JP2020066206A - Decorative polycarbonate film and molded article formed from the same - Google Patents

Abstract

To provide a decorative polycarbonate film less in scratch resistance, heat resistance and generation of cut powders during cutting, and useful for decorative molding applications, and a molded article using the same.SOLUTION: There is provided a laminate consisting of a polycarbonate resin layer (A) and a polycarbonate resin layer (B), and satisfying following conditions. (I) both of glass transition temperature Tg (a) of a polycarbonate resin (a) used in (A) and glass transition temperature Tg (b) of a polycarbonate rein (b) used in (B) are 140°C or higher, and further satisfy a relationship of |Tg(a)-Tg(b)|≤10°C. (II) thickness of the (B) is 40 to 100 μm. (III) pencil hardness defined in ISO15184 measured from a (B) side is H or more. (IV) the polycarbonate resin (a) is constituted by a specific constitutional unit (A). (V) warpage rate when the laminate is treated at 100°C×1 hr. is 10% or less.SELECTED DRAWING: None

Description

  The present invention relates to a decorative polycarbonate film and a molded product formed from the same. The present invention also relates to a polycarbonate film for decorating, which is useful for decorating and molding, and has little scratch resistance, heat resistance, and generation of cutting chips during cutting, and a molded product using the same.

  Polycarbonate resin film is generally excellent in transparency, heat resistance and mechanical strength, so it is suitable for OA / electronic device displays and touch panels, instrument panels, membrane switch panels for home appliances (washing machines, microwave ovens, etc.). It is used. Among them, as a thermoforming film used for automobile interiors, particularly for car navigation front panel applications, it is required to have excellent deep drawability during thermoforming and have high hardness and scratch resistance. However, since the polycarbonate resin film has a soft surface and is easily scratched, the pencil hardness is only about 2B, and there is a problem that scratches once generated are conspicuous.

  Patent Document 1 discloses a method of laminating an acrylic resin layer on a polycarbonate resin film in order to improve the above-mentioned surface characteristics, and further, Patent Document 2 discloses that a hard coat treatment is performed on the acrylic resin layer. Although a method is known, the acrylic resin layer and the hard coat layer are likely to be cracked in the deep-drawn portion and the formability is poor.

  Further, as in Patent Document 3, a method of adding rubber particles to a surface acrylic layer in order to improve thermoformability has been proposed, but the hardness becomes low and scratches easily occur. Further, by lowering the glass transition temperature by adding a plasticizer to the polycarbonate resin of the main layer, the difference in the glass transition temperature from the acrylic resin of the surface layer is reduced, and the moldability is said to be improved. By lowering the glass transition temperature of (1), a phenomenon in which the polycarbonate resin of the laminate film is melted by the high heat of the injection material during insert molding and the molded product is broken, that is, so-called gate damage occurs.

  On the other hand, Patent Document 4 proposes a method of laminating a special high-hardness polycarbonate resin in place of the acrylic resin, but since the difference in glass transition temperature between the main layer resin and the surface layer resin is large, there is a problem in moldability. there were. Further, there is a problem that chips are generated when the film is cut into a predetermined size, the end surface shape of the product is deteriorated when the decorative molded product is formed, and the chips adhere to the surface of the sheet, resulting in a defective product.

  So far, in the polycarbonate film for decoration, scratch resistance, heat resistance, and a polycarbonate decorative film excellent in moldability when decorated using the film with less generation of chips during cutting is It doesn't exist yet.

JP, 2007-160892, A JP, 2008-049623, A JP, 2010-125645, A International Publication No. 2014/061817

  An object of the present invention is to provide a decorative polycarbonate film which is useful for decorative molding, in which scratch resistance, heat resistance, and generation of chips during cutting are small.

The inventors of the present invention used a polycarbonate resin containing a specific structural unit as a surface layer resin of a laminate, and both the surface layer resin and the main layer resin had a glass transition temperature of 140 ° C. or higher, and the difference in the glass transition temperature was It has been found that the above object can be achieved by setting the surface layer thickness to a specific range and the warp amount of the film made of the laminate to a specific range at 10 ° C. or lower. As a result of further studies based on such findings, the present invention has been completed.
That is, according to the present invention, the object of the invention is achieved by the following.

（式（１）中、Ｗは、単結合、置換もしくは無置換の炭素原子数１〜１０のアルキレン基、置換もしくは無置換の炭素原子数１〜１０アルキリデン基、硫黄原子または酸素原子を示す。）
（Ｖ）（Ｉ）〜（ＩＶ）を満たす該樹脂層（Ａ）と樹脂層（Ｂ）からなる積層体を１００℃×１時間処理した際の反り率が、１０％以下である。 1. A laminated body in which a polycarbonate resin layer (B) is laminated on one surface of a polycarbonate resin layer (A), which is characterized by satisfying the following conditions (I) to (V): Polycarbonate film.
(I) The glass transition temperature Tg (a) of the polycarbonate resin (a) used in the polycarbonate resin layer (A) and the glass transition temperature Tg (b) of the polycarbonate resin (b) used in the polycarbonate resin layer (B) are both The temperature is 140 ° C. or higher, and the relationship of | Tg (a) −Tg (b) | ≦ 10 ° C. is satisfied.
(II) The thickness of the polycarbonate resin layer (B) is 40 to 100 μm.
(III) The pencil hardness defined by ISO15184 measured from the polycarbonate resin layer (B) side is H or higher.
(IV) The polycarbonate resin (a) is composed of the structural unit (a1) represented by the following formula (1).

(In the formula (1), W represents a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms, a sulfur atom or an oxygen atom. )
(V) The warpage rate when the laminate comprising the resin layer (A) and the resin layer (B) satisfying (I) to (IV) is treated at 100 ° C. for 1 hour is 10% or less.

（式（１）中、Ｗは、単結合、置換もしくは無置換のアルキレン基、置換もしくは無置換のアルキリデン基、硫黄原子または酸素原子を示す。）
で表される構成単位（ｂ１）、
下記式（２）

（式（２）中、Ｒ^１〜Ｒ^２は夫々独立して水素原子、炭素原子数１〜６のアルキル基である。）
で表される構成単位（ｂ２）、および
下記式（３）

（式（３）中、Ｒ^３〜Ｒ^４は夫々独立して炭素原子数１〜６のアルキル基であり、Ｘは単結合、置換もしくは無置換の炭素原子数１〜１０のアルキレン基、置換もしくは無置換の炭素原子数１〜１０のアルキリデン基である。）
で表される構成単位（ｂ３）から構成され、全構成単位における構成単位（ｂ１）の割合が２５〜７５モル％、構成単位（ｂ２）の割合が５〜１５モル％、構成単位（ｂ３）の割合が２０〜６０モル％であるポリカーボネート共重合体または共重合ポリカーボネートブレンド物である前記１に記載の加飾用ポリカーボネートフィルム。 2. The polycarbonate resin (b) has the following formula (1)

(In the formula (1), W represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylidene group, a sulfur atom or an oxygen atom.)
A structural unit (b1) represented by
Formula (2) below

(In the formula (2), R ^{1 and} R ² are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
And a structural unit (b2) represented by the following formula (3)

(In formula (3), R ^{3 to} R ⁴ are each independently an alkyl group having 1 to 6 carbon atoms, and X is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted group. Alternatively, it is an unsubstituted alkylidene group having 1 to 10 carbon atoms.)
Of the structural unit (b3), the proportion of the structural unit (b1) in all the structural units is 25 to 75 mol%, the proportion of the structural unit (b2) is 5 to 15 mol%, and the structural unit (b3). The polycarbonate film for decoration according to 1 above, which is a polycarbonate copolymer or a copolymerized polycarbonate blend having a ratio of 20 to 60 mol%.

