DESCRIPTION

NOVEL DEHYDROABIETIC ACID POLYMER

[Technical Field]
[0001] The present invention relates to a novel dehydroabietic acid polymer  and more specifically  the present invention relates to a novel dehydroabietic acid polymer obtained by using a dehydroabietic acid that is one of the constituent components included in rosin  and a composite material containing the polymer.
[Background Art]
[0002] In recent years  from the viewpoint of global environment protection  reduced dependence on oil as a resource has been investigated  and various natural resources have attracted great attention. Similarly  in the field of plastics  reduction of oil-dependency has been examined  and as a result  for example  polylactic acid that uses lactic acid obtained by the fermentation of glucose as a raw material has been widely used for packaging materials and the like.
[0003] According to “Polylactic Acids: Foundation and Application of Plastics Derived from Plants”  written by Hideto Tsuji  published by Yoneda Shuppan  2008  polylactic acids have an excellent transparency  but have low heat resistance  and therefore  the application of polylactic acid to molded products made by injection molding or the like is limited only to a use that does not include exposure to a high temperature.
[0004] Further  besides polylactic acid  as is shown in the “Handbook of Polyester Resin” written by Eiichiro Takiyama  published by Nikkan Kogyo Shimbun  Ltd.  1988 and in the “Handbook of Polycarbonate Resin” written by Seiichi Honma  published by Nikkan Kogyo Shimbun  Ltd.  1992  PET (polyethylene terephthalate) and PC (polycarbonate) are caused hydrolysis in a high temperature and high humidity environment or in an acidic or alkaline environment and  as a result  exhibit low moisture resistance. Therefore  improvement thereof is required.
[0005] Meanwhile  rosin that can be obtained from pine tree is known as one of important bio-based industrial raw materials. Rosin is composed of various carboxylic acids  and among the carboxylic acids  it is known that abietic acid is utilized in polymer materials (see  for example  Japanese Patent Application Laid-Open (JP-A) Nos. 2008-274150 and 6-87946).
For example  JP-A Nos. 2008-274150 and 6-87946 disclose a technology of preparing a rosin-modified phenol resin or a rosin-modified epoxy resin by modifying a terminal portion of a phenol resin or an epoxy resin with abietic acid and using these resins as an additive for a coating material or the like. However  since these resins consist of a phenol resin or an epoxy resin as a main skeleton thereof  these materials depend on oil and  therefore  they are not environmentally friendly enough.
[0006] Further  a polymer obtained by the polymerization of abietic acid and a polyhydric alcohol is also known (see  for example  JP-A No. 6-33395). However  since the polymer described in JP-A No. 6-33395 polymerizes randomly and complicatedly  the polymer cannot form a linear polymer having a high molecular weight. Accordingly  such a polymer cannot be utilized for industrial use as a molded article or the like.

SUMMARY OF INVENTION
[Technical Problem]
[0007] An object of the present invention is to provide a novel dehydroabietic acid polymer that is able to use a raw material derived from rosin  which is a natural product  and this polymer has high heat resistance and high moisture and water resistance.
Another object of the present invention is to provide a composite material containing the novel dehydroabietic acid polymer.
[Solution to Problem]
[0008] Means to solve the problem are as follows.
<1> A dehydroabietic acid polymer including a repeating unit containing a dehydroabietic acid skeleton.
<2> The dehydroabietic acid polymer according to item <1>  wherein the repeating unit includes a dimer structure in which two dehydroabietic acid skeletons bond directly or through a linking group.
<3> The dehydroabietic acid polymer according to item <1> or item <2>  being a polyester obtained by using a dehydroabietic acid derivative and a diol compound.
<4> The dehydroabietic acid polymer according to any one of items <1> to <3>  wherein the repeating unit is a repeating unit represented by the following Formula (I):

wherein  in Formula (I)  L1 represents a single bond or a divalent linking group  and L2 represents an alkylene group or an arylene group.
<5> The dehydroabietic acid polymer according to item <4>  wherein the repeating unit represented by Formula (I) is a repeating unit represented by the following Formula (II):

wherein  in Formula (II)  L1 and L2 respectively have the same definition as L1 and L2 in Formula (I).
<6> The dehydroabietic acid polymer according to item <4> or item <5>  wherein  in Formula (I) or (II)  L1 represents a single bond  -O-  -S-  -CO-  -SO2-  -O(CnH2n)O-  -CO(CnH2n)CO-  -CnH2n-  or -C(-R1)(-R2)-; each of R1 and R2 independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; and n represents an integer of from 1 to 12.
<7> The dehydroabietic acid polymer according to item <1>  being a polymer including a repeating unit represented by the following Formula (III):

wherein  in Formula (III)  L3 represents a single bond or a divalent linking group.
<8> The dehydroabietic acid polymer according to any one of items <1> to <7>  wherein a weight average molecular weight of the polymer is from 5 000 to 500 000.
<9> A composite material including the dehydroabietic acid polymer according to any one of items <1> to <8>.
<10> A dehydroabietic acid being a compound represented by the following Formula (IV):

wherein  in Formula (IV)  L1 represents a single bond or a divalent linking group; Y represents -OH  -OR  -OCOR  -OCOOR  or -OSO2R; and R represents an alkyl group or an aryl group.
[Advantageous Effects of Invention]
[0009] According to the present invention  a novel dehydroabietic acid polymer is able to use a raw material derived from rosin and has high heat resistance and high moisture and water resistance.
Further  according to present invention  a composite material containing the novel dehydroabietic acid polymer may be provided.

BRIEF DESCRIPTION OF DRAWINGS
[0010] Fig. 1 shows a 1H-NMR spectrum of compound (4-I) used in Example 4.
Fig. 2 shows a 1H-NMR spectrum of the dehydroabietic acid polymer obtained in Example 4.

DESCRIPTION OF EMBODIMENTS
[0011] [Dehydroabietic Acid Polymer]
Herein below  the dehydroabietic acid polymer of the present invention is described.
The dehydroabietic acid polymer of the present invention is a polymer having a repeating unit containing a dehydroabietic acid skeleton.
[0012] The dehydroabietic acid polymer of the present invention exhibits high heat resistance and high moisture and water resistance. Further  the dehydroabietic acid that is the raw material of the dehydroabietic acid polymer of the present invention can be obtained from rosin derived from pine tree.
Accordingly  the polymer of the present invention can be provided as a novel bio-based polymer which is superior to conventional bio-based polymers such as polylactic acid in terms of heat resistance and moisture and water resistance.
Moreover  the dehydroabietic acid polymer of the present invention can be utilized for various applications in various forms  for example  in the form of a sheet  a film  a fiber  a molded material  or the like  by putting the characteristics of high heat resistance and high moisture and water resistance into practical use.
[0013] The dehydroabietic acid polymer of the present invention is described in detail.
The dehydroabietic acid polymer of the present invention is a homopolymer obtained by the polymerization using dehydroabetic acid represented by the following Formula (A) or a derivative thereof as a raw material monomer  or a copolymer obtained by the polymerization using the monomer represented by the following Formula (A) or a derivative thereof and other monomer  and has a repeating unit containing a dehydroabietic acid skeleton in the molecular structure.
[0014]

[0015] Here  the “dehydroabietic acid skeleton” in the present invention means a skeleton represented by the following Formula (B)  which is derived from the above dehydroabietic acid.
[0016]

[0017] The dehydroabietic acid polymer of the present invention is not limited as long as the polymer contains the skeleton represented by Formula (B) above  that is a dehydroabietic acid skeleton  as the main skeleton.
[0018] The weight average molecular weight of the dehydroabietic acid polymer of the present invention is not limited  but is preferably from 5 000 to 500 000  and more preferably from 10 000 to 200 000. When the weight average molecular weight is within this range  the dehydroabietic acid polymer has excellent properties in terms of molding and the like  and becomes satisfactory in view of industrial use.
[0019] Here  the weight average molecular weight in the present invention is a value obtained by the measurement of molecular weight (in terms of polystyrene) by gel permeation chromatography (GPC).
[0020] The dehydroabietic acid polymer of the present invention has moldability and also has excellent heat resistance and excellent moisture and water resistance. The reason for this is considered as follows: namely  the tricyclic portion of the dehydroabietic acid skeleton (the tricyclic portion in the structural formula shown below) is essentially heat-stable and highly hydrophobic  and further  an isopropyl group and a methyl group on the tricyclic portion increase the hydrophobility  and therefore  the dehydroabietic acid polymer of the present invention has the above characteristics.
[0021]

