of carboxylic acid groups in the molecule such as adipic acid, sebacic acid and fumaric acid Or derivatives thereof. However, in order to maintain a high melting point and not impair the film strength, in this case, it is desirable that 70 mol% or more of the film is composed of lactic acid units.

<Acrylic resin (component B)>
Acrylic resins (component B) used in the present invention are methacrylic acid esters such as cyclohexyl methacrylate, 4-tert-butylcyclohexyl methacrylate, methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isopropyl acrylate, acrylic One or more monomers selected from acrylic acid esters such as 2-ethylhexyl acid are polymerized. These monomers can be used alone or in admixture of two or more. Of these, a homopolymer of methyl methacrylate or a copolymer with other monomers is preferable.

  Examples of monomers copolymerizable with methyl methacrylate include other alkyl methallylic esters, alkyl acrylates, aromatic vinyl compounds such as styrene, vinyl toluene and α-methyl styrene, acrylonitrile, methacrylonitrile, etc. Vinyl cyanides, maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide, unsaturated carboxylic acid anhydrides such as maleic anhydride, and unsaturated acids such as acrylic acid, methacrylic acid and maleic acid It is done. Among these monomers copolymerizable with methyl methacrylate, acrylic acid alkyl esters are particularly excellent in heat decomposition resistance. A methacrylic resin obtained by copolymerizing alkyl acrylates is preferable because of its high fluidity during molding.

  The amount of alkyl acrylates used when methyl acrylate is copolymerized with methyl methacrylate is preferably 0.1% by weight or more from the viewpoint of thermal decomposition resistance, and 15% from the viewpoint of heat resistance. % Or less is preferable. The content is more preferably 0.2% by weight or more and 14% by weight or less, and particularly preferably 1% by weight or more and 12% by weight or less.

  Among these alkyl acrylates, methyl acrylate and ethyl acrylate are particularly most preferable in terms of the above improvement effect even when they are copolymerized with a small amount of methyl methacrylate. The said monomer which can be copolymerized with methyl methacrylate can also be used 1 type or in combination of 2 or more types.

  The weight average molecular weight of the acrylic resin (component B) is preferably 50,000 to 200,000. The weight average molecular weight is preferably 50,000 or more from the viewpoint of the strength of the molded product, and preferably 200,000 or less from the viewpoint of molding processability and fluidity. A more preferable range is 70,000-150,000. In the present invention, isotactic polymethacrylate and syndiotactic polymethacrylate can be used simultaneously.

  As a method for producing an acrylic resin, for example, generally used polymerization methods such as cast polymerization, bulk polymerization, suspension polymerization, solution polymerization, emulsion polymerization, and anionic polymerization can be used. From this viewpoint, bulk polymerization or solution polymerization without using a suspending agent or an emulsifier is desirable. When solution polymerization is performed, a solution prepared by dissolving a mixture of monomers in an aromatic hydrocarbon solvent such as toluene, ethylbenzene, or xylene can be used. In the case of polymerization by bulk polymerization, the polymerization can be started by irradiation with free radicals generated by heating or ionizing radiation as is usually done.

  As the initiator used in the polymerization reaction, any initiator generally used in radical polymerization can be used. For example, an azo compound such as azobisisobutylnitrile, benzoyl peroxide, lauroyl peroxide, t-butylperoxy An organic peroxide such as -2-ethylhexanoate is used. In particular, when the polymerization is carried out at a high temperature of 90 ° C. or higher, solution polymerization is common, so that the peroxide has a 10-hour half-life temperature of 80 ° C. or higher and is soluble in the organic solvent used, An azobis initiator or the like is preferable. Specifically, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, cyclohexane peroxide, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 1,1 -Azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) isoptyronitrile, etc. can be mentioned. These initiators are used in the range of 0.005 to 5% by weight.

  As the molecular weight regulator used as necessary for the polymerization reaction, any one used in general radical polymerization is used. For example, mercaptan compounds such as butyl mercaptan, octyl mercaptan, dodecyl mercaptan, 2-ethylhexyl thioglycolate are particularly preferable. These molecular weight regulators are added in a concentration range such that the degree of polymerization is controlled within the above range.

<Resin composition>
In the resin composition of the present invention, the ratio between the aliphatic polyester resin (component A) and the acrylic resin (component B) is determined by the characteristics of the specific component A, component B and the film to be obtained (optical). Properties and mechanical properties), but may be set in a range of (99/1) to (1/99) in a weight ratio (A component / B component), preferably (99 / 1) to (50/50), more preferably (80/20) to (50/50), and still more preferably (70/30) to (50/50).

  The resin composition of the present invention preferably has the above-described stereocomplex crystallinity (S) of 80% or more in DSC measurement. When the stereocomplex crystallinity is 80% or more, the thermal shrinkage rate at 90 ° C. of the film obtained therefrom can be reduced. The stereocomplex crystallinity of the resin composition is more preferably 90% or more, still more preferably 95% or more, and particularly preferably the stereocomplex crystallinity is 100%.