3. 1 or 2, wherein the melt viscosity of the polycarbonate resin (a) and the polycarbonate resin (b) according to JIS K7199 according to JIS K7199 satisfies a shear rate of 122 (1 / s) and a heating temperature of 280 ° C. of 1,200 Pa · S or less. The polycarbonate film for decoration according to [4].
4. The polycarbonate film for decorating according to any one of 1 to 3 above, wherein the laminate has a total thickness of 100 to 500 μm.
5. A decorative molded product obtained by injection-molding a thermoplastic resin on the decorative side surface of the decorative polycarbonate film according to any one of 1 to 4 above.

  The decorative polycarbonate film of the present invention and a molded product formed from the same have scratch resistance, heat resistance, and little generation of chips at the time of cutting, and are excellent in decorative moldability. It is preferably used as a display front plate. Therefore, the industrial effect it produces is exceptional.

It is the schematic which showed an example of the decorative molded product using the polycarbonate film for decoration in this invention.

  Hereinafter, the present invention will be described in detail.

The decorative polycarbonate film of the present invention is a film in which the polycarbonate resin layer (B) is laminated on one surface of the polycarbonate resin layer (A).
By stacking the polycarbonate resin layer (A) and the polycarbonate resin layer (B), generation of chips during cutting can be suppressed.

<Polycarbonate resin layer (A)>
The polycarbonate resin layer (A) in the present invention comprises a structural unit (a) represented by the following formula (1).

（式（１）中、Ｗは、単結合、置換もしくは無置換のアレン基、置換もしくは無置換のアルキリデン基、硫黄原子または酸素原子を示す。）

(In the formula (1), W represents a single bond, a substituted or unsubstituted allene group, a substituted or unsubstituted alkylidene group, a sulfur atom or an oxygen atom.)

(Polycarbonate resin (a))
The polycarbonate resin (a) used in the polycarbonate resin layer (A) of the decorative polycarbonate film in the present invention is different from the polycarbonate resin (b) used in the polycarbonate resin layer (B).

  The polycarbonate resin (a) in the present invention is preferably an aromatic polycarbonate resin obtained by reacting a dihydric phenol with a carbonate precursor. In particular, a polycarbonate resin containing at least a carbonate structural unit derived from bisphenol A is preferable.

  Preferred examples of the reaction method include an interfacial polycondensation method, a melt transesterification method, a solid-state transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound. The polycarbonate resin may be produced by any production method, and in the case of interfacial polycondensation, a monohydric phenol endcapping agent is usually used. The polycarbonate resin may be a branched polycarbonate obtained by polymerizing a trifunctional or higher polyfunctional component in addition to the dihydric phenol or the bifunctional alcohol. It may also be a branched polycarbonate resin obtained by polymerizing a polyfunctional phenol such as a trifunctional phenol, and further by copolymerizing an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid, a polyorganosiloxane component, and a vinyl monomer. It may be a copolycarbonate.

  Examples of the dihydric phenol for inducing the polycarbonate resin (a) used in the polycarbonate resin layer (A) in the present invention include 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A) and 4,4 ′. -Dihydroxy-1,1-biphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylthioether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy Diphenyl sulfide, 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4- Hydroxyphenyl) pentane, 4,4-bis (4-hydroxy) Phenyl) heptane, 2,2-bis (4-hydroxyphenyl) octane, 1,1-bis (4-hydroxyphenyl) decane and the like are preferably exemplified. The most preferred dihydric phenol is bisphenol A.

Further, the viscosity average molecular weight of the polycarbonate resin (a) in the present invention is preferably 1.5 × 10 ^{4 to} 2.5 × 10 ⁴ , and more preferably 1.8 × 10 ^{4 to} 2.3 × 10 ⁴ . . When the viscosity average molecular weight is less than the lower limit, good mechanical properties are difficult to develop. On the other hand, when the viscosity average molecular weight exceeds the upper limit, the appearance of the film may deteriorate.

The viscosity average molecular weight in the present invention is obtained by inserting the specific viscosity (ηsp) obtained from a solution of 0.7 g of a polycarbonate resin dissolved in 100 ml of methylene chloride at 20 ° C. into the following equation.
ηsp / c = [η] + 0.45 × [η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  The glass transition temperature of the polycarbonate resin (a) in the present invention is preferably 140 to 160 ° C, more preferably 140 to 155 ° C, and further preferably 140 to 150 ° C. The temperature difference between the glass transition temperature of the polycarbonate resin (a) and the glass transition temperature of the polycarbonate resin (b) is 10 ° C or lower, preferably 8 ° C or lower, and more preferably 6 ° C or lower. When the glass transition temperature of the polycarbonate resin (a) is 140 ° C. or higher, heat resistance is sufficient, and when the glass transition temperature is 160 ° C. or lower, it is not necessary to raise the molding processing temperature and molding becomes easy. If the temperature difference between the glass transition temperature of the polycarbonate resin (a) and the glass transition temperature of the polycarbonate resin (b) exceeds the above upper limit, the amount of warpage of the sheet increases due to heat shrinkage during insert molding, which makes molding difficult. Therefore, it is not preferable.

  The polycarbonate resin (a) of the present invention may appropriately contain a resin other than bisphenol A-polycarbonate resin as long as the effect of the present invention is not significantly impaired. Other resins may be contained in one kind, or may be contained in two or more kinds in any combination and ratio. Examples of other resins include thermoplastic polyester resins such as polyethylene terephthalate resin (PET resin), polytrimethylene terephthalate (PTT resin), polybutylene terephthalate resin (PBT resin); polystyrene resin (PS resin), high impact resin. Polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylene propylene rubber -Styrene resin such as styrene copolymer (AES resin); polyethylene resin (PE resin), polypropylene resin (PP resin), cyclic cycloolefin resin (COP resin), cyclic cycloolefin copolymer (COP) Polyolefin resin such as resin; polyamide resin (PA resin); polyimide resin (PI resin); polyetherimide resin (PEI resin); polyurethane resin (PU resin); polyphenylene ether resin (PPE resin); polyphenylene sulfide resin (PPS resin) ); Polysulfone resin (PSU resin); polymethacrylate resin (PMMA resin); and the like.

<Polycarbonate resin layer (B)>
The polycarbonate resin layer (B) in the present invention comprises a structural unit (b) represented by the following formula (1) as a main structural unit.
<Polycarbonate resin (b)>
The polycarbonate resin (b) in the present invention may contain a polycarbonate copolymer and / or a copolymerized polycarbonate blend, and as the main constituent unit, (b) the following formula (1)

（式（１）中、Ｗは単結合、置換もしくは無置換の炭素原子数１〜１０のアルキレン基、置換もしくは無置換の炭素原子数１〜１０のアルキリデン基である。）
で表される構成単位（ｂ１）、
下記式（２）

(In the formula (1), W is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms.)
A structural unit (b1) represented by
Formula (2) below

（式（２）中、Ｒ^１〜Ｒ^２は夫々独立して水素原子、炭素原子数１〜６のアルキル基である。）
で表される構成単位（ｂ２）、および
下記式（３）

(In the formula (2), R ^{1 and} R ² are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
And a structural unit (b2) represented by the following formula (3)

（式（３）中、Ｒ^３〜Ｒ^４は夫々独立して炭素原子数１〜６のアルキル基であり、Ｘは単結合、置換もしくは無置換の炭素原子数１〜１０のアルキレン基、置換もしくは無置換の炭素原子数１〜１０のアルキリデン基である。）
で表される構成単位（ｂ３）から構成されることが好ましい。

(In formula (3), R ^{3 to} R ⁴ are each independently an alkyl group having 1 to 6 carbon atoms, and X is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted group. Alternatively, it is an unsubstituted alkylidene group having 1 to 10 carbon atoms.)
It is preferably composed of the structural unit (b3) represented by

  Here, "mainly" means that 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more, most preferably 100 mol% of all carbonate constitutional units excluding the terminals. It is preferably 100 mol%.