[0022] Moreover  the ester structure at the 18th position (*) of the dehydroabietic acid skeleton is extremely stable and has excellent resistance toward hydrolysis  and thus  the excellent moisture and water resistance of the dehydroabietic acid polymer of the present invention was attained.
[0023] As described above  conventional bio-based polymers obtained by using biomass resources generally have problems in that they are inferior in heat resistance or moisture and water resistance; however  the dehydroabietic acid polymer of the present invention exhibits excellent heat resistance and excellent moisture and water resistance  even though the dehydroabietic acid polymer can also be produced by using a raw material derived from biomass resources.
[0024] The dehydroabietic acid polymer of the present invention also includes a derivative of a dehydroabietic acid polymer which is obtained by further subjecting a polymer having a repeating unit containing a dehydroabietic acid skeleton to a chemical treatment or the like.
[0025] In a preferable embodiment of the dehydroabietic acid polymer of the present invention  a dimer structure which is formed by bonding two dehydroabietic acid skeletons directly or through a linking group is contained in the repeating unit. For example  this dimer structure is represented by the skeleton represented by the following Formula (C).
[0026]

[0027] In Formula (C)  L1 represents a single bond or a divalent linking group.
[0028] The dehydroabietic acid polymer of the present invention is preferably a polyester polymer obtained by using a dehydroabietic acid derivative and a diol compound.
[0029] In a preferred specific embodiment in a case in which the dehydroabietic acid polymer of the present invention is a polyester polymer  the dehydroabietic acid polymer is a polymer having a repeating unit represented by the following Formula (I).
[0030]

[0031] In Formula (I)  L1 represents a single bond or a divalent linking group; and L2 represents an alkylene group or an arylene group.
[0032] Examples of the divalent linking group represented by L1 include  but are not particularly limited to  -O-  -S-  -CO-  -SO2-  -O(CnH2n)O-  -CO(CnH2n)CO-  -(CnH2n)- (wherein n represents an integer of from 1 to 12  and preferably an integer of from 1 to 6)  and -C(-R1)(-R2)- (wherein R1 and R2 each independently represent a hydrogen atom  an alkyl group having from 1 to 8 carbon atoms (preferably  having from 2 to 4 carbon atoms)  or the like).
L1 preferably represents a single bond  -O-  -S-  -CH2-  or the like.
[0033] The alkylene group represented by L2 preferably has from 1 to 20 carbon atoms  and particularly preferably from 2 to 12 carbon atoms. The alkylene group represented by L2 may be straight chain  branched  or cyclic  and may further have a substituent.
The alkylene group represented by L2 may have a structure in which at least one carbon atom in the molecular chain is replaced with an oxygen atom.
[0034] Specific examples of the alkylene group represented by L2 include -(CH2)2-  -(CH2)3-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  and -CH2CH2OC6H4OCH2CH2-.
[0035] The arylene group represented by L2 preferably has from 6 to 20 carbon atoms  and particularly preferably from 6 to 15 carbon atoms. The arylene group represented by L2 may be a monocycle or a condensed ring  and may further have a substituent.
[0036] Specific examples of the arylene group represented by L2 include -C6H4- and -C6H4-C(CH3)2-C6H4-.
L2 preferably represents -(CH2)3-  -(CH2)10-  or -CH2CH2(OCH2CH2)3-.
[0037] The repeating unit represented by Formula (I) is preferably a repeating unit represented by the following Formula (II).
[0038]

[0039] In Formula (II)  L1 and L2 have the same definitions as L1 and L2 in Formula (I)  respectively  and preferable ranges thereof are also the same.
[0040] Examples of the polyester polymer include: in Formula (II) 
a polyester polymer having a structure in which L1 represents a single bond  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents an oxygen atom  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents a sulfur atom  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -CO-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -SO2-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -O(CH2)2O-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -O(CH2)3O-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -O(CH2)4O-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -O(CH2)8O-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -O(CH2)12O-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
[0041] a polyester polymer having a structure in which L1 represents -CO(CH2)2CO-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -CO(CH2)6CO-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -CO(CH2)10CO-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -CH2-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -(CH2)2-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -(CH2)3-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -(CH2)4-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -(CH2)8-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -(CH2)12-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -CH(-CH3)-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
[0042] a polyester polymer having a structure in which L1 represents -C(-CH3)2-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -CH(-CH2CH3)-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -C(CH3)(-CH2CH3)-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -C(-CH2CH3)2-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -CH(-CH2CH2CH3)-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -C(-CH3)(-CH2CH2CH3)-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -C(-CH2CH3)(-CH2CH2CH3)-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-; and
a polyester polymer having a structure in which L1 represents -C(-CH2CH2CH3)2-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -(CH2)12-  -CH2CH2OCH2CH2-  -CH2CH2(OCH2CH2)2-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-.
[0043] Among them  a polyester polymer having a structure in which L1 represents a single bond  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents an oxygen atom  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents a sulfur atom  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -CO-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -SO2-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -O(CH2)2O-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -O(CH2)3O-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -O(CH2)4O-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -CO(CH2)2CO-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -CO(CH2)4CO-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -CH2-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -(CH2)2-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -(CH2)3-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -(CH2)4-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -C6H4-  -(CH2)8-  -(CH2)10-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-;
a polyester polymer having a structure in which L1 represents -CH(-CH3)-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4-; and
a polyester polymer having a structure in which L1 represents -C(-CH3)2-  and L2 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -(CH2)6-  -(CH2)8-  -(CH2)10-  -CH2CH2(OCH2CH2)3-  -CH2CH2OC6H4OCH2CH2-  -C6H4-  or -C6H4C(CH3)2C6H4- are more preferable.
[0044] Particularly preferable polyester polymers are a polyester polymer having a structure  in which L1 represents a single bond  and L2 represents -(CH2)3-  -(CH2)10-  or -CH2CH2(OCH2CH2)3-;
a polyester polymer having a structure  in which L1 represents an oxygen atom  and L2 represents -(CH2)3-  -(CH2)10-  or -CH2CH2(OCH2CH2)3-;
a polyester polymer having a structure  in which L1 represents a sulfur atom  and L2 represents -(CH2)3-  -(CH2)10-  or -CH2CH2(OCH2CH2)3-; and
a polyester polymer having a structure  in which L1 represents -CH2-  and L2 represents -(CH2)3-  -(CH2)10-  or -CH2CH2(OCH2CH2)3-.
[0045] The dicarboxylic acid compound or derivative thereof which can be used as the raw material of the dehydroabietic acid polymer  that is a polyester polymer  may be a compound represented by the following Formula (IV) or a derivative thereof.
[0046]

[0047] In Formula (IV)  L1 represents a single bond or a divalent linking group; Y represents a chlorine atom  -OH  -OR  -OCOR  -OCOOR  or -OSO2R; and R represents an alkyl group or an aryl group.
[0048] In particular  a compound having a structure represented by Formula (IV)  in which L1 represents a single bond  -O-  -S-  -CO-  -SO2-  -O(CnH2n)O-  -CO(CnH2n)CO-  -(CnH2n)- (wherein n represents an integer of from 1 to 12)  or -C(-R1)(-R2)- (wherein R1 and R2 each independently represent a hydrogen atom or an alkyl group having from 1 to 8 carbon atoms) is preferable  and a compound having a structure represented by Formula (IV)  in which L1 represents a single bond  -O-  -S-  or -CH2- is more preferable.
[0049] Examples of the diol compound include aliphatic diols such as ethylene glycol  1 2-propanediol  1 3-propanediol  1 4-butanediol  1 6-hexanediol  1 8-octanediol  1 10-decanediol  1 12-dodecanediol  diethylene glycol  triethylene glycol  tetraethylene glycol  or 1 4-bis(2-hydroxyethoxy)benzene; and aromatic diols such as hydroquinone  2 2-bis(4-hydroxyphenyl)propane  and from the viewpoint of not lowering the degree of plant composition  1 3-propanediol  1 10-decanediol  and the like are more preferable.
[0050] Further  another example of the dehydroabietic acid polymer of the present invention is a polymer including a repeating unit represented by the following Formula (III). This polymer is a single molecule self-condensation type polymer.
[0051]

