JP5570180B2 - Laminated molded parts - Google Patents

Description

  The present invention relates to a laminated molded member having a layer made of a composition containing a polycarbonate having a predetermined structure as a main component and having excellent surface hardness and slipperiness and good appearance. The present invention also relates to a siloxane copolymer polycarbonate useful for producing the laminated member and the like.

  Polycarbonate resin exhibits excellent electrical properties, flame retardancy, transparency, dimensional stability, mechanical properties, and is lightweight, so it is widely used in the fields of electrical and electronics, automobiles, and building materials. Yes. In particular, polycarbonate resin derived from bisphenol A is inexpensive and has excellent transparency and impact strength. Therefore, it is molded into sheets and films as an alternative to inorganic glass, and is widely used in electrical and electronic parts and building materials. Yes. However, the polycarbonate resin derived from bisphenol A has a drawback of being inferior in surface hardness.

As means for solving this problem, various methods for modifying the surface of a molded article of a polycarbonate resin derived from bisphenol A have been proposed. For example, a method of applying a hard coat to a surface using a silicone or acrylic material, and acrylic A method of laminating layers of a polymer material has been proposed. Patent Document 1 proposes to improve the surface strength by forming a thin layer made of a resin composition in which a predetermined filler is dispersed in a transparent resin matrix on the surface of a polycarbonate resin substrate. Yes.
In these methods, it is necessary to laminate a layer made of a material different from the polycarbonate resin on the surface of a substrate mainly made of a polycarbonate resin such as a polycarbonate resin derived from bisphenol A. There has been a problem that warpage is likely to occur due to the difference in linear expansion coefficient and the difference in linear expansion coefficient. In addition, from the viewpoint of recycling after use, there is also a drawback that it is difficult to separate and collect.

  Patent Document 2 discloses a scratch resistance property (surface) by using a polycarbonate resin having 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane (hereinafter abbreviated as CBPZ) as one of the starting materials. It has been proposed to improve (hardness). However, the polycarbonate resin made of CBPZ has a drawback that it tends to be thermally deteriorated (easily burnt) when a molded body is obtained by a heat-melt molding method, and has an appearance when used as a display panel mounted on an electric / electronic device. A good laminated molded body could not be obtained.

On the other hand, Patent Documents 3 to 8 propose cast films, extrusion-molded films, and injection-molded articles made of a polycarbonate copolymer having a siloxane structural unit. Absent.
Further, in order to continuously produce a film-like or sheet-like molded body, a process such as transporting and winding a long film on a support is necessary, and the transport is stably performed. The sheet-like and film-like molded bodies are required to have a certain degree of slipperiness.

Japanese Patent Laid-Open No. 2007-14450 Special table 2009-500195 gazette Japanese Patent Laid-Open No. 5-65354 Japanese Patent Laid-Open No. 5-65399 Japanese Patent Laid-Open No. 5-200761 Japanese Patent Laid-Open No. 5-200827 Japanese Patent Laid-Open No. 5-202181 JP-A-5-202182

The problem to be solved by the present invention is to improve the appearance of a laminated molded member made of a polycarbonate resin excellent in surface hardness and slipperiness.
More specifically, an object of the present invention is to provide a laminated molded member made of a polycarbonate resin composition that has excellent surface hardness, excellent slipperiness, and good appearance.
Another object of the present invention is to provide a siloxane copolymer polycarbonate that is useful for producing a laminated molded member having excellent surface hardness, excellent slipperiness, and good appearance.

  As a result of intensive studies to solve the conventional problems, the present inventors have found that a siloxane using a bisphenol compound having a predetermined structure having a methyl group in an aromatic ring and a compound having a siloxane structure having a predetermined structure as raw materials Acquired knowledge that copolycarbonate is a material that is difficult to be thermally deteriorated (easily burned), acts as a lubricant, contributes to an improvement in slipperiness, and can be formed with a high surface hardness. It was. The siloxane copolymer polycarbonate having the above structure can be heat-melt coextruded with a polycarbonate resin derived from bisphenol A, and has a high surface hardness, good slipperiness, and appearance by a simple heat-melt coextrusion molding method. The present inventors have found that an excellent laminated molded member can be obtained, and have completed the present invention.