  In the structural unit (b1) represented by the formula (1), W is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms. Is preferred.

  Examples of the dihydric phenol that induces the polycarbonate resin (b1) in the present invention include 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A) and 4,4′-dihydroxy-1,1-biphenyl. , 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylthioether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 4,4 -Bis (4-hydroxyphenyl) heptane, 2,2-bis 4-hydroxyphenyl) octane, 1,1-bis (4-hydroxyphenyl) decane are preferably exemplified, most preferred dihydric phenol is bisphenol A.

  In the polycarbonate resin (b) in the present invention, the ratio of the structural unit (b1) to all the structural units is preferably 30 to 70 mol%, more preferably 35 to 65 mol%, and further preferably 40 to 60 mol%. When the ratio of the structural unit (b1) exceeds the upper limit, scratch resistance is poor, which is not preferable. On the other hand, when the ratio of the structural unit (b1) is less than the lower limit, scratch resistance is improved, but chips are likely to be generated during cutting, which is not preferable.

In the structural unit (b2) represented by the above formula (2), R ^{1 and} R ² are preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

  Preferred examples of the dihydric phenol for deriving the structural unit (b2) include 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. The most preferred dihydric phenol is 9,9-bis (4-hydroxy-3-methylphenyl) fluorene.

  In the polycarbonate resin (b) of the present invention, the ratio of the structural unit (b2) to all structural units is preferably 5 to 15 mol%. When the proportion of the structural unit (b2) exceeds 15 mol%, the heat resistance is improved, but the melt viscosity becomes high, which is not preferable. When the proportion of the structural unit (b2) is less than 5 mol%, the heat resistance is poor, which is not preferable.

In the structural unit (b3) represented by the formula (3), it is preferable that R ^{3 to} R ⁴ are each independently an alkyl group having 1 to 4 carbon atoms, and X is a single bond, substituted or unsubstituted. Is preferably an alkylene group having 1 to 5 carbon atoms or a substituted or unsubstituted alkylidene group having 1 to 5 carbon atoms.

  Examples of the dihydric phenol for deriving the structural unit (b3) include 2,2-bis (4-hydroxy-3-methylphenyl) propane (hereinafter referred to as bisphenol C) and 2,2-bis (4-hydroxy-3). -Isopropylphenyl) propane, 2,2-bis (3-t-butyl-4-hydroxyphenyl) propane and the like are preferred, and the most preferred dihydric phenol is bisphenol C.

  In the polycarbonate resin (b) of the present invention, the ratio of the structural unit (b3) to all the structural units is preferably 20 to 60 mol%, more preferably 30 to 50 mol%. When the proportion of the structural unit (b3) exceeds 60 mol%, the heat resistance is poor, which is not preferable.

  Furthermore, as the dihydric phenol for deriving the structural units other than the structural units (b1), (b2) and (b3), 2,6-dihydroxynaphthalene, hydroquinone, resorcinol, and an alkyl group having 1 to 3 carbon atoms are preferable. Substituted with resorcinol, 3- (4-hydroxyphenyl) -1,1,3-trimethylindan-5-ol, 1- (4-hydroxyphenyl) -1,3,3-trimethylindan-5-ol, 6,6'-dihydroxy-3,3,3 ', 3'-tetramethylspiroindan, 1-methyl-1,3-bis (4-hydroxyphenyl) -3-isopropylcyclohexane, 1-methyl-2- ( 4-hydroxyphenyl) -3- [1- (4-hydroxyphenyl) isopropyl] cyclohexane, 1,6-bis (4-hydroxyphenyl) Yl) -1,6-hexanedione, and the like. Other details of the polycarbonate are described in, for example, WO03 / 080728, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. Has been done.

  The polycarbonate resin (b) in the present invention is obtained by reacting a dihydric phenol with a carbonate precursor. Preferred examples of the reaction method include an interfacial polycondensation method, a melt transesterification method, a solid-state transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound. In the case of interfacial polycondensation, a monohydric phenol end-stopper is usually used. Further, it may be a branched polycarbonate obtained by polymerizing a trifunctional component, or a copolymerized polycarbonate obtained by copolymerizing an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, and a vinyl monomer.

  In the reaction using, for example, phosgene as the carbonate precursor, the reaction is usually performed in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the solvent, for example, a halogenated hydrocarbon such as methylene chloride or chlorobenzene is used. A catalyst such as a tertiary amine or a quaternary ammonium salt may be used to accelerate the reaction. At that time, the reaction temperature is usually 0 to 40 ° C., and the reaction time is several minutes to 5 hours.

  The transesterification reaction using, for example, a carbonic acid diester as a carbonate precursor is carried out by a method in which an aromatic dihydroxy component in a predetermined proportion is stirred with a carbonic acid diester while heating in an inert gas atmosphere to distill the alcohol or phenols produced. Be seen. The reaction temperature varies depending on the boiling point of the alcohol or phenols produced, etc., but is usually in the range of 120 to 300 ° C. From the initial stage of the reaction, the reaction is completed while reducing the pressure to distill off the produced alcohol or phenols. Further, a catalyst usually used in transesterification reaction may be used to accelerate the reaction. Examples of the carbonic acid diester used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferable.

  Monofunctional phenols that are commonly used as end terminators can be used. Especially in the case of reactions using phosgene as carbonate precursor, monofunctional phenols are commonly used as molecular terminators for molecular weight control, and the resulting polycarbonate resins are based on monofunctional phenols at the ends. Because it is blocked by the group, it has better thermal stability than those that do not. Specific examples of the monofunctional phenols include phenol, m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, 1-phenylphenol, 2-phenylphenol, p-tert-butylphenol, Examples thereof include p-cumylphenol, isooctylphenol, p-long chain alkylphenol and the like.

  The polycarbonate resin in the present invention may be copolymerized with an aliphatic diol, if necessary. For example, isosorbide: 1,4: 3,6-dianhydro-D-sorbitol, tricyclodecanedimethanol (TCDDM), 4,8-bis (hydroxymethyl) tricyclodecane, tetramethylcyclobutanediol (TMCBD), 2, 2,4,4-tetramethylcyclobutane-1,3-diol, mixed isomers, cis / trans-1,4-cyclohexanedimethanol (CHDM), cis / trans-1,4-bis (hydroxymethyl) cyclohexane, Cyclohex-1,4-ylenedimethanol, trans-1,4-cyclohexanedimethanol (tCHDM), trans-1,4-bis (hydroxymethyl) cyclohexane, cis-1,4-cyclohexanedimethanol (cCHDM), cis -1,4-bis (hydroxymethyl) Cyclohexane, cis-1,2-cyclohexanedimethanol, 1,1'-bi (cyclohexyl) -4,4'-diol, spiroglycol, dicyclohexyl-4,4'-diol, 4,4'-dihydroxybicyclohexyl, And poly (ethylene glycol) are preferred.