  In the present invention, the ratio of the cyclic carbodiimide compound (C component) in the resin composition is based on the total amount of 100 parts by weight of the aliphatic polyester resin (A component) and the acrylic resin (B component). (C component) is preferably contained in an amount of 0.001 to 5 parts by weight. If the amount of component C is within this range, the moisture stability and hydrolysis resistance of the resin composition and the film obtained therefrom can be suitably increased.

  From this viewpoint, the content ratio of the cyclic carbodiimide compound (component C) is more preferably 0.01 to 5 parts by weight per 100 parts by weight of the total amount of the aliphatic polyester resin (component A) and the acrylic resin (component B). More preferably, the range of 0.1 to 4 parts by weight is selected. If the amount is less than this range, the effect of the cyclic carbodiimide compound (component C) may not be recognized effectively, and even if it is applied in a large amount beyond this range, the hydrolysis stability will be further improved. Not expected.

  When the aliphatic polyester resin (component A) contains polylactic acid, the lactide content is preferably based on the total amount of the aliphatic polyester resin (component A) and the acrylic resin (component B). It is 0-1000 ppm, More preferably, it is 0-200 ppm, More preferably, it is the range of 0-100 ppm. A lower lactide content is preferable from the viewpoint of physical properties such as hue and stability of the resin composition, but even if an excessive reduction operation is applied, further improvement in physical properties is not expected and it is not preferable from the viewpoint of cost. A case occurs.

  The carboxyl group concentration of the resin composition is preferably 0 to 30 equivalents / ton, more preferably 0 to 10 equivalents, based on the total amount of the aliphatic polyester resin (component A) and the acrylic resin (component B). / Ton, more preferably in the range of 0 to 5 equivalents / ton, particularly preferably in the range of 0 to 1 equivalent / ton. Reduction of the carboxyl group concentration can be easily achieved by using a cyclic carbodiimide compound (C component).

  In the present invention, the resin composition contains other resin components other than the aliphatic polyester-based resin (component A), the acrylic resin (component B), and the cyclic carbodiimide compound (component C). It can contain in the range which is not.

  Specific examples of other resin components include polyolefins such as polyethylene and polypropylene, styrene resins such as polystyrene and styrene acrylonitrile copolymer, polyamide, polyphenylene sulfide resin, polyether ether ketone resin, polyester, polysulfone, polyphenylene oxide, and polyimide. , Thermoplastic resins such as polyetherimide and polyacetal, and thermosetting resins such as phenol resin, melamine resin, silicone resin, and epoxy resin. These can contain 1 or more types.

  Furthermore, arbitrary additives can be mix | blended with the resin composition of this invention according to various objectives within the range which does not impair the effect of this invention remarkably. The type of additive is not particularly limited as long as it is generally used for blending resins and rubber-like polymers.

  Examples of the additive include inorganic fillers and pigments such as iron oxide. Also, lubricants such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylene bisstearamide, mold release agent, paraffinic process oil, naphthenic process oil, aromatic process oil, paraffin, Softeners and plasticizers such as organic polysiloxanes and mineral oils, hindered phenolic antioxidants, antioxidants such as phosphorus thermal stabilizers, hindered amine light stabilizers, benzotriazole ultraviolet absorbers, benzophenone ultraviolet rays Examples include absorbents, cyclic imino ester ultraviolet absorbers, triazine ultraviolet absorber flame retardants, and antistatic agents. Specific examples of the benzophenone compound used as the benzophenol antioxidant include 2,2 ′, 4,4′-tetrahydroxybenzophenone and 2,2′-dihydroxy-4,4′-dimethoxybenzophenone. . Of these, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone is preferred. Benzophenone can be used alone or in combination of two or more. Such compounds are commercially available from Sipro Kasei Co., Ltd. as SEESORB107 and SEESORB106 (trade names) and can be easily used.

  Specific examples of the cyclic imino ester compound used as the cyclic imino ester ultraviolet absorber include 2,2′-bis (3,1-benzoxazin-4-one) and 2,2′-p-phenylenebis. (3,1-benzoxazin-4-one), 2,2′-m-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis ( 3,1-benzoxazin-4-one), 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one), 2,2 ′-(1,5-naphthalene) Bis (3,1-benzoxazin-4-one), 2,2 ′-(2-methyl-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2 ′-(2- Nitro-p-phenylene) bis (3,1-benzoxa Down 4-one) and 2,2 '- (such as 2-chloro -p- phenylene) bis (3,1-benzoxazin-4-one) is illustrated. Among them, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazin-4-one) And 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one) are preferred, especially 2,2′-p-phenylenebis (3,1-benzoxazine-4 -On) is preferred.

  Further, reinforcing agents such as organic fibers, glass fibers, carbon fibers, and metal whiskers, coloring agents, and electrostatic adhesion improving agents can be used. Moreover, said mixture is mentioned.

