JP2006089509A - Method of recovering aromatic polycarbonate or its alloy from molded article to mold the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high-quality aromatic polycarbonate or a polymer alloy containing the same which is recovered from molded articles and can be stably molded at a low cost without causing failures relating to surface properties such as surface defect, external appearance failure, and adhesion failure in fabrication, and its molding method, and to provide a molding method of these polymers. <P>SOLUTION: The aromatic polycarbonate or the polymer alloy containing the same is obtained by incorporating a branched aromatic polycarbonate into an aromatic polycarbonate or its alloy recovered from molded articles and adjusting the melt relaxation time of the resulting mixed aromatic polycarbonate (polymer alloy) to ≥0.7 times the melt relaxation time of the aromatic polycarbonate of the initial raw material or to ≥1.05 times the melt relaxation time of the recovered polycarbonate (polymer alloy), and the molding method comprises molding the above aromatic polycarbonate or the polymer alloy. Molded articles are molded by this molding method. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an improved molding method for recovering and molding an aromatic polycarbonate or a polymer alloy containing an aromatic polycarbonate from a molded article, and an improved aromatic polycarbonate or aromatic polycarbonate.

Thermoplastic resins have been used in various molded products in recent years. Optical materials such as CD-ROM, DVD, and DVD-R are provided with a dye recording layer and a reflective layer on a polycarbonate substrate. In addition, molded articles having a coating film or a metal reflection layer made of a thermoplastic resin as a base material are widely used for automobile bumpers, dashboards, headlamps, and rear lamps. In addition, there is an increasing tendency to use a molded plate in which a polycarbonate plate is provided with an ultraviolet protection layer and a hard coat layer as a transparent soundproof wall even on highways.
In addition, polymer alloys composed of polycarbonate (PC) and acrylonitrile-butadiene-styrene resin (ABS) can be used for impact strength, dimensional stability, and non-halogen flame retardants. It is used as an electrical / electronic / optical housing for printers. These are coated on the surface for improving the commercial value, and on the back surface, surface treatment such as coating for electromagnetic wave shielding, plating, and sputtering is performed.
Regarding these molded products, the handling of defective products generated in the manufacturing process or used products is attracting attention. It is important not to landfill or incinerate as waste, but to reuse it as a resource. In recent years, efforts have been made to collect used products, sort out the corresponding molded products, collect used thermoplastic resins, and recycle them (see Patent Documents 1 and 2). In addition, from the administrative aspect, as required by the Home Appliance Recycling Law, recycling of the product is required.

  However, when PC or PC alloy is injection-molded from virgin resin, or when recovered PC or PC alloy is injection-molded, the conventional method has a poor appearance at the fluid end, coating, and plating. Adhesion failure is likely to occur when secondary processing such as vapor deposition is performed, and in the case of hollow molding, the parison drawdown is large, and in the case of sheet molding, there are problems such as increased neck-in. there were.

JP 2001-287225 A JP 2004-027072 A

  The problem to be solved by the present invention is to recover an aromatic polycarbonate or a polymer alloy containing the same from a molded article without causing a failure related to surface characteristics such as surface defects, poor appearance, and poor adhesion in secondary processing. Another object of the present invention is to provide an aromatic polycarbonate which can be molded with high quality, inexpensively and stably, or a polymer alloy containing the same, and a molding method thereof.