  The polycarbonate resin (b) in the present invention may be copolymerized with a fatty acid, if necessary. For example, 1,10-dodecanedioic acid (DDDA), adipic acid, hexanedioic acid, isophthalic acid, 1,3-benzenedicarboxylic acid, terephthalic acid, 1,4-benzenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, Preferable examples include 3-hydroxybenzoic acid (mHBA) and 4-hydroxybenzoic acid (pHBA).

  The polycarbonate resin (b) in the present invention contains a polyester carbonate obtained by copolymerizing an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. The aliphatic difunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of the aliphatic difunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosanedioic acid, and cyclohexanedicarboxylic acid. Alicyclic dicarboxylic acids such as acids are preferred. These carboxylic acids may be copolymerized within a range that does not impair the purpose.

  The polycarbonate resin (b) in the present invention may optionally be copolymerized with a constitutional unit containing a polyorganosiloxane unit.

  The polycarbonate resin (b) in the present invention may be a branched polycarbonate by copolymerizing a constituent unit containing a trifunctional or higher polyfunctional aromatic compound, if necessary. Examples of trifunctional or higher polyfunctional aromatic compounds used in the branched polycarbonate include 4,6-dimethyl-2,4,6-tris (4-hydrodiphenyl) heptene-2,2,4,6-trimethyl- 2,4,6-Tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1 -Tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, and 4- {4- [1,1-bis ( Suitable examples include trisphenol such as 4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol. Of these, 1,1,1-tris (4-hydroxyphenyl) ethane is preferable. The constituent unit derived from such a polyfunctional aromatic compound is preferably 0.03 to 1.5 mol%, more preferably 0.1 to 100 mol% in total with the constituent units from other divalent components. ˜1.2 mol%, particularly preferably 0.2 to 1.0 mol%.

  Further, the branched structural unit is not only derived from a polyfunctional aromatic compound, but also derived from a polyfunctional aromatic compound such as a side reaction which occurs during a polymerization reaction by a melt transesterification method. May be. The ratio of such branched structure can be calculated by 1H-NMR measurement.

  The viscosity average molecular weight (Mv) of the polycarbonate resin (b) in the present invention is preferably 15,000 to 25,000, and a polycarbonate resin having a viscosity average molecular weight of less than 15,000 has practically sufficient toughness and crack resistance. May not be obtained. On the other hand, a polycarbonate resin having a viscosity average molecular weight of more than 25,000 requires a high film-forming temperature, so that the laminate has a strong yellow tint, and the color tone of the image is changed particularly when used as a display cover, which is not preferable.

The viscosity average molecular weight of the polycarbonate resin (b) in the present invention is determined by first measuring the specific viscosity (η _SP ) calculated by the following formula at 20 ° C. from a solution prepared by dissolving 0.7 g of the polycarbonate resin in 100 ml of methylene chloride and Ostwald viscometer. Is obtained using
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T0 is the number of seconds of methylene chloride dropping, t is the number of seconds of dropping the sample solution]
The viscosity average molecular weight Mv was calculated from the determined specific viscosity (η _SP ) by the following mathematical formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83
c = 0.7

(Additive)
The polycarbonate resin of the present invention may contain functional agents known per se, such as a release agent, a heat stabilizer, and an ultraviolet absorber, as long as the effects of the present invention are not impaired.

<Film manufacturing method>
Examples of the method for producing a decorative polycarbonate film in the present invention include a method of laminating and integrating a polycarbonate resin layer (A) and a polycarbonate resin layer (B) by melt coextrusion molding, or a polycarbonate resin layer (A). And a polycarbonate resin layer (B) are adhered to each other via a pressure-sensitive adhesive or an adhesive, and the respective layers are separately formed in advance and laminated, or a method of thermocompression bonding is preferably used. Among them, melt coextrusion molding is more preferable because of economical efficiency, production stability, and ease of secondary molding.

  In the coextrusion molding method, the polycarbonate resin of each layer is melted, and the multilayered resin is adhered to a roll to perform molding. Specifically, the polycarbonate resin (a) used for the polycarbonate resin layer (A) and the polycarbonate resin (b) used for the polycarbonate resin layer (B) are melt extruded using different extruders, and a multi-manifold die is produced. It is a method of obtaining a laminated body extruded from a feed block die, and the total thickness and thickness of the obtained laminated body are controlled by adjusting the extrusion rate of each extruder, the film forming speed, the die slip interval, etc. It is possible to The laminated body coming out of the die is formed by using three cooling rolls which are in a positional relationship in which the central axes of rotation are parallel and on the same plane, and which are arranged close to each other. Take over. The first cooling roll and the second cooling roll may be configured by a metal roll or a metal elastic roll, or may be configured by combining a metal roll and a metal elastic roll.

  At this time, the rotation speed of the third cooling roll with respect to the second cooling roll is preferably 0.995 to 1.015 times. If the rotation speed of the third cooling roll with respect to the second cooling roll is smaller than 0.995 times, cooling proceeds slowly, but good sheeting may not be possible due to the slow speed, and if it is larger than 1.015 times, the take-up speed is increased. Since the sheeting becomes good because the sheet becomes faster, the polycarbonate resin film exerts a stretching action in the extrusion direction, so that the heat expansion and contraction in the extrusion direction becomes large, and the heat expansion and contraction in the width direction may be out of balance and it may be difficult to put into practical use. .

  Further, it is preferable that the temperature of the first cooling roll is set to 130 to 145 ° C, the temperature of the second cooling roll is set to 135 to 150 ° C, and the temperature of the third cooling roll is set to 125 to 140 ° C. Polycarbonate resin (A) is usually extruded at 260 to 280 ° C., whereas if the temperatures of the first to third cooling rolls are below the respective lower limits, cooling is too fast and heat shrinkage becomes large, and the temperature of each cooling roll is high. When the value exceeds the upper limit, the sheet may not be cooled sufficiently and may be taken by a cooling roll to prevent sheeting. The temperature control of these first to third cooling rolls can be easily performed by the conventional roll temperature control means.

  In addition, it may be difficult to wind the film as it is due to lack of slipperiness of the surface. In such a case, it is preferable to attach a protect film and wind the film. In such a case, a known protective film such as polyethylene-based or polypropylene-based can be used.

(Extrusion temperature and melt viscosity)
The melt viscosity of the polycarbonate resin (a) and the polycarbonate resin (b) in the present invention is 1200 Pa · S or less in melt viscosity (shear rate 121 (1 / s), heating temperature 280 ° C.) by a capillograph according to JISK7199. It is preferably 1050 Pa · s or less. If it exceeds 1200 Pa · s, the flow of the resin in the pipe, polymer filter, and die becomes poor, and stagnant portions are likely to occur, which causes burns and gels, which causes defects in the appearance of the laminate. In addition, die streaks are likely to occur, streak-shaped defects when the surface of the laminate is viewed with reflected light are increased, and haze of the laminate is deteriorated. On the other hand, although it is possible to simply raise the temperature to lower the melt viscosity, it is not preferable because the resin is easily deteriorated by heat and yellowing occurs. The discharge rate and the temperature settings of the extruder, polymer pipes, dies, etc. are controlled so that the resin temperature becomes 280 ° C. or lower.

  In the case of co-extrusion molding, two kinds of resins merge in a layered manner inside the multi-manifold die or the feed block die, so it is necessary to match the extrusion melt viscosities of both resins as much as possible. That is, it is necessary to control the resin temperature and the melt viscosity by setting the discharge rate, the temperature of the extruder, the polymer pipe, the die, etc. so that the difference in the melt viscosity between the polycarbonate resin (a) and the polycarbonate resin (b) becomes small. . The difference in melt viscosity between the polycarbonate resin (a) and the polycarbonate resin (b) is preferably 300 Pa · S or less, more preferably 200 Pa · S or less. When the difference in melt viscosity is more than 300 Pa · S, an unstable state such as disturbance of the interface between the polycarbonate resin layer (A) and the polycarbonate resin layer (B) or a wrapping phenomenon is likely to occur, resulting in poor appearance.