  The resin composition of the present invention can be produced by a known method. For example, aliphatic polyester resins (component A), acrylic resins (component B), and cyclic carbodiimide compounds (using a single kneader, twin screw extruder, Banbury mixer, Brabender, various kneaders, etc.) Component C) and, if necessary, the above-mentioned other components can be added, melted and kneaded to produce a resin composition.

  In addition, after blending an aliphatic polyester-based resin (component A) and a cyclic carbodiimide compound (component C) first, blending with an acrylic resin (component B) is an aliphatic polyester-based resin (component A). Since hydrolyzability can be improved at an early stage, it is preferable.

<Manufacture of film>
Since the resin composition of the present invention is used as a film, it can be formed using a molding technique such as extrusion molding or cast molding. For example, the film can be formed using an extruder equipped with a T die, a circular die, or the like.

  When an unstretched film is obtained by extrusion molding, it is possible to use a material in which an aliphatic polyester resin (component A), an acrylic resin (component B) and a cyclic carbodiimide compound (component C) are melt-kneaded in advance. It can also be formed through melt-kneading at the time of forming.

  An unstretched film can be produced by extruding a molten film onto a cooling drum and then bringing the film into close contact with a rotating cooling drum and cooling. At this time, the molten film is blended with an electrostatic adhesion agent such as quaternary phosphonium salt of sulfonic acid, and an electric charge is easily applied from the electrode to the film melting surface in a non-contact manner, whereby the film is adhered to the rotating cooling drum. By making it, an unstretched film with few surface defects can be obtained.

  In addition, a common solvent for aliphatic polyester resin (component A), acrylic resin (component B) and cyclic carbodiimide compound (component C), for example, a solvent such as chloroform, methylene dichloride, etc., aliphatic polyester resin An unstretched film can also be cast-molded by dissolving the (A component), the acrylic resin (B component) and the cyclic carbodiimide compound (C component), followed by cast drying and solidification.

<Extension>
The unstretched film obtained from the resin composition of the present invention can be uniaxially stretched in the mechanical flow direction (MD) or can be uniaxially stretched in the direction (TD) perpendicular to the mechanical flow direction. Further, a biaxially stretched film can be produced by stretching by a sequential biaxial stretching method of roll stretching and tenter stretching, a simultaneous biaxial stretching method by tenter stretching, a biaxial stretching method by tubular stretching, or the like.

  Here, the stretching ratio is preferably 0.1 to 1000% or less, preferably 0.2 to 600%, more preferably 0.3 to 300% in at least one direction. By setting the draw ratio within this range, a stretched film that is preferable in terms of birefringence, heat resistance, and strength can be obtained.

  The stretch ratio is an area stretch ratio (longitudinal ratio × horizontal ratio), preferably in the range of 1 to 15, more preferably 1.01 to 10, still more preferably 1.1 to 5, particularly preferably 1.1 to 3. It is.

  When heat treatment is performed in order to set the crystallinity of the film to 10% or more, it is essential that both the vertical magnification and the horizontal magnification exceed 1 time, that is, the film is stretched. (Stretch ratio of 1 times or less) is, for example, the heat resistance evaluation described in the edition of the electrical film for electronics (2006) electric and electronic materials study, and the heat resistance evaluation (90 ° C., 5 ° Transparency may be lowered by heat treatment for a long time, which is not preferable as an optical film.

  The stretching temperature is preferably selected from the glass transition temperature (Tg) to the crystallization temperature (Tc) of the resin composition. In order to suppress Re and Rth, a temperature range higher than Tg, as close to Tc as possible, and in which crystallization of the aliphatic polyester resin (component A) does not proceed is more preferably employed.

  Since the molecular chain is fixed at a temperature lower than Tg, it is difficult to suitably advance the stretching operation, and it is difficult to set Re and Rth to 20 nm or less, respectively. Crystallization of (Component A) proceeds, and in this case as well, it is difficult to make the stretching process proceed well.

  Therefore, as the stretching temperature, it is preferable to select a crystallization temperature (Tc) from a temperature range in which crystallization of the aliphatic polyester resin (component A) is difficult to proceed from the base of Tg to Tc, for example, Tg. From the viewpoint of achieving both film physical properties and stabilization of the stretching process, the stretching temperature is suitably set in the temperature range of Tg + 5 ° C. to Tc ° C., more preferably Tg + 10 ° C. to Tc ° C., and even more preferably Tg + 20 ° C. to Tc ° C. The upper limit of the stretching temperature may be set as appropriate in consideration of the apparatus characteristics because the film properties and the stretching process stabilization are in conflict.

<Heat treatment>
The stretched film is preferably heat treated. The heat shrinkage rate of the stretched film can be suitably reduced by this heat treatment.

  In particular, when the aliphatic polyester-based resin (component A) contains stereocomplex polylactic acid, the stereocomplex phase polylactic acid can be crystallized, and the storage elastic modulus E ′ is determined by dynamic viscoelasticity (DMA) measurement. A value greater than 50 MPa can be maintained without exhibiting a minimum value in a temperature range from room temperature (25 ° C.) to 150 ° C.

