JP7367524B2 - Polycarbonate copolymers and molded products - Google Patents

Description

The present invention relates to a polycarbonate copolymer having a structural unit derived from a dihydroxy compound and a structural unit derived from a branched organopolysiloxane, and a molded article containing the polycarbonate copolymer.

In recent years, polycarbonate resins using ether group-containing diols typified by isosorbide, which is a plant-derived raw material, have been developed out of consideration for the environment (see Patent Documents 1 and 2). Polycarbonate resins using isosorbide are known to have excellent heat resistance, weather resistance, and impact resistance, and are also known to be applied to interior and exterior parts of automobiles (see Patent Document 3).

On the other hand, a resin composition containing a polycarbonate resin containing a structural unit derived from isosorbide and a silicone compound is known (see Patent Document 4). Patent Document 4 describes that inclusion of a silicone compound improves scratch resistance. Furthermore, in Patent Document 5, by containing a polycarbonate resin containing a structural unit derived from isosorbide and a silicone compound having a diorganosiloxane structure or a specific organosilsesquioxane structure, abrasion resistance is improved and moldability is improved. It is described that the product has good transparency and excellent initial appearance, mechanical properties, etc.

International publication WO2004/111106 International publication WO2007/063823 Japanese Patent Application Publication No. 2013-209585 Japanese Patent Application Publication No. 2015-199954 Japanese Patent Application Publication No. 2017-008140

In recent years, the use of polycarbonate resin molded products having structural units derived from isosorbide, for example, for interior and exterior parts for vehicles such as automobiles, has been considered. Polycarbonate resins are required to provide a beautiful appearance to the molded product due to the transparency of the resin itself, and to prevent scratches that may occur when the surface of the molded product is rubbed with a tissue, for example. In other words, polycarbonate resins and molded products thereof are desired to have excellent transparency and scratch resistance.

However, there is still room for improvement in the molded articles of conventional polycarbonate resin compositions described in Patent Documents 4 and 5, etc. in terms of increasing scratch resistance while maintaining high transparency.

The present invention has been made in view of such problems, and provides a polycarbonate copolymer that can yield molded products with excellent transparency and scratch resistance, and molded products thereof.

One embodiment of the present invention includes a structural unit derived from a dihydroxy compound represented by the following formula (1),
A polycarbonate copolymer having a structural unit derived from a branched organopolysiloxane having a hydroxyl group,
The branched organopolysiloxane has a polysiloxane skeleton and an organic group containing a reactive functional group and a compatible group bonded to the siloxane bond of the polysiloxane skeleton, and the organic group serves as the reactive functional group. having at least the above hydroxyl group,
A structural unit derived from a dihydroxy compound represented by the following formula (1), in which the compatible group is a polar group having one or more of an aromatic group, an oxygen atom, a sulfur atom, and a nitrogen atom. and,
A polycarbonate copolymer having a structural unit derived from a branched organopolysiloxane having a hydroxyl group.

Another aspect of the invention is a molded article comprising the polycarbonate copolymer described above.

According to the above-mentioned polycarbonate copolymer, a molded article having both excellent transparency and scratch resistance can be obtained. In other words, a molded article containing a polycarbonate copolymer has excellent transparency and can prevent scratches from occurring when the molded article is wiped with a tissue, for example.

Embodiments of the present invention will be described in detail below. However, the explanation of the configuration and the like described below is an example of the embodiment of the present invention, and the present invention is limited to the following content unless it exceeds the gist thereof. Not done. Furthermore, when the expression "~" is used in this specification, it is used in a meaning that includes the numerical values or physical values described before and after it. In addition, numerical values or physical values described as upper limits and lower limits are used in a meaning that includes those values.

[Polycarbonate copolymer]
The polycarbonate copolymer is a polycarbonate resin having at least a structural unit derived from a dihydroxy compound represented by formula (1) and a structural unit derived from a branched organopolysiloxane. Branched organopolysiloxane has hydroxyl groups. A polycarbonate copolymer is a polymer obtained by polymerizing a dihydroxy compound represented by formula (1) and a branched organopolysiloxane, and a copolymer of a dihydroxy compound represented by formula (1) and a branched organopolysiloxane. It is a combination. The polycarbonate copolymer may contain structural units derived from monomers other than the dihydroxy compound represented by formula (1) and the branched organopolysiloxane. In the following explanation, the structural unit derived from the dihydroxy compound represented by formula (1) will be appropriately referred to as "structural unit (a1)", and the structural unit derived from branched organopolysiloxane will be appropriately referred to as "constituent unit (a1)". "Constituent unit (a2)". A structural unit derived from a monomer other than the dihydroxy compound represented by formula (1) and the branched organopolysiloxane, which constitutes the polycarbonate copolymer, is appropriately referred to as a "constituent unit (a3)." Note that the structural unit refers to a unit that constitutes a polymer, and is a concept that includes units forming a repeating structure in a polymer chain and units bonded to the ends of the polymer chain. Therefore, the polycarbonate copolymer is a polymer having repeating structural units of the structural unit (a1), the structural unit (a2), and the structural unit (a3) which is an optional component, and the structural unit (a1). , a polymer having the structural unit (a3) which is a selective component as a unit of a repeating structure and a structural unit (a2) at the end of the polymer chain; This concept includes a polymer having a structural unit (a2) and a structural unit (a3) which is a selective component at the terminal.

Examples of the dihydroxy compound represented by formula (1) include isosorbide (ie, ISB), isomannide, and isoidet, which are in a stereoisomeric relationship with each other. The polycarbonate copolymer can contain, as the structural unit (a1), a structural unit derived from at least one compound selected from the group consisting of ISB, isomannide, and isoidet. Among these, ISB is most preferred from the viewpoints of ease of acquisition and production, weather resistance, optical properties, moldability, heat resistance, and carbon neutrality. ISB is obtained by dehydration condensation of sorbitol, which is produced from various starches that are abundant and easily available as plant-derived resources. Note that the structural unit (a1) is specifically represented by formula (3). The structure represented by formula (3) is referred to as an "isosorbide skeleton," and the isosorbide skeleton is a concept that includes structural units derived from not only ISB but also isomannide and isoidet.

The dihydroxy compound represented by formula (1) is easily oxidized gradually by oxygen. Therefore, during storage or during handling during manufacturing, it is preferable to prevent moisture from being mixed in, to prevent decomposition due to oxygen, and to use an oxygen scavenger or use a nitrogen atmosphere. For example, when isosorbide is oxidized, decomposition products such as formic acid may be generated. If isosorbide containing these decomposed products is used as a raw material for producing a polycarbonate copolymer, there is a risk that the resulting polycarbonate copolymer will be colored. Furthermore, not only may the physical properties be significantly deteriorated, but also the polymerization reaction may be affected, making it impossible to obtain a high molecular weight polymer.

The polycarbonate copolymer has, as the structural unit (a3), one type selected from the group consisting of aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, and ether group-containing dihydroxy compounds other than the dihydroxy compound represented by formula (1). It is preferable that the structural unit (a3-1) derived from the above dihydroxy compound is included. In this case, the impact resistance of the polycarbonate copolymer is improved. That is, the polycarbonate copolymer preferably contains the structural unit (a1), the structural unit (a2), and the structural unit (a3-1). In this case, the impact resistance of the polycarbonate copolymer can be improved. In addition, in the following explanation, the dihydroxy compound represented by formula (1) is appropriately referred to as "first dihydroxy compound", and aliphatic dihydroxy compound, alicyclic dihydroxy compound, or alicyclic dihydroxy compound represented by formula (1) An ether group-containing dihydroxy compound other than the dihydroxy compound is appropriately referred to as a "second dihydroxy compound." As the second dihydroxy compound, one type or two or more types of compounds can be used.

The aliphatic dihydroxy compound may be a straight chain aliphatic dihydroxy compound or a branched chain aliphatic dihydroxy compound, such as ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1 , 4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1, Examples include 9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol.

Examples of the alicyclic dihydroxy compound include 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol. Methanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5- Examples include norbornane dimethanol and 1,3-adamantanedimethanol.

Examples of ether group-containing dihydroxy compounds other than the dihydroxy compound represented by formula (1) include diethylene glycol, triethylene glycol, polyethylene glycol (molecular weight 150 to 2000), poly-1,3-propylene glycol, and polytetramethylene glycol. can be mentioned.

From the viewpoint of increasing the impact resistance of the polycarbonate copolymer, the second dihydroxy compound is preferably an aliphatic dihydroxy compound or an alicyclic dihydroxy compound, and more preferably an alicyclic dihydroxy compound. Among the alicyclic dihydroxy compounds, cyclobutanediol, cyclohexanedimethanol, and tricyclodecane dimethanol are preferred from the viewpoint of further improving impact resistance and heat resistance.

In the polycarbonate copolymer, the content of the structural unit (a3) such as the structural unit (a3-1) is preferably 5% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. Further, it is preferably 55% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less. When the content of the structural unit (a3) such as the structural unit (a3-1) is at least the above lower limit, sufficient mechanical properties can be obtained. Further, when the content of the structural unit (a3) such as the structural unit (a3-1) is below the above upper limit, sufficient heat resistance can be obtained.

In the polycarbonate copolymer, the content of the structural unit (a1) is preferably 5% by mass or more, more preferably 25% by mass or more, and even more preferably 40% by mass or more. Further, it is preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or less. When the content of the structural unit (a1) is at least the above lower limit, sufficient mechanical properties and heat resistance can be obtained. Moreover, when the structural unit (a1) is below the above upper limit, the melt processability of the polycarbonate copolymer will be good.

In the polycarbonate copolymer, the content of the structural unit (a2) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.7% by mass or more. Further, it is preferably 6% by mass or less, more preferably 4% by mass or less, and even more preferably 2% by mass or less. When the content of the structural unit (a2) is at least the above lower limit, the scratch resistance is further improved. Moreover, sufficient heat resistance is obtained as the content rate of the structural unit (a2) is below the said upper limit. The structural unit (a2) may be present in the chain or at the end of the polycarbonate copolymer.

Branched organopolysiloxane is a polymer having a siloxane bond as a main chain, has a branched structure in the polysiloxane skeleton, and has an organic group bonded to the siloxane bond. Specifically, it is a polymer having a polysiloxane skeleton having a branched structure and a substituent (that is, an organic group) bonded to the siloxane bond of the polysiloxane skeleton. Branched organopolysiloxanes can have one or more organic groups. Preferably, it has a plurality of organic groups.

The polycarbonate copolymer has excellent transparency by having at least the structural unit (a1) derived from the dihydroxy compound represented by the above formula (1) and the structural unit (a2) derived from the branched organopolysiloxane. It has both durability and scratch resistance.