(surface treatment)
The decorative polycarbonate film of the present invention can be subjected to various surface treatments. The surface treatment includes decorative coating, AR coating, hard coating, water / oil repellent coating, hydrophilic coating, ultraviolet absorption coating, infrared absorption coating, electromagnetic absorption coating, heat generation coating, antistatic coating, antistatic coating, conductive coating. In addition, various surface treatments such as metalizing (plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), thermal spraying, etc.) can be performed, and it can be suitably used for display covers and touch panels.

<Decorative film>
(Total thickness)
The thickness of the laminated decorative polycarbonate film in the present invention is preferably 100 to 500 μm, more preferably 125 to 380 μm, and further preferably 200 to 300 μm. For example, when the insert film is formed as a display cover by insert molding, the thick film requires a long time for molding, the followability to a three-dimensional shape is deteriorated, and the cost is increased. On the other hand, when it is thin, handling is difficult, and wrinkles and tears are likely to occur in the decorating film during insert molding. The thickness can be adjusted by adjusting the discharge rate of the extruder or the film forming speed.

(Interlayer thickness)
The thickness of the resin layer (B) in the present invention is in the range of 40 to 100 μm, preferably 50 μm or more, and more preferably 60 μm or more and 80 μm or less. When the thickness of the resin layer (B) is less than 40 μm, the pencil hardness measured from the resin layer (B) side of the polycarbonate decorative film is low. On the other hand, when the thickness is more than 100 μm, chips are likely to be generated when the decorative film is punched by a cutting machine, and a problem of reduction in processing yield is likely to occur.

(Pencil hardness)
In the present invention, the pencil hardness measured from the resin layer (B) side based on JIS K5400 is preferably H or higher, more preferably 2H or higher.

(Appearance / Haze / Hue)
The decorative polycarbonate film of the present invention preferably has a haze value of 0.5% or less according to JIS K 7136. The melt viscosity of the polycarbonate resin (a) and the polycarbonate resin (b) is 1200 Pa · S or less in terms of melt viscosity (shear rate 121 (1 / s), heating temperature 280 ° C.) according to JIS K7199 and a difference in melt viscosity. Is adjusted to be in the range of 300 Pa · S or less, the die streak generated in the coextrusion molding is very weak, and a laminate having a small haze can be obtained. In addition, a laminate having a small hue b * and less appearance defects such as burns and gels due to heat deterioration can be obtained. A polycarbonate resin having a melt viscosity of more than 1200 Pa · S requires a high film-forming temperature, so that die streaks are strongly generated and haze is increased. Furthermore, the yellow color of the laminate becomes stronger, and the color tone of the image changes, especially when used as a display cover, which is not preferable. The hue b * is preferably 0.5 or less.

(Glass-transition temperature)
The glass transition temperatures Tg (a) and Tg (b) of the polycarbonate resin (a) and the polycarbonate resin (b) according to the present invention according to JIS K7121 are 140 ° C. or higher. When the temperature is lower than 140 ° C., the polycarbonate decorative film along the mold gate portion is likely to be broken (gate damage) during insert molding. Furthermore, the Tg difference satisfies the relationship of | Tg (a) −Tg (b) | ≦ 10 ° C. If the difference is greater than 10 ° C., the thermal behavior of the polycarbonate resin layer (A) and the polycarbonate resin layer (B) will differ when the laminate is heat treated, and for example, wrinkles will occur in the molded product when insert molding is performed. .

(Warp rate of polycarbonate film for decoration)
The film for decoration produced by melt coextrusion molding preferably has a small warpage in consideration of various surface treatments and post-processing such as decoration molding.

The method of calculating the amount of warpage of the decorative film is to cut out six pieces of 100 mm length × 100 mm width from the laminate at the time of manufacturing, and dry these six test pieces under the condition of 100 ° C. × 1 hour. Immediately thereafter, the resin layer (A) was placed flat on a horizontally placed desk with the side facing up, and the floating amount was measured at a total of 8 points at the four corners of the film and the intermediate points. The maximum floating amount (maximum warpage amount) among the six measured sheets was obtained, and the value calculated by the following formula was used as the warpage rate (%).
Warp rate (%) = 100 × maximum warp amount (mm) / 100 (mm)
In addition, the floating amount in which the resin layer (A) side is concave was set to be positive.
The warpage rate is 10% or less, preferably 5% or less, more preferably 3% or less.

(Polycarbonate film for decoration)
The decorative polycarbonate film of the present invention is a film in which the decorative layer (C) is applied to one surface of a film obtained by laminating and integrating the polycarbonate resin layer (A) and the polycarbonate resin layer (B).

  That is, the decorative polycarbonate film is preferably composed of the layer (A), the layer (B), and the layer (C), and the layer (C) is preferably on the layer (A) side. An adhesive layer may be provided between the C layer and the molded product.

  The adhesive layer in the present invention is a portion for assisting the adhesion between the decorative polycarbonate film or the decorative layer and the resin injected into the mold.

  The decorative layer in the polycarbonate film for decoration of the present invention is a layer provided for imparting the design property of the decorative film, and is a pattern layer expressing patterns, characters, pattern-like patterns and the like. Examples of the pattern include wood grain, stone grain, cloth grain, sand grain, geometric pattern, letters, stripe-shaped or gradation pattern.

  The pattern can be usually formed by a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, sublimation transfer printing, and ink jet printing with a printing ink. As the ink constituting the pattern layer, colorants, dyes, pigments and the like, and as commercial products, ISX ink, IPX ink, INQ ink manufactured by Teikoku Ink Mfg. Co., FM ink manufactured by Jujo Chemical Co., Ltd. are all suitable. The ink can be used, and as the method for applying these inks, all the methods conventionally used for forming a pattern layer, such as screen printing, can be preferably used.

  The thickness of the design can be appropriately adjusted according to the form of the design.

  When the adhesive layer is provided, its material is not particularly limited as long as it is a resin having high compatibility with both the resin constituting the decorative polycarbonate film and the pattern layer and the resin injected into the mold, but a binder layer that can be used Preferred examples of (adhesive layer) include IBM-003 (trade name) manufactured by Teikoku Ink Mfg. Co., Ltd. and IMD binder B-2 (trade name) manufactured by Jujo Chemical Co., Ltd.

<Decorated molded product using a polycarbonate film for decoration>
A decorative molded product using the decorative polycarbonate film of the present invention includes a base material and the above-described decorative polycarbonate film formed on the surface thereof. The base material is a molded product having the shape of various parts described below. The base material is made of various resins such as thermoplastic resin and thermosetting resin.

  The method for producing a decorative molded article using the decorative polycarbonate film of the present invention comprises, for example, a step of decorating a molded body with a decorative layer using the vacuum forming decorative film of the present invention. Is. A TOM (Three dimension Overlay Method) method is preferably used as a vacuum forming method for laminating a decorative film on a molded body as an adherend. In the TOM method, for example, air is sucked by a vacuum pump or the like in both spaces inside the device divided by the decorative film fixed to the fixed frame, and the inside of the device is evacuated. At the same time, the decorative film is heated by an infrared heater until it reaches a predetermined temperature for softening, and at the timing when the decorative film is heated and softened, by sending the atmosphere to only one side of the internal space of the device, in a vacuum atmosphere, The decorative film is firmly attached to the three-dimensional shape of the molded body. If necessary, pressure air pressing from the silicone rubber sheet side may be appropriately used together. After the decorative film adheres to the molded body, the silicone rubber sheet is released from the decorative film, and the molded decorative film is removed from the fixed frame to obtain a decorative molded product.