That is, the means for solving the above problems are as follows.
[1] One or more general formulas (A1)
(Where X ¹ is
And one or more general formulas (A2)
(Where X ² is
R ¹ ′ and R ² ′ are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl group having 1 to 20 carbon atoms, each of which may have a substituent, carbon Represents an alkoxy group having 1 to 5 atoms or an aryl group having 6 to 12 carbon atoms; each of R ³ and R ⁴ has a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a substituent. And represents an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms; Represents an integer of ~ 20. ) And a compound having one or more types of siloxane structures, and a compound having one or more types of siloxane structures are obtained by reacting a compound having one or more types of siloxane structures with one or more types of siloxane structures. 0.1 to 10% by weight with respect to the compound represented by the general formula (A1) + one or more compounds represented by the general formula (A2) + one or more compounds having a siloxane structure, and a glass transition A layer composed of a first composition containing a siloxane copolymer polycarbonate having a temperature (Tg) of 130 to 160 ° C. as a main component, and 2,2-bis (4-hydroxyphenyl) adjacent to the first layer And a layer composed of a second composition containing a polycarbonate derived from propane as a main component, and the surface of the layer composed of the first composition is a pencil. Degrees H or a is laminated member.
[2] The compound having one or more types of siloxane structures is a compound selected from the group consisting of General Formula (B), General Formula (C), General Formula (D), and General Formula (E) [1] Laminate forming member.
Wherein R ^{5 to} R ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a carbon atom. An alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, an alkyl group having 1 to 5 carbon atoms or 2 carbon atoms as a substituent. Can also have an alkenyl group of ˜5, an alkoxy group of 1 to 5 carbon atoms; R ¹⁰ represents an aliphatic group of 1 to ¹⁰ carbon atoms or represents a bond;
Represents a linear or branched homopolymer or a block or random copolymer comprising a combination of structural units selected from: a degree of polymerization of 1 to 200; and R ^{11 to} R ¹⁵ are each independently Hydrogen atom, alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 12 carbon atoms, alkenyl group having 2 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, or 7 to 17 carbon atoms When these groups have carbon atoms, the substituents are alkyl groups having 1 to 5 carbon atoms, alkenyl groups having 2 to 5 carbon atoms, and alkoxy groups having 1 to 5 carbon atoms. Can also be included. Z is
R ¹⁶ and R ¹⁷ are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl group having 1 to 20 carbon atoms, each having a substituent, and the number of carbon atoms Represents an alkoxy group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms, or R ¹⁶ and R ¹⁷ are bonded to form a carbocyclic ring having 5 to 20 carbon atoms or a heterocyclic ring having 5 to 12 elements. R ¹⁸ and R ¹⁹ are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl group having 1 to 9 carbon atoms, each of which may have a substituent, carbon Represents an alkoxy group having 1 to 5 atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms; c represents an integer of 0 to 20; )
[3] The laminate forming member according to [2], wherein the compound having one or more types of siloxane structures is a compound represented by the general formula (D).
[4] The laminate member according to [2], wherein the compound having one or more types of siloxane structures is a compound represented by the general formula (E).
[5] The laminate forming member according to [2], wherein the compound having one or more types of siloxane structures is a compound represented by the general formula (B).
[6] The laminated member according to [2], wherein the compound having one or more types of siloxane structures is a compound represented by the general formula (C).
[7] R ^{11 to} R ^{15 in} general formula (B), general formula (C), general formula (D), and general formula (E) are each a methyl group, an n-butyl group, and a phenyl group. The laminated member according to any one of [2] to [6], which is a selected group .
[8 ] The laminated member according to any one of [1] to [ 7 ], wherein the intrinsic viscosity [η] of the siloxane copolymer polycarbonate is 0.2 to 1.0 [dl / g].
[ 9 ] The laminate forming member according to any one of [1] to [ 8 ], wherein the carbonate-forming compound is phosgene.
[ 10 ] The laminated molded member according to any one of [1] to [ 9 ], wherein the first and second compositions are molded by a melt coextrusion method.
[ 11 ] The laminated molded member according to any one of [1] to [ 10 ], which is in the form of a sheet or film.

According to the present invention, it is possible to provide a laminated molded member having excellent surface hardness, good slipperiness, and good appearance.
Further, according to the present invention, it is possible to provide a siloxane copolymer polycarbonate useful for producing a laminated molded member having excellent surface hardness, excellent slipperiness, and good appearance.

Hereinafter, the present invention will be described in detail.
The laminate-forming member of the present invention is derived from a first composition containing a predetermined siloxane copolymer polycarbonate as a main component and 2,2-bis (4-hydroxyphenyl) propane adjacent to the first layer. It is related with the lamination | stacking formation member which has at least the layer which consists of a 2nd composition which contains the polycarbonate as a main component.
First, the first and second compositions will be described in detail.
1. First composition The first composition is:
One or more general formulas (A)
(Where X is
R ¹ and R ² are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl group having 1 to 20 carbon atoms, each having a substituent, and the number of carbon atoms Represents an alkoxy group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms, or R ¹ and R ² are bonded to form a carbocyclic ring having 5 to 20 carbon atoms or a heterocyclic ring having 5 to 12 elements. R ³ and R ⁴ each represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl group having 1 to 9 carbon atoms, each of which may have a substituent, carbon Represents an alkoxy group having 1 to 5 atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms; a represents an integer of 0 to 20; ) And a siloxane copolymer polycarbonate obtained by reacting a compound having one or more types of siloxane structures with a carbonate-forming compound.

In the present invention, only one compound represented by the general formula (A) may be used, or two or more compounds may be used in combination. However, the polycarbonate of the present invention does not contain units derived from bisphenols other than the compound represented by the general formula (A).
Specific examples of the compound represented by the general formula (A) include 1,1′-biphenyl-3,3′-dimethyl-4,4′-diol, 1,1′-biphenyl-2,2′-. Dimethyl-4,4′-diol, bis (4-hydroxy-3-methylphenyl) ether, bis (4-hydroxy-2-methylphenyl) ether, bis (4-hydroxy-3-methylphenyl) sulfoxide, bis ( 4-hydroxy-2-methylphenyl) sulfoxide, bis (4-hydroxy-3-methylphenyl) sulfide, bis (4-hydroxy-2-methylphenyl) sulfide, bis (4-hydroxy-3-methylphenyl) ketone, Bis (4-hydroxy-2-methylphenyl) ketone, 1,1′-bis (4-hydroxy-3-methylphenyl) ethane, 1,1′-bis (4- Droxy-2-methylphenyl) ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-2-methylphenyl) propane, 2,2-bis (4 -Hydroxy-3-methylphenyl) butane, 2,2-bis (4-hydroxy-2-methylphenyl) butane, 2,2-bis (4-hydroxy-3-methylphenyl) hexafluoropropane, 2,2- Bis (4-hydroxy-2-methylphenyl) hexafluoropropane, 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-2-methylphenyl) ) -1-phenylethane, bis (4-hydroxy-3-methylphenyl) diphenylmethane, bis (4-hydroxy-2-methylphenyl) Diphenylmethane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclopentane, 1,1-bis (4-hydroxy-2-methylphenyl) cyclopentane, 1,1-bis (4-hydroxy-3- Methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-2-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) -3,3,5-trimethylcyclo Hexane, 1,1-bis (4-hydroxy-2-methylphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclododecane, 1, 1-bis (4-hydroxy-2-methylphenyl) cyclododecane, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9- (4-hydroxy-2-methylphenyl) fluorene, 3,3′-dimethyl-4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisphenol, 2,2′-dimethyl-4, 4 ′-[1,4-phenylenebis (1-methylethylidene)] bisphenol, 3,3′-dimethyl-4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisphenol, 2,2 Examples include '-dimethyl-4,4'-[1,3-phenylenebis (1-methylethylidene)] bisphenol. Two or more of these may be used in combination.