The branched organopolysiloxane is not particularly limited as long as it has a hydroxyl group and a branched structure. A branched organopolysiloxane has a polysiloxane skeleton and an organic group bonded to the siloxane bonds of the polysiloxane skeleton. The organic group bonded to the polysiloxane skeleton is not particularly limited, and includes a hydrocarbon group, a hydrocarbon group having an ether bond, a hydrocarbon group substituted with at least one kind of functional group, and the like.

In the branched organopolysiloxane, the organic group bonded to the siloxane bond of the polysiloxane skeleton preferably has a reactive functional group, a compatible group, or both a reactive functional group and a compatible group. That is, it is preferable that the organic group has a reactive functional group and/or a compatible group. In this case, transparency and scratch resistance are further improved. The organic group can have a reactive functional group and a compatible group at its terminal and/or inside. From the viewpoint of improving the reactivity during polymerization and promoting contact with the structural unit (a1) derived from the dihydroxy compound of the polycarbonate copolymer, the organic group has a reactive functional group or phase at least at its terminal. Preferably, it has a soluble group.

The branched organopolysiloxane has hydroxyl groups as described above. The hydroxyl group may be bonded to a siloxane bond or may be bonded to an organic group. When the hydroxyl group is bonded to an organic group, this organic group can serve as a reactive functional group and/or a compatible group. The branched organopolysiloxane may have one hydroxyl group, or may have two or more. When the branched organopolysiloxane has one hydroxyl group, the branched organopolysiloxane can be a unit constituting the terminal end of the polymer chain of the polycarbonate copolymer. When the branched organopolysiloxane has two or more hydroxyl groups, the branched organopolysiloxane can serve as a repeating structural unit constituting the polycarbonate copolymer.

A reactive functional group is composed of one or more atoms selected from carbon atoms, hydrogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, silicon atoms, and halogens, and is Among these, it refers to a group whose chemical structure can be changed by contact with another type of functional group or by heating within the temperature range of normal use or molding. Specifically, reactive functional groups include, for example, oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, silicon atoms, halogens, or carbon-hydrogen multiple bonds (i.e., double bonds, triple bonds, etc.). It is a functional group having an unsaturated bond). Further, the reactive functional group may have not only the reactivity as defined above but also compatibility at the same time.

Compatible groups indicate interactions with the whole or part of the constituent units of the polycarbonate copolymer through ionic interactions, hydrogen bonds, dipole interactions, etc., and are This is a group that improves compatibility. Specifically, the compatible group is, for example, an alcoholic hydroxyl group or a group having an ether bond.

The branched organopolysiloxane may have both a reactive functional group and a compatible group as an organic group, and may have multiple types of reactive functional groups and/or multiple types of compatible groups. Good too. The total content of reactive functional groups and compatible groups is not particularly limited, but is preferably 1 or more per 1000 molecular weight of the branched organopolysiloxane, more preferably 1.5 per 1000 molecular weight of the branched organopolysiloxane. or more, and more preferably 1.8 or more per 1000 molecular weight of the branched organopolysiloxane. Further, the total content of reactive functional groups and compatible groups is preferably 12 or less per 1000 molecular weight of the branched organopolysiloxane, more preferably 9 or less per 1000 molecular weight of the branched organopolysiloxane, and It is 6 or less per 1000 molecular weight of organopolysiloxane. By setting the total content of reactive functional groups and compatible groups to the above lower limit or more, the structural unit (a1) derived from the dihydroxy compound of the polycarbonate copolymer and the branched organopolysiloxane of the polycarbonate copolymer are combined. The transparency of the polycarbonate copolymer is further improved, and the branched organopolysiloxane is covalently incorporated into the polycarbonate copolymer structure. The structural unit (a2) derived from siloxane is immobilized on the surface of the polycarbonate copolymer, and the durability against scratches (specifically, scratch resistance) of the polycarbonate copolymer is further improved. In addition, by controlling the total content of reactive functional groups and compatible groups to be less than or equal to the upper limit above, the structural unit (a2) becomes more likely to segregate near the surface of the polycarbonate copolymer, further improving scratch resistance. do. Incidentally, the number of reactive functional groups and compatible groups per molecular weight of 1000 can be measured by the method described in Examples described below.

The reactive functional group is not particularly limited, but from the viewpoint of high reactivity, it may be, for example, a functional group having a carbon-carbon multiple bond such as a double bond, and/or a functional group containing an oxygen atom. Preferably, it is at least one functional group selected from the group consisting of an alkenyl group, an ester group, a methacryloyl group, an acryloyl group, a cyclic ether group, an alcoholic hydroxyl group, and a phenolic hydroxyl group. From the viewpoint of higher reactivity, the reactive functional group is more preferably an alcoholic hydroxyl group. The number of carbon atoms in the functional group having a carbon-carbon multiple bond is preferably 2 to 20, more preferably 2 to 6.

The alkenyl group may include a branched structure or a cyclic structure. Preferably, it is an alkenyl group having 2 to 20 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms, still more preferably a vinyl group, propenyl group, isopropenyl group, or butenyl group, and particularly preferably a vinyl group. It is. As the number of carbon atoms in the alkenyl group decreases, the nonpolar portion becomes smaller, and the compatibility with the structural unit (a1) derived from the dihydroxy compound of the polycarbonate copolymer is further increased. Further, examples of the alkenyl group include those having an internal olefin structure and those having a terminal olefin structure, and those having a terminal olefin structure are preferable from the viewpoint of high reactivity.

The ester group is preferably a group represented by formula (4) or formula (5).

In formula (4), g=1, and in formula (5), h=0 or 1. R ⁸ in formulas (4) and (5) is a monovalent group, and may include a branched structure or a cyclic structure. From the viewpoint of compatibility with the structural unit (a1) derived from the dihydroxy compound of the polycarbonate copolymer and reactivity with the dihydroxy compound, R ⁸ is preferably an organic group such as a hydrocarbon group having 1 to 20 carbon atoms. More preferably, it is an organic group such as a hydrocarbon group having 1 to 6 carbon atoms. The carbon It is more preferable that the number is small.

On the other hand, when priority is given to improving scratch resistance, a large number of carbon atoms may work advantageously. Therefore, from the viewpoint of improving scratch resistance, R ⁸ is preferably a hydrocarbon group having 6 to 30 carbon atoms, more preferably a hydrocarbon group having 10 to 30 carbon atoms. When the number of carbon atoms is large, the hydrocarbon groups form a structure close to crystallization near the surface of the polycarbonate copolymer, which further improves the scratch resistance of the surface of the molded product.

R ⁹ in formulas (4) and (5) is a divalent linking group, and is a group that connects the ester group and the polysiloxane skeleton. R ⁹ is not particularly limited as long as it is a divalent linking group, and may contain a branched structure or a cyclic structure, or may contain atoms other than carbon atoms and hydrogen atoms, but R 9 may not be directly bonded to a silicon atom. The atoms that do this are atoms other than oxygen atoms. R ⁹ is preferably an organic group having 1 to 20 carbon atoms, more preferably an organic group having 1 to 10 carbon atoms. When the number of carbon atoms in R ⁹ is small within the above range, the nonpolar portion becomes small and the compatibility with the structural unit (a1) derived from the dihydroxy compound of the polycarbonate copolymer increases. This further improves the transparency of the polycarbonate copolymer.

The structures of the methacryloyl group and acryloyl group are not particularly limited, but from the viewpoint of high reactivity and compatibility, methacryloyloxy groups and acryloyloxy groups are preferred. Further, it is preferable that the methacryloyloxy group or the acryloyloxy group and the polysiloxane skeleton are bonded through a divalent linking group. As the divalent linking group, the same organic group as R ⁹ in formula (4) and formula (5) can be used. The methacryloyl group, acryloyl group, methacryloyloxy group, and the linking group in the acryloyloxy group are preferably organic groups having 1 to 20 carbon atoms, more preferably organic groups having 1 to 10 carbon atoms. When the number of carbon atoms is small within the above range, the compatibility with the structural unit (a1) derived from the dihydroxy compound of the polycarbonate copolymer is further enhanced.

The cyclic ether group is not particularly limited as long as it has a cyclic ether structure, but is preferably a group represented by formula (6) or formula (7).

In formula (6), i=0 or 1, and in formula (6), j=0 or 1. k and m are each independently an integer of 0 to 8. R ¹⁰ in formulas (6) and (7) is a divalent linking group, and is a group that connects the cyclic ether group and the polysiloxane skeleton. ^R10 is not particularly limited as long as it is a divalent linking group, and may contain a branched structure or a cyclic structure, and may contain atoms other than carbon atoms and hydrogen atoms, but it is directly bonded to a silicon atom. Atoms are atoms other than oxygen atoms. R ¹⁰ is preferably an organic group having 1 to 20 carbon atoms, more preferably an organic group having 1 to 10 carbon atoms. When the number of carbon atoms is small within the above range, the nonpolar portion becomes small and the compatibility with the structural unit (a1) derived from the dihydroxy compound of the polycarbonate copolymer is further enhanced.

The cyclic ether group is more preferably a group represented by formula (8), formula (9), or formula (10).

When the organopolysiloxane contains a cyclic ether group represented by formula (8), formula (9), or formula (10), the combination with the structural unit (a1) derived from the dihydroxy compound of the polycarbonate copolymer Greater compatibility. This is because the cyclic ethers represented by formulas (8), (9), and (10) have high reactivity and high polarity.

The organic group of the organopolysiloxane preferably has a cyclic ether group and an ester group, as in the groups represented by formulas (11) to (18).

When the organic group of the organopolysiloxane has a cyclic ether group and an ester group, further improvement in compatibility with the structural unit (a1) derived from the dihydroxy compound of the polycarbonate copolymer can be expected. This is because it has a highly polar ester group in addition to a highly reactive and polar cyclic ether group.

The alcoholic hydroxyl group is not particularly limited as long as it has a structure having a hydroxyl group bonded to a carbon atom, and one organic group may have one or more hydroxyl groups. The hydroxyl group is preferably bonded to at least the terminal end of the organic group. Further, the phenolic hydroxyl group is not particularly limited as long as it has a structure having a hydroxyl group bonded to an aryl group, and the aryl group may have one or more hydroxyl groups. More preferred is an alcoholic hydroxyl group represented by formula (19). It is preferable that the branched polyorganosiloxane has a plurality of organic groups, and each organic group has an alcoholic hydroxyl group. In this case, the reactivity during polymerization is improved, and the compatibility within and/or between molecules constituting the polycarbonate copolymer is improved.