  As a method of molding the decorative molded product, a decorative molding method in a mold in injection molding is used, in which a decorative molding laminate vacuum-formed along the injection mold is set in the mold. There is an insert molding method in which a molten resin is injected into the product and the laminate is welded to the product simultaneously with the injection molding. In addition, regarding the decoration in the injection molding die, the decorative molding film is pasted on the mold cavity side by vacuum pressure and simultaneously molded during injection molding so that heat and pressure are applied to the laminated body The method of sticking to a molded body is mentioned. Further, a method of lamination by vacuum forming or pressure forming can be mentioned. Further, it is also preferably used in an in-mold transfer molding method in which only a decorative layer is transferred to a molded product when a decorative molding film is simultaneously molded at the time of injection molding by a decorative method in an injection molding die. Furthermore, in recent years, the NGF molding method developed by Fuse Vacuum Co., Ltd., which has been attracting attention as a new decoration molding method, uses two chambers to control vacuum and compressed air, and TOM is used for three-dimensional decoration molding by applying it. It can be preferably applied to a new decorative molding method such as a construction method. In these thermoforming processes, the laminate is preformed into a mold shape by vacuum forming, injection molding is performed, and the decorative polycarbonate film of the present invention is attached to the molded product and the molded product is taken out. After that, it is necessary to trim the film, and when the decorative polycarbonate film of the present invention is used, chips are less likely to be generated and the trimming property is good, and it is possible to efficiently obtain a decorated molded product. It will be possible. Various methods such as infrared heater, electric heater, high-frequency induction, halogen lamp, microwave, high-temperature derivative (steam, etc.), laser, etc. can be used as the heating method of the decorative polycarbonate film during thermoforming.

  Decorative molded articles using the decorative polycarbonate film in the present invention, automobile interior materials, automobile indicator panels, electrical appliances, cosmetics cases, building materials interior and exterior products, various equipment and products and miscellaneous goods cases, switches, Keys, key pads, handles, levers, buttons, housings and exterior parts of personal computers, mobile phones and mobile devices such as home appliances and AV devices can be mentioned. Decorative molded products have excellent transferability of the decorative layer, high surface hardness, excellent weather resistance and heat resistance, and various electronic / electrical devices, vehicle parts, machine parts, other building materials, agricultural / fishery materials, It is useful as various products such as transport containers, packaging containers, and sundries.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. In the examples, "part" means "part by weight". The resins used and the evaluation methods used in the examples are as follows.
(1) Polymer composition ratio (NMR)
Each repeating unit was measured by proton NMR of JNM-AL400 manufactured by JEOL Ltd., and the polymer composition ratio (molar ratio) was calculated.
(2) Glass transition temperature (Tg)
Using a thermal analysis system DSC-2910 manufactured by TA Instruments Co., Ltd. using 8 mg of resin, in a nitrogen atmosphere (nitrogen flow rate: 40 ml / min) in accordance with JIS K7121, temperature rising rate: It was measured under the condition of 20 ° C./min.
(3) Total film thickness (d)
The thickness of the central portion of the stretched film obtained in the example was measured with an electronic micro film thickness meter manufactured by Anritsu.
(4) Film interlayer thickness It was measured by observing the cross section of the film using a laser microscope VA-9710 manufactured by Keyence Corporation. It is the value at the center in the film width direction.
(5) Pencil hardness Based on JIS K5400, the pencil is kept at an angle of 45 degrees with respect to the polycarbonate resin layer (B) side surface of the laminate film cut out into 80 mm x 60 mm in a thermostatic chamber at an atmospheric temperature of 23 ° C. A line was drawn while a load of 750 g was applied, and the surface condition was visually evaluated.
(6) Hue Using a spectral haze meter-SH-7000 manufactured by Nippon Denshoku Industries Co., Ltd., the hue b * value in accordance with JIS Z8781-4 was measured.
(7) Haze A haze value according to JIS K7136 was measured using a spectroscopic haze meter-SH-7000 manufactured by Nippon Denshoku Industries Co., Ltd.
(8) Die streak of decorative film The film surface was visually observed by reflection to confirm the level of the die streak.
(9) Molded product Wrinkles and tears The decorated molded product using the decorative film obtained in the present invention is visually observed to see if there are wrinkles at the corners or breaks (gate damage) in the decorative film at the gate portion. Was evaluated.
(10) Chips A metal bar coater is used for the polycarbonate resin layer (A) of the polycarbonate film for decoration to obtain an ultraviolet curable paint (beam set manufactured by Arakawa Chemical Industry Co., Ltd.) so as to have a thickness of 3 μm. 575CL), dried, and then cured using an ultraviolet irradiation device so as to have an integrated light amount of 600 mJ / cm ² , to prepare a decorating film having a hard coat layer laminated on one side, and the decorating film is When 10 sheets were stacked and punched with a cutting machine, the presence or absence of chips was evaluated.
(11) Melt viscosity For each of the polycarbonate resin (a) and the polycarbonate resin (b), a capillary length of 10.0 mm, a capillary diameter of 1.0 mm, a melting temperature of 240 ° C to 280 ° C, and a shear rate of Toyo Seiki are used. Was arbitrarily changed and measured, and the melt viscosity at a shear rate of 121 sec-1 was read from the obtained melt viscosity curve.
(12) Warp ratio Six pieces of 100 mm in length × 100 mm in width are cut out from the laminate at the time of melt coextrusion molding, and these six test pieces are dried at 100 ° C. for 1 hour. Immediately thereafter, the resin layer (A) was placed flat on a horizontally placed desk with the side facing up, and the floating amount was measured at a total of 8 points at the four corners of the film and the intermediate points.
The floating amount was measured at a total of 8 points, that is, the four corners of the film and the intermediate points.
The maximum floating amount (maximum warpage amount) among the six measured sheets was obtained, and the value calculated by the following formula was used as the warpage rate (%).
Warp rate (%) = 100 × maximum warp amount (mm) / 100 (mm)
The warp amount when floating on the resin layer (A) side is positive (+), and the warp amount when floating on the resin layer (B) side is negative (-).

[Resin composition]
(Production Example 1)
Resin A-1: Teijin Ltd. polycarbonate resin Panlite L-1225JM pellets were used for evaluation. The melt viscosity according to JIS K7199 by a capillograph was 480 Pa · S at a shear rate of 122 (1 / s) and a heating temperature of 280 ° C.

(Production Example 2)
Resin A-2: Polycarbonate resin pellets (Panlite L-1250 manufactured by Teijin Ltd., viscosity average molecular weight 23,700) and polyester thermoplastic elastomer are preliminarily pre-dried to obtain polycarbonate resin / polyester thermoplastic elastomer = After mixing with a V-type blender so as to be 90/10 (100/11. 1) (parts by weight), the mixture was extruded at a cylinder temperature of 260 ° C using a twin-screw extruder to be pelletized to obtain a resin A-2. . The glass transition temperature of the resin A-2 was 110 ° C., and the melt viscosity according to JIS K7199 was 490 Pa · S at a shear rate of 122 (1 / s) and a heating temperature of 280 ° C.

(Production Example 3)
Resin A-3: polycarbonate resin Panlite L-1250 manufactured by Teijin Ltd. was used for evaluation. The melt viscosity by a capillograph according to JIS K7199 was 1300 Pa · S at a shear rate of 122 (1 / s) and a heating temperature of 280 ° C.