  When a polylactic acid that is a crystalline resin and an acrylic resin that is an amorphous resin are blended, the crystallization temperature Tc of the resulting resin composition shifts to the high temperature side, so the vicinity of the crystallization temperature Tc of the resin composition Homopolylactic acid having a melting point of 2 is difficult to crystallize because the stretched film starts melting at the crystallization temperature of the resin composition, but the melting point of stereocomplex polylactic acid exceeds the crystallization temperature of the resin composition. Therefore, the obtained stretched film can be heat-treated at a high temperature, and the stretched film can be easily crystallized, which is preferable.

The heat treatment temperature varies depending on the ratio of the aliphatic polyester resin (component A) to the acrylic resin (component B) and the specific composition of each. For example, when stereocomplex polylactic acid is used as the aliphatic polyester resin the heat treatment temperature, when the crystal melting temperature of the stereocomplex-phase polylactic acid and Tm ^*, preferably 90~Tm ^* (℃), more preferably ^{110~ (Tm * -10) (℃} ), more preferably 120 ~ (Tm ^* -20) (° C).

  The heat treatment is preferably performed in the range of 1 second to 30 minutes. When the heat treatment temperature is high, a relatively short time is required, and when the heat setting temperature is low, a relatively long time is required. For example, a film having a Tc of 140 ° C. requires at least 30 seconds at 140 ° C., but heat treatment for 10 seconds at 150 ° C. may cause the film to have a thermal shrinkage rate of less than 5% at 90 ° C. for 5 hours. it can.

  The film thus obtained can be subjected to surface activation treatment such as plasma treatment, amine treatment or corona treatment by a conventionally known method if desired.

(Characteristics of film)
(Thickness)
The thickness of the film of the present invention is preferably 1 to 300 μm, more preferably 10 to 300 μm, and still more preferably 20 to 150 μm. It is preferably 10 μm or more from the viewpoint of difficulty in wrinkling during handling (preventing wrinkles). Moreover, it is preferable that it is 200 micrometers or less from a viewpoint of transparency.
(Photoelastic coefficient)
The absolute value of the photoelastic coefficient of the film of the present invention is preferably less than 10 × 10 ⁻¹² / Pa, more preferably less than 8 × 10 ⁻¹² / Pa, still more preferably less than 5 × 10 ⁻¹² / Pa, particularly preferably. Is less than 3 × 10 ⁻¹² / Pa.

  The photoelastic coefficient (CR) is described in various documents (for example, see Non-Patent Document 1 etc.) and is a value defined by the following equation. The closer the value of the photoelastic coefficient is to zero, the smaller the change in birefringence due to external force, which means that the change in birefringence designed for each application is small.

CR = Δn / σR
Δn = nx−ny
Where CR is a photoelastic coefficient, σR is an extension stress, Δn is a birefringence difference, nx is a refractive index in the extension direction, and ny is a refractive index in a direction perpendicular to the extension direction.

(Surface direction retardation (Re) and thickness direction retardation (Rth))
The retardation (Re) in the plane direction and the retardation (Rth) in the thickness direction of the film of the present invention are products of the birefringence difference Δn and the thickness d (nm), and Re and Rth are defined by the following equations, respectively. The
Re = (nx−ny) × d
Rth = ((nx + ny) / 2−nz) × d
nx represents the refractive index in the longitudinal direction. ny represents the refractive index in the width direction. nz represents the refractive index in the thickness direction. d represents thickness (nm).
Both Re and Rth of the film of the present invention are preferably 10 nm or less, more preferably 5 nm or less, and further 4 nm or less. A material having values of Re and Rth in this range is preferable because phase difference spots due to orientation caused by molding in extrusion molding and cast molding are unlikely to occur.

(Stereo complex crystallinity: S)
The film of the present invention preferably has a stereocomplex phase polylactic acid crystal melting peak of 190 ° C. or higher in DSC measurement, and further has a stereocomplex crystallinity (S) defined by the following formula from the crystal melting peak intensity of DSC measurement. ) Is preferably 80% or more, more preferably 90 to 100%, still more preferably 97 to 100%, and particularly preferably 100%.
That is, the film of the present invention preferably has a highly formed stereocomplex phase of polylactic acid.
S (%) = [ΔHms / (ΔHmh + ΔHms)] × 100
ΔHms represents the crystal melting enthalpy (J / g) of the stereocomplex phase polylactic acid. ΔHmh represents the crystal melting enthalpy (J / g) of homophase polylactic acid.
The stereocomplex crystallinity (S) is a parameter indicating the ratio of stereocomplex polylactic acid crystals that are finally produced in the heat treatment process.
In the present invention, the crystal melting peak appearing at 190 ° C. or higher in DSC measurement is a crystal melting peak attributed to melting of the stereocomplex phase polylactic acid, and the crystal melting peak appearing below 190 ° C. is the melting phase of homophase polylactic acid. Is a crystal melting peak attributed to.