  Among these, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) ethane, bis (4-hydroxy-3-methylphenyl) ) Methane, 1,1′-biphenyl-3,3′-dimethyl-4,4′-diol, 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, bis (4-hydroxy) 3-methylphenyl) diphenylmethane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, and 9,9-bis (4-hydroxy-3methylphenyl) fluorene are preferred.

  The one or more bisphenols of the general formula (A) are preferably purified to a purity of 98% or more, more preferably 99% or more. In particular, those having a large number of isomers such as 2,4'-dihydroxy compounds are not preferred because the reactivity is lowered and the control of polymerization becomes difficult.

  The compound having one or more siloxane structures is preferably a compound selected from the group consisting of General Formula (B), General Formula (C), General Formula (D), and General Formula (E).

In the formula, R ^{5 to} R ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or the number of carbon atoms. An alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, an alkyl group having 1 to 5 carbon atoms or 2 to 2 carbon atoms as a substituent. Can also have 5 alkenyl groups, alkoxy groups of 1 to 5 carbon atoms; R ¹⁰ represents an aliphatic group of 1 to ¹⁰ carbon atoms or represents a bond;

It represents a linear or branched homopolymer or a block or random copolymer comprising a combination of structural units selected from: a degree of polymerization of 1 to 200 (preferably 5 to 100, more preferably 10 to 80). R ^{11 to} R ¹⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl having 6 to 12 carbon atoms. Group, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, It can also have a C1-C5 alkyl group, a C2-C5 alkenyl group, and a C1-C5 alkoxy group. Z is

It is. R ¹⁶ and R ¹⁷ are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an optionally substituted group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1-5) an alkyl group, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms, or R ¹⁶ and R ¹⁷ are bonded to each other to form 5 to 20 carbon atoms (preferably 5 to 10, more preferably 5 to 7) represents a group that forms a carbocyclic ring or a heterocyclic ring having 5 to 12 elements; R ¹⁸ and R ¹⁹ are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, An iodine atom, or an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or 6 to 6 carbon atoms, each optionally having a substituent 12 represents an aryl group; c is 0 to 20 (preferably Properly 1 to 10, more preferably an integer of 1 to 5).

In the formula (B), the hydroxy group is preferably substituted at the para position with respect to —C (R ⁹ ) (R ¹⁹ —Y) —. In formula (B), R ^{5 to} R ⁸ are preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (more preferably 1 to 5 carbon atoms). One of R ⁵ and R ⁶ is a hydrogen atom and the other is an alkyl group having 1 to 10 carbon atoms (more preferably 1 to 5 carbon atoms); and one of R ⁷ and R ⁸ is a hydrogen atom and the other is More preferably, it is an alkyl group having 1 to 10 carbon atoms (more preferably 1 to 5 carbon atoms). In addition, it is preferable that the substitution position of an alkyl group is a meta position with respect to -C (R < ⁹ >) (R < ¹⁰ > -Y)-.

In formula (C), the hydroxy group is preferably substituted at the ortho or para position relative to -R ¹⁰ -Y, more preferably substituted at the ortho position. In formula (C), R ⁵ and R ⁶ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (more preferably 1 to 5 carbon atoms), or an alkoxy group having 1 to 5 carbon atoms. Preferably, both are hydrogen atoms.

In formula (D), the hydroxy group is preferably substituted at the para position with respect to -Z-, and -R ¹⁰ -Y is substituted at the meta position with respect to -Z-. Is preferred. In formula (D), R ^{5 to} R ⁸ are each preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (more preferably 1 to 5 carbon atoms), all of which are hydrogen atoms. It is more preferable that

In the formula (E), the hydroxy group is preferably substituted at the ortho position or the para position with respect to —R ¹⁰ —Y—Si (R ¹¹ ) (R ¹² ) —R ¹⁰ —. More preferably, it is substituted. In formula (E), R ^{5 to} R ⁸ are each an alkyl group having 1 to 10 carbon atoms (more preferably 1 to 5 carbon atoms) or an alkoxy group having 1 to 5 carbon atoms. It is more preferable that all are hydrogen atoms.

Substituents of the siloxane segment in the general formula (B), general formula (C), general formula (D), and general formula (E), that is, R ^{11 to} R ¹⁵ are a methyl group and an n-butyl group, respectively. Or a group selected from phenyl groups. These may be the same or different from each other.

Examples of the siloxane compound represented by the formula (B) include a compound represented by the following formula (B ′).

R ¹⁰ and R ¹⁵ in the formula (B ') are respectively synonymous with R ¹⁰ and R ¹⁵ in the formula (B), x is a number from 10 to 80.
Wherein (B '), R ¹⁰ is preferably (more preferably _{C 5 ~ 10) C 1 ~} 10 alkylene group, and R ¹⁵ is C ₁ ~ ₁₀ (more preferably C ₁ ~ ₅₎ It is preferably an alkyl group, and x is preferably a number of 20 to 60.

  Examples of the siloxane compound represented by the general formula (B) include compounds having the following structural formula, but are not limited thereto. In the compound of the following structural formula, the siloxane segment may be linear or branched, and two or more segments may be the same as or different from each other.

The Y ^b preferably contains 1 to 200 (preferably 5 to 100, more preferably 10 to 80, still more preferably 20 to 70, still more preferably 20 to 60) dimethylsiloxane units. Among them, in particular, α-11-bis (4-hydroxyphenyl) undecane-ω-butyl-polydimethylsiloxane and α-3-bis (4-hydroxyphenyl) -2-methylpropane-ω-butyl-polydimethylsiloxane Is preferred.

Examples of the compound represented by the formula (C) include a compound represented by the following formula (C ′).