The above object of the present invention has been achieved by the following means (1), (2), (9) and (10).
(1) Aromatic polycarbonate (B) is recovered from a molded article having a foreign substance or a heterogeneous layer on a substrate made of aromatic polycarbonate (A), and branched aromatic to the aromatic polycarbonate (B). The melting relaxation time of the mixed aromatic polycarbonate (D) obtained by blending the polycarbonate (C) is 0.7 times or more of the melting relaxation time of the aromatic polycarbonate (A) or the aromatic polycarbonate (B). A method for molding an aromatic polycarbonate, wherein the molding is performed after adjusting to be 1.05 times or more of the melting relaxation time,
(2) On a substrate made of a polymer alloy (F) containing 20 parts by weight or more and less than 100 parts by weight of the aromatic polycarbonate (A) and 80 parts by weight or less of a thermoplastic resin (E) other than the aromatic polycarbonate. Melting of the mixed polymer alloy (I) obtained by recovering the polymer alloy (G) from a molded article having foreign matter or a foreign layer and blending the polymer alloy (G) with the branched aromatic polycarbonate (H) Molding after adjusting the relaxation time to be 0.7 times or more of the melting relaxation time of the aromatic polycarbonate (A) or 1.05 times or more of the melting relaxation time of the polymer alloy (G). A method for molding an aromatic polycarbonate polymer alloy characterized by the following.
(9) Aromatic polycarbonate (B) is recovered from a molded article having foreign matter or having a heterogeneous layer on a substrate made of aromatic polycarbonate (A), and branched aromatic to the aromatic polycarbonate (B). Mixed aromatic polycarbonate (D) obtained by blending polycarbonate (C), the melting relaxation time of which is 0.7 times or more the melting relaxation time of aromatic polycarbonate (A), or the above aromatic polycarbonate Mixed aromatic polycarbonate (D) having a melting relaxation time of (B) of 1.05 times or more.
(10) On a substrate made of a polymer alloy (F) containing 20 parts by weight or more and less than 100 parts by weight of the aromatic polycarbonate (A) and 80 parts by weight or less of a thermoplastic resin (E) other than the aromatic polycarbonate. A mixed polymer alloy (I) obtained by recovering a polymer alloy (G) from a molded article having a foreign substance or a foreign layer and blending the polymer alloy (G) with a branched aromatic polycarbonate (H). And a mixed polymer alloy having a melting relaxation time of 0.7 times or more of the melting relaxation time of the aromatic polycarbonate (A) or 1.05 times or more of the melting relaxation time of the polymer alloy (G) ( I).

Some preferred embodiments of the present invention are listed below.
(3) The molding method according to the above (1) or (2), wherein the branched aromatic polycarbonate (C or H) has a degree of branching of 1.5 to 10 per 1,000 units of the monomer of the aromatic dihydroxy compound,
(4) Any one of the above (1) to (3), wherein the branched aromatic polycarbonate (C or H) has a degree of branching of 2.5 to 5.0 per 1,000 units of the monomer of the aromatic dihydroxy compound. Molding method according to
(5) The thermoplastic resin (E) is an acrylonitrile / butadiene / vinyl aromatic copolymer, an acrylonitrile / vinyl aromatic polymer, an acrylonitrile / ethylene propylene copolymer / vinyl aromatic polymer, or a polybutadiene-containing vinyl aromatic. The molding method according to any one of the above (2) to (4), which is at least one styrenic resin selected from the group consisting of polymers,
(6) The heterogeneous layer is a dye-containing layer, a metal reflective layer, a photosensitive layer, a protective layer, an undercoat layer, a coating layer, a hard coat layer, an antireflection layer, an antiglare layer, a viewing angle expansion layer, an ultraviolet ray prevention layer. , A heat ray absorbing layer, a heat ray reflecting layer, an electromagnetic wave absorbing layer, an electromagnetic wave reflecting layer, an adhesive layer, a pressure-sensitive adhesive layer, and a cellulose derivative layer, as described in any one of (1) to (5) above. Molding method,
(7) The molding method according to any one of (1) to (6) above, wherein the molding method includes injection molding,
(8) A molded product obtained by the molding method according to any one of (1) to (7) above.

  According to the invention described in the above (1), (2), (9) and (10), the aromatic polycarbonate recovered from the molded product or the polymer alloy thereof does not cause the above-described failure related to the surface characteristics, It is possible to provide an aromatic polycarbonate or a polymer alloy containing the aromatic polycarbonate that can be molded stably with high quality, at low cost, and a molding method thereof.

  The present invention relates to a PC or PC polymer alloy in which an appropriate amount of a branched aromatic polycarbonate is blended with the recovered aromatic polycarbonate (PC) or aromatic polycarbonate polymer alloy (PC polymer alloy) in order to improve the surface characteristics of the molded product, and , And these molding methods.

“Aromatic polycarbonate” refers to a polycarbonate using a diol component containing an aromatic group such as bisphenol A as a diol component constituting the polycarbonate. A polycarbonate using only a diol component containing an aromatic group is preferred.
The “aromatic polycarbonate polymer alloy” refers to a polymer alloy with an aromatic polycarbonate and other compatible thermoplastic resin.
“Surface characteristics of molded article” refers to a chemical or physical property relating to the surface of a molded article obtained by molding PC or PC polymer alloy (both of which are also referred to as “polycarbonate (polymer alloy)”). The surface characteristics include surface defects, poor appearance, poor adhesion in secondary processing, and the like.
“Branched aromatic polycarbonate” refers to an aromatic polycarbonate having a branch.
Below, the shaping | molding method of this invention is demonstrated in detail.