[0052] In Formula (III)  L3 represents a single bond or a divalent linking group.
[0053] Examples of the divalent linking group represented by L3 include  but are not particularly limited to  -(CnH2n)-  -CO(CnH2n)-  -(CnH2n)CO2-L4-  and -CO(CnH2n)CO2-L4- (wherein n represents an integer of from 1 to 12  and more preferably an integer of from 1 to 8  and the alkylene group in L3 may be straight chain  branched  or cyclic and may further have a substituent. The alkylene group in L3 may have a structure in which at least one carbon atom in the molecular chain is replaced with an oxygen atom. L4 represents an arylene group  preferably an arylene group having from 6 to 20 carbon atoms  and particularly preferably an arylene group having from 6 to 15 carbon atoms. The arylene group represented by L4 may be a monocycle or a condensed ring  and may further have a substituent.).
L3 preferably represents -(CH2)4-  -CO(CH2)3-  -(CH2)3CO2-C6H4-C(CH3)2-C6H4-  -CO(CH2)2CO2-C6H4-C(CH3)2-C6H4-  or the like.
[0054] Examples of a monomer (self-condensation type monomer) that is used for synthesizing the polymer including a repeating unit represented by Formula (III) include a compound represented by the following Formula (V) and a derivative thereof.
[0055]

[0056] In Formula (V)  L3 represents a single bond or a divalent linking group. Y represents a chlorine atom  -OH  -OR  -OCOR  -OCOOR  or -OSO2R  and R represents an alkyl group or an aryl group.
[0057] In particular  a compound having a structure represented by Formula (V)  in which L3 represents -(CH2)2-  -(CH2)3-  -CH2CH(CH3)-  -(CH2)4-  -CH2CH2OCH2CH2-  -CO(CH2)2-  -CO(CH2)3-  -CO(CH2)4-  -(CH2)2CO2-C6H4-C(CH3)2-C6H4-  -(CH2)3CO2-C6H4-C(CH3)2-C6H4-  -(CH2)4CO2-C6H4-C(CH3)2-C6H4-  -CO(CH2)2CO2-C6H4-C(CH3)2-C6H4-  -CO(CH2)3CO2-C6H4-C(CH3)2-C6H4-  or -CO(CH2)4CO2-C6H4-C(CH3)2-C6H4- is preferable  and a compound having a structure represented by Formula (V)  in which L3 represents -(CH2)4-  -CO(CH2)3-  -(CH2)3CO2-C6H4-C(CH3)2-C6H4-  or -CO(CH2)2CO2-C6H4-C(CH3)2-C6H4- is more preferable.
[0058] [Method for Producing Dehydroabietic Acid Polymer]
The method for producing the dehydroabietic acid polymer of the present invention is described.
The dehydroabietic acid polymer of the present invention is not particularly limited as long as the polymer is  as described above  a homopolymer obtained by the polymerization using dehydroabetic acid represented by Formula (A) above or a derivative thereof as a raw material monomer  or a copolymer obtained by the polymerization using dehydroabetic acid derivatives represented by Formula (A) above and other monomer  and has a repeating unit containing a dehydroabietic acid skeleton in the molecular structure.
[0059] The dehydroabietic acid used for the production of the dehydroabietic acid polymer can be obtained from rosin.
[0060] Rosin is a resin component which can be obtained from pine tree   and is classified into three types: “gum rosin”  “tall rosin”  and “wood rosin”  according to the extraction method. The components included in rosin are different depending on their extraction method or the growing district of pines  but generally  the components are a mixture of diterpene resin acids  such as abietic acid (1)  neoabietic acid (2)  palustric acid (3)  levopimaric acid (4)  dehydroabietic acid (5)  pimaric acid (6)  and isopimaric acid (7)  the structures of which are shown below.
[0061]

[0062] Among these diterpene resin acids  the compounds represented by (1) to (4) may cause disproportionation by a heat treatment in the present of a certain kind of metal catalyst  to be modified into dehydroabietic acid (5) and dihydroabietic acid (8) having the following structure.
[0063]

[0064] Namely  the dehydroabietic acid (5) which is necessary for carrying out the synthesis of the dehydroabietic acid polymer of the present invention can be obtained relatively easily by subjecting rosin  which is a mixture of various resin acids  to an appropriate chemical treatment  and can also be industrially produced at low costs. Further  the dihydroabietic acid (8) and the dehydroabietic acid (5) can be readily separated by a known method.
[0065] The dehydroabietic acid polymer of the present invention can be synthesized  for example  according to the following synthetic route 1 or 2. Here  the synthetic routes 1 and 2 are examples of a synthetic route for synthesizing the polymer having a repeating unit represented by Formula (II) above  which is a polyester polymer  as the dehydroabietic acid polymer of the present invention.

[0066] (Synthetic Route 1)
(Synthetic Route 1)


[0067] (Synthetic Route 2)

[0068] In the above synthetic route 1  L1  L2  and Y are those explained in Formula (IV)  respectively.
In the above synthetic route 2  L1  L2  R  and Y are those explained in Formula (IV)  respectively.
[0069] Herein below  the process (the process shown at the right hand end in the synthetic routes 1 and 2) of synthesizing the polyester polymer  which is the final product  from the compound represented by Formula (IV) above or a derivative thereof and a diol compound  in the synthetic routes 1 and 2  is described in detail. Note that  details on the synthesis examples of the polyester polymer according to the synthetic routes 1 and 2 are further explained specifically in the Examples described below.
[0070] In the synthetic routes 1 and 2  in the process of synthesizing the polymer (polyester polymer) having a repeating unit represented by Formula (II)  the polyester polymer can be synthesized by polycondensation reaction between a diol compound (preferably  an aliphatic diol compound) and the dicarboxylic acid chloride or diester included in the compound represented by Formula (IV).
[0071] Specific examples of the synthetic method include methods (for example  a melt polymerization method such as a transesterification method  a direct esterification method  or an acid chloride method  a low temperature solution polymerization method  a high temperature solution polycondensation method  an interfacial polycondensation method  or the like) described  for example  in Shin Kobunshi Jikkengaku (New Polymer Experimentology) 3  Kobunshi no Gosei Hanno (Synthesis and Reaction of Polymer) (2)  pages 78 to 95  Kyoritsu Press (1996); and particularly  an acid chloride method or an interfacial polycondensation method is preferably used in the present invention.
[0072] The transesterification method is a method in which the aliphatic diol compound and the dicarboxylic acid ester are heated in the molten state or in the solution state  as necessary in the presence of a catalyst  thereby allowing to react dealcoholation polycondensation  to synthesize the polyester.
[0073] The direct esterification method is a method in which the aliphatic diol compound and the dicarboxylic acid compound are heated in the molten state or in the solution state  in the presence of a catalyst  thereby allowing to react dehydration polycondensation  to synthesize the polyester.
[0074] The acid chloride method is a method in which the aliphatic diol compound and the dicarboxylic acid chloride compound are heated in the molten state or in the solution state  as necessary in the presence of a catalyst  thereby allowing to react HCl-elimination polycondensation  to synthesize the polyester.
[0075] The interfacial polymerization method is a method including dissolving the aliphatic diol compound in water  dissolving the dicarboxylic acid compound in an organic solvent  and allowing to react polycondensation at the water/ organic solvent interface using a phase transfer catalyst  thereby synthesizing the polyester.
[0076] Further  in a case in which the dehydroabietic acid polymer of the present invention is synthesized as a polymer having a repeating unit represented by Formula (III) above  the polymer can be synthesized by using a self-condensation type monomer derived from dehydroabietic acid  and allowing this monomer to react self-condensation. An example of a synthetic route for synthesizing the polymer having a repeating unit represented by Formula (III) above  that is a polyester polymer  as the dehydroabietic acid polymer of the present invention  is the following synthetic route 3.