(Production Example 4)
Resin B-1: A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 4,555 parts of a 48% aqueous sodium hydroxide solution and 22,730 parts of ion-exchanged water, and 9,9-bis ( 4-hydroxyphenyl) fluorene (manufactured by Honshu Chemical) 596 parts, bisphenol C (manufactured by Honshu Chemical) 1,213 parts, bisphenol A (manufactured by Nippon Steel Chemical) 2,159 parts, and hydrosulfite 7.94 parts (Japanese) After dissolving 415 parts of methylene chloride, 2,000 parts of phosgene was blown thereinto with stirring at 15 to 25 ° C. for about 70 minutes. After the blowing of phosgene, 650 parts of 48% aqueous sodium hydroxide solution and 89.9 parts of p-tert-butylphenol were added, stirring was restarted, and after emulsification, 3.94 parts of triethylamine were added, and the mixture was further stirred at 28 to 35 ° C. for 1 hour. Then the reaction was completed.

  After completion of the reaction, the product was diluted with methylene chloride and washed with water, and then hydrochloric acid was added to acidify and wash with water, and washing with water was repeated until the conductivity of the aqueous phase became almost the same as that of ion-exchanged water. A methylene solution was obtained. Then, this solution was passed through a filter having an opening of 0.3 μm, and the solution was added dropwise to warm water in a kneader with an isolation chamber having a foreign matter outlet at the bearing portion, and while methylene chloride was distilled off, the polycarbonate resin was flaked, and then the The liquid-containing flakes were crushed and dried to obtain powder.

  Then, to 100 parts by weight of the powder, 0.05 parts by weight of Irgafos 168 (manufactured by Ciba Specialty Chemicals), 0.1 parts by weight of S-100A (manufactured by Riken Vitamin), 0.3 parts of Chemisorb 79 (Kemipro Chemicals) Manufactured) and uniformly mixed, and then the powder is melt-kneaded and extruded by a vent type twin-screw extruder [KTX-46 manufactured by Kobe Steel, Ltd.] while being extruded to give a polycarbonate resin composition (B-1 ) A pellet was obtained. The melt viscosity according to JIS K7199 by a capillograph was 900 Pa · S at a shear rate of 122 (1 / s) and a heating temperature of 280 ° C. Various evaluations were performed using the pellets, and the results are shown in Table 1.

(Production Example 5)
Resin B-2: 2,023 parts of bisphenol C (manufactured by Honshu Chemical), 596 parts of 9,9-bis (4-hydroxyphenyl) fluorene (manufactured by Honshu Chemical), bisphenol A (manufactured by Nippon Steel Chemical) 1, Polycarbonate resin composition (B-2) pellets were obtained in the same manner as in Production Example 1, except that 440 parts and p-tert-butylphenol were 82.8 parts. The melt viscosity according to JIS K7199 by a capillograph was 1040 Pa · S at a shear rate of 122 (1 / s) and a heating temperature of 280 ° C. Various evaluations were performed using the pellets, and the results are shown in Table 1.

(Production Example 6)
Resin B-3: In a reactor equipped with a stirrer and a distillation column, 5,2-bis (4-hydroxy-3-methylphenyl) propane 56.3 parts (0.22 mol) and diphenyl carbonate 49.2 parts ( 0.23 mol) and 0.000005 parts of sodium hydroxide and 0.0016 parts of tetramethylammonium hydroxide as a catalyst were charged, and the atmosphere was replaced with nitrogen. The mixture was dissolved while heating to 180 ° C. Then, the stirrer was rotated and the internal temperature of the reactor was kept at 220 ° C. The pressure in the reactor was reduced from 101.3 kPa to 13.3 kPa over 40 minutes while distilling off by-produced phenol. Subsequently, the pressure inside the reactor was maintained at 13.3 kPa, and the ester exchange reaction was carried out for 80 minutes while further distilling off the phenol.

  The internal pressure was reduced in absolute pressure from 13.3 kPa to 2 kPa, the temperature was further raised to 260 ° C., and the distilled phenol was removed to the outside of the system. Further, the temperature was raised, and after reaching 0.3 Pa or less in the reactor, the internal pressure was maintained and the polycondensation reaction was performed. The final internal temperature in the reactor was 295 ° C. The polycondensation reaction was terminated when the stirrer of the reactor became a predetermined stirring power. The polymerization reaction time in the reactor was 140 minutes. Then, in the molten state, 0.0023 parts (4 × 10 −5 mol / bisphenol 1 mol) of dodecylbenzenesulfonic acid tetrabutylphosphonium salt was added as a catalyst neutralizing agent and reacted at 295 ° C. for 10 minutes at 10 Torr or less. The resulting polymer was sent to a vented twin-screw extruder [KTX-46 manufactured by Kobe Steel, Ltd.] by a gear pump. Tris (2,4-di-tert-butylphenyl) phosphite and phosphorous acid were added in the middle of the extruder, the barrel temperature of the inlet was 230 ° C, the barrel temperature of the outlet was 270 ° C, the polycarbonate resin outlet temperature was 285 ° C, and the The mixture was extruded in a melt-kneading manner while being extruded in a strand form from the exit of the twin-screw extruder, cooled with water and solidified, and then pelletized with a rotary cutter to obtain polycarbonate resin (B-3) pellets. The results of evaluation using the pellets are shown in Table 1. The melt viscosity according to JIS K7199 by a capillograph was 790 Pa · S at a shear rate of 122 (1 / s) and a heating temperature of 280 ° C.

(Production Example 7)
Resin B-4: 9,9-bis (4-hydroxyphenyl) fluorene (manufactured by Honshu Chemical Co., Ltd.), bisphenol C (manufactured by Honshu Chemical Co., Ltd.) 2,023 parts, bisphenol A (manufactured by Nippon Steel Chemical Co., Ltd.) 1, Polycarbonate resin composition (B-4) pellets were obtained in the same manner as in Resin B-1 except that 799 parts and 87.6 parts of p-tert-butylphenol were used. The results of evaluation using the pellets are shown in Table 1. The melt viscosity according to JIS K7199 by a capillograph was 430 Pa · S at a shear rate of 122 (1 / s) and a heating temperature of 280 ° C.

(Production Example 8)
Resin B-5: Polycarbonate resin Panlite L-1225L manufactured by Teijin Limited was used. The results of evaluation using pellets are shown in Table 1. The melt viscosity according to JIS K7199 by a capillograph was 740 Pa · S at a shear rate of 122 (1 / s) and a heating temperature of 280 ° C.
Resin B-6: PMMA Acrypet VH-001 manufactured by Mitsubishi Rayon Co., Ltd. was used. It evaluated using the pellet. The melt viscosity according to JIS K7199 by a capillograph was 420 Pa · S at a shear rate of 122 (1 / s) and a heating temperature of 280 ° C.
Resin B-7: Arkema heat-resistant acrylic Altsgrass HT-121 was used. It evaluated using the pellet. The melt viscosity according to JIS K7199 by a capillograph was 240 Pa · S at a shear rate of 122 (1 / s) and a heating temperature of 280 ° C.