R ¹⁰ and R ¹⁵ in the formula (C ') are respectively synonymous with R ¹⁰ and R ¹⁵ in the formula (C), x is a number from 10 to 80.
Wherein (C '), R ¹⁰ is preferably (more preferably _{C 5 ~ 10) C 1 ~} 10 alkylene group, and R ¹⁵ is C ₁ ~ ₁₀ (more preferably C ₁ ~ ₅₎ It is preferably an alkyl group, and x is preferably a number of 20 to 60.

  Examples of the siloxane compound represented by the general formula (C) include, but are not limited to, the following structural formulas. In the compound of the following structural formula, the siloxane segment may be linear or branched, and two or more segments may be the same as or different from each other.

The Y ^c preferably contains 1 to 200 (preferably 5 to 100, more preferably 10 to 80, still more preferably 20 to 70, still more preferably 20 to 60) dimethylsiloxanes. Among them, in particular, α-3- (2-hydroxyphenyl) propyl-ω-butyl-polydimethylsiloxane, α-3- (4-hydroxyphenyl) propyl-ω-butyl-polydimethylsiloxane, α-3- (4 -Hydroxy-3-methoxy-phenyl) propyl-ω-butyl-polydimethylsiloxane is preferred.

Examples of the compound represented by the formula (D) include a compound represented by the following formula (D ′).

R ¹⁰ and R ¹⁵ in the formula (D ') has the same meaning as R ¹⁰ and R ¹⁵ in the formula (D), x is a number from 10 to 80.
Wherein (D '), R ¹⁰ is preferably C ₁ ~ ₁₀ (more preferably C ₁ ~ ₅₎ is an alkylene group of, R ¹⁵ is alkyl of C ₁ ~ ₁₀ (more preferably C ₁ ~ ₅₎ It is preferably a group, and x is more preferably 20 to 60.

  Examples of the siloxane compound represented by the general formula (D) include, but are not limited to, the following structural formulas. In the compound of the following structural formula, the siloxane segment may be linear or branched, and two or more segments may be the same as or different from each other.

Y ^d contains 1 to 200 (preferably 5 to 100, more preferably 10 to 80, more preferably 20 to 70, and still more preferably 20 to 60) dimethylsiloxane. Among these, 2,2-bis (4-hydroxy-3-polydimethylsiloxypropyl) propane is particularly preferable.

Examples of the compound represented by the formula (E) include a compound represented by the following formula (E ′).

R ¹⁰ in formula (E ′) has the same meaning as R ¹⁰ in formula (E), and x is a number from 10 to 80.
Wherein (E '), R ¹⁰ is preferably (more preferably _{C 1 ~ 5) C 1 ~} 10 alkylene group, x is preferably a number of 20 to 60.

  Examples of the siloxane compound represented by the general formula (E) include, but are not limited to, the following structural formulas. In the compound of the following structural formula, the siloxane segment may be linear or branched, and two or more segments may be the same as or different from each other.

The Y ^e preferably contains 1 to 100 (preferably 5 to 100, more preferably 10 to 80, still more preferably 20 to 70, still more preferably 20 to 60) dimethylsiloxane. Among these, α, ω-bis [3- (2-hydroxyphenyl) propyl] polydimethylsiloxane is particularly preferable.

The compound represented by the one or more general formulas (A) in the siloxane copolymer polycarbonate is composed of all monomer components (compound represented by one or more general formulas (A) + one or more siloxane structures). 90 to 99.9% by weight, and more preferably 95 to 99.5% by weight, based on the compound having a).
The siloxane copolymer polycarbonate is produced by using two or more compounds each having a siloxane structure, a compound represented by the general formula (A), and a compound represented by the general formula (B). However, the siloxane copolymer polycarbonate does not contain units derived from bisphenols other than these monomers. Preferred examples include a siloxane copolymer polycarbonate containing units each derived from one compound represented by the general formula (A) and one compound represented by the general formula (B); and two general formulas And a siloxane copolymer polycarbonate containing units each derived from a compound represented by (A) and a compound represented by one type of general formula (B).

On the other hand, examples of the carbonic acid ester forming compound usable in the present invention include phosgene and diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate. And bisallyl carbonate.
In the production of the siloxane copolymer polycarbonate, only one type of the carbonic acid ester forming compound may be used, or two or more types may be used in combination.

  The siloxane copolymer polycarbonate may be prepared by various methods used for producing a polycarbonate from bisphenol A and a carbonate ester-forming compound, for example, a direct reaction of bisphenols and phosgene (phosgene method), and bisphenols and bisaryl carbonates. It can be produced by adopting any method such as transesterification reaction (transesterification method).

  In the phosgene method and the transesterification method, the phosgene method is preferable in consideration of the reactivity of one or more compounds represented by the general formula (A) and one or more compounds having a siloxane structure.

  In the phosgene method, the bisphenols and phosgene are usually reacted in the presence of an acid binder and a solvent. Examples of the acid binder include pyridine and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and examples of the solvent include methylene chloride and chloroform. Furthermore, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt is used to accelerate the condensation polymerization reaction, and phenol, pt-butylphenol, p-cumylphenol are used for adjusting the degree of polymerization. It is preferable to add a monofunctional compound such as a long-chain alkyl-substituted phenol as a molecular weight regulator. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfite, or a branching agent such as phloroglucin or isatin bisphenol may be added. The reaction is usually in the range of 0 to 150 ° C, preferably 5 to 40 ° C. While the reaction time depends on the reaction temperature, it is generally 0.5 min-10 hr, preferably 1 min-2 hr. Further, during the reaction, it is desirable to maintain the pH of the reaction system at 10 or more.

  On the other hand, in the transesterification method, the bisphenols and bisaryl carbonate are mixed and reacted at a high temperature under reduced pressure. The reaction is usually carried out at a temperature in the range of 150 to 350 ° C., preferably 200 to 300 ° C., and the degree of vacuum is preferably 1 mmHg or less at the end, and phenols derived from the bisaryl carbonate produced by the transesterification reaction Is distilled out of the system. The reaction time depends on the reaction temperature and the degree of reduced pressure, but is usually about 1 to 24 hours. The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon. Moreover, you may react by adding a molecular weight regulator, antioxidant, and a branching agent as needed.