(Melting relaxation time)
The melting relaxation time is a relaxation time of melt viscoelasticity and represents a relaxation time of stress relaxation in a melt such as a resin.
When the stress is measured while keeping a certain strain on the resin, the stress decreases with time. This phenomenon is called stress relaxation, and the value obtained by dividing the stress that changes with time by the strain is called relaxation modulus. The relaxation time is the time for which the stress is reduced to 1 / e.
The melting relaxation time τ is an elastic modulus (storage elastic modulus: G ′) corresponding to a stress having no phase delay with respect to strain, an elastic modulus corresponding to a stress corresponding to a strain rate (loss elastic modulus: G ″), And it calculates | requires by following formula (1) by the value of frequency (omega) used when measuring the said two elasticity modulus.

(Aromatic polycarbonate)
The aromatic polycarbonate used in the present invention can be produced by a known method such as a melting method or an interface method using an aromatic dihydroxy compound or the like as a raw material.
The melting method refers to a method in which an aromatic dihydroxy compound and a carbonic acid diester are used as raw materials and melt polycondensed in the presence of a transesterification catalyst.
The interfacial method refers to a method in which an alkali metal salt of an aromatic dihydroxy compound and phosgene are used as raw materials, and polycondensation is performed at the interface between an organic solvent that dissolves the produced polycarbonate and an aqueous alkali solution.

[Melting method]
Although the aromatic dihydroxy compound, carbonic acid diester, and transesterification catalyst used for a melting method are demonstrated below, this invention is not limited to these.
<Aromatic dihydroxy compound>
As the aromatic dihydroxy compound, a compound represented by the following formula (2) can be used.

（式（２）中、Ａは、単結合、置換されていてもよい炭素数１〜１０の直鎖状、分岐状若しくは環状の２価の炭化水素基、又は、−Ｏ−、−Ｓ−、−ＣＯ−若しくは−ＳＯ₂−で示される２価の基であり、Ｘ及びＹは、ハロゲン原子又は炭素数１〜６の炭化水素基であり、ｐ及びｑは、０又は１の整数である。なお、ＸとＹ及びｐとｑは、それぞれ、同一でも相互に異なるものでもよい。）

(In Formula (2), A is a single bond, a C1-C10 linear, branched or cyclic divalent hydrocarbon group which may be substituted, or -O-, -S-. , —CO— or —SO ₂ —, wherein X and Y are a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and p and q are each an integer of 0 or 1 (X and Y and p and q may be the same or different from each other.)

  Typical aromatic dihydroxy compounds include, for example, bis (4-hydroxydiphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4-hydroxy-3-methylphenyl) propane. 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3) , 5-dibromophenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxybiphenyl, 3,3 ′, 5,5 '-Tetramethyl-4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) Sulfide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone. These aromatic dihydroxy compounds can be used alone or in admixture of two or more. Among these, 2,2-bis (4-hydroxyphenyl) propane (also referred to as bisphenol A) is preferable.

<Carbonated diester>
As the carbonic acid diester used in the present invention, a compound represented by the following formula (3) can be used.

（式（３）中、Ｒは、置換されていてもよい炭素数１〜１８の直鎖状、分岐状又は環状の１価の炭化水素基であり、２つのＲは、同一でも相互に異なるものでもよい。）

(In Formula (3), R is a C1-C18 linear, branched or cyclic monovalent hydrocarbon group which may be substituted, and two Rs are the same or different from each other. It may be a thing.)

  Typical carbonic acid diesters include, for example, substituted diphenyl carbonates typified by diphenyl carbonate, ditolyl carbonate, and the like, and dialkyl carbonates typified by dimethyl carbonate, diethyl carbonate, di-t-butyl carbonate, and the like. These carbonic acid diesters can be used alone or in admixture of two or more. Among these, diphenyl carbonate or substituted diphenyl carbonate is preferable.

  Moreover, said carbonic acid diester may substitute the quantity of the 50 mol% or less preferably 30 mol% or less with the dicarboxylic acid or dicarboxylic acid ester preferably. Representative dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate. When substituted with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate is obtained.