R ¹¹ in formula (19) is a divalent linking group, and is a group that bonds the alcoholic hydroxyl group and the polysiloxane skeleton. R ¹¹ is not particularly limited as long as it is a divalent linking group, and may contain a branched structure or a cyclic structure, and may contain atoms other than carbon atoms and hydrogen atoms, but is directly bonded to a silicon atom. Atoms are atoms other than oxygen atoms. R ¹¹ is preferably an organic group having 1 to 20 carbon atoms, more preferably an organic group having 1 to 10 carbon atoms. When the number of carbon atoms in R ¹¹ is small within the above range, the nonpolar portion becomes small and the compatibility with the structural unit (a1) derived from the dihydroxy compound of the polycarbonate copolymer is further enhanced. Further, it is more preferable that R ¹¹ contains at least one kind of atom selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom, and even more preferably at least an oxygen atom. In this case, the polarity of the alcoholic hydroxyl group becomes higher, and the compatibility with the structural unit (a1) derived from the dihydroxy compound of the polycarbonate copolymer further increases. As the organic group having an alcoholic hydroxyl group, for example, a group represented by formula (20) is more preferable, and a group represented by formula (21) is even more preferable.

In formula (20), R ¹² is a divalent organic group, but the atom directly bonded to the silicon atom is other than the oxygen atom. R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a monovalent organic group having 1 to 10 carbon atoms or a hydrogen atom. n is an integer from 1 to 100.

式（２０）及び式（２１）で表される有機基は、極性が高い。そのため、分岐オルガノポリシロキサンが式（２０）、式（２１）で表される有機基を有する場合には、ポリカーボネート共重合体のジヒドロキシ化合物に由来する構成単位（ａ１）との相溶性がより向上する。特に、式（２１）で表される有機基は、立体障害が小さいことから、反応性にも優れる。

The organic groups represented by formulas (20) and (21) have high polarity. Therefore, when the branched organopolysiloxane has an organic group represented by formula (20) or formula (21), the compatibility with the structural unit (a1) derived from the dihydroxy compound of the polycarbonate copolymer is further improved. do. In particular, the organic group represented by formula (21) has low steric hindrance and therefore has excellent reactivity.

Compatible groups exhibit interactions such as ionic interactions, hydrogen bonds, and dipolar interactions with the entire polycarbonate copolymer or some of the constituent units, and are constituent units derived from the dihydroxy compound of the polycarbonate copolymer. It is not particularly limited as long as it is a group that improves compatibility with (a1). The compatible group may be a group that has reactivity in addition to compatibility.

Considering that the polycarbonate copolymer is a polar resin, the compatible group is a group having polarity, that is, a group having one or more of an aromatic group, an oxygen atom, a sulfur atom, and a nitrogen atom. It is preferable that there be. As the group having an aromatic group, a phenyl group, a naphthyl group, an anthracenyl group, and a biphenyl group are preferable. As the group having an oxygen atom, an alcoholic hydroxyl group, a polyalkylene glycol group, a cyclic ether group, and an ester group are preferable. As the group having a sulfur atom, a mercapto group, a thiirane group, and a polyethylene sulfide group are preferable. The nitrogen atom-containing group is preferably an amino group, a monoalkylamino group, a dialkylamino group, an aziridine group, an azetidine group, a pyrrolidine group, or a piperidine group. From the viewpoint of further improving the compatibility with the structural unit (a1) derived from the dihydroxy compound of the polycarbonate copolymer, it is more preferable to have a polyalkylene glycol group and/or an ester group as the compatible group.

The polyalkylene glycol group is not particularly limited as long as it has a polyalkylene structure, but is preferably a group represented by formula (22).

In the formula (22), X=1, and in the formula (22), Y=an integer from 1 to 100. Y is preferably an integer of 2 or more, more preferably an integer of 3 or more. Y is preferably an integer of 25 or less, more preferably 20 or less, and even more preferably 15 or less. If Y is greater than or equal to the above lower limit, the polarity of the branched organopolysiloxane will improve, and the compatibility with the structural unit (a1) derived from the hydroxy compound of the polycarbonate copolymer will increase. Moreover, when Y is below the above upper limit, it becomes easy to maintain the viscosity of the organopolysiloxane within a manageable range.

R ¹⁸ in formula (22) is a divalent linking group, and is a group that connects the polyalkylene glycol group and the polysiloxane skeleton. R ¹⁸ is not particularly limited as long as it is a divalent linking group, and may contain a branched structure or a cyclic structure, and may contain atoms other than carbon atoms and hydrogen atoms, but is directly bonded to a silicon atom. Atoms are atoms other than oxygen atoms. R ¹⁷ in formula (22) is preferably an organic group having 1 to 10 carbon atoms, more preferably an organic group having 1 to 5 carbon atoms. When the number of carbon atoms is small within the above range, the nonpolar portion becomes small and the compatibility with the structural unit (a1) derived from the dihydroxy compound of the polycarbonate copolymer is further enhanced.

The organic group of the branched organopolysiloxane preferably has a polyalkylene glycol group and an ester group, such as the groups represented by formulas (23) to (26). In this case, further improvement in compatibility with the structural unit (a1) derived from the dihydroxy compound of the polycarbonate copolymer can be expected. This is because the organic group has a highly polar ester group in addition to a highly polar polyalkylene glycol group.

In formulas (23) to (26), m is an integer from 1 to 100. m is preferably an integer of 2 or more, more preferably an integer of 3 or more. m is preferably an integer of 25 or less, more preferably 20 or less, and even more preferably 15 or less. If m is greater than or equal to the above lower limit, the polarity of the branched organopolysiloxane will improve, and the compatibility with the structural unit (a1) derived from the hydroxy compound of the polycarbonate copolymer will increase. Moreover, when m is below the above upper limit, it becomes easy to maintain the viscosity of the organopolysiloxane within a manageable range. Among formulas (23) to (26), groups represented by formula (23) and/or formula (25) are preferred. Moreover, it is more preferable that the branched organopolysiloxane has formula (23) and formula (25) as organic groups.

R ¹⁷ in formulas (17) to (20) is preferably an organic group having 1 to 10 carbon atoms, more preferably an organic group having 1 to 5 carbon atoms. When the number of carbon atoms is small within the above range, the nonpolar portion becomes small and the compatibility with the structural unit (a1) derived from the dihydroxy compound of the polycarbonate copolymer is further enhanced.

In organopolysiloxane, the siloxy unit represented by (R ¹ R ² R ³ SiO _1/2 ) is generally an M unit, the siloxy unit represented by (R ⁴ R ⁵ SiO _2/2 ) is a D unit, The siloxy unit represented by (R ⁶ SiO _3/2 ) is called a T unit, and the siloxy unit represented by (SiO _4/2 ) is called a Q unit. Moreover, O _1/2 R ⁷ represents an organooxy group directly bonded to a silicon atom, and O _1/2 H represents a hydroxyl group directly bonded to a silicon atom. By changing the composition ratio of M units, D units, T units, and Q units, differences in the properties of the organopolysiloxane appear, so the above composition ratios are usually selected appropriately to obtain the desired properties. Synthesize siloxane. More specifically, the M unit is used for end-capping, and by using the M unit, a triorganosiloxy group is introduced at the end, making it possible to suppress an undesired increase in molecular weight. Furthermore, since a linear component is introduced into the organopolysiloxane by introducing the D unit, the flexibility of the molecular skeleton increases. Further, by introducing the T unit and/or the Q unit, a cyclic structure and a branched component are introduced into the organopolysiloxane, and the shape of the organopolysiloxane molecule approaches a spherical shape.

As the branched organopolysiloxane, it is preferable to use, for example, one represented by the general compositional formula (2) shown below. In this case, transparency and scratch resistance are further improved.
(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d (O _1/2 R ⁷ ) _e ( O _1/2 H) _f ...(2)

If R ¹ to R ⁶ in formula (2) are not a reactive functional group or a compatible group, their structures are not particularly limited, but R ¹ to R ⁶ are each independently a hydrogen atom or a carbon atom having 1 carbon number. ~20 monovalent hydrocarbon groups. Specific examples thereof include a hydrogen atom, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and an alkyl group containing a cyclic structure having 1 to 20 carbon atoms. Among these, hydrogen atoms, alkyl groups such as methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, s-butyl groups, t-butyl groups, octyl groups, and cyclohexyl groups are preferable, and hydrogen atoms and methyl groups are preferable. More preferred.

In formula (2), a, which means the proportion of M units, satisfies 0≦a<1. a is preferably 0.1 or more, more preferably 0.15 or more, still more preferably 0.3 or more, particularly preferably 0.5 or more. Further, a is preferably 0.8 or less, more preferably 0.7 or less. By setting the M unit to the above lower limit value or more, it is possible to suppress the formation of undesired high molecular weight components during the synthesis of the branched organopolysiloxane, and to suppress the increase in viscosity of the branched organopolysiloxane, resulting in good handling properties. become. Further, by controlling the M unit to be equal to or less than the above upper limit value, an excessive decrease in molecular weight can be suppressed, and an increase in low-boiling components can be suppressed.

The type of siloxy unit in the M unit in the branched organopolysiloxane is not particularly limited, but when the branched organopolysiloxane contains a trimethylsiloxy group as an M unit, the amount of trimethylsiloxy group in all M units is 50 mol. % or less, more preferably 25 mol % or less, even more preferably 5 mol % or less, and particularly preferably 0. By controlling the amount of trimethylsiloxy groups in all M units to be equal to or less than the above upper limit or to zero, the transparency of the polycarbonate copolymer can be kept higher. This is because the trimethylsiloxy group may reduce the compatibility with the polycarbonate copolymer having an isosorbide skeleton.

In formula (2), b, which means the proportion of D units, satisfies 0≦b<1. b is preferably 0.8 or less, more preferably 0.5 or less, still more preferably 0.1 or less. By setting the D unit to be less than or equal to the above upper limit, the branched organopolysiloxane molecule changes from a linear shape to a spherical shape. As a result, the branched organopolysiloxane molecule takes a structure in which reactive functional groups and/or compatible groups are arranged radially outward from the polysiloxane skeleton, and the reactive functional groups and/or compatible groups It becomes easier to come into contact with the copolymer. As a result, the reactive functional group and/or the compatible group become more likely to coordinate with the polar element in the polycarbonate copolymer, improving the compatibility.

Further, in formula (2), c indicating the proportion of T units and d indicating the proportion of Q units are numbers satisfying c+d>0. c and d preferably satisfy c+d≧0.15, more preferably satisfy c+d≧0.25. By setting c+d to the above lower limit value or more, the branched organopolysiloxane molecules change from linear to spherical. As a result, as described above, the reactive functional group and/or compatible group becomes easier to coordinate with the polar element in the polycarbonate copolymer, improving compatibility. Further, c and d are c+d≦1, preferably c+d≦0.9, more preferably c+d≦0.7, and even more preferably c+d≦0.5. By setting c+d to the above upper limit value or less, it becomes easy to maintain the viscosity of the branched organopolysiloxane within a manageable range.