[0077] (Synthetic Route 3)
(Synthetic Route 3)

[0078] In the above synthetic route 3  L3 and Y are those explained in Formula (V)  respectively.
[0079] Details on the synthesis example of the polymer including a repeating unit represented by Formula (III) are further explained specifically in the Examples described below.
[0080] The dehydroabietic acid polymer of the present invention as described above can be used singly as a polymer material. Alternatively  the dehydroabietic acid polymer of the present invention and various materials may be mixed to produce a composite material.
In the following  the composite material containing the dehydroabietic acid polymer of the present invention is described.
[0081] [Composite Material Containing Dehydroabietic Acid Polymer]
The dehydroabietic acid polymer of the present invention may be mixed with various materials for the purpose of improving the physical properties  to produce a composite material.
[0082] In a case in which the dehydroabietic acid polymer is used to produce a composite material  polymer alloying (mixing of different kinds of polymers) and mixing of a filler are especially important  and by carrying out these processes  the impact resistance  heat resistance  durability  moldability  and the like can be improved.
[0083] As the polymers used for polymer alloying  two or ore kinds of the dehydroabietic acid polymers of the present invention having different polymer characteristics may be used  or the dehydroabietic acid polymer of the present invention and a polymer other than the dehydroabietic acid polymer may be used in combination.
[0084] Examples of the polymer other than the dehydroabietic acid polymer of the present invention  which may be used for polymer alloying  include:
1) olefin-based resins (a homopolymer of a-olefin such as ethylene  propylene  1-butene  1-pentene  1-hexene  or 4-methyl-1-pentene; a homopolymer of cycloolefin such as cyclopentene  cyclohexene  cyclooctene  cyclopentadiene  1 3-cyclohexadiene  bicyclo[2.2.1]hept-2-ene  tricyclo[4.3.0.12 5]deca-3 7-diene  or tetracyclo[4.4.0.12 5.17 10]dodec-3-ene; a copolymer of a-olefins described above  a copolymer of a-olefin and other monomer capable of copolymerization  for example  vinyl acetate  maleic acid  vinyl alcohol  methacrylic acid  methyl methacrylate  ethyl methacrylate  or the like; or the like);
[0085] 2) polyester-based resins (a copolymer of a dicarboxylic acid monomer  such as terephthalic acid  isophthalic acid  2 6-naphthalenedicarboxylic acid  1 4-naphthalenedicarboxylic acid  succinic acid  adipic acid  or sebacic acid  and a diol or polyhydric alcohol monomer  such as ethylene glycol  propylene glycol  1 4-butylene glycol  1 4-cyclohexanedimethanol  diethylene glycol  triethylene glycol  polypropylene glycol  polyoxytetramethylene glycol  an alkylene oxide adduct of a bisphenol compound or a derivative thereof  trimethylolpropane  glycerin  or pentaerythritol; a polycondensation product of hydroxycarboxylic acid or the like  such as lactic acid  ß-hydroxybutyric acid  p-hydroxybenzoic acid  or 2 6-hydroxynaphthoic acid; or the like);
[0086] 3) polyamide-based resins (a polymer having an acid-amide bond in the chain thereof  which is obtained by polycondensation of a lactam having a three or more-membered ring structure  or an ?-amino acid or dibasic acid capable of polymerization with a diamine or the like  specifically  a polymer of e-caprolactam  aminocaproic acid  enantlactam  7-aminoheptanoic acid  11-aminoundecanoic acid  9-aminononanoic acid  a-pyrrolidone  a-piperidone  or the like; or a polymer obtained by polycondensation of a diamine  such as hexamethylenediamine  nonamethylenediamine  undecamethylenediamine  dodecamethylenediamine  or meta-xylenediamine  with a dicarboxylic acid  such as terephthalic acid  isophthalic acid  adipic acid  sebacic acid  dodecane dibasic acid  or glutaric acid  or a copolymer thereof  for example  nylon-4  nylon-6  nylon-7  nylon-8  nylon-11  nylon-12  nylon-6 6  nylon-6 10  nylon-6 11  nylon-6 12  nylon-6T  a nylon-6/ nylon-6 6 copolymer  a nylon-6/ nylon-12 copolymer  a nylon-6/ nylon-6T copolymer  a nylon-6I/ nylon-6T copolymer  or the like);
[0087] 4) rubbers and elastomers (natural rubber  isoprene rubber  butadiene rubber  1 2-polybutadiene rubber  styrene-butadiene rubber  chloroprene rubber  nitrile rubber  butyl rubber  ethylene-propylene rubber  chlorosulfonated polyethylene  acrylic rubber  epichlorohydrin rubber  polysulfide rubber  silicone rubber  fluorine-containing rubber  urethane rubber  or the like);
[0088] and  in addition to the above polymers  resins such as a polycarbonate-based resin  an acryl-based resin  a urethane-based resin  polyvinyl alcohol  a vinyl chloride-based resin  a styrene-based resin  polyacrylonitrile  polyvinylidene chloride  a fluororesin  polyacetal  polysulfone  ABS resin  or polyetheretherketone.
[0089] Among the above polymers  which may be used for polymer alloying  polylactic acid  poly(ß-hydroxylactic acid)  polybutylene succinate  or the like is preferably used from the viewpoint of not lowering the degree of plant composition.
[0090] Polymer alloying is generally performed by melt kneading; however  in a case in which phase separation occurs when performing simple kneading  a homogeneous phase is formed by  for example  using a compatibilizing agent  secondarily conducting block polymerization or graft polymerization  or dispersing one of the polymers in a cluster form.
[0091] Further  from the viewpoint of performing polymer alloying without impairing the characteristics of the dehydroabietic acid polymer of the present invention  the content ratio (on the basis of mass) of the dehydroabietic acid polymer of the present invention in the polymer alloy is preferably from 20% to 100%  and more preferably from 50% to 100%.
[0092] Moreover  the dehydroabietic acid polymer of the present invention can be improved to have desired polymer physical properties by mixing with various kinds of filler. In particular  mixing of filler is effective in improving the heat resistance  durability  and impact resistance.
[0093] Either an inorganic filler or an organic filler may be used as the filler.
Examples of a useful inorganic filler include fibrous inorganic fillers such as glass fiber  carbon fiber  graphite fiber  metallic fiber  potassium titanate whisker  aluminium borate whisker  magnesium-based whisker  silicon-based whisker  wollastonite  sepiolite  slug fiber  zonolite  ellestadite  gypsum fiber  silica fiber  silica alumina fiber  zirconia fiber  boron nitride fiber  silicon nitride fiber  or boron fiber; and plate-like or granular inorganic fillers such as glass flake  non-swelling mica  fullerene  carbon nanotube  carbon black  graphite  metallic foil  ceramic beads  talc  clay  mica  sericite  zeolite  bentonite  dolomite  kaolin  fine powdered silicic acid  feldspar powder  potassium titanate  shirasu balloon  calcium carbonate  magnesium carbonate  barium sulfate  calcium oxide  aluminium oxide  titanium oxide  magnesium oxide  aluminium silicate  silicon oxide  aluminium hydroxide  magnesium hydroxide  gypsum  novaculite  dawsonite  or terra alba.
Examples of a useful organic filler include synthetic fibers such as cellulose nanofiber  polyester fiber  nylon fiber  acrylic fiber  regenerated cellulose fiber  acetate fiber  or aramid fiber; natural fibers of kenaf  rami  cotton  jute  hemp  sisal  Manila hemp  flax  linen  silk  wool  or the like; fibrous organic fillers obtained from microcrystalline cellulose  sugar cane  wood pulp  wastepaper  used paper  or the like; and granular organic fillers such as organic pigments.
[0094] In most cases  a flame retardant is mixed with the dehydroabietic acid polymer of the present invention to produce a composite material  which is applied as a practical product.
A flame retardant is a material that makes a polymer material hard to burn or inhibits the spread of flame.
A halogen-based compound (a bromine or chlorine compound) or a phosphorus-based compound (an aromatic phosphate ester or the like) is mainly used as the flame retardant. However  these flame retardants generate substances which are toxic to the human body  or produce environmentally hazardous substances by fire  and therefore  improvement is required. From the viewpoints described above  aluminium hydroxide or magnesium hydroxide  each of which has attracted attention as a material superior in flame retarding effect and environmental safety  is preferably used as the flame retardant that is used in combination with the dehydroabietic acid polymer of the present invention.
[0095] A material (a flame retarding aid)  which enhances the flame retardency when used in combination with a flame retardant or forms a carbonized membrane on a resin surface to suppress the spread of fire  is also useful for the composite material containing the dehydroabietic acid polymer of the present invention. Specifically  an antimony compound as an inorganic material  or an organic aromatic compound (a phenol derivative or the like) is preferably used.
[0096] Further  to the dehydroabietic acid polymer of the present invention  in addition to the above substances  additives that are generally used  for example  plasticizers  stabilizers  impact resistance enhancers  crystal nucleating agents  slipping agents  antistatic agents  surfactants  pigments  dyes  fillers  antioxidants  processing aids  ultraviolet absorbents  anti-fog agents  antifungal agents  mildew-proofing agents  or the like  may be added alone or in a combination of two or more kinds of them.
[0097] The composite material of the present invention  which is obtained by mixing the materials described above  can be processed (molded) by various methods. As a method for molding  for example  extrusion molding  injection molding  or the like is used. The molded articles obtained as described above are used in applications such as constituent parts of automobile  electric household appliances  electrical and electronic equipments (OA or media related equipments  optical instruments  communication equipments  or the like)  machine parts  materials for housing and construction  or various vessels such as containers or bottles; however  the present invention is not particularly limited thereto.
[0098] The disclosure of Japanese Patent Application No. 2009-151456  filed on June 25  2009  is incorporated by reference herein in its entirety.
All publications  patent applications  and technical standards mentioned in this specification are herein incorporated by reference to the same extent as if such individual publication  patent application  or technical standard was specifically and individually indicated to be incorporated by reference.