[Examples 1 to 3]
<Production of a decorative polycarbonate film provided with a decorative layer>
As shown in Table 2-1, resin A-1 as the polycarbonate resin (a) forming the polycarbonate resin layer A, resin B-1 as the polycarbonate resin (b) forming the polycarbonate resin layer B, each having a screw diameter of 40 mm Using a single screw extruder, a polycarbonate resin (a) has a cylinder temperature of 260 ° C and a polycarbonate resin (b) has a cylinder temperature of 280 ° C. After the surface of the polycarbonate resin layer A was touched and cooled, edge trimming was performed to prepare a polycarbonate film for decoration having a two-layer structure and a width of 400 mm. The thickness and total thickness of the polycarbonate resin layer B were appropriately adjusted by the discharge amount of each extruder and the winding speed of the cooling roll. On one side of the polycarbonate resin layer (A) side of the decorative polycarbonate film obtained by the above-mentioned production method, an insert molding ink "IPX screen ink (trade name)" manufactured by Teikoku Ink Mfg. Co., Ltd. was screen-printed. It was applied and dried with hot air at 80 ° C. for 30 minutes to form a decorative layer (pattern layer).
Further, an insert molding binder "IMB-003 binder (trade name)" manufactured by Teikoku Ink Mfg. Co., Ltd. was applied onto the colored layer (pattern layer) by screen printing, and dried with hot air at 80 ° C for 30 minutes. By providing the binder layer (adhesive layer), a decorative polycarbonate film having a decorative layer was obtained.

<Decorated molding using a polycarbonate film for decoration>
After drying the polycarbonate resin pellets (Panlite L-1225ZL100 manufactured by Teijin Ltd.) with a hot air dryer at 120 ° C. for 5 hours, a molding machine with a cylinder diameter of 50 mmφ and a mold clamping force of 46,950 kN made by Nissei Plastic Industries FN8000 injection molding. Machine and the mold of FIG. 1 are used to perform the injection molding using the decorative polycarbonate film provided with the decorative layer obtained in Examples 1 to 3 to obtain the simulated touch panel cover shown in FIG. Molded. Molding was performed at a cylinder temperature of 300 ° C., a hot runner setting temperature of 300 ° C., a mold temperature of 100 ° C. on both the fixed side and the movable side, and a cooling time of 10 seconds. The decorative film having a decorative layer was cut into sheets, sandwiched between mold frames, sucked with a vacuum pump, and fixed to the mold.
The results are shown in Table 2-1.

[Example 4]
Except that the polycarbonate resin (b) was changed to the resin B-2, the same operation as in Example 1 was performed and the same evaluation was performed. The results are shown in Table 2-1.

[Comparative Example 1]
Except that the polycarbonate resin (b) was changed to the resin B-3 and the cylinder temperature of the polycarbonate resin (b) was changed to 270 ° C., the same operation as in Example 1 was performed and the same evaluation was performed. The results are shown in Table 2-2.

[Comparative Example 2]
Except that the polycarbonate resin (b) was changed to the resin B-4, the cylinder temperature of the polycarbonate resin (b) was changed to 260 ° C, and the temperature of the T die was changed to 260 ° C, the same operation as in Example 1 was performed, Similar evaluation was performed. The results are shown in Table 2-2.

[Comparative Example 3]
Resin B-5 was extruded from a T-die with a width of 650 mm using a single screw extruder having a screw diameter of 40 mm at a cylinder temperature of 280 ° C., one side was touched with a cooling roll to cool, and then edge trimming was performed to form a single layer. A structured film having a width of 400 mm was prepared. The total thickness was appropriately adjusted by the discharge rate of each extruder and the winding speed of the cooling roll. The molding method was the same as in Example 1, and the same evaluation was performed. The results are shown in Table 2-2.

[Comparative Example 4]
Except that the polycarbonate resin (a) was changed to resin A-2 and the polycarbonate resin (b) was changed to PMMA of resin B-6, the cylinder temperature of both resins was changed to 260 ° C, and the temperature of the T die was changed to 260 ° C. The same operation as in Example 1 was performed and the same evaluation was performed. The results are shown in Table 2-2.

[Comparative Example 5]
Except that the polycarbonate resin (b) was changed to the heat-resistant acrylic resin of Resin B-7, the cylinder temperature of Resin B-7 was changed to 260 ° C, and the temperature of the T-die was changed to 260 ° C, the same operation as in Example 1 was performed. The same evaluation was performed. The results are shown in Table 2-2.

[Comparative Example 6]
Except for changing Resin B-5 of Comparative Example 3 to Resin B-1, the same operation as in Comparative Example 3 was performed and the same evaluation was performed. The results are shown in Table 2-2.

[Comparative Example 7]
Except that the polycarbonate resin (a) was changed to the resin A-3, the same operation as in Example 1 was performed and the same evaluation was performed. The results are shown in Table 2-2.

Resin B-5: L-1225L
Resin B-6: Acrylic VH-001
Resin B-7: Heat-resistant acrylic Altsgrass HT-121

Resin A-1: L-1225JM
Resin A-2: L-1250 + polyester thermoplastic elastomer (10% by weight added)
Resin A-3: L-1250

  The polycarbonate film for decorating of the present invention and a molded product formed therefrom have scratch resistance and heat resistance, have a glass transition temperature of 140 ° C. or higher, generate little cutting chips during cutting, and are decorative molded. Its excellent properties make it extremely useful as an interior material for automobiles and as a front panel for in-vehicle displays.

1. Mold 2. Multi-layer film 3. Frame for fixing film 4. Vacuum drawing groove

Claims (5)

A polycarbonate film for decoration, which is a laminate in which a polycarbonate resin layer (B) is laminated on one surface of a polycarbonate resin layer (A), and which satisfies the following conditions.
(I) The glass transition temperature Tg (a) of the polycarbonate resin (a) used in the polycarbonate resin layer (A) and the glass transition temperature Tg (b) of the polycarbonate resin (b) used in the polycarbonate resin layer (B) are both The temperature is 140 ° C. or higher, and the relationship of | Tg (a) −Tg (b) | ≦ 10 ° C. is satisfied.
(II) The thickness of the polycarbonate resin layer (B) is 40 to 100 μm.
(III) The pencil hardness defined by ISO 15184 measured from the polycarbonate resin layer (B) side is H or higher.
(IV) The polycarbonate resin (a) is composed of the structural unit (A) represented by the following formula (1).
(V) The warpage rate when the laminate comprising the resin layer (A) and the resin layer (B) satisfying (I) to (IV) is treated at 100 ° C. for 1 hour is 10% or less.

(In the formula (1), W represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylidene group, a sulfur atom or an oxygen atom.) The polycarbonate resin (b) has the following formula (1)

(In the formula (1), W represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylidene group, a sulfur atom or an oxygen atom.)
A structural unit (b1) represented by
(B) The following formula (2)

(In the formula (2), R ^{1 and} R ² are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
And a structural unit (b2) represented by the following formula (3)

(In formula (3), R ^{3 to} R ⁴ are each independently an alkyl group having 1 to 6 carbon atoms, and X is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted group. Alternatively, it is an unsubstituted alkylidene group having 1 to 10 carbon atoms.)
Of the structural unit (b3), the proportion of the structural unit (b1) in all the structural units is 25 to 75 mol%, the proportion of the structural unit (b2) is 5 to 15 mol%, and the structural unit (b3). The polycarbonate film for decoration according to claim 1, which is a polycarbonate copolymer or a copolymerized polycarbonate blend having a ratio of 20 to 60 mol%.   The melt viscosity of the polycarbonate resin (a) and the polycarbonate resin (b) according to JIS K7199 according to Capirograph satisfies 1,200 Pa · S or less at a shear rate of 122 (1 / s) and a heating temperature of 280 ° C. 2. The polycarbonate film for decoration according to any one of 2.   The polycarbonate film for decoration according to claim 1, wherein the laminated body has a total thickness of 100 to 500 μm. A decorative molded article, characterized in that a thermoplastic resin is injection-molded on the decorative side surface of the polycarbonate decorative film according to any one of claims 1 to 4.

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