The branched organopolysiloxane may be an MQ resin in which the siloxy units are M units and Q units, an MT resin in which the siloxy units are M units and T units, and the siloxy units are D units and T units. It may be a DT resin consisting of siloxy units, a DQ resin consisting of a D unit and a Q unit, and a TQ resin consisting of a siloxy unit consisting of a T unit and a Q unit. Further, the siloxy unit may be an MDT resin consisting of M units, D units, and T units, or the siloxy unit may be an MDQ resin consisting of M units, D units, and Q units, and the siloxy units may be M units. The siloxy unit may be an MTQ resin consisting of D units, T units, and Q units, or the siloxy units may be M units, D units, T units, and DTQ resins. It may also be an MDTQ resin consisting of Q units. Among these, MTQ resin and MQ resin are preferred.

From the viewpoint that the branched organopolysiloxane molecules tend to take a spherical shape, and as a result, the reactive groups and compatible groups easily come into contact with the polycarbonate resin, the branched organopolysiloxane preferably contains at least M units and Q units. preferable. When the branched organopolysiloxane contains M units and Q units, the content of M units based on all silicon atoms is preferably 10 mol% or more, more preferably 15 mol% or more, and even more preferably 30 mol%. or more, and particularly preferably 50 mol% or more. Moreover, it is preferably 80 mol% or less, more preferably 70 mol% or less. By setting the M unit content to the above lower limit value or more, it is possible to suppress the formation of undesired high molecular weight components during the synthesis of the branched organopolysiloxane, and to suppress the increase in viscosity of the branched organopolysiloxane, which improves handling properties. becomes good. Further, by controlling the M unit to be equal to or less than the above upper limit value, an excessive decrease in molecular weight can be suppressed, and an increase in low-boiling components can be suppressed. Further, when the branched organopolysiloxane contains M units and Q units, the content of Q units relative to all silicon atoms is preferably 15 mol% or more, more preferably 25 mol%. By setting the Q unit content to the above lower limit value or more, the molecule changes from a linear shape to a spherical shape. As a result, as described above, the reactive functional group and/or compatible group becomes easier to coordinate with the polar element in the polycarbonate copolymer, improving compatibility. Further, the content of Q units is preferably 90 mol% or less, more preferably 70 mol% or less, and still more preferably 50 mol% or less. By setting the Q unit content to the above upper limit value or less, it becomes easy to maintain the viscosity of the branched organopolysiloxane within a manageable range.

The structural unit represented by (O _1/2 R ⁷ ) in formula (2) is an organooxy group directly bonded to the silicon atom in the branched organopolysiloxane, that is, an organooxy group forming a Si-O-C bond. It means. When focusing on the content of organooxy groups directly bonded to silicon atoms relative to the total weight of the branched organopolysiloxane, the amount of organooxy groups directly bonded to silicon atoms is not particularly limited, but is preferably 0.07% by weight or more, The content is more preferably 0.5% by weight or more, preferably 4% by weight or less, and even more preferably 2% by weight or less. By setting the organooxy group content to the above lower limit value or more, aggregation of organopolysiloxane molecules is suppressed due to steric repulsion due to the organooxy groups. Therefore, the branched organopolysiloxane does not become a solid but easily becomes a liquid and exhibits appropriate fluidity, resulting in the advantage that the productivity of the polycarbonate copolymer is greatly improved. In addition, by setting the content of alkoxy groups directly bonded to silicon atoms to the above lower limit value or more, the organooxy group is coordinated to the polar site in the structural unit (a1) derived from the dihydroxy compound of the polycarbonate copolymer, The compatibility between the structural unit (a1) derived from the dihydroxy compound of the polycarbonate copolymer and the structural unit (a2) derived from the branched organopolysiloxane of the polycarbonate copolymer is improved, and the transparency of the polycarbonate copolymer is improved. Improve more. Further, by controlling the organooxy group content to be equal to or lower than the above upper limit, the stability of the branched organopolysiloxane during long-term storage is improved. Furthermore, since the phenomenon in which alcohol is produced due to the elimination of organooxy groups due to heating is suppressed, the working environment can be improved.

R ⁷ is not particularly limited as long as it is an organic group having 1 to 7 carbon atoms, but is preferably a methyl group, ethyl group, or isopropyl group.

The structural unit represented by (O _1/2 H) in formula (2) means a hydroxyl group directly bonded to the silicon atom in the branched organopolysiloxane, that is, a hydroxyl group forming a Si--O--H bond. The content of hydroxyl groups directly bonded to silicon atoms based on the total weight of the branched organopolysiloxane is not particularly limited, but is preferably 0.01% by weight or more, more preferably 0.03% by weight or more, and preferably 2.0% by weight. % or less, more preferably 1.0% by weight or less. By setting the content of hydroxyl groups directly bonded to silicon atoms to the above lower limit value or more, the hydroxyl groups are coordinated to the polar sites in the structural unit (a1) derived from the dihydroxy compound of the polycarbonate copolymer, and the hydroxyl groups of the polycarbonate copolymer are The compatibility between the structural unit (a1) derived from the dihydroxy compound and the structural unit (a2) derived from the branched organopolysiloxane of the polycarbonate copolymer is improved, and the transparency of the polycarbonate copolymer is further improved. In addition, by keeping the content of hydroxyl groups directly bonded to silicon atoms below the above upper limit, stability during long-term storage is improved, and the viscosity does not become too high, for example, to the extent that handling properties are not impaired. can be suppressed.

In formula (2), the value of e representing the amount of the structural unit represented by (O _1/2 R ⁷ ) and the value of f representing the amount of the structural unit represented by O _1/2 H are 0≦e+f. <4, and the value of e+f is not particularly limited within this range, but the value of e+f is preferably 0.005 or more, more preferably 0.01 or more, and even more preferably 0.02 or more. Further, the value of e+f is preferably 2 or less, more preferably 1 or less, even more preferably 0.5 or less, and particularly preferably 0.1 or less. By setting the value of e+f to the above lower limit value or more, the alkoxy group or hydroxyl group directly bonded to the silicon atom coordinates to the polar site in the structural unit (a1) derived from the dihydroxy compound of the polycarbonate copolymer, and the polycarbonate copolymer The compatibility between the structural unit (a1) derived from the dihydroxy compound of the polymer and the structural unit (a2) derived from the branched organopolysiloxane of the polycarbonate copolymer is improved, and the transparency of the polycarbonate copolymer is further improved. do. Furthermore, by setting the value of e+f to be less than or equal to the above upper limit value, stability during long-term storage is improved.

The number average molecular weight (Mn) of the branched organopolysiloxane is not particularly limited, but is preferably 500 or more, more preferably 800 or more, and even more preferably 1200 or more. Further, it is preferably 100,000 or less, more preferably 10,000 or less, even more preferably 5,000 or less, and particularly preferably 3,000 or less. By setting Mn to the above lower limit value or more, volatile components are reduced. Moreover, by controlling Mn to be less than or equal to the above upper limit value, the viscosity becomes low and the handleability becomes good.

Although the weight average molecular weight (Mw) of the branched organopolysiloxane is not particularly limited, it is preferably 700 or more, more preferably 1000 or more, and even more preferably 1300 or more. Further, it is preferably 150,000 or less, more preferably 15,000 or less, even more preferably 10,000 or less, and particularly preferably 7,500 or less. By setting Mw to the above lower limit value or more, volatile components are reduced. Moreover, by setting Mw to be less than or equal to the above upper limit value, the viscosity becomes low and the handleability becomes good.

The Mn and Mw described above are values measured according to the method described in the Examples described later.

Although the amount of the low boiling point component contained in the branched organopolysiloxane is not particularly limited, it is preferable that the amount of the low boiling point component is small. In this case, the flash point becomes higher, which not only makes it easier to maintain safety during transportation and storage, but also causes problems such as volatile components evaporating during kneading with polycarbonate copolymer and molding, contaminating manufacturing equipment. It becomes difficult. The amount of low-boiling components contained in the branched organopolysiloxane can be expressed as a weight loss rate when heated at 110°C for 2 hours under a reduced pressure of 0.15 torr, and this weight loss rate is 10% by weight. It is preferably at most 8% by weight, more preferably at most 5% by weight, and even more preferably at most 5% by weight.

In addition to the branched structure, the branched organopolysiloxane may have a cage structure, or may not have a cage structure. When the branched organopolysiloxane has a cage structure, the branched organopolysiloxane becomes an extremely rigid molecule. Therefore, when the branched organopolysiloxane has a cage structure, the elastic modulus of the polycarbonate copolymer is improved. On the other hand, when the branched organopolysiloxane does not have a cage structure, the viscosity is lower than when the branched organopolysiloxane has a cage structure, resulting in better handling properties.

Whether or not the branched organopolysiloxane has a cage structure can be confirmed using, for example, infrared absorption spectrum analysis. In an infrared absorption spectrum analysis in the wave number range of 1000 to 1200 cm ^-1 , if it has a cage structure, it has an absorption peak of Si--O stretching vibration in the wave number range of 1070 to 1150 cm ^-1 . On the other hand, in the case of not having a cage structure, the maximum absorption wave number of Si--O stretching vibration is in the wave number range of 1030 to 1060 cm ^-1 . Note that in the wave number region of 1070 to 1150 cm ^-1 , there is a characteristic absorption band derived from organic molecules other than Si--O derived from the cage structure. For example, C-O origin of hydroxyl group, C-O-C origin of ester, C-O-C origin of acid anhydride, C-O-C origin of ether, C-N origin of amine, sulfonic acid and sulfoxide. Those derived from C-S in fluorine compounds, from P=O or PO in phosphorus compounds, and from inorganic salts SO ₄ ^2- or ClO ₄ ^- are known as structures with high absorption strength. Therefore, care must be taken not to confuse these with the Si--O stretching vibration.

The method for producing the branched organopolysiloxane is not particularly limited. For example, one or more selected from the group consisting of disiloxane compounds, hydrolysates thereof, disilazane compounds, hydrolysates thereof, alkoxysilane compounds, hydrolysates thereof, and partially hydrolyzed condensates of alkoxysilane compounds. There is a method of condensation. Alternatively, a method of condensing a chlorosilane compound, a hydrolyzate thereof, or a partially hydrolyzed condensate thereof may be used. Alternatively, a method of ring-opening polymerization of a cyclic siloxane compound, a chain polymerization including anionic polymerization of a cyclic siloxane compound, etc. may be used. Branched organopolysiloxanes can also be produced by combining a plurality of production methods.