EXAMPLES
[0099] Herein below  the present invention will be specifically described with respect to Examples  but the present invention is not limited to these Examples.
[0100] First  the compounds used in the synthesis of the dehydroabietic acid polymers of the present invention were synthesized from dehydroabietic acid as shown in the following synthesis examples [1] to [5].
[0101] [1] Synthesis Example of Dicarboxylic Acid Compound Having a Structure Represented by Formula (IV) in which L1 Represents a Single Bond and Y Represents -OH

(Synthetic Route)

[0102] a) Dehydroabietic acid (135 g  0.500 mol) was placed in a 1L three-necked flask equipped with a condenser tube  and was dissolved in acetic acid (450 mL). To the reaction system  orthoperiodic acid dihydrate (20.4 g  0.0895 mol) and iodine (93 g  0.366 mol) were added. Thereafter  concentrated sulfuric acid (15 mL)/ water (90 mL) was added thereto dropwise  followed by stirring at 60°C for 5 hours. Then  the reaction liquid was left to cool  and then the reaction liquid was poured into water  stirred for one hour  and subjected to filtration. The resulting residue was washed by pouring methanol over it  to obtain compound (1-I) (128 g  0.300 mol  60%).
[0103] b) The compound (1-I) (27.0 g  63.3 mmol) was placed in a 200 mL three-necked flask equipped with a condenser tube  and was dissolved in N N-dimethylacetamide (60 mL). To the reaction system  potassium carbonate (11 g  79.5 mmol) was added  and then benzyl chloride (8.41 g  66.4 mmol) was added dropwise  followed by stirring at 50°C for 3 hours. The reaction liquid was left to cool  then the reaction liquid was added to water  extracted with ethyl acetate  followed by separating the layers  and then the organic layer was washed with a saturated aqueous solution of sodium chloride  and dried over magnesium sulfate. The solvent was evaporated under reduced pressure  and the resulting concentrate was washed by pouring methanol over it  to obtain compound (1-II) (29.2 g  56.5 mmol  89.2%).
[0104] c) The compound (1-II) (21.7 g  42.0 mmol) was placed in a 500 mL three-necked flask equipped with a condenser tube  and was dissolved in hexamethylphosphoric triamide (200 mL). To the reaction system  dichlorobis(triphenylphosphine)nickel(II) (27.5 g  42.0 mmol)  tricyclohexylphosphine (1.18 g  4.21 mmol)  potassium iodide (7.0 g  42.1 mmol)  and zinc (6.3 g  96.3 mmol) were added  followed by stirring at 60°C for 5 hours. Then  the reaction liquid was left to cool  and then the reaction liquid was added to dilute hydrochloric acid  extracted with ethyl acetate  and subjected to filtration using celite  followed by separating the layers  and then the organic layer was washed with a saturated aqueous solution of sodium hydrogencarbonate and a saturated aqueous solution of sodium chloride  and subsequently dried over magnesium sulfate. The solvent was evaporated under reduced pressure  and the resulting concentrate was purified by silica gel column chromatography  to obtain compound (1-III) (6.54 g  8.40 mmol  40.0%).
[0105] d) The compound (1-III) (2.8 g  3.59 mmol) was placed in a 200 mL autoclave  and was dissolved in tetrahydrofuran (60 mL). To the reaction system  10% Pd-C (0.3 g) was added  followed by stirring at 60°C under a hydrogen pressure of 5 MPa for 12 hours. Then  the reaction liquid was left to cool  and the reaction liquid was filtrated  thereby removing the solvent  and then the residue was washed by pouring methanol over it  to obtain compound (1-IV) (2.05 g  95.0%) that was a dicarboxylic acid compound.
[0106] 1H-NMR data of the compound (1-IV) are shown below.
[0107] 1H NMR (300 MHz  CDCl3) d 0.90 to 2.40 (m  42H)  2.49 to 2.77 (m  2H)  2.81 to 3.09 (m  4H)  6.88 to 6.98 (m  2H)  6.98 (s  2H)
[0108] [2] Synthesis Example of Dicarboxylic Acid Compound Having a Structure Represented by Formula (IV) in which L1 Represents an Oxygen Atom and Y Represents -OH

(Synthetic Route)

[0109] a) Dehydroabietic acid (90.1 g  0.300 mol) was placed in a 1L three-necked flask equipped with a condenser tube and was dissolved in acetic acid (500 mL)  and nitrogen was blown into the flask at room temperature. Thereafter  bromine (53.0 g  0.330 mol) was added thereto dropwise  followed by stirring at room temperature for 8 hours. Then  the reaction liquid was poured into water  stirred for one hour  and then subjected to filtration. The resulting residue was washed by pouring methanol over it  to obtain compound (2-I) (61.1 g  0.161 mol  53.7%).
[0110] b) The compound (2-I) (7.50 g  20.0 mmol) was placed in a 200 mL three-necked flask equipped with a condenser tube  and was dissolved in N N-dimethylacetamide (30 mL). To the reaction system  potassium carbonate (3.28 g  23.7 mmol) was added  and then benzyl chloride (2.66 g  21.0 mmol) was added dropwise  followed by stirring at 50°C for 3 hours. Then  the reaction liquid was added to water  extracted with ethyl acetate  followed by separating the layers  and then the organic layer was washed with a saturated aqueous solution of sodium chloride  and dried over magnesium sulfate. The solvent was evaporated under reduced pressure  and the resulting concentrate was washed by pouring methanol over it  to obtain compound (2-II) (7.01 g  14.9 mmol  74.5%).
[0111] c) The compound (2-II) (11.7 g  25.0 mmol) was placed in a 200 mL three-necked flask equipped with a reflux tube  and was dissolved in 1 4-dioxane (20 mL)  and then an aqueous solution (20 mL) obtained by dissolving potassium hydroxide (14.0 g  250 mmol) was added thereto. To the reaction system  tris(benzylideneacetone)dipalladium(0) (1.14 g  1.24 mmol) and di-tert-butylphosphino-2’-4’-6’-triisopropylbiphenyl (1.10 g  2.59 mmol) were added  followed by refluxing at 100°C for 5 hours. Then  the reaction liquid was left to cool  and then the reaction liquid was added to dilute hydrochloric acid  extracted with ethyl acetate  and subjected to filtration using celite  followed by separating the layers  and then the organic layer was washed with a saturated aqueous solution of sodium hydrogencarbonate and a saturated aqueous solution of sodium chloride  and subsequently dried over magnesium sulfate. The solvent was evaporated under reduced pressure  and the resulting concentrate was purified by silica gel column chromatography  to obtain compound (2-III) (9.22 g  22.7 mmol  90.8%).
[0112] d) The compound (2-III) (2.44 g  6.00 mmol) and the compound (2-II) (2.34 g  5.00 mmol) were placed in a 100 mL three-necked flask equipped with a condenser tube  and were suspended in toluene (20 mL). To the reaction system  tripotassium phosphate (2.55 g  12.0 mmol)  palladium acetate (0.11 g  0.5 mmol)  and di-tert-butylphosphino-2’-4’-6’-triisopropylbiphenyl (0.21 g  0.5 mmol) were added  followed by stirring at 100°C for 5 hours. Then  the reaction liquid was left to cool  and then the reaction liquid was added to dilute hydrochloric acid  extracted with ethyl acetate  and subjected to filtration using celite  followed by separating the layers  and then the organic layer was washed with a saturated aqueous solution of sodium hydrogencarbonate and a saturated aqueous solution of sodium chloride  and subsequently dried over magnesium sulfate. The solvent was evaporated under reduced pressure  and the resulting concentrate was purified by silica gel column chromatography  to obtain compound (2-IV) (1.0 g  1.26 mmol  25.2%).
[0113] e) The compound (2-IV) (2.90 g  3.65 mmol) was placed in a 200 mL autoclave  and was dissolved in tetrahydrofuran (60 mL). To the reaction system  10% Pd-C (0.3 g) was added  followed by stirring at room temperature under a hydrogen pressure of 5 MPa for 3 hours. Then  the reaction liquid was filtrated  and the solvent was evaporated under reduced pressure  and then the resulting concentrate was washed by pouring methanol over it  to obtain compound (2-V) (2.02 g  3.29 mmol  90.1%) that was a dicarboxylic acid compound.
[0114] 1H-NMR data of the compound (2-V) are shown below.
[0115] 1H NMR (300 MHz  CDCl3) d 0.90 to 2.30 (m  42H)  2.75 to 3.02 (m  4H)  3.10 to 3.38 (m  2H)  6.59 (s  2H)  6.93 (s  2H)
[0116] [3] Synthesis Example of Dicarboxylic Acid Compound Having a Structure Represented by Formula (IV) in which L1 Represents a Sulfur Atom and Y Represents -OH