  In the aspect in which the siloxane copolymer polycarbonate is melt-extruded to produce the laminated member of the present invention, the siloxane copolymer polycarbonate preferably has an intrinsic viscosity of 0.2 to 1.0 dl / g. More preferably, the viscosity is more than 0.3 dl / g and not more than 0.6 dl / g, more preferably 0.33 to 0.4 dl / g, and more than 0.33 dl / g and less than 0.4 dl / g. Even more preferably. When the intrinsic viscosity of the siloxane copolymer polycarbonate is within the above range, the mechanical strength is sufficient when it is molded into a sheet or film, and the moldability is also good.

The siloxane copolymer polycarbonate preferably has a glass transition temperature (Tg) of 130 to 165 ° C. Since the glass transition temperature is in the above range, it can be molded as a laminated molded member by a simple method such as a heat-melt coextrusion method together with a polycarbonate resin derived from bisphenol A, which will be described later. The Tg of the siloxane copolymer polycarbonate is preferably 130 to 160 ° C, and more preferably 140 to 160 ° C.
In addition, a viscosity becomes the said range as the weight average molecular weight (polystyrene conversion) measured by GPC is about 30,000-70,000.

  Examples of the siloxane copolymer polycarbonate include 9,9-bis (4-hydroxy-3methylphenyl) fluorene (BCFL), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1- At least selected from bis (4-hydroxy-3-methylphenyl) ethane, bis (4-hydroxy-3-methylphenyl) methane, 1,1′-biphenyl-3,3′-dimethyl-4,4′-diol It is a siloxane copolymer polycarbonate obtained by reacting one kind and at least one of the compounds represented by the general formulas (B) to (E) with a carbonate ester-forming compound. In this example, the ratio of BCFL is preferably equal to or less than that of the other compound represented by the general formula (A). For example, one or more types of the general formula (A) It is preferable that it is about 20 to 50 weight% in the total weight of the compound made. However, it is not limited to this range.

  Other examples of the siloxane copolymer polycarbonate include 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane (CBPZ), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) ethane, bis (4-hydroxy-3-methylphenyl) methane, 1,1′-biphenyl-3,3′-dimethyl-4,4′-diol A siloxane copolymer polycarbonate obtained by reacting at least one selected from the group consisting of compounds represented by the general formulas (B) to (E) with a carbonate-forming compound. In this example, the ratio of CBPZ is preferably equal to or greater than that of the other compound represented by the general formula (A). For example, the CBPZ ratio is represented by one or more general formulas (A). It is preferable that it is about 50 to 90 weight% in the total weight of the compound made. However, it is not limited to this range.

  Other examples of the siloxane copolymer polycarbonate include 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane and at least compounds represented by the general formulas (B) to (E). It is a siloxane copolymer polycarbonate obtained by reacting one kind with a carbonate ester-forming compound.

Other examples of the siloxane copolymer polycarbonate include one or more general formulas (A1)
(Where X ¹ is
And one or more general formulas (A2)
(Where X ² is
R ¹ ′ and R ² ′ are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl group having 1 to 20 carbon atoms, each of which may have a substituent, carbon Represents an alkoxy group having 1 to 5 atoms or an aryl group having 6 to 12 carbon atoms; each of R ³ and R ⁴ has a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a substituent. And represents an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms; Represents an integer of ~ 20. ) And a compound having one or more types of siloxane structures, and a compound having one or more types of siloxane structures are obtained by reacting a compound having one or more types of siloxane structures with one or more types of siloxane structures. 0.1 to 10% by weight with respect to the compound represented by the general formula (A1) + one or more compounds represented by the general formula (A2) + one or more compounds having a siloxane structure, and a glass transition It is a siloxane copolymer polycarbonate having a temperature (Tg) of 130 to 160 ° C.
The compound having one or more siloxane structures is preferably selected from the group of compounds represented by formulas (B) to (E), and preferred examples of these compounds are the same as described above. . The compound represented by the formula (A2) includes 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) ethane, and bis (4 It is preferably at least one selected from -hydroxy-3-methylphenyl) methane and 1,1'-biphenyl-3,3'-dimethyl-4,4'-diol.

  The first composition contains the siloxane copolymer polycarbonate as a main component. Here, “containing as a main component” refers to a state of containing 50% by weight or more based on the total weight of all components of the composition (all components excluding the solvent when a solvent is included), more preferably 70% by weight or more, more preferably 90% by weight or more.

The first composition may contain one or more additives in addition to the siloxane copolymer polycarbonate which is a main component. Examples of additives include additives added for the purpose of ensuring the stability and releasability required during molding, specifically, hindered phenolic and phosphite antioxidants; Silicon-based, fatty acid ester-based, fatty acid-based, fatty acid glyceride-based, natural wax and other lubricants and mold release agents; benzotriazole-based, benzophenone-based, dibenzoylmethane-based, salicylate-based light stabilizers; polyalkylene glycol And antistatic agents such as fatty acid glycerides; These will be added in an amount of about 1% by weight or less with respect to the siloxane copolymer polycarbonate which is the main component.
In the present invention, the first composition preferably does not contain polycarbonate resins other than the siloxane copolymer polycarbonate contained as a main component.

2. Second Composition The second composition used in the present invention contains, as a main component, a polycarbonate derived from 2,2-bis (4-hydroxyphenyl) propane, that is, bisphenol A.
The polycarbonate which the second composition contains as a main component may be any as long as it is a polycarbonate having a repeating unit derived from bisphenol A. However, when the laminated molded member of the present invention is formed by the melt coextrusion method, the difference in glass transition temperature between the first composition and the second composition is 10 ° C. or less (more preferably 5 ° C. or less). The glass transition temperature of the polycarbonate contained in the second composition as a main component is preferably about 140 to 155 ° C. Some polycarbonates having units derived from bisphenol A having a glass transition temperature in the above range are commercially available, for example, “Iupilon E-2000R”, “Iupilon S-1000R”, “ Examples include "Iupilon S-2000R", "Iupilon S-3000R", "Iupilon H-3000R" and "Iupilon H-4000" (all manufactured by Mitsubishi Engineering Plastics). It is also preferable to do this.