These carbonic acid diesters (including the above-mentioned substituted dicarboxylic acids or esters of dicarboxylic acids; the same shall apply hereinafter) are usually used in excess with respect to the aromatic dihydroxy compounds. That is, it is used in a molar ratio within the range of 1.001 to 1.3, preferably 1.01 to 1.2 with respect to the aromatic dihydroxy compound. When the molar ratio is in the above range, the heat stability and hydrolysis resistance are good, the rate of the transesterification reaction does not decrease, and the production of a polycarbonate having a desired molecular weight is easy.
Further, the polycarbonate may be treated with a terminal blocking agent such as an allyloxy compound or a monocarboxy compound, if necessary.

<Transesterification catalyst>
In the polycarbonate production method of the present invention, the catalyst species is not limited, but in general, an alkali metal compound, an alkaline earth metal compound, a basic boron compound, a basic phosphorus compound, a basic ammonium compound, an amine compound, etc. These basic compounds are used. These may be used alone or in combination of two or more. The catalyst is used in an amount of 0.05 to 5 μmol, preferably 0.08 to 4 μmol, and more preferably 0.1 to 2 μmol with respect to 1 mol of the aromatic dihydroxy compound. When the amount of the catalyst used is in the above range, sufficient polymerization activity necessary for producing a polycarbonate having a desired molecular weight is obtained, the polymer hue is good, and the fluidity during molding does not deteriorate.

<Melting polycondensation>
In the melt polycondensation of the present invention, a known method is applied, and the reaction conditions such as the use amount ratio of the carbonic acid diester and the transesterification catalyst with respect to the aromatic dihydroxy compound, the temperature and the reaction time may be arbitrarily set according to the purpose. Good.

[Interface method]
Below, the alkali metal salt of the aromatic dihydroxy compound used for an interface method, phosgene, and an organic solvent are demonstrated.

<Alkali metal salt of aromatic dihydroxy compound>
As the aromatic dihydroxy compound, those used in the melting method are preferable.
As the alkali metal salt of the aromatic dihydroxy compound, it is preferable to use an alkali metal salt obtained by dissolving an aromatic dihydroxy compound in an alkaline aqueous solution, and an alkali metal salt isolated as an alkali metal salt may be used.

<Phosgene>
The phosgene is preferably as pure as possible and preferably does not contain impurities such as carbon tetrachloride and methylene chloride.

<Organic solvent>
Any organic solvent can be used without particular limitation as long as it dissolves the produced aromatic polycarbonate.

<Interfacial polycondensation>
In the interfacial polycondensation of the present invention, a known method is applied, and the use conditions of phosgene and alkali to the aromatic dihydroxy compound, the reaction solution concentration, temperature, reaction time and other reaction conditions are arbitrarily set according to the purpose. May be.

(Branched aromatic polycarbonate (C or H))
The branched aromatic polycarbonate of the present invention preferably has a degree of branching of 1.5 to 10 per 1,000 units of aromatic dihydroxy compound monomer, and more preferably has a degree of branching of 2.5 to 5.0. .

  The branched aromatic polycarbonate of the present invention may not have a longer melting relaxation time than the aromatic polycarbonate to be blended or its alloy. Even a branched aromatic polycarbonate with a short melting relaxation time due to its low molecular weight can be blended with other aromatic polycarbonates to achieve a certain molecular weight as a whole, thereby exhibiting branching performance and a long melting relaxation time. This is because there are cases.

  As the aromatic dihydroxy compound used for the production of the branched aromatic polycarbonate by the melting method, it is possible to use a compound obtained by adding an appropriate amount of the 2,4′-bisphenol compound represented by the formula (4) to the aromatic dihydroxy compound. preferable.

（式（４）中、Ａ’は、単結合、炭素数１〜８のアルキレン基、炭素数２〜８のアルキリデン基、炭素数５〜１５のシクロアルキレン基、炭素数５〜１５のシクロアルキリデン基又は、−Ｏ−，−Ｓ−，−ＣＯ−，−ＳＯ−，−ＳＯ₂−で示される２価の基からなる群から選ばれるものである。）

(In Formula (4), A 'is a single bond, a C1-C8 alkylene group, a C2-C8 alkylidene group, a C5-C15 cycloalkylene group, and a C5-C15 cycloalkylidene. A group or a divalent group represented by -O-, -S-, -CO-, -SO-, -SO _2- .)