(Synthetic Route)

[0117] a) Dehydroabietic acid (30.1 g  100 mmol) was placed in a 300 mL three-necked flask and was dissolved in methylene chloride (100 mL). While blowing nitrogen into the flask  oxalyl chloride (10.3 mL  120 mol) was added thereto dropwise  followed by stirring at room temperature for one hour  and then the flask was placed in an ice bath and methanol (50 mL) was added thereto dropwise  followed by stirring for 3 hours. Then  the reaction solution was added to a saturated aqueous solution of sodium hydrogencarbonate  extracted with methylene chloride  followed by separating the layers  and then the organic layer was washed with a saturated aqueous solution of sodium chloride  and dried over magnesium sulfate. The solvent was evaporated under reduced pressure  and the resulting concentrate was washed by pouring methanol over it  to obtain compound (3-I) (26.7 g  84.9 mmol  84.9%).
[0118] b) The compound (3-I) (12.6 g  40.0 mmol) was placed in a 200 mL three-necked flask  and was dissolved in methylene chloride (30 mL). Then  disulfur dichloride (4.07 g  30.4 mmol) was added thereto  and then the flask was placed in an ice bath and titanium tetrachloride (8.70 g  45.9 mmol) was added thereto dropwise  followed by stirring at room temperature for 3 hours. Then  the reaction liquid was added to ice-water  extracted with ethyl acetate  followed by separating the layers  and then the organic layer was washed with a saturated aqueous solution of sodium chloride  and dried over magnesium sulfate. The solvent was evaporated under reduced pressure  and the resulting concentrate was purified by silica gel column chromatography  to obtain compound (3-II) (10.5 g  15.9 mmol  79.5%).
[0119] c) The compound (3-II) (10.5 g  15.9 mmol) was placed in a 500 mL three-necked flask equipped with a reflux tube  and was dissolved in a mixed solvent of ethanol (300 mL) and water (20 mL). Then  potassium hydroxide (20 g  0.356 mol) was added thereto  and the resulting mixture was refluxed at 80°C for 18 hours. Then  the reaction liquid was left to cool  and then the reaction liquid was added to water  neutralized with dilute hydrochloric acid  extracted with ethyl acetate  followed by separating the layers  and then the organic layer was washed with a saturated aqueous solution of sodium chloride  and dried over magnesium sulfate. The solvent was evaporated under reduced pressure  and the resulting concentrate was washed by pouring methanol over it  to obtain compound (3-III) (7.25 g  11.9 mmol  74.8%) that was a dicarboxylic acid compound.
[0120] 1H-NMR data of the compound (3-III) are shown below.
[0121] 1H NMR (300 MHz  CDCl3) d 0.90 to 2.10 (m  42H)  2.70 to 2.98 (m  4H)  3.60 to 3.80 (m  2H)  6.65 (s  2H)  6.97 (s  2H)
[0122] [4] Synthesis Example of Dicarboxylic Acid Compound Having a Structure Represented by Formula (IV) in which L1 Represents Methylene and Y Represents -OH
(Synthetic Route)

[0123] Dehydroabietic acid (30.1 g  0.100 mol) and a 36% aqueous formaldehyde solution (4.17 g  0.0500 mol) were placed in a 500 mL three-necked flask and were dissolved in methylene chloride (100 mL). To the reaction system  sulfuric acid (20 mL) was added dropwise  followed by stirring at room temperature for 3 hours. Then  the reaction liquid was added to water  extracted with methylene chloride  followed by separating the layers  and then the organic layer was washed with a saturated aqueous solution of sodium chloride  and dried over magnesium sulfate. The solvent was evaporated under reduced pressure  and the resulting concentrate was purified by silica gel column chromatography  to obtain compound (4-I) (20.0 g  0.0326 mol  65.2%) that was a dicarboxylic acid compound.
[0124] 1H-NMR data of the compound (4-I) are shown below.
[0125] 1H NMR (300 MHz  CDCl3) d 0.90 to 2.30 (m  42H)  2.76 to 2.98 (m  4H)  3.00 to 3.18 (m  2H)  3.96 (s  2H)  6.68 (s  2H)  6.95 (s  2H)  11.10 (br-s  2H) 
[0126] [5] Synthesis Example of Self-Condensation Type Monomer

(Synthetic Route)

[0127] a) Methyl dehydroabietate (the compound (3-I) obtained in [3] above) (44.0 g  0.140 mol) and succinic anhydride (20.7 g  0.207 mol) were placed in a 500 mL three-necked round-bottomed flask and were dissolved in methylene chloride (240 mL). To the reaction mixture  anhydrous aluminuim chloride (63.6 g  0.477 mol) was added with small portion at a temperature of 10°C to 15°C. The mixture was stirred at room temperature for 3 hours  then  the reaction liquid was added to ice-water  extracted with methylene chloride  followed by separating the layers  and then the organic layer was washed with water  and dried over magnesium sulfate. The solvent was evaporated under reduced pressure  and then methanol was added to the resulting concentrate to conduct crystallization and washing by pouring  thereby obtaining compound (5-I) (49.6 g  0.120 mol  85.7%).
[0128] b) The compound (5-I) (37.0 g  89.3 mmol) and triethylsilane (31.2 g  0.268 mol) were placed in a 300 mL three-necked round-bottomed flask equipped with a condenser tube and were suspended. The resulting suspension was heated to 40°C  and to the reaction system  trifluoroacetic acid (70.6 g  0.619 mol) was added dropwise  followed by stirring at 65°C for 12 hours. Then  the reaction solution was left to cool  and then the reaction solution was added to ice  extracted with ethyl acetate  followed by separating the layers  the organic layer was washed with a saturated aqueous solution of sodium hydrogencarbonate  followed by adjusting the pH to 3  and then dried over magnesium sulfate. The solvent was evaporated under reduced pressure  and then n-hexane was added to the resulting concentrate to conduct crystallization and washing by pouring  thereby obtaining compound (5-II) (32.0 g  79.9 mmol  89.5%).
[0129] c) The compound (5-II) (6.70 g  16.7 mmol) was placed in a 100 mL three-necked round-bottomed flask and was dissolved in methylene chloride (20 mL). To the reaction mixture  oxalyl chloride (1.7 mL  21.5 mmol) was added dropwise  followed by stirring at room temperature for 2 hours. Then  the reaction solution was concentrated  and the resulting concentrate was dissolved in tetrahydrofuran (30 mL). To the reaction system  sodium borohydride (1.3 g  34.4 mmol) was added  followed by stirring at room temperature for 5 hours. Then  the reaction liquid was added to water  and 6 N hydrochloric acid was added thereto  and then the resulting mixture was extracted with ethyl acetate  followed by separating the layers  the organic layer was washed with water  and dried over magnesium sulfate. The solvent was evaporated under reduced pressure  and the resulting concentrate was purified by column chromatography  to obtain compound (5-III) (3.2 g  8.28 mmol  49.6%) that was a self-condensation type monomer.
[0130] 1H-NMR data of the compound (5-III) are shown below.
[0131] 1H NMR (300 MHz  CDCl3) d 1.07 to 1.98 (m  23H)  2.12 to 2.39 (m  2H)  2.50 to 2.70 (m  2H)  2.77 to 2.95 (m  2H)  3.00 to 3.19 (m  1H)  3.60 to 3.75 (m  2H)  3.65 (s  3H)  6.89 (s  1H)  6.97 (s  1H)