(Shrinkage factor)
The film of the present invention has a longitudinal direction (MD) shrinkage ratio and a transverse direction (TD) shrinkage ratio of preferably 5% or less, more preferably 4% or less, at 90 ° C. for 5 hours. Preferably, this can be achieved by selecting stereocomplex polylactic acid as the component A.

(Storage modulus: E ')
The film of the present invention has a storage elastic modulus (E ′) measured by dynamic viscoelasticity (DMA) that does not exhibit a minimum value in a temperature range from room temperature (25 ° C.) to 150 ° C. and is greater than 50 MPa. It is preferable to have.
Such a film has good dimensional stability because, for example, E ′ does not exhibit a minimum value when heated to a temperature range of about 150 ° C. required in the manufacturing process of a polarizing film.
In addition, since E ′ has a value larger than 50 MPa, deformation hardly occurs due to an external force, phase difference hardly occurs, and good workability can be exhibited in the manufacturing process of the polarizing film.

(Polarizing plate protective film)
The film of the present invention is useful as a polarizing plate protective film. A polarizing plate protective film is used as a constituent member of a polarizing plate, and is a polarizing film (for example, a high polymerization degree PVA base film impregnated with or adsorbed with a dichroic dye such as polyiodine or a dichroic dye) Is a film used for the purpose of improving the strength of the polarizing film, protecting it from heat and moisture, preventing crystal deterioration, and the like.
The polarizing plate protective film made of the film of the present invention can be used as a constituent member of a polarizing plate for displays such as liquid crystal displays, plasma displays, organic EL displays, field emission displays, rear projection televisions. The polarizing plate protective film made of the film of the present invention can be subjected to surface functionalization treatment such as antireflection treatment, transparent conductive treatment, electromagnetic wave shielding treatment, gas barrier treatment, and antifouling treatment as necessary.

(Retardation film)
The film of the present invention is useful as a retardation film. The retardation film comprising the film of the present invention can control the retardation produced by changing the blend ratio of the aliphatic polyester resin (component A) and the acrylic resin (component B), for example, When stereocomplex polylactic acid is used as the aliphatic polyester resin (component A), the birefringence strong in the longitudinal direction (MD) when the stereocomplex polylactic acid exceeds 50% by weight and the acrylic resin is less than 50% by weight. In the opposite case, a strong birefringence can be obtained in the width direction (TD). Furthermore, it can be changed to an appropriate blend ratio depending on the necessary phase difference, and the phase difference can be controlled by further stretching, and can be suitably used as a phase difference plate of a liquid crystal panel display.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention does not receive limitation at all by this.
The evaluation methods used in the present invention and examples will be described below.
(1) Molecular weight:
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were measured by gel permeation chromatography (GPC) and converted to standard polystyrene.
GPC measurement equipment
Detector: Differential refractometer RID-6A manufactured by Shimadzu Corporation
Column: Tosoh Corporation TSKgel G3000HXL, TSKgel G4000HXL, TSKgel G5000HXL and TSKguardcolumnHXL-L connected in series, or Tosoh Corporation TSKgel G2000HXL, TSKgel G3000HXL, TSKgel G3000HXL
10 μl of a sample having a concentration of 1 mg / m1 (chloroform containing 1% hexafluoroisopropanol) was injected at a temperature of 40 ° C. and a flow rate of 1.0 ml / min using chloroform as an eluent.

(2) Carboxyl group concentration:
The sample was dissolved in purified o-cresol, dissolved in a nitrogen stream, and bromocresol blue was used as an indicator, and the sample was determined with an ethanol solution of 0.05 N potassium hydroxide.

(3) Stereocomplex crystallinity (S), crystal melting temperature:
The stereocomplex crystallinity (S) and the crystal melting temperature of stereocomplex polylactic acid were determined by measuring the crystal melting temperature and the crystal melting enthalpy using DSC (TA-2920 manufactured by TA Instruments). It calculated | required according to the following formula.
S (%) = [ΔHms / (ΔHmh + ΔHms)] × 100
(However, ΔHms is the crystal melting enthalpy of stereocomplex phase crystals, and ΔHmh is the crystal melting enthalpy of homophase crystals.)

(4) Film heat shrinkage:
In accordance with ASTM D1204, after treatment at 90 ° C. for 5 hours, the temperature was returned to room temperature (25 ° C.), the heat shrinkage rate was determined from the change in length, and the haze value was further determined.

(5) Photoelastic coefficient:
Polymer Engineering and Science 1999, 39, P.A. The birefringence measuring apparatus described in detail in 2349-2357 was used.
A film tensioning device was placed in the laser beam path, and birefringence was measured while applying a tensile stress at 23 ° C. The strain rate during stretching was 50% / min (between chucks: 10 mm, chuck moving speed: 5 mm / min), and the test piece width was 8 mm. From the relationship between the birefringence difference (Δn) and the extensional stress (σR), the photoelastic coefficient (CR) was calculated by determining the slope of the straight line by least square approximation.
CR = Δn / σR
Δn = n _x - n _y
(CR: photoelastic coefficient, sigma] R: tensile stress, [Delta] n: birefringence difference, _{n x:} refractive index in the stretching direction, _{n y:} extension direction perpendicular refractive index)

(6) Total light transmittance:
Measurements were performed according to ASTM D1003.