The appropriate amount of the 2,4′-bisphenol compound is such that the amount of the 2,4′-bisphenol compound is usually in the range of 100 to 50,000 ppm by weight, preferably 100 to 10,000, based on the aromatic dihydroxy compound. It is preferable to set within the range of ppm by weight, more preferably 200 to 7,000 ppm by weight, and particularly preferably 300 to 3,000 ppm by weight. When the amount of the 2,4′-bisphenol compound is in the above range, the degree of branching and the fluidity under high load are sufficient, gelation does not occur, and polymer molding is easy.
Moreover, you may use the polyfunctional compound shown to following formula (5) as a branching agent instead of the said 2, 4-bisphenol compound.

The branched aromatic polycarbonate produced by the melting method is obtained with a partial rearrangement reaction during the polymerization reaction. This rearrangement reaction is also called Fries rearrangement, in which a carbonyl group forming a carbonic ester bond is rearranged to the 2nd or 4th position of the aromatic ring.
The branched aromatic polycarbonate produced by the melting method preferably has a viscosity average molecular weight of 16,000 or more. From the viewpoint of mechanical strength, those with 18,000 or more are more preferable. Moreover, since there exists a tendency for fluidity | liquidity to worsen when a viscosity average molecular weight is remarkably large, 60,000 or less are preferable and 50,000 or less are more preferable.

  As a method for producing a branched aromatic polycarbonate by the melting method of the present invention, for example, known methods such as JP-A Nos. 2001-302780, 2002-308976, and 2003-119369 can be used. it can.

The branched aromatic polycarbonate by the interfacial method can be produced by a known interfacial polymerization method except that a polyfunctional compound is used as a branching agent in addition to the raw material of the aromatic polycarbonate as a raw material.
The polyfunctional compound is a compound represented by the following formula (5), and three or more functional groups from the group consisting of a phenolic hydroxyl group, a carboxyl group, an ester group, an acid halide group or an acid anhydride group A compound having is preferred.
(HO−) _n A ″ Y ¹ Y ² (5)
(In the formula, A ″ represents an organic residue containing an aromatic ring, HO— represents a phenolic hydroxyl group directly bonded to the aromatic ring of A ″, and n represents a natural number of 1, 2, 3 or 4. Y ¹ and Y ² both represent a hydrogen atom, a carboxyl group, an ester group, an acid halide group or an acid anhydride group directly bonded to the aromatic ring of A ″.)

In the multifunctional compound represented by the formula (5), n is preferably 3 or 4, and the multifunctional compound is more preferably a trifunctional compound.
The organic residue containing an aromatic ring represented by A ″ is a single aromatic ring, a structure in which a plurality of aromatic rings are connected by a carbon-carbon single bond, or a plurality of aromatic rings. It means a structure linked by any non-aromatic structure, and these may be bonded to an arbitrary substituent such as an alkyl group or a halogen atom as long as the effects of the present invention are not disturbed.
Such a polyfunctional compound is 0.01 mol% or more, usually 1 mol% or less, preferably 0.05 to 0.8 mol%, particularly preferably 0.1 mol%, based on the starting aromatic dihydroxy compound. It is preferable to add an amount of ˜0.6 mol%.

  As a method for producing a branched aromatic polycarbonate by the interface method of the present invention, for example, known methods such as JP-A-10-212346 and JP-B-3-15658 can be used.

The reason for blending and molding a branched aromatic polycarbonate having a long melting relaxation time in the aromatic polycarbonate or its alloy will be described below.
In the case of molding an aromatic polycarbonate (PC), there is a problem that the failure related to the surface characteristics is likely to occur. In particular, when the collected PC is used for molding, the above-described failure occurs more remarkably.
This may be due to the shape of the molecular structure that cannot be detected by molecular weight or fluidity. In the polycarbonate (polymer alloy) recovered from the molded product, the yarn-like polymer spreads in the molten state, but it is considered that the spread is reduced in the molding process.
As a measure for detecting the shape of the molecular structure and its change, there is a relaxation time of melt viscoelasticity. The longer the melting relaxation time, the larger the polymer chain spread. Polycarbonate (polymer alloy) recovered from the molded product is considered to have a shorter melting relaxation time than the initial raw material. In general, a branched PC has a longer melting relaxation time than a straight-chain PC.
In the present invention, a high-quality molded product having no failure related to the surface characteristics can be obtained by blending the recovered aromatic polycarbonate or its alloy with a branched aromatic polycarbonate having a long melting relaxation time.