[0132] [Example 1]
(Synthesis of Dehydroabietic Acid Polymer (A))

[0133] a) The compound (1-IV) (1.00 g  1.67 mmol) was placed in a 50 mL three-necked flask and was suspended in methylene chloride (10 mL). Then  oxalyl chloride (0.3 mL  3.50 mmol) was added thereto dropwise  and a catalytic amount of N N-dimethylformamide was added  followed by stirring at room temperature for 2 hours. Thereafter  the reaction solution was concentrated  to obtain compound (1-V) (1.06 g  1.67 mmol  q. y.).
[0134] b) The compound (1-V) (1.06 g  1.67 mmol)  that was a dicarboxylic acid compound  and 1 3-propanediol (127 mg  1.67 mmol) were placed in a 50 mL three-necked flask equipped with a nitrogen inlet tube  and were dissolved in 1 2-dichlorobenzene (1.5 mL). While blowing nitrogen into the flask  the resulting mixture was stirred and heated to 100°C  and reaction was carried out for one hour  subsequently at 170°C for 5 hours  and further  at 200°C for 5 hours. The reaction solution was left to cool  then the reaction product was dissolved in dichloromethane (5 mL)  and poured into 2-propanol (200 mL)  and then the precipitates separated were filtered off. The precipitates were dissolved in tetrahydrofuran (5 mL)  and insoluble matters were removed  and then the resulting solution was poured into 2-propanol (200 mL)  and the reprecipitated polymer was filtered off  washed with 2-propanol  and dried  to obtain a powdery polyester (0.98 g)  which was designated as dehydroabietic acid polymer (A).
The weight average molecular weight of the dehydroabietic acid polymer (B) as measured by GPC was 12 000. Further  concerning the thermal physical properties of the dehydroabietic acid polymer (A)  the glass transition temperature Tg as measured by DSC at a temperature raising rate of 10 °C/min was 200°C.
[0135] 1H-NMR data of the dehydroabietic acid polymer (A) are shown below.
[0136] 1H NMR (300 MHz  CDCl3) d 0.90 to 2.40 (m  44H)  2.49 to 2.77 (m  2H)  2.81 to 3.09 (m  4H)  3.39 to 4.37 (m  4H)  6.88 to 6.98 (m  2H)  6.98 (s  2H)

[0137] [Example 2]
(Synthesis of Dehydroabietic Acid Polymer (B))


[0138] Acid chloride (2-VI) (1.96 g  3.01 mmol) was obtained in a manner substantially similar to that in Example 1  except that the compound (2-V) (1.85 g  3.01 mmol) was used as the dicarboxylic acid compound  and thereafter  the obtained acid chloride and 1 3-propanediol (229 mg  3.01 mmol) were allowed to undergo polycondensation reaction and subjected to treatment  to obtain a polyester (1.45 g)  which was designated as dehydroabietic acid polymer (B).
The weight average molecular weight of the dehydroabietic acid polymer (B) as measured by GPC was 10 700. Further  concerning the thermal physical properties of the dehydroabietic acid polymer (B)  the glass transition temperature Tg as measured by DSC at a temperature raising rate of 10 °C/min was 138°C.
[0139] 1H-NMR data of the dehydroabietic acid polymer (B) are shown below.
[0140] 1H NMR (300 MHz  CDCl3) d 0.90 to 2.30 (m  44H)  2.75 to 3.02 (m  4H)  3.10 to 3.38 (m  2H)  4.00 to 4.30 (m  4H)  6.59 (s  2H)  6.93 (s  2H)

[0141] [Example 3]
(Synthesis of Dehydroabietic Acid Polymer (C))


[0142] Acid chloride (3-IV) was obtained in a manner substantially similar to that in Example 1  except that the compound (3-III) (3.15 g  4.99 mmol) was used as the dicarboxylic acid compound  and thereafter  the compound (3-IV) (3.33 g  4.99 mmol) and 1 3-propanediol (380 mg  4.99 mmol) were placed in a 50 mL three-necked flask  and were dissolved in dichloromethane (10 mL). Absolute pyridine (10 mL) was added thereto  and while blowing nitrogen into the flask  the resulting mixture was stirred at room temperature for one hour  then the temperature of the mixture was raised to 40°C  and reaction was carried out for 2 hours and subsequently at 60°C for 3 hours. The reaction solution was left to cool  then the reaction product was poured into methanol (100 mL)  and the precipitates separated were filtered off. The precipitates were dissolved in tetrahydrofuran (30 mL)  and insoluble matters were removed  and then the resulting solution was poured into methanol (100 mL)  to perform reprecipitation. The resulting polymer was filtered off  washed with methanol  and dried  to obtain a powdery polyester (1.85 g)  which was designated as dehydroabietic acid polymer (C).
The weight average molecular weight of the dehydroabietic acid polymer (C) as measured by GPC was 6 600. Further  concerning the thermal physical properties of the dehydroabietic acid polymer (C)  the glass transition temperature Tg as measured by DSC at a temperature raising rate of 10 °C/min was 105°C.
[0143] 1H-NMR data of the dehydroabietic acid polymer (C) are shown below.
[0144] 1H NMR (300 MHz  CDCl3) d 0.90 to 2.29 (m  44H)  2.70 to 2.98 (m  4H)  3.19 to 3.49 (m  2H)  3.98 to 4.27 (m  4H)  6.85 (s  2H)  7.47(s  2H)
[0145] [Example 4]
(Synthesis of Dehydroabietic Acid Polymer (D))


[0146] Acid chloride (4-II) was obtained in a manner substantially similar to that in Example 1  except that the compound (4-I) (24.5 g  40.0 mmol) was used as the dicarboxylic acid compound  and thereafter  the compound (4-II) (26.0 g  40.0 mmol) and 1 3-propanediol (3.04 g  40.0 mmol) were placed in a 200 mL three-necked flask equipped with a nitrogen inlet tube  and were dissolved in dichloromethane (20 mL). Absolute pyridine (50 mL) was added thereto dropwise  and while blowing nitrogen into the flask  the resulting mixture was stirred at room temperature for one hour  then the temperature of the mixture was raised to 50°C  and reaction was carried out for one hour  subsequently at 100°C for 3 hours  and further  at 120°C for 5 hours. The reaction liquid was left to cool  then the reaction product was poured into methanol (1 L)  and then the precipitates separated were filtered off. The precipitates were dissolved in tetrahydrofuran (50 mL)  and insoluble matters were removed  and then the resulting solution was poured into methanol (1 L)  and the reprecipitated polymer was filtered off  washed with methanol  and dried  to obtain a powdery polyester (21.5 g)  which was designated as dehydroabietic acid polymer (D).
The weight average molecular weight of the dehydroabietic acid polymer (D) as measured by GPC was 11 600. Further  concerning the thermal physical properties of the dehydroabietic acid polymer (D)  the glass transition temperature Tg as measured by DSC at a temperature raising rate of 10 °C/min was 125°C.
[0147] 1H-NMR data of the dehydroabietic acid polymer (D) are shown below.
[0148] 1H NMR (300 MHz  CDCl3) d 0.90 to 2.30 (m  44H)  2.76 to 2.98 (m  4H)  3.00 to 3.18 (m  2H)  3.96 (s  2H)  4.02 to 4.25 (m  4H)  6.68 (s  2H)  6.95(s  2H)
[0149] Fig. 1 shows a 1H-NMR spectrum of compound (4-I) used in the Example. Further  Fig. 2 shows a 1H-NMR spectrum of the obtained dehydroabietic acid polymer (D).
[0150] [Example 5]
(Synthesis of Dehydroabietic Acid Polymer (E))