(7) Polarizing plate durability:
After heat treatment at 90 ° C. for 5 hours, the temperature was returned to room temperature (25 ° C.), and the durability of the film was evaluated according to the following criteria.
○: No cracking even when bent 10 times.
Δ: No cracking even when bent twice.
X: Cracked when bent.

(8) Measurement of heads:
Using a Nippon Denshoku Co., Ltd. Hazemeter MDH2000, a 40 μm thick film was used, and the measurement was performed according to 6.4 of JIS K7105-1981.
If the haze exceeds 1.6%, the transparency is judged to be poor. When the haze was 0 to 1.6%, it was judged that it could be applied as a film for optical use. When the haze was 1% or less, it was judged to be suitable transparency as an optical film.

(9) Measuring method of glass transition temperature:
It calculated | required using DSC (TA-2920 by TA instrument company).

(10) In-plane retardation (Re), thickness direction retardation (Rth):
The refractive index in the longitudinal direction _{(n x)} and the width direction of the refractive index _{(n y)} was measured with a spectroscopic ellipsometer (manufactured by JASCO Corporation M-0.99).
Following from: (nm d) the phase difference in the plane direction of the film and (Re), phase difference (Rth) in the thickness, the refractive index in the longitudinal direction _(n x), the refractive index in the width direction _(n y), the thickness Obtained from each equation.
_{Re = (n x -n y)} × d
Rth = ((n _x + _ny ) / 2−n _z ) × d

(11) Measurement of high temperature mechanical properties (DMA):
A sample (strip shape, film width 4 mm, chuck distance 20 mm) was measured using the following apparatus.
Measuring device: RSA-III manufactured by TA Instruments
Measurement mode: Automatic tension, automatic strain control method Measurement temperature range: 20 to 200 ° C
Temperature increase rate: 3 ° C / min
Measurement frequency: 1Hz
DMA properties (existence of minimum value)
None: Minimal value does not appear in the temperature range from room temperature (25 ° C) to 150 ° C.
Existence: Minimal value appears in the temperature range from room temperature (25 ° C) to 150 ° C.
Further, the E ′ value at 150 ° C. was determined.

(12) Evaluation of film shape stability:
A 50 cm × 50 cm film was allowed to stand on a stainless steel plate at 100 ° C. for 30 minutes, and then the formation of surface irregularities was determined.
X: Concavities and convexities of 1 mm or more are generated, and it can be recognized that the surface is clearly wavy.
(Triangle | delta): The unevenness | corrugation of 0.2 or more and less than 1 mm generate | occur | produces, and it can recognize that the surface is wavy visually.
○: Concavities and convexities of less than 0.2 mm, which can be regarded as almost flat by visual observation.

(13) Isocyanate gas generation test:
The sample was heated at 160 ° C. for 5 minutes, and generation of isocyanate gas was confirmed by pyrolysis GC / MS analysis. GC / MS used was GC / MS Jms Q1000GC K9 manufactured by JEOL Ltd.

(14) Hydrolysis resistance:
The reduced viscosity retention when the obtained sample was treated at 80 ° C. and 95% RH for 100 hours with a constant temperature and humidity machine was evaluated.

  The hydrolytic stability of the sample was indicated as “Good” when the reduced viscosity retention was 80 to less than 95%, and as “Excellent” when 95% to 100%. Those less than 80% were expressed as “Fail” and indicated as “x”.

[Reference Example 1] Production of cyclic carbodiimide compound (component C):
o- nitrophenol (0.11 mol) and pentaerythrityl tetra bromide (0.025 mol), potassium carbonate _{(0.33mol), N, N- N} 2 dimethylformamide 200ml in reactor installed with a stirrer and a heating device After charging in an atmosphere and reacting at 130 ° C. for 12 hours, DMF was removed under reduced pressure, and the resulting solid was dissolved in 200 ml of dichloromethane and separated three times with 100 ml of water. The organic layer was dehydrated with 5 g of sodium sulfate, and dichloromethane was removed under reduced pressure to obtain an intermediate product D (nitro form).
Next, intermediate product D (0.1 mol), 5% palladium carbon (Pd / C) (2 g), and 400 ml of ethanol / dichloromethane (70/30) were charged into a reactor equipped with a stirrer, and 5 hydrogen substitution was performed. The reaction was performed in a state where hydrogen was constantly supplied at 25 ° C., and the reaction was terminated when there was no decrease in hydrogen. When Pd / C was recovered and the mixed solvent was removed, an intermediate product E (amine body) was obtained.
Next, triphenylphosphine dibromide (0.11 mol) and 150 ml of 1,2-dichloroethane were charged and stirred in a reactor equipped with a stirring device, a heating device, and a dropping funnel in an N ₂ atmosphere. A solution prepared by dissolving the intermediate product E (0.025 mol) and triethylamine (0.25 mol) in 50 ml of 1,2-dichloroethane was gradually added dropwise thereto at 25 ° C. After completion of dropping, the reaction is carried out at 70 ° C. for 5 hours. Thereafter, the reaction solution was filtered, and the filtrate was separated 5 times with 100 ml of water. The organic layer was dehydrated with 5 g of sodium sulfate, and 1,2-dichloroethane was removed under reduced pressure to obtain an intermediate product F (triphenylphosphine compound).
Next, in a reactor equipped with a stirrer and a dropping funnel, di-tert-butyl dicarbonate (0.11 mol), N, N-dimethyl-4-aminopyridine (0.055 mol), and dichloromethane 150 ml under N2 atmosphere. Charge and stir. Thereto, 100 ml of dichloromethane in which the intermediate product F (0.025 mol) was dissolved was slowly added dropwise at 25 ° C. After dropping, react for 12 hours. Then, the compound (MW = 516) shown by the following structural formula was obtained by refine | purifying the solid substance obtained by removing dichloromethane. The structure was confirmed by NMR and IR.