Furthermore, there are no particular limitations on the method of introducing reactive functional groups and compatible groups. For example, one or more types selected from the group consisting of alkoxysilane compounds, disiloxane compounds, disilazane compounds, hydrolysates thereof, and partially hydrolyzed condensates thereof, each having a reactive functional group and/or a compatible group. There is a method of condensing. Alternatively, a method may be used in which a different type of group introduced into the organopolysiloxane is converted into a reactive functional group or a compatible group by a chemical method. Furthermore, these methods may be combined.

As a method of converting a different type of group into a reactive functional group and/or a compatible group by a chemical method, for example, an organopolysiloxane having a structure in which a hydrogen atom is directly bonded to a silicon atom is converted into a reactive functional group and/or a compatible group. A method of reacting a soluble group with a compound having an alkenyl group (specifically, a hydrosilylation method), or a method of reacting a reactive functional group and/or a compatible group with a compound having an alkenyl group with an organopolysiloxane having a thiol group. and a method in which an organopolysiloxane having an alkenyl group is reacted with a compound having a reactive functional group and/or a compatible group and a thiol group.

In addition, the branched organopolysiloxane obtained after the reaction is subjected to column chromatography, gel permeation chromatography (i.e., GPC), extraction with a solvent, distillation of unnecessary components, etc. to obtain the desired epoxy equivalent and molecular weight. The branched organopolysiloxane having the branched organopolysiloxane may be fractionated. Further, low boiling point components may be removed by subjecting the branched organopolysiloxane to treatments such as depressurization and heating.

When producing a branched organopolysiloxane, a solvent may or may not be used. When using a solvent, water and organic solvents can be used, and organic solvents are particularly preferred. Preferred organic solvents include tetrahydrofuran, toluene, hexane, heptane, acetone, ethyl acetate, methanol, ethanol, isopropanol, chloroform, and dichloromethane. Tetrahydrofuran, toluene, and methanol are more preferred from the viewpoint of solubility, ease of removal, and low environmental toxicity. Further, these solvents such as water and organic solvents may be used alone, or two or more types may be used in combination. Furthermore, the type of solvent may be changed depending on the reaction step. Further, when an organopolysiloxane skeleton is formed by hydrolyzing and condensing an alkoxysilane compound, a chlorosilane compound, etc., hydrolysis can be promoted by adding an appropriate amount of water.

The reaction temperature in producing the branched organopolysiloxane is not particularly limited, and is usually -40 to 200°C, more preferably -20 to 150°C, and even more preferably 0 to 130°C. At temperatures lower than this temperature range, the reaction for forming the desired organopolysiloxane skeleton and the reaction for introducing reactive functional groups and/or compatible groups may become difficult to proceed. On the other hand, at temperatures higher than this temperature range, undesired reactions such as decomposition of reactive functional groups and/or compatible groups may proceed.

When producing a branched organopolysiloxane, the pressure for carrying out the reaction is not particularly limited, and it is usually carried out at 0.6 to 1.4 atm, but it is carried out at 0.8 to 1.2 atm. It is preferably carried out at a pressure of 0.9 to 1.1 atm. If the pressure is lower than this range, the boiling point of the solvent will decrease when a solvent is used, and it may not be possible to raise the reaction system to an appropriate reaction temperature. On the other hand, if the pressure is higher than this range, the boiling point of the solvent will rise, which has the advantage of increasing the temperature of the reaction system and accelerating the reaction, but since the reaction will take place under pressurized conditions, there is a risk of equipment damage or explosion. This will be accompanied by

The polycarbonate copolymer can have structural units derived from one or more branched organopolysiloxanes. In addition, the polycarbonate copolymer may contain organopolysiloxanes other than branched organopolysiloxanes together with structural units derived from branched organopolysiloxanes represented by formula (2), for example, within a range that does not impair the desired effects of the present invention. It may have a structural unit derived from From the viewpoint of maintaining higher transparency of the polycarbonate copolymer, the content of organopolysiloxanes other than branched organopolysiloxane is preferably 500 parts by weight or less, and 100 parts by weight, based on 100 parts by weight of branched organopolysiloxane. It is more preferably at most 50 parts by weight, even more preferably at most 50 parts by weight.

[Method for producing polycarbonate copolymer]
The polycarbonate copolymer can be produced by a commonly used method for producing polycarbonate copolymers. The polycarbonate copolymer can be produced by, for example, a solution polymerization method using phosgene or a melt polymerization method in which a carbonic acid diester and a dihydroxy compound are reacted.

The polycarbonate copolymer is produced, for example, by copolymerizing a first dihydroxy compound, a branched organopolysiloxane, and a second dihydroxy compound added as necessary in a reactor. Furthermore, other copolymerizable monomers may be added to the reactor for copolymerization. During polymerization, each monomer raw material may be added into the reactor at once, or each monomer raw material may be added at different timings.

When producing a polycarbonate copolymer, it is desirable to install a filter to prevent contamination by foreign matter. The installation position of the filter is preferably on the downstream side of the extruder, and the size (opening) of the filter for removing foreign matter is preferably 100 μm or less, which is the filtration accuracy for 99% removal. In particular, when the incorporation of minute foreign matter is to be avoided, such as in film applications, the thickness is more preferably 40 μm or less, and even more preferably 10 μm or less.

From the viewpoint of preventing contamination of foreign matter after extrusion, it is preferable to extrude the polycarbonate copolymer in a clean room with a higher cleanliness than Class 7 defined in JIS B9920:2002. More preferably, extrusion is carried out in a clean room with a higher cleanliness than class 6.

Furthermore, when cooling the extruded polycarbonate copolymer and forming it into chips, it is preferable to use a cooling method such as air cooling or water cooling. During air cooling, it is preferable to use air from which foreign substances have been removed in advance using a Hepa filter or the like. In this case, re-deposition of foreign matter in the air can be prevented. When cooling with water, it is preferable to use water from which metals have been removed using an ion exchange resin or the like, and from which foreign substances have been removed using a filter. From the viewpoint of obtaining filtration accuracy of 99% removal, the opening of the filter is preferably 0.45 to 10 μm.

The molecular weight of a polycarbonate copolymer can be expressed by reduced viscosity, and the higher the reduced viscosity, the higher the molecular weight. The reduced viscosity is preferably 0.30 dL/g or more, more preferably 0.35 dL/g or more. On the other hand, the reduced viscosity is preferably 1.20 dL/g or less, more preferably 1.00 dL/g or less, and even more preferably 0.80 dL/g or less. By adjusting the reduced viscosity within the above range, fluidity during molding can be improved, and productivity and moldability can be further improved. Therefore, molded products with complex shapes can be manufactured with high productivity, making them suitable for electrical/electronic equipment parts, automobile interior/exterior parts, and the like. The reduced viscosity of the polycarbonate copolymer was determined by precisely adjusting the concentration of the polycarbonate copolymer to 0.6 g/dL using methylene chloride as a solvent, and at a temperature of 20.0°C ± 0.1°C. Measure using an Ubbelohde viscosity tube.

The glass transition temperature of the polycarbonate copolymer is preferably 90°C or higher. In this case, heat resistance is further improved. From the same viewpoint, the glass transition temperature of the polycarbonate copolymer is more preferably 100°C or higher, and even more preferably 110°C or higher. On the other hand, the glass transition temperature of the polycarbonate copolymer is preferably 145°C or lower. In this case, the fluidity during molding is increased, and even when molded products with complex shapes are molded, the polycarbonate copolymer or the resin composition containing the same can easily reach the end of the mold, and the desired result can be obtained. Molded products can be obtained. Further, a decrease in strength at the weld portion can be suppressed. From the viewpoint of further enhancing these effects, the glass transition temperature of the polycarbonate copolymer is more preferably 135°C or lower, and even more preferably 125°C or lower. The glass transition temperature of a polycarbonate copolymer can be measured by the method described below.

The total light transmittance of the polycarbonate copolymer is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more. In addition, a tissue abrasion test is performed on the polycarbonate copolymer, and the number of visible scratches in the worn area of the polycarbonate copolymer after the test is preferably 40 or less, more preferably 30 or less, and 15 or less. The following are more preferable.

[Polycarbonate resin composition]
A polycarbonate resin composition can be produced by blending other resins, elastomers, additives, etc. with the polycarbonate copolymer. In the following description, the polycarbonate resin composition is appropriately referred to as a "resin composition", and a polycarbonate copolymer having at least structural units (a1) and structural units (a2) is appropriately referred to as a "first resin composition". Polycarbonate resin. The resin composition can contain a plurality of first polycarbonate resins having different structures. Moreover, the resin composition can contain, in addition to the first polycarbonate, a second polycarbonate resin different from the first polycarbonate resin within a range that does not impair the desired effects of the present invention. Further, the resin composition can contain resins other than the polycarbonate resin, elastomers, additives, etc. within a range that does not impair the desired effects of the present invention.

(Additive)
Various additives can be further added to the resin composition within a range that does not impair the above-mentioned desired effects. Additives include catalyst deactivators, antioxidants, ultraviolet absorbers, light stabilizers, mold release agents, colorants, neutralizers, antistatic agents, lubricants, lubricants, plasticizers, flame retardants, and fillers. etc.

- Catalyst deactivator The catalyst deactivator has the property of deactivating the polymerization catalyst of the polycarbonate copolymer. It can improve the color tone of polycarbonate copolymers and improve their thermal stability. As the catalyst deactivator, for example, an acidic compound can be used. As such an acidic compound, a compound having a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, or an ester thereof can be used.

- Antioxidant As the antioxidant, general antioxidants used for resins can be used. From the viewpoints of oxidation stability, thermal stability, and good jet black tone due to coloring, phosphite antioxidants, sulfur antioxidants, and phenolic antioxidants are preferred. As the antioxidant, one type of compound may be used, or two or more types of compounds may be used in combination.

- Ultraviolet absorber The resin composition can contain an ultraviolet absorber within a range that does not impair the desired effects of the present invention. Examples of the ultraviolet absorber include 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzo Triazole, 2-(2'-hydroxy-5-methylphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(2H -benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-p-phenylenebis(1,3-benzoxazin-4-one) . The content of the ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.05 to 1 part by weight, based on 100 parts by weight of the polycarbonate copolymer.

- Light stabilizer The resin composition can contain a light stabilizer within a range that does not impair the desired effects of the present invention. As the light stabilizer, for example, a compound derived from an amine compound can be used. Preferably, a compound having a secondary amine structure and a melting point of 85° C. or higher is preferred. Compounds having a secondary amine structure are more basic than primary amines. The higher the basicity of the light stabilizer made of an amine compound, the more stable the polycarbonate is against light, and the more deterioration due to hydrolysis is suppressed.