[0151] The compound (5-III) (2.0 g  5.17 mmol) was placed in a 50 mL three-necked round-bottomed flask equipped with a nitrogen inlet tube  and tetraethyl orthotitanate (100 mg  0.438 mmol) was added thereto. Under a reduced pressure of 200 mmHg to 250 mmHg  while letting dry nitrogen flow gently  the temperature of the mixture was gradually raised to 200°C  the mixture was heated for 2 hours  and the generated methanol was distilled off. Further  the mixture was heated at 220°C for 2 hours  and then at 250°C for 2 hours. The viscous liquid was left to cool  and then methanol was added thereto  the precipitates separated were filtered off  and the precipitates were washed with methanol. The resulting precipitates were dried and ground  to obtain a powdery polyester (1.80 g)  which was designated as dehydroabietic acid polymer (E).
The weight average molecular weight of the dehydroabietic acid polymer (E) as measured by GPC was 9 700. Further  concerning the thermal physical properties of the dehydroabietic acid polymer (E)  the glass transition temperature Tg as measured by DSC at a temperature raising rate of 10 °C/min was 102°C.
[0152] 1H-NMR data of the dehydroabietic acid polymer (E) are shown below.
[0153] 1H NMR (300 MHz  CDCl3) d 1. 07 to 1.98 (m  23H)  2.12 to 2.41 (m  2H)  2.45 to 2.71 (m  2H) 2.72 to 2.95 (m  2H)  2.96 to 3.15(m  1H)  3.92 to 4.25 (m  2H)  6.88 (s  1H)  6.96(s  1H)
[0154] [Evaluation]
Using the dehydroabietic acid polymers (A) to (E) obtained in Examples 1 to 5 and commercially available PC (polycarbonate)  PET (polyethylene terephthalate)  and PLA (polylactic acid) as comparative polymers in Comparative Examples 1 to 3  physical properties  that is  glass transition temperature Tg (°C)  coefficient of water absorption (%)  and degree of hydrolysis of the polymers were compared and evaluated. The evaluation results are shown in Table 1 below.
[0155] Details on the PC  PET  and PLA used as the comparative polymers in Comparative Examples 1 to 3 are as follows.
PC: polycarbonate manufactured by Teijin Chemicals Ltd.  trade name: PANLIGHT L-1225Y  Tg: 150°C
PET: polyethylene terephthalate manufactured by Sigma-Aldrich Corporation  trade name: POLY(ETHYLENE TEREPHTHALATE) GRANULAR  Tg: 67°C
PLA: polylactic acid manufactured by Mitsui Chemicals  Inc.  trade name: LACEA H-140  Tg: from 57°C to 60°C
[0156]
The coefficient of water absorption was measured as follows.
Each (1 g) of the dehydroabietic acid polymers (A) to (E) obtained in Examples 1 to 5 and the commercially available PC  PET  and PLA in Comparative Examples 1 to 3 was heat pressed (at a temperature of from 160°C to 250°C) to prepare a film having a thickness of 200 µm. The obtained film was dipped in water at 23°C for 24 hours  and then water droplets residing on the surfaces were wiped out well  and the weight of the film was measured quickly. The coefficient of water absorption was calculated according to the following equation.
Coefficient of Water Absorption (%) = (Weight of Film After Dipping in Water - Weight of Film Before Dipping in Water)/Weight of Film Before Dipping in Water
[0157]
The degree of hydrolysis was measured as follows.
Each (1 g) of the dehydroabietic acid polymers (A) to (E) obtained in Examples 1 to 5 and the commercially available PC  PET  and PLA used as comparative polymers in Comparative Examples 1 to 3 was dissolved in THF (tetrahydrofuran) (30 mL) and in 1 2-dichloroethane (30 mL)  respectively  and 1 N NaOH aqueous solution (10 mL) was added to the THF solution  and on the other hand  sulfuric acid (0.1 mL) was added to the 1 2-dichloroethane solution  followed by stirring for 24 hours. The solution that had been stirred was poured in water  and the weight average molecular weight of the precipitates separated was measured by GPC.
With regard to the dehydroabietic acid polymers and the comparative polymers  the ratio of the weight average molecular weight after hydrolysis relative to the weight average molecular weight before hydrolysis was designated as the degree of hydrolysis.

[0158] TABLE 1
Dehydroabietic Acid Polymer or Comparative Polymer Glass Transition Temperature
Tg (°C) Water Absorption
(%) Degree of Hydrolysis
Acid Alkali
Example 1 (A) 200 0.18 0.93 0.97
Example 2 (B) 138 0.2 0.91 0.96
Example 3 (C) 105 0.21 0.9 0.94
Example 4 (D) 125 0.17 0.91 0.97
Example 5 (E) 102 0.19 0.92 0.97
Comparative
Example 1 PC 150 0.25 0.7 0.03
Comparative
Example 2 PET 67 0.52 0.75 0.08
Comparative
Example 3 PLA 57-60 0.34 0.13 0.02

[0159] As shown in Table 1  it was understood that the dehydroabietic acid polymers (A) to (E) (polyester polymers) obtained in Examples 1 to 5 exhibited improved heat resistance and improved moisture and water resistance  as compared to the PLA. Further  it was also understood that  as compared to the PET and PC  the dehydroabietic acid polymers (A) to (E) exhibited improved moisture and water resistance.
[0160] A multi-purpose test piece according to JIS K 7139 was prepared by injection molding using the dehydroabietic acid polymer of each of the Examples. All of the dehydroabietic acid polymers of the Examples exhibited excellent moldability  and it was confirmed that the obtained test pieces were substances superior in strength usable as a member for electronic equipments.

CLAIMS:
1. A dehydroabietic acid polymer comprising a repeating unit containing a dehydroabietic acid skeleton.

2. The dehydroabietic acid polymer according to claim 1  wherein the repeating unit comprises a dimer structure in which two dehydroabietic acid skeletons bond directly or via a linking group.

3. The dehydroabietic acid polymer according to claim 1 or claim 2  comprising a polyester obtained using a dehydroabietic acid derivative and a diol compound.

4. The dehydroabietic acid polymer according to any one of claims 1 to 3  wherein the repeating unit is a repeating unit represented by the following Formula (I):

wherein  in Formula (I)  L1 represents a single bond or a divalent linking group  and L2 represents an alkylene group or an arylene group.

5. The dehydroabietic acid polymer according to claim 4  wherein the repeating unit represented by Formula (I) is a repeating unit represented by the following Formula (II):

wherein  in Formula (II)  L1 and L2 respectively have the same definition as L1 and L2 in Formula (I).

6. The dehydroabietic acid polymer according to claim 4 or claim 5  wherein  in Formula (I) or (II)  L1 represents a single bond  -O-  -S-  -CO-  -SO2-  -O(CnH2n)O-  -CO(CnH2n)CO-  -CnH2n-  or -C(-R1)(-R2)-; each of R1 and R2 independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; and n represents an integer of from 1 to 20.

7. The dehydroabietic acid polymer according to claim 1  comprising a polymer comprising a repeating unit represented by the following Formula (III):

wherein  in Formula (III)  L3 represents a single bond or a divalent linking group.

8. The dehydroabietic acid polymer according to any one of claims 1 to 7  wherein a weight average molecular weight of the polymer is from 5 000 to 500 000.

9. A composite material comprising the dehydroabietic acid polymer according to any one of claims 1 to 8.

10. A dehydroabietic acid derivative comprising a compound represented by the following Formula (IV):

wherein  in Formula (IV)  L1 represents a single bond or a divalent linking group; Y represents -OH  -OR  -OCOR  -OCOOR  or -OSO2R; and R represents an alkyl group or an aryl group.

ABSTRACT
The present invention provides a dehydroabietic acid polymer comprising a repeating unit containing a dehydroabietic acid skeleton  and a composite material including the same.