[Reference Example 2] Production of poly-L-lactic acid (A-1):
As a component A, 0.005 parts by weight of tin octylate is added to 100 parts by weight of L-lactide (manufactured by Musashino Chemical Laboratory, Inc., optical purity 100%), and a reactor equipped with a stirring blade in a nitrogen atmosphere. The reaction is carried out at 180 ° C. for 2 hours, and 1.2 times equivalent of phosphoric acid is added as a catalyst deactivator to the tin octylate, and then the remaining lactide is removed at 13.3 Pa to form chips. L-lactic acid was obtained.
The obtained poly L-lactic acid had a weight average molecular weight of 152,000, a glass transition temperature (Tg) of 55 ° C., and a melting point of 175 ° C.

[Reference Example 3] Production of stereocomplex polylactic acid (A-2):
In Reference Example 1, polymerization was carried out under the same conditions except that L-lactide was changed to D-lactide (manufactured by Musashino Chemical Laboratory, Inc., optical purity 100%) to obtain poly-D lactic acid.
The obtained poly-D-lactic acid had a weight average molecular weight of 151,000, a glass transition temperature (Tg) of 55 ° C., and a melting point of 175 ° C.
Obtained poly D-lactic acid, poly L-lactic acid obtained by the operation of Reference Example 1, 50 parts by weight and 0.1 parts by weight of phosphate metal salt (“ADEKA STAB” NA-71 manufactured by ADEKA) After blending with a blender and vacuum drying at 110 ° C. for 5 hours, melt kneading while evacuating at a cylinder temperature of 250 ° C. and a vent pressure of 13.3 Pa, extruding the strand into a water tank, chipping with a chip cutter, and component A As a result, a polylactic acid composition having a stereocomplex crystallinity (S) of 100% and a crystal melting temperature of 216 ° C. was obtained.

[Reference Example 4] Acrylic resin (component B):
“Acrypet” VH001 manufactured by Mitsubishi Rayon Co., Ltd. was used as an acrylic resin (component B).

[Examples 1 to 4]
The aliphatic polyester resin (component A) obtained by the operation of the reference example and the acrylic resin (component B) described in reference example 4 were mixed at the quantitative ratio shown in Table 1 to obtain an aliphatic polyester resin (component A). ) And acrylic resin (component B) per 100 parts by weight in total, 0.5 parts by weight of tetrabutylphosphonium 3,5-dicarboxybenzenesulfonate was mixed with a Henschel mixer.
Then, after drying at 110 ° C. for 5 hours, the cyclic carbodiimide compound (component C) obtained by the operation of Reference Example 1 was mixed and melt kneaded at a cylinder temperature of 230 ° C. with a twin screw extruder, a die temperature of 220 The film was melt-extruded into a film having a thickness of 210 μm at ° C., adhered to the surface of the mirror-cooled drum by an electrostatic casting method using a platinum-coated linear electrode, and solidified to obtain an unstretched film.
The obtained unstretched film was stretched 1.1 to 2.0 times in the longitudinal direction and 1.1 to 2.0 times in the transverse direction at 100 ° C. Next, heat setting was performed at 120 to 140 ° C. to obtain a biaxially stretched film having a thickness of about 40 μm. Table 1 shows the resin composition, film production conditions, and film properties.

[Comparative Examples 1-4]
In the same manner as in Example 1, the types and amount ratios of A component and B component described in Table 1 were extruded, stretched, and formed into a film. The heat treatment temperature was 120 ° C. The results are listed in Table 1.
In Comparative Example 4, a carbodiimide compound having a linear structure (“Carbodilite LA-1” manufactured by Nisshinbo Chemical Co., Ltd.) instead of the cyclic carbodiimide compound (C component) synthesized in Reference Example 1 was used as the C component. Using.