The second composition may contain one or more additives in addition to the polycarbonate as the main component. Examples of the additive are the same as those of the additive that can be added to the first composition. The additive will be added in an amount of about 1% by weight or less based on the polycarbonate as the main component.
Moreover, in this invention, it is preferable that a 2nd composition does not contain polycarbonate resins other than the polycarbonate which contains as a main component.

3. Laminate-forming member The laminate-formed product of the present invention has at least a layer made of the first composition and a layer made of the second composition adjacent to the first layer, and the first composition. The surface of the layer made of is a laminated member having a pencil hardness of H or higher and a static friction coefficient of 0.4 or lower. The siloxane copolymer polycarbonate contained in the first composition as a main component contains a siloxane structure unit, so that it also acts as a lubricant and contributes to a reduction in the coefficient of static friction. May cause white turbidity and reduce the appearance. As a result of intensive studies by the present inventor, if the copolymerization ratio of the siloxane compound is 0.1 to 10% by weight (preferably 0.5 to 5% by weight), poor appearance due to a unit having a siloxane structure is caused. Thus, it was found that a laminate-forming member having a good surface hardness and good sliding property can be provided more stably.
In this specification, “pencil hardness H or higher” means that a pencil scratch test (conforming to JIS-K5600-5-4; using Mitsubishi Pencil UNI H) is performed on the surface of the sample 5 times. In this case, the occurrence of scratches is 2 times or less. Further, the higher the coefficient of static friction, the better. However, satisfying these characteristics can be used for applications requiring high surface hardness, and enables stable continuous production.

There is no restriction | limiting in particular about the manufacturing method of the lamination | stacking formation member of this invention. It can be molded by a known molding method such as melt extrusion molding, injection molding, compression molding or wet molding. In particular, the siloxane copolymer polycarbonate is less likely to be thermally deteriorated, and thus is suitable as a raw material for a heat melt molding method such as a melt extrusion molding method.
An example of the manufacturing method of the laminated molded member of the present invention is as follows.
First, the first and second compositions are prepared. For example, the first composition is prepared by mixing the siloxane-copolymerized polycarbonate powder and optionally an additive. The second composition is prepared similarly. Next, the second composition is introduced into the main extruder and the first composition is introduced into the sub-extruder, respectively, the cylinder temperature is set to about 220 to 320 ° C., and each is melted. Extrude. The melt extruded into a sheet is then passed between two horizontal rolls set at a surface temperature of about 110 to 160 ° C. to obtain a sheet-shaped or film-shaped laminated molded member.
The above method is an example and is not limited to this condition. Manufacturing conditions such as temperature conditions can be set as appropriate. Moreover, although the example of the manufacturing method of the laminated molded member which consists of two layers was shown above, it is of course possible to manufacture the laminated molded member which consists of three layers or more in the coextrusion method.

  There is no restriction | limiting in particular about the shape of the laminated molding member of this invention. The thing shape | molded by the sheet form and the film form is mentioned. Moreover, there is no restriction | limiting in particular also about the thickness of the layer which consists of a 1st composition, and the layer which consists of a 2nd composition, and there is no restriction | limiting in particular also about the relative relationship. Since the layer made of the first composition containing the siloxane copolymer polycarbonate as a main component exhibits particularly high hardness, for example, the substrate made of the second composition (for example, the thickness is about 20 to 30,000 μm) An example is a mode in which a layer having a high surface hardness (for example, a thickness of about 30 to 300 μm) made of the first composition is formed on the surface.

The laminated molded member of the present invention can be widely used as a member in the electric / electronic field, automobile field, and building material field. In particular, it has a high surface hardness and a good appearance, so that it is useful as a member for a display panel mounted on an electric / electronic device.
Since the two layers constituting the laminated molded member of the present invention both contain polycarbonates as the main component, the adhesion is good, and warping due to differences in water absorption and linear expansion coefficients occurs. It is hard to occur. Moreover, compared with the member mixed with other polymers, and the member which formed the coating layer which consists of other polymers, it is preferable also from a viewpoint of recycling.
Further, the surface hardness of the layer mainly composed of the siloxane copolymer polycarbonate of the present invention is further increased by laminating a known thermosetting or ultraviolet curing hard coat on the surface layer (opposite the substrate made of the second composition). It can also be improved.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention does not receive a restriction | limiting at all to a following example.

1. Synthesis of polycarbonate [Synthesis Example 1]
To 700 ml of 7.0 w / w% aqueous sodium hydroxide solution, 30.0 g (0,9-bis (4-hydroxy-3-methylphenyl) fluorene (Honshu Chemical Co., Ltd., hereinafter abbreviated as “BCFL”) 0.079 mol), 2,2-bis (4-hydroxy-3-methylphenyl) propane (manufactured by Honshu Chemical Industry Co., Ltd., hereinafter abbreviated as “BPC”) 60.1 g (0.235 mol), triethylbenzylammonium chloride 08 g and 0.2 g of hydrosulfite were dissolved.
To this, 500 ml of methylene chloride was added and stirred, while maintaining at 15 ° C., 45 g of phosgene was blown in over 30 minutes.
After completion of phosgene blowing, 2.36 g of pt-butylphenol (hereinafter abbreviated as “PTBP”) and 0.91 g of a siloxane monomer having the following structure (manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter abbreviated as “Si-1”) were added. The mixture was vigorously stirred to emulsify the reaction solution. After emulsification, 1 ml of triethylamine was added, and the mixture was stirred at 20 to 25 ° C. for about 1 hour for polymerization.