  The blending amount of the branched aromatic polycarbonate (C) to be blended with the recovered polycarbonate (B) is the melting relaxation time of the resulting mixed aromatic polycarbonate (D) based on the aromatic polycarbonate (A) before molding. The blending is preferably performed so that the melting relaxation time of the aromatic polycarbonate (A) before molding is 0.7 times or more, more preferably 0.7 to 5.0 times, and 1.0 to 2.5 times. Is particularly preferred. Further, when the recovered aromatic polycarbonate (B) is used as a reference, the melting relaxation time of the obtained mixed aromatic polycarbonate (D) is 1.05 times or more of the melting relaxation time of the recovered aromatic polycarbonate (B). It is preferable to mix | blend so that 1.05-5.0 times may be more preferable, and 1.25-3.0 times are especially preferable.

  The blending amount of the branched aromatic polycarbonate (H) to be blended with the recovered polymer alloy (G) is the melting relaxation time of the resulting mixed polymer alloy (I) based on the aromatic polycarbonate (A) before molding. The blending is preferably performed so that the melting relaxation time of the aromatic polycarbonate (A) before molding is 0.7 times or more, more preferably 0.7 to 5.0 times, and 1.0 to 2.5 times. Is particularly preferable, and when the recovered polymer alloy (G) is used as a reference, the melting relaxation time of the obtained mixed polymer alloy (I) is 1.05 times or more of the melting relaxation time of the recovered polymer alloy (G). It is preferable to mix | blend so that it may become, 1.05-5.0 times are more preferable, and 1.25-3.0 times are especially preferable.

  The branched aromatic polycarbonate of the present invention can be produced by a known method such as a melting method or an interface method using an aromatic dihydroxy compound or the like as a raw material. Specific examples of the branched aromatic polycarbonate include NOVAREX M7022A, NOVAREX M7027A, NOVAREX M7020A, and SYK T6181 manufactured by Mitsubishi Engineering Plastics.

(Measurement method of branching degree)
Using GPC-RI / Viscometer / MALLS, the weight average molecular weight, mean square radius, viscosity, and differential refractive index were measured for each fraction separated by molecular weight, and per 1,000 units of aromatic dihydroxy compound monomer by the following method. The degree of branching λ _w was determined.

ｎ₀：溶媒の屈折率
ｄｎ／ｄｃ：ポリマー濃度変化に対する屈折率の変化
λ₀：真空中のレーザー光の波長
Ｎ_A：アボガドロ数（６．０２２×１０²³）
ｃ：ポリマーの濃度
Ｒ（θ）：散乱角θにおける散乱光の相対強度
Ｍｗ：重量平均分子量
Ａ₂：第２ビリアル係数
Ｐ（θ）：散乱光の角度依存性を表すファクター

n ₀ : refractive index of solvent dn / dc: change in refractive index with respect to polymer concentration change λ ₀ : wavelength of laser light in vacuum N _A : Avogadro number (6.022 × 10 ²³ )
c: Concentration of polymer R (θ): Relative intensity of scattered light at scattering angle θ Mw: Weight average molecular weight A ₂ : Second virial coefficient P (θ): Factor representing angle dependence of scattered light

＜Ｒｇ²＞：平均二乗半径
上式（７）（Ｚｉｍｍの式）より、縦軸にＫ・ｃ／Ｒ（θ）、横軸にｓｉｎ²（θ／２）を濃度別にプロットし、θ→０の外挿点を求めると、式(７)は、下式（８）のようになる。

<Rg ² >: Mean square radius From the above equation (7) (Zimm equation), K · c / R (θ) is plotted on the vertical axis and sin ² (θ / 2) is plotted on the horizontal axis by concentration, and θ → When the extrapolation point of 0 is obtained, the equation (7) becomes the following equation (8).

ｃ→０への外挿点が１／Ｍｗで、傾きが２Ａ₂である。よって、切片よりＭｗを、傾きより第２ビリアル係数Ａ₂を求めた。
次に、縦軸にＫ・ｃ／Ｒ（θ）、横軸にｃを取り、同測定角度での測定値をプロットし、ｃ→０への外挿点を求めると、式（７）は下式（９）のように表される。

The extrapolation point from c → 0 is 1 / Mw, and the slope is 2A ₂ . Therefore, Mw was obtained from the intercept, and the second virial coefficient A ₂ was obtained from the slope.
Next, taking K · c / R (θ) on the vertical axis and c on the horizontal axis, plotting the measured values at the same measurement angle, and finding the extrapolation point from c → 0, equation (7) is It is expressed as the following formula (9).

θ→０の外挿点が１／