From the viewpoint of being able to reduce the rate of change in the molded product before and after the light resistance test, the secondary amine structure preferably has nitrogen as part of the cyclic structure, and more preferably has a piperidine structure. preferable. The piperidine structure defined here may be any structure as long as it is a saturated six-membered cyclic amine structure, and includes those in which a part of the piperidine structure is substituted with a substituent. Examples of the substituent that the piperidine structure may have include an alkyl group having 4 or less carbon atoms, and a methyl group is particularly preferred.

As the compound having a secondary amine structure and a melting point of 85° C. or higher, one having a plurality of secondary amine structures is preferable. More preferably, it is a compound having a plurality of secondary amine structures having a piperidine structure. More preferably, it is a compound in which a plurality of piperidine structures are connected by an ester structure.

From the viewpoint of improving bleed-out resistance, the absolute value of the difference in solubility parameters (that is, SP value) between the polycarbonate copolymer and the amine compound (specifically, the light stabilizer) is 0.0 to 15. .0 is preferred. The SP value is calculated using the Hoy method. From the viewpoint of further improving bleed-out resistance, the absolute value of the difference in SP values is more preferably 0.0 to 12.0, even more preferably 0.0 to 8.0, and even more preferably 0.0 to 6.0. Particularly preferred.

As mentioned above, the melting point of the light stabilizer is preferably 85° C. or higher. In this case, the smoothness and bleed-out resistance of the polycarbonate copolymer after the light resistance test can be improved. From the viewpoint of further enhancing this improving effect, the melting point of the light stabilizer is more preferably 90 to 300°C, even more preferably 100 to 250°C, and particularly preferably 110 to 200°C.

Further, from the viewpoint that weather resistance is further improved with a small amount, the terminal functional group equivalent of the light stabilizer is preferably 100 to 500 g/eq. From the viewpoint that the effect of improving weather resistance can be obtained with a smaller amount, the terminal functional group equivalent of the light stabilizer is more preferably 100 to 350 g/eq, and even more preferably 100 to 300 g/eq.

From the viewpoint of further improving the weather resistance of the molded article, the molecular weight of the light stabilizer is preferably 5000 or less, more preferably 3000 or less. The molecular weight of the light stabilizer is preferably 300 or more, more preferably 400 or more, from the viewpoint of suppressing a decrease in heat resistance and further suppressing mold contamination and surface appearance deterioration during molding.

Such light stabilizers include 2,2,6,6-tetramethyl-4-piperidinol, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)butane-1,2,3,4 -tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and β,β,β,β-tetramethyl-2,4,8,10-tetraoxaspiro [5,5] Condensate with undecane-3,9-diethanol, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis Mixed esters with (2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane and the like can be mentioned. Among these, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate (SP value 19.2, melting point 130°C), 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)- A mixed ester with 2,4,8,10-tetraoxaspiro[5.5]undecane (SP value 18.5, melting point 95°C) is preferred. As the light stabilizer, one type of compound may be used alone, or two or more types of compounds may be used.

The content of the light stabilizer in the polycarbonate resin composition is preferably 0.001 to 5 parts by mass, more preferably 0.005 to 3 parts by mass, and 0.01 to 3 parts by mass, based on 100 parts by mass of the polycarbonate copolymer. 1 part by mass is more preferred. Coloring can be prevented by adjusting the content of the light stabilizer within the above range. Furthermore, when a coloring agent is added, for example, deep and clear jet black or other colors can be obtained. Furthermore, since a sufficient light resistance effect is obtained, when the resin composition is molded, a molded product suitable for, for example, automobile interior and exterior parts can be obtained.

As the light stabilizer, as mentioned above, for example, an amine compound having a secondary amine structure is preferable, but an amine compound different from these preferable forms may be further used in combination. As the amine compound that can be used in combination, an amine compound having a tertiary amine structure is preferable. In this case, the effect of photostability can be exhibited for a longer period of time. From the viewpoint of further enhancing this effect, it is more preferable to combine a secondary amine having a piperidine structure and a tertiary amine having a piperidine structure as the light stabilizer.

- Coloring agent Examples of the coloring agent include inorganic pigments, organic pigments, and organic dyes and pigments such as organic dyes. The coloring agents may be used alone or in combination of two or more.

Examples of inorganic pigments include carbon black and oxide pigments. Examples of oxide pigments include titanium oxide, zinc white, Bengara, chromium oxide, iron black, titanium yellow, zinc-iron brown, copper-chromium black, copper-iron black, and the like.

Examples of organic dyes and pigments include phthalocyanine dyes and pigments, condensed polycyclic dyes and pigments, and dyes and pigments. Examples of condensed polycyclic dye pigments include azo, thioindigo, perinone, perylene, quinacridone, dioxazine, isoindolinone, and quinophthalone. Examples of dyes and pigments include anthraquinone-based, perinone-based, perylene-based, methine-based, quinoline-based, heterocyclic-based, methyl-based, and the like.

As the colorant, inorganic pigments are preferred. In this case, even when the molded product is used outdoors, for example, image clarity can be maintained for a long period of time.

The content of the colorant in the polycarbonate resin composition is preferably 0.05 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and 0.1 to 2 parts by mass, based on 100 parts by mass of the polycarbonate copolymer. Parts by mass are more preferred. By adjusting the content of the colorant within the above range, it is possible to obtain a solution-dyed molded product with high image clarity, and it is possible to further prevent an increase in the surface roughness of the molded product.

When the resin composition is toned to a jet black tone, the lightness L ^* is preferably from 0.1 to 10, more preferably from 0.1 to 6. Moreover, the glossiness is preferably 85% or more, more preferably 88% or more. In this case, the molded product becomes suitable for automobile interior and exterior parts.

- Filler The resin composition can contain fillers such as inorganic fillers and organic fillers within a range that can maintain the design. Examples of inorganic fillers include glass fibers, glass milled fibers, glass flakes, glass beads, silica, alumina, titanium oxide, calcium sulfate powder, gypsum, gypsum whiskers, barium sulfate, talc, mica, and calcium silicates such as wollastonite. , carbon black, graphite, iron powder, copper powder, molybdenum disulfide, silicon carbide, silicon carbide fiber, silicon nitride, silicon nitride fiber, brass fiber, stainless steel fiber, potassium titanate fiber, and whiskers thereof. Examples of organic fillers include powdered organic fillers such as wood flour, bamboo flour, coconut starch, cork powder, and pulp powder; balloon-shaped and spherical organic fillers such as cross-linked polyester, polystyrene, styrene-acrylic copolymer, and urea resin. Agent; Examples include fibrous organic fillers such as carbon fiber, synthetic fiber, and natural fiber.

-Lubricant The resin composition can contain a lubricant within a range that does not impair the desired effects of the present invention. Lubricants are also called flow modifiers. Examples of the lubricant include oils made of hydrocarbon compounds such as fatty acid amide and paraffin oil, silicone oils, branched organopolysiloxanes, ester compounds such as carboxylic acid esters, and fluorine waxes. Fatty acid amides are preferred from the viewpoint of further increasing transparency and maintaining physical properties.

[Method for producing polycarbonate resin composition]
The resin composition is prepared by adding the above components in a predetermined ratio, at the same timing, or in any order to a mixer such as a tumbler, V-type blender, Nauta mixer, Banbury mixer, kneading roll, or extruder, and mixing. Manufactured by At least a polycarbonate copolymer is used in the production of the resin composition, and other resins, elastomers, additives, etc. are added as necessary during mixing.

[Molding]
The molded article is obtained by molding a polycarbonate copolymer or a resin composition, and contains at least the polycarbonate copolymer. Molding can be performed by any molding method. As the molding method, for example, hot press molding, injection molding, injection compression molding, and injection press molding are suitably used. As the runner used for molding, either a cold runner method or a hot runner method can be used. Further, molding by insert molding, in-mold coating molding, two-color molding, sandwich molding, etc. is also possible. From the viewpoint of improving the design, it is also possible to use adiabatic molding and rapid heating and cooling molding.

(Applications of molded products)
The molded product has excellent abrasion resistance without being coated with paint, for example, and can reduce scratches that occur when wiped with a tissue or the like. Therefore, the process and cost for painting can be reduced. Because of these effects, the molded product can be applied to various parts. In addition, the molded product has excellent smoothness, and it is possible to improve transparency by further selecting materials, so it is also possible to improve, for example, sharpness. Furthermore, it is thought that by adding a light stabilizer, an ultraviolet inhibitor, etc., it becomes possible to maintain effects such as excellent transparency over a long period of time even in an environment exposed to light. Moreover, the transparency of the entire molded product can be maintained. However, molded products include not only transparent ones but also ones colored with the above-mentioned coloring agent.

As described above, the polycarbonate copolymer has a structural unit (a1) derived from a dihydroxy compound represented by formula (1) and a structural unit (a2) derived from a branched organopolysiloxane. A molded article containing such a polycarbonate copolymer is, for example, a polycarbonate resin that has structural units derived from a dihydroxy compound represented by formula (1) and does not have structural units derived from a branched organopolysiloxane. Compared to molded products made from mixtures of and branched organopolysiloxane, the branched organopolysiloxane is covalently incorporated into the polymer structure, which suppresses mold contamination during molding due to branched organopolysiloxane bleed-out. This has the advantage of suppressing the deterioration in scratch resistance that can occur when a molded product is repeatedly abraded with tissue or when the surface of a molded product is washed.

Since the above-mentioned effects can be exhibited, the molded product makes it possible to provide high-quality parts with a luxurious and solid feel. Although there are no particular restrictions on the application of the molded product, the molded product is suitable for housing materials, film members, building materials, interior products, exterior products, and interior and exterior parts for vehicles such as automobiles.

Examples of automotive exterior parts to which molded products are applied include fenders, bumpers, fascias, door panels, side garnishes, pillars, radiator grills, side protectors, side moldings, rear protectors, rear moldings, various spoilers, bonnets, and roof panels. , trunk lid, detachable top, wind reflector, mirror housing, and outer door handle. Examples of automotive interior parts include instrument panels, center console panels, meter parts, various switches, car navigation parts, and car audio-visual parts. It is also possible to apply it to automobile computer parts and the like. Although the molded article is suitable for the above uses, it is not limited to these uses at all.

[Reason why the present invention is effective]
Although the reason why the present invention is effective is not yet clear, it is presumed as follows.
By using a branched organopolysiloxane as a copolymerization component of the polycarbonate copolymer along with the dihydroxy compound represented by formula (1), the wear resistance is improved and the abrasion scratches and scratches that may occur during use of the molded product are improved. It can be prevented. Furthermore, when the polycarbonate copolymer contains a branched organopolysiloxane into which reactive functional groups and/or compatible groups are introduced as a copolymerization component, the branched organopolysiloxane is covalently incorporated into the polycarbonate copolymer. At the molecular level, the compatible group portion and/reactive functional group portion of the structural unit (a2) formed by coordinating with the polar element of the polycarbonate copolymer or forming intermolecular interactions. The organopolysiloxane is dispersed. Therefore, high transparency can be maintained while exhibiting excellent scratch resistance.