After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing with water was repeated until the conductivity of the previous solution (aqueous phase) became 10 μS / cm or less. The obtained polymer solution was dropped into warm water maintained at 60 ° C., and the solvent was removed by evaporation to obtain a white powdery precipitate. The resulting precipitate was filtered and dried at 120 ° C. for 24 hours to obtain a polymer powder.
The intrinsic viscosity at 20 ° C. of a solution having a concentration of 0.5 g / dl using methylene chloride as a solvent of this polymer was 0.38 dl / g. The results obtained polymer was analyzed by infrared absorption spectrum, absorption by carbonyl group at the position in the vicinity of 1770 cm ^-1, observed absorption by ether bond position near 1240 cm ^-1, represented by the following structural formula having a carbonate bond Siloxane copolymer polycarbonate (hereinafter abbreviated as PC-1).

[Synthesis Example 2]
Synthesis was performed in the same manner as in Example 1 except that 0.91 g of Si-1 was changed to 0.91 g of a siloxane monomer having the following structure (manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter abbreviated as “Si-2”).

  The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-2) was 0.37 dl / g. Confirmation that it was polycarbonate was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 3]
Synthesis was performed in the same manner as in Example 1 except that 0.91 g of Si-1 was changed to 0.91 g of a siloxane monomer having the following structure (manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter abbreviated as “Si-3”).

  The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-3) was 0.38 dl / g. Confirmation that it was polycarbonate was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 4]
The synthesis was performed in the same manner as in Example 1 except that 0.91 g of Si-1 was changed to 0.91 g of a siloxane monomer having the following structure (manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter abbreviated as “Si-4”).

  The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-4) was 0.36 dl / g. Confirmation that it was polycarbonate was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 5]
BCFL 30.0 g (0.079 mol) and BPC 60.1 g (0.235 mol) were changed to BCFL 30.0 g (0.079 mol) and BPC 60.6 g (0.237 mol), and Si-1 0.91 g Was synthesized in the same manner as in Example 1 except that Si was changed to 0.46 g. The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-5) was 0.39 dl / g. Confirmation that it was polycarbonate was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 6]
BCFL 30.0 g (0.079 mol) and BPC 60.1 g (0.235 mol) were changed to BCFL 30.0 g (0.079 mol) and BPC 50.5 g (0.221 mol), and Si-1 0.91 g Was synthesized in the same manner as in Example 1 except that Si-1 was changed to 4.55 g. The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-6) was 0.33 dl / g. Confirmation that it was polycarbonate was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 7]
The synthesis was performed in the same manner as in Example 1 except that 0.91 g of Si-1 was changed to 0.46 g of Si-1 and 0.45 g of Si-4. The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-7) was 0.37 dl / g. Confirmation that it was polycarbonate was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 8]
BCFL 30.0 g (0.079 mol) and BPC 60.1 g (0.235 mol) were converted into 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane (Honshu Chemical Co., Ltd., hereinafter “CBPZ”). (Abbreviation) 72.1 g (0.244 mol) and 1,1′-biphenyl-3,3′-dimethyl-4,4′-diol (manufactured by Honshu Chemical Industry Co., Ltd., hereinafter abbreviated as “CBP”) 18.0 g ( The synthesis was performed in the same manner as in Example 1 except that the amount was changed to 0.084 mol). The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-8) was 0.33 dl / g. Confirmation that it was polycarbonate was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 9]
BCFL 30.0 g (0.079 mol) and BPC 60.1 g (0.235 mol) were converted into 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane (Honshu Chemical Co., Ltd. The synthesis was performed in the same manner as in Example 1 except that it was changed to 90.1 g (0.283 mol) (abbreviated as “CBPAP”). The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-9) was 0.38 dl / g. Confirmation that it was polycarbonate was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 10]
BCFL 30.0 g (0.079 mol) and BPC 60.1 g (0.235 mol) were changed to BCFL 30.0 g (0.079 mol) and BPC 61.0 g (0.238 mol), and Si-1 0.91 g Synthesis was performed in the same manner as in Example 1 except that was not added. The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-10) was 0.40 dl / g.

[Synthesis Example 11]
BCFL 30.0 g (0.079 mol) and BPC 60.1 g (0.235 mol) were changed to BCFL 30.0 g (0.079 mol) and BPC 61.0 g (0.238 mol), and Si-1 0.91 g Was synthesized in the same manner as in Example 1, except that Si-1 was changed to 0.046 g. The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-11) was 0.39 dl / g.

[Synthesis Example 12]
BCFL 30.0 g (0.079 mol) and BPC 60.1 g (0.235 mol) were changed to BCFL 30.0 g (0.079 mol) and BPC 47.4 g (0.185 mol), and Si-1 0.91 g Was synthesized in the same manner as in Example 1 except that Si-1 was changed to 13.65 g. The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-12) was 0.30 dl / g.

[Synthesis Example 13]
BCFL 30.0 g (0.079 mol) and BPC 60.1 g (0.235 mol) were changed to CBPZ 94.7 g (0.320 mol), PTBP 2.36 g was changed to 1.92 g, Si-1 0.91 g Synthesis was performed in the same manner as in Synthesis Example 1 except that was not added. The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-13) was 0.37 dl / g.

[Synthesis Example 14]
BCFL 30.0 g (0.079 mol) and BPC 60.1 g (0.235 mol) were mixed with CBPAP 45.1 g (0.142 mol) and 2,2-bis (4-hydroxyphenyl) propane (Mitsui Chemicals, Synthesis was carried out in the same manner as in Example 1 except that it was changed to 45.0 g (0.197 mol). The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-14) was 0.39 dl / g.