Claims (17)

  Aliphatic polyester resin (component A), acrylic resin (component B), compound having at least a cyclic structure in which one carbodiimide group is bonded to the first nitrogen and the second nitrogen by a bonding group (C Component).   The resin composition according to claim 1, wherein in component C, the number of atoms forming the cyclic structure is 8 to 50. The resin composition according to claim 1, wherein the component C is represented by the following formula (1).

(In the formula, Q is a divalent to tetravalent linking group that is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may contain a hetero atom.) The resin composition according to claim 3, wherein Q is a divalent to tetravalent linking group represented by the following formula (1-1), (1-2), or (1-3).

(In the formula, Ar ¹ and Ar ² are each independently an aromatic group having 2 to 4 carbon atoms and 5 to 15 carbon atoms. R ¹ and R ² are each independently 1 to 2 carbon atoms having 1 to 4 carbon atoms. 20 aliphatic groups, 2 to 4 valent alicyclic groups having 3 to 20 carbon atoms, or combinations thereof, or these aliphatic groups, alicyclic groups and 2 to 4 valent aromatic carbon atoms having 5 to 15 carbon atoms X ¹ and X ² are each independently a divalent to tetravalent aliphatic group having 1 to 20 carbon atoms, a divalent to tetravalent carbon atom having 3 to 20 alicyclic groups, 2 to 4 A valent aromatic group having 5 to 15 carbon atoms, or a combination thereof, s is an integer of 0 to 10. k is an integer of 0 to 10. When s or k is 2 or more, X ¹ or X ² as a repeating unit may be different from other X ¹ or X ^2. X ³ is a divalent to tetravalent carbon number. An aliphatic group having 1 to 20 carbon atoms, an alicyclic group having 2 to 4 carbon atoms having 3 to 20 carbon atoms, an aromatic group having 2 to 4 carbon atoms having 5 to 15 carbon atoms, or a combination thereof, provided that Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ may contain a hetero atom, and when Q is a divalent linking group, Ar ¹ , Ar ² , R 3 ¹ , R ² , X ¹ , X ² and X ³ are all divalent groups, and when Q is a trivalent linking group, Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ^{One of 2} and X ³ is a trivalent group, and when Q is a tetravalent linking group, one of Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ One of them is a tetravalent group or two are trivalent groups.) The resin composition according to claim 1, wherein the component C is represented by the following formula (2).

(Wherein Q _a is a divalent linking group that is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may contain a hetero atom.) Q _a is represented by the following formula (2-1), (2-2) or a divalent linking group is 5. The resin composition according to the formula (2-3).

(In the formula, Ar _a ¹ , Ar _a ² , R _a ¹ , R _a ² , X _a ¹ , X _a ² , X _a ³ , s and k are represented by the formulas (1-1) to (1-3), respectively. ^{Ar 1, Ar 2, R 1} , R 2, X 1, is the same as ^{X 2,} X ^3, s and k in.) The resin composition according to claim 1, wherein the component C is represented by the following formula (3).

(Wherein Q _b is a trivalent linking group which is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may contain a hetero atom. Y represents a cyclic structure. It is a carrier to be supported.) Q _b is represented by the following formula (3-1), (3-2) or (3-3) a trivalent linking group is 7. The resin composition according represented by.

(In the formula, Ar _b ¹ , Ar _b ² , R _b ¹ , R _b ² , X _b ¹ , X _b ² , X _b ³ , s and k are represented by the formulas (1-1) to (1-3), respectively. Are the same as Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s, and k, with one of these being a trivalent group.)   The resin composition according to claim 7, wherein Y is a single bond, a double bond, an atom, an atomic group or a polymer. The resin composition according to claim 1, wherein the component C is represented by the following formula (4).

(Wherein Q _c is a tetravalent linking group that is an aliphatic group, an aromatic group, an alicyclic group, or a combination thereof, and may have a hetero atom. Z ¹ and Z ² are A carrier carrying a ring structure.) 11. The resin composition according to claim 10, wherein Q _c is a tetravalent linking group represented by the following formula (4-1), (4-2), or (4-3).

(In the formula, Ar _c ¹ , Ar _c ² , R _c ¹ , R _c ² , X _c ¹ , X _c ² , X _c ³ , s and k are respectively represented by formulas (1-1) to (1-3) Are the same as Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s and k, provided that one of them is a tetravalent group or two are 3 Valent group.) The resin composition according to claim 10, wherein Z ¹ and Z ² are each independently a single bond, a double bond, an atom, an atomic group or a polymer.   The resin composition of Claim 1 in which A component contains polylactic acid-type resin.   The resin composition according to claim 13, wherein the polylactic acid-based resin forms a stereocomplex crystal.   The resin composition according to claim 1, wherein the component B contains a methyl methacrylate polymer.   The film which consists of a resin composition in any one of Claims 1-15. The film of Claim 16 whose absolute value of a photoelastic coefficient is less than 10 * 10 < ^-12 > / Pa.