Furthermore, since the polysiloxane portion (that is, the polysiloxane skeleton) of the branched organopolysiloxane has a low surface free energy, the structural unit (a2) derived from the branched organopolysiloxane segregates on the surface of the molded product. This segregation results in the formation of domains or films that buffer the stresses exerted during wear. In other words, stress relaxation occurs. This suppresses the occurrence of abrasion scars (specifically, abrasions) and reduces the number of abrasion scratches. As a result, it is thought that scratches that occur when wiping with a tissue or the like can be reduced while maintaining the original transparency of the polycarbonate resin. Therefore, polycarbonate copolymers make it possible to manufacture high-quality molded products with enhanced aesthetic appearance, and the high quality of the molded products can be maintained for a long time.

On the other hand, if an organopolysiloxane without a branched structure in the polysiloxane skeleton is used and its molecular weight is low, it is thought that the viscous dissipation energy for stress relaxation will be insufficient, making it difficult to improve wear resistance. On the other hand, when the molecular weight of the organopolysiloxane without a branched structure is high, the domain size of the structural units derived from the organopolysiloxane in the polycarbonate copolymer becomes large, which is thought to impair transparency.

In addition, when the branched organopolysiloxane has a reactive functional group and/or a compatible group and is represented by formula (2), the structural unit (a2) derived from the branched organopolysiloxane and the polycarbonate copolymer The compatibility with the structural unit (a1) derived from the dihydroxy compound is further improved. Therefore, it is thought that incompatible interfaces are less likely to occur, and the transparency of the molded product as a whole is further improved.

Examples of polycarbonate copolymers are shown below, but the present invention is not limited by the following examples unless the gist of the invention is exceeded. In the following description, "parts" and "%" indicate "parts by mass" and "% by mass," respectively. In addition, in this specification, "mass part" and "weight part", "mass %" and "weight %" each have substantially the same meaning.

[Evaluation method]
In the following, the physical properties and characteristics of the polycarbonate copolymer and branched organopolysiloxane were evaluated by the following method.

(1) Test piece production method Pellets of the polycarbonate resin composition were dried at 100° C. for 8 hours under reduced pressure of 200 Pa or less. Next, the dried pellets were press-formed into sheets (width 70 mm x length 70 mm x thickness 0 .5mm) was molded. This press-formed sheet is used as a test piece.

(2) Tissue abrasion test The abrasion test was conducted using a flat abrasion tester (Daieikagaku Seiki Seisakusho, model: PA-300A). First, a tissue (flower box manufactured by Nippon Paper Crecia Co., Ltd.) was folded four times, and the tip had a radius of curvature R of 45 mm, and was attached to an abrasion element measuring 20 mm long x 20 mm wide x 50 mm high. Next, the test piece obtained in (1) above was placed on a test stand, and the abrasion element was moved back and forth 500 times. The reciprocating motion was performed under the conditions of a load of 9.8 N, a stroke of 40 mm, and a speed of 50 stroke/min. Thereafter, the appearance of the worn area of the test piece was visually observed, and the scratch resistance was evaluated based on the following criteria.
"◎": There were 15 or less scratches in the wear area. "〇": There were more than 15 scratches and no more than 30 scratches in the wear area. "×": There were 30 scratches in the wear area. If it exceeds

(3) Total light transmittance Using the test piece obtained in (1) above, use a simultaneous color and turbidity measuring device (Nippon Denshoku Industries Co., Ltd., model: COH-400), in accordance with JIS K7105. It was measured using A case where the total light transmittance is 90% or more is considered to be a pass.

(4) Glass transition temperature The glass transition temperature was measured using a differential scanning calorimeter DSC6220 (manufactured by SII Nanotechnology). Approximately 10 mg of the resin was placed in an aluminum pan made by the same company and sealed, and measurement was started at 200°C under a nitrogen stream of 50 mL/min and cooled to 30°C at a rate of 20°C/min. The temperature was maintained at 30°C for 3 minutes, and the temperature was again raised to 200°C at a rate of 20°C/min. From the DSC data during temperature rise, the temperature at the intersection of the straight line extending the baseline on the low temperature side to the high temperature side and the tangent line drawn at the point where the slope of the curve of the step-like change part of the glass transition is maximum. A certain extrapolated glass transition start temperature was determined and used as the glass transition temperature.

(5) Measurement of content of reactive functional groups/compatible groups 50 mg of each branched organopolysiloxane was weighed, and 15 mg of toluene was added as an internal standard. Furthermore, about 1 g of deuterated chloroform was added and dissolved, and the relaxation delay was measured for 20 seconds using 400 MHz ¹ H-NMR (AL-400 manufactured by JEOL Ltd.). Based on the ratio of the signal intensity of each component to the signal intensity of internal standard toluene and the weighed value, the content of reactive functional groups and compatible groups per 1 g (mmol/g), that is, the reactivity per 1000 molecular weight. The number of functional groups and the number of compatible groups were calculated.

(6) ²⁹ Si-NMR measurement Equipment: JNM-ECS400 manufactured by JEOL Ltd., TUNABLE (10), Si-free, AT10 probe Measurement conditions: Relaxation Delay/15 seconds, number of SCANs/1024 times, measurement mode/non-gated decoupled Pulse method (NNE), spin/none, measurement temperature/25℃
Preparation of sample: Tris(2,4-pentanedionato)chromium III was added to deuterated chloroform at a concentration of 0.5% to obtain a solvent for ²⁹ Si-NMR measurement. 1.5 g of organopolysiloxane to be measured was weighed, dissolved in 2.5 ml of ²⁹ Si-NMR measurement solvent, and placed in a 10 mmΦ Teflon (registered trademark) NMR sample tube.

(7) Measurement of molecular weight of branched organopolysiloxane The number average molecular weight (Mn) and weight average molecular weight (Mw) of each organopolysiloxane were measured by gel permeation chromatography (GPC) under the following conditions, and were converted to standard polystyrene values. It was shown as The sample used was an approximately 10% THF solution, which was filtered through a 0.45 μm filter before measurement.
Equipment: TOSOH HLC-8220 GPC (manufactured by Tosoh Corporation)
Column: KF-G, KF-401HQ, KF-402HQ, KF-402.5HQ (manufactured by Showa Denko K.K.), column temperature 40°C
Eluent: Tetrahydrofuran, flow rate 0.3 mL/min

(8) Measurement of viscosity of branched organopolysiloxane The viscosity of branched organopolysiloxane was measured under the following conditions.
Device: DV-II+Pro (manufactured by BROOK FIELD)
Cone: CPE-42
Measurement temperature: 25℃
Measurement sample amount: 1g

(9) Measurement of refractive index of branched organopolysiloxane The refractive index of branched organopolysiloxane was measured at 20° C. using RX-7000α (manufactured by ATAGO).

[Branched organopolysiloxane]
In Examples 1 to 5 described below, the following silicone oils A to C were used as branched organopolysiloxanes, respectively. The raw materials, manufacturing method, and characteristics of each silicone oil are as follows.

<Raw materials, etc.>
1,1,3,3-tetramethyldisiloxane (manufactured by NuSil Technology)
Polytetramethoxysilane (Mitsubishi Chemical Corporation MS-51)
Methoxypolyethylene glycol monomethacrylate (Blenmar PME-400 manufactured by NOF Corporation)
Ethylene glycol monovinyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)
1-hexene (manufactured by Tokyo Chemical Industry Co., Ltd.)
Toluene (manufactured by Kishida Chemical Co., Ltd.)
Methanol (manufactured by Kishida Chemical Co., Ltd.)
Tetrahydrofuran (manufactured by Kishida Chemical Co., Ltd.)
Heptane (manufactured by Kishida Chemical Co., Ltd.)
1N hydrochloric acid (manufactured by Kishida Chemical Co., Ltd.)
Platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (manufactured by Aldrich, platinum concentration 2%)

<Silicone oil A>
1,1,3,3-tetramethyldisiloxane 1040 parts, polytetramethoxysilane 422 parts as raw materials for the precursor of silicone oil A, tetrahydrofuran 943 parts as a solvent, and a mixture of 1N hydrochloric acid 115 parts and methanol 115 parts as a catalyst. Hydrolytic condensation was carried out at 40° C. for 5 hours. After adding 938 parts of heptane and removing hydrochloric acid by washing with demineralized water, the solvent was distilled off to obtain a silicone oil A precursor.
35.0 parts by weight of methoxypolyethylene glycol monomethacrylate was dissolved in 23.9 parts by weight of toluene, and 10.0 parts by weight of the silicone oil A precursor obtained above, 11.5 parts by weight of toluene, and a platinum concentration of 2%. A mixture of 0.05 parts by weight of a xylene solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added thereto, and the mixture was stirred at 90°C for 3.5 hours. Next, 2.5 weight of ethylene glycol monovinyl ether was added and stirred at 80°C for 22.5 hours.
After adding 4.1 parts by weight of activated carbon to the solution that was allowed to cool to around room temperature and stirring for 8 hours, the activated carbon was filtered off and the solvent was distilled off to obtain silicone oil A.

Reactive functional group/compatible group:
Methoxypolyethylene glycol group 1.6 mmol/g
Content of methoxypolyethylene glycol group per molecular weight 1000: 1.6 2-(2-hydroxyethoxy)ethyl group 0.34 mmol/g
Content of 2-(2-hydroxyethoxy)ethyl groups per 1000 molecular weight: 0.34 Reactive functional groups/groups other than compatible groups:
Methyl group 4.5 mmol/g


Coefficients in equation (2):
a=0.67, b=0.3, c=0, d=0.30
(The value of e+f could not be calculated, but at the silicone oil A precursor stage, e+f = 0.04, and it is thought that the value of e+f at the post-polymerization stage is the same as or smaller than that at the precursor stage. )
Methoxy group amount: Could not be calculated, but was 1.2% by weight at the silicone oil A precursor stage Mn: 2500
Mw:5600
Refractive index: 1.461
Viscosity: 420mPa・s

<Silicone oil B>
After dissolving 161 parts by weight of ethylene glycol monovinyl ether in 166 parts by weight of toluene, the mixture was heated to 85°C. After adding 0.17 parts by weight of a xylene solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex with a platinum concentration of 2%, it was heated to 85°C with silicone oil A precursor. A mixture of 150 parts by weight of silicone oil B precursor synthesized in a similar manner and 167 parts by weight of toluene was added and stirred for 2 hours. The mixture was further stirred at 120°C for 2 hours. After cooling to around room temperature, 150 parts by weight of silica gel was added and stirred for 30 minutes, the silica gel was filtered off, and the solvent was distilled off to obtain silicone oil B.