2. Production and Evaluation of Laminate-Forming Member A scale-up trial was performed at the same raw material charging ratio as in Synthesis Examples 1 to 9, and 30 kg or more of polymer powder capable of sheet forming was produced. The powder obtained by mixing 0.01% by weight of tris (2,4-ditertiary butylphenyl) phosphite to each of the obtained powders of PC-1 to 9 was sub-extruder (25 mm single-screw extruder with vent, Musashino Kikai) MK-25 manufactured by Co., Ltd., cylinder temperature 290 ° C) and polycarbonate resin (Mitsubishi Engineering Plastics Co., Ltd., Iupilon E-2000R; glass transition temperature 150 ° C) as main extruder (30mm single-screw extruder with vent, Musashinokikai) Introduced into MK-30 manufactured by Co., Ltd., cylinder temperature 290 ° C., passed through a feed block type T die, cooled by two horizontal rolls (roll temperature: 150 ° C.), and laminated extruded sheet (surface 100 μm thick) PC-1 to 9 and a polycarbonate resin having a thickness of 200 μm on the back surface were obtained. With respect to the surface of the obtained laminated sheet, a pencil scratch test (based on JIS-K5600-5-4), measurement of a static friction coefficient, and visual evaluation of the sheet appearance were performed.

  A scale-up trial was conducted at the same raw material charging ratio as in Synthesis Examples 10 to 14, and 30 kg or more of polymer powder capable of sheet forming was produced. A laminated extruded sheet for a comparative example was prepared in the same manner as described above except that the obtained powders of PC-10 to 14 were used, and evaluated in the same manner.

The results are shown in the table below. The evaluation method is as follows.
The intrinsic viscosity is a value measured by preparing a 0.5% dichloromethane solution of each polymer at a temperature of 20 ° C. and using a Huggins constant of 0.45.
The glass transition temperature (Tg) is a value measured by a Shimadzu Corporation DCS-50 under a nitrogen stream (Tg calculation by the tangent method).
The melt volume rate (MVR) is a value measured at 300 ° C. under a 1.2 kg load by Toyo Seiki Co., Ltd .: DA.
Pencil scratch test is measured using UNI made by Mitsubishi Pencil in accordance with JIS-K5600-5-4, and the surface of the laminated molding sample (PC-1 to 14) is measured 5 times, and scratches are generated. If it was less than 2 times, it was considered acceptable.
The static friction coefficient is a value measured at 6 ball using a tribogear portable friction meter TYPE: 94i-II manufactured by Shinto Kagaku Co., Ltd.

Claims (11)

One or more general formulas (A1)
(Where X ¹ is
And one or more general formulas (A2)
(Where X ² is
R ¹ ′ and R ² ′ are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl group having 1 to 20 carbon atoms, each of which may have a substituent, carbon Represents an alkoxy group having 1 to 5 atoms or an aryl group having 6 to 12 carbon atoms; each of R ³ and R ⁴ has a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a substituent. And represents an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms; Represents an integer of ~ 20. ) And a compound having one or more types of siloxane structures, and a compound having one or more types of siloxane structures are obtained by reacting a compound having one or more types of siloxane structures with one or more types of siloxane structures. 0.1 to 10% by weight with respect to the compound represented by the general formula (A1) + one or more compounds represented by the general formula (A2) + one or more compounds having a siloxane structure, and a glass transition A layer composed of a first composition containing a siloxane copolymer polycarbonate having a temperature (Tg) of 130 to 160 ° C. as a main component, and 2,2-bis (4-hydroxyphenyl) adjacent to the first layer And a layer composed of a second composition containing a polycarbonate derived from propane as a main component, and the surface of the layer composed of the first composition is a pencil. Degrees H or a is laminated member. 2. The compound according to claim 1, wherein the compound having one or more siloxane structures is a compound selected from the group consisting of General Formula (B), General Formula (C), General Formula (D), and General Formula (E). Laminate forming member.
Wherein R ^{5 to} R ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a carbon atom. An alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, an alkyl group having 1 to 5 carbon atoms or 2 carbon atoms as a substituent. Can also have an alkenyl group of ˜5, an alkoxy group of 1 to 5 carbon atoms; R ¹⁰ represents an aliphatic group of 1 to ¹⁰ carbon atoms or represents a bond;
Represents a linear or branched homopolymer or a block or random copolymer comprising a combination of structural units selected from: a degree of polymerization of 1 to 200; and R ^{11 to} R ¹⁵ are each independently Hydrogen atom, alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 12 carbon atoms, alkenyl group having 2 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, or 7 to 17 carbon atoms When these groups have carbon atoms, the substituents are alkyl groups having 1 to 5 carbon atoms, alkenyl groups having 2 to 5 carbon atoms, and alkoxy groups having 1 to 5 carbon atoms. Can also be included. Z is
R ¹⁶ and R ¹⁷ are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl group having 1 to 20 carbon atoms, each having a substituent, and the number of carbon atoms Represents an alkoxy group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms, or R ¹⁶ and R ¹⁷ are bonded to form a carbocyclic ring having 5 to 20 carbon atoms or a heterocyclic ring having 5 to 12 elements. R ¹⁸ and R ¹⁹ are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl group having 1 to 9 carbon atoms, each of which may have a substituent, carbon Represents an alkoxy group having 1 to 5 atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms; c represents an integer of 0 to 20; ) The layered member according to claim 2, wherein the compound having one or more types of siloxane structures is a compound represented by the general formula (D). The layered member according to claim 2, wherein the compound having one or more types of siloxane structures is a compound represented by the general formula (E). The layered member according to claim 2, wherein the compound having one or more types of siloxane structures is a compound represented by the general formula (B). The layered member according to claim 2, wherein the compound having one or more types of siloxane structures is a compound represented by the general formula (C). Formula (B), the general formula (C), and the general formula (D), and R ¹¹ to R ¹⁵ in the general formula (E) are each a methyl group, n- butyl group, or and a group selected from a phenyl group The layered member according to any one of claims 2 to 6. The lamination forming member according to any one of claims 1 to 7 , wherein the intrinsic viscosity [η] of the siloxane copolymer polycarbonate is 0.2 to 1.0 [dl / g]. The laminate-forming member according to any one of claims 1 to 8 , wherein the carbonate-forming compound is phosgene. The laminated molded member according to any one of claims 1 to 9 , wherein the first and second compositions are formed by a melt coextrusion method. Laminate molding member according to any one of claims 1 to 10 which is a sheet or film.