Reactive functional group/compatible group:
2-(2-hydroxyethoxy)ethyl group 4.8 mmol/g
Content of 2-(2-hydroxyethoxy)ethyl groups per molecular weight 1000: 4.8 Reactive functional groups/groups other than compatible groups:
Methyl group 12 mmol/g

Coefficients in equation (2):
a=0.67, b=0.02, c=0, d=0.31
(The value of e+f could not be calculated, but at the stage of silicone oil B precursor, e+f = 0.04, and it is thought that the value of e+f at the stage after polymerization is the same as or smaller than that at the stage of the precursor. )
Methoxy group amount: Could not be calculated, but was 1.2% by weight at the stage of silicone oil B precursor Mn: 1700
Mw:2400
Refractive index: 1.458
Viscosity: 1000mPa・s

<Silicone oil C>
After dissolving 20.1 parts by weight of silicone oil C precursor synthesized in the same manner as silicone oil A precursor in 45.1 parts by weight of toluene, the solution was heated to 50°C to form platinum(0) with a platinum concentration of 2%. 0.02 parts by weight of -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution was added and stirred. 12.2 parts by weight of 1-hexene was added thereto, and the mixture was stirred at 50°C for 17 hours. Next, 5.4 weight of ethylene glycol monovinyl ether was added and stirred at 50°C for 8 hours.
After adding 7.3 parts by weight of activated carbon to the solution that was allowed to cool to around room temperature and stirring for 3 hours, the activated carbon was filtered off and the solvent was distilled off to obtain silicone oil C.

Reactive functional group/compatible group:
2-(2-hydroxyethoxy)ethyl group 1.7 mmol/g
Content of 2-(2-hydroxyethoxy)ethyl groups per 1000 molecular weight: 1.7 Reactive functional groups/groups other than compatible groups:
Methyl group 11 mmol/g
Hexyl group 3.4 mmol/g

Coefficients in equation (2):
a=0.64, b=0.03, c=0, d=0.33
(The value of e+f could not be calculated, but at the silicone oil C precursor stage, e+f = 0.03, and it is thought that the value of e+f at the post-polymerization stage is the same as or smaller than the precursor stage. )
Methoxy group amount: Could not be calculated, but was 0.7% by weight at the stage of silicone oil C precursor Mn: 1600
Mw: 1800
Refractive index: 1.448
Viscosity: 190mPa・s

[Linear chain organopolysiloxane]
In Comparative Examples 2 and 3, silicone oil D and silicone oil E were used, respectively.

<Silicone oil D>
Silicone oil D: BY16-201 (manufactured by Toray Dow Corning, carbinol-terminated dimethylsiloxane)
Refractive index: 1.412
Kinematic viscosity: 45mm ² /s (25°C)

Silicone oil E: X-22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd., carbinol-terminated dimethylsiloxane)
Reactive group equivalent: 470g/mol
Viscosity: 35mm ² /s

[Polycarbonate copolymer]
In Examples 1 to 5 and Comparative Examples 1 to 3 described below, the following dihydroxy compounds were used as raw materials for polycarbonate copolymers other than branched organopolysiloxanes.
First dihydroxy compound: Isosorbide (i.e., ISB): Manufactured by Roquette Fleuret, product name: POLYSORB
Second dihydroxy compound: 1,4-cyclohexanedimethanol (i.e., CHDM): (cis, trans mixture, manufactured by SK Chemical Co., Ltd.)
Diphenyl carbonate (i.e., DPC): manufactured by Mitsubishi Chemical Corporation

[Example 1]
ISB 59.6g (0.408mol), CHDM 25.2g (0.175mol), DPC 124.87g (0.583mol), silicone oil 1.0g, and calcium acetate monohydrate 3.08 x 10 as a catalyst. ^-3 g (1.75×10 ^-5 mol) was charged into the reactor, and the inside of the reactor was replaced with nitrogen under reduced pressure. The raw materials were dissolved in the reactor at 150° C. for 30 minutes with stirring under a nitrogen atmosphere. As the first reaction step, the temperature was raised to 210° C. over 30 minutes, and the reaction was carried out for 30 minutes at normal pressure. Next, the pressure was reduced from normal pressure to 13.3 kPa over 90 minutes, and maintained at 13.3 kPa for 30 minutes to extract the generated phenol from the reaction system. Next, as a second reaction step, the temperature of the heating medium was raised to 220° C. over 15 minutes, while the pressure was reduced to 133 Pa or less over 20 minutes, and the generated phenol was extracted from the reaction system. When a predetermined stirring power was reached, the pressure was restored with nitrogen, and the contents were extracted in the form of a strand and made into pellets using a rotary cutter. The pellets were dried in a hot air dryer at 100°C for 8 hours. Using the polycarbonate copolymer pellets thus obtained, the various evaluations described above were performed. The evaluation results and blending ratios are shown in Table 1. The compounding ratio of each component shown in Table 1 is a mutual compounding ratio of the components, and is expressed in mass % ratio.

[Examples 2 to 5]
Polycarbonate copolymer pellets were obtained in the same manner as in Example 1, except that the type and amount of silicone oil used were changed as shown in Table 1. Next, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Examples 1 to 3]
Polycarbonate copolymer pellets were obtained in the same manner as in Example 1, except that the type and amount of silicone oil used were changed as shown in Table 1. Next, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1. Note that Comparative Example 1 is a polycarbonate resin produced without using organopolysiloxane. Comparative Examples 2 and 3 are polycarbonate copolymers produced using unbranched linear organopolysiloxanes.

In Examples and Comparative Examples, the amount of silicone oil blended can be approximated to the weight percent of the silicone oil-derived structural unit (a2) in the resulting polycarbonate copolymer.

As shown in Table 1, Comparative Example 1 does not have a structural unit derived from organopolysiloxane, so the results of the tissue abrasion test are unsatisfactory. In other words, Comparative Example 1 has insufficient scratch resistance. Comparative Examples 2 and 3 have linear organopolysiloxane-derived structural units that do not have a branched structure, but have low total light transmittance and insufficient transparency. In addition, in Comparative Examples 2 and 3, since the transparency was rejected, the evaluation by the tissue abrasion test was omitted.

As shown in Table 1, Examples 1 to 5 have structural units derived from branched organopolysiloxane as well as structural units derived from ISB. Examples 1 to 5 all have excellent transparency and also excellent scratch resistance. Furthermore, it has a sufficiently high glass transition point and excellent heat resistance.

In Example 1, the structural unit (a2) derived from branched organopolysiloxane has a group represented by the above formula (23) (however, m=8) and a group represented by formula (25) as the organic group. (However, m=8), and has a group represented by formula (21). In Examples 2 and 4, the structural unit derived from branched organopolysiloxane has a group represented by the above formula (21) as an organic group. In Examples 3 and 5, the structural unit derived from the branched organopolysiloxane has a hexyl group and a group represented by the above formula (21) as organic groups.

Examples 2 and 3 have better scratch resistance than Examples 4 and 5 while maintaining transparency. This is because the number of structural units derived from the branched organopolysiloxane that segregates on the surface of the molded article increases as the number of structural units derived from the branched organopolysiloxane increases in the polycarbonate copolymer.

Examples 1 and 2 have further improved transparency compared to Example 3. This is because silicone oil A and silicone oil B have a larger total number of reactive functional groups and/or compatible groups than silicone oil C, resulting in improved compatibility.

In this way, by including the structural unit (a1) derived from the dihydroxy compound represented by formula (1) and the structural unit (a2) derived from the branched organopolysiloxane, high transparency can be maintained and the molded product It can be seen that a polycarbonate copolymer can be obtained that has improved abrasion resistance (specifically, scratch resistance) while enhancing the aesthetic appearance. This is because the branched organopolysiloxane has a hydroxyl group, which acts at least as a reactive functional group and is covalently incorporated into the polycarbonate copolymer structure.

Claims (11)

A structural unit derived from a dihydroxy compound represented by the following formula (1),
A polycarbonate copolymer having a structural unit derived from a branched organopolysiloxane having a hydroxyl group,
The branched organopolysiloxane has a polysiloxane skeleton and an organic group containing a reactive functional group and a compatible group bonded to the siloxane bond of the polysiloxane skeleton, and the organic group serves as the reactive functional group. having at least the above hydroxyl group,
A polycarbonate copolymer, wherein the compatible group is a polar group having one or more of an aromatic group, an oxygen atom, a sulfur atom, and a nitrogen atom.

The polycarbonate copolymer according to claim 1, wherein the compatible group is an alkoxy group or an alkylene glycol group . Polycarbonate copolymer according to claim 1 or 2 , wherein the compatible group of the organic group has one or more ether bonds. The polycarbonate copolymer according to any one of claims 1 to 3, wherein the branched organopolysiloxane is a polymer represented by the following formula (2).
(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d (O _1/2 R ⁷ ) _e ( O _1/2 H) _f ...(2)
(R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently a hydrocarbon group having 1 to 20 carbon atoms, a reactive functional group, a compatible group, or a hydrogen atom, and R ⁷ is an organic group having 1 to 7 carbon atoms, and a to f are numbers greater than or equal to 0 that satisfy a+b+c+d=1, 0<c+d≦1, and 0≦e+f<4.) The polycarbonate copolymer according to claim 4, wherein in the above formula (2), the value of c+d satisfies 0.15≦c+d≦0.9. The polycarbonate copolymer according to claim 4 or 5, wherein in the formula (2), the value of a satisfies 0.1≦a≦0.8. The polycarbonate copolymer according to any one of claims 4 to 6, wherein in the above formula (2), the value of b satisfies 0≦b≦0.8. The polycarbonate according to any one of claims 2 to 7 , wherein the total content of the reactive functional groups and the compatible groups per 1000 molecular weight of the branched organopolysiloxane is 1.5 or more and 12 or less. Copolymer. The polycarbonate according to any one of claims 1 to 8, wherein the polycarbonate copolymer has a content of structural units derived from the branched organopolysiloxane of 0.5% by mass or more and 6.0% by mass or less. Copolymer. The above-mentioned polycarbonate copolymer has a structural unit derived from a dihydroxy compound (excluding the above-mentioned branched organopolysiloxane) different from the dihydroxy compound represented by the above formula (1), and The polycarbonate copolymer according to any one of claims 1 to 9, wherein the content of the structural unit derived from the dihydroxy compound represented by formula (1) is 5% by mass or more and 90% by mass or less. A molded article comprising the polycarbonate copolymer according to any one of claims 1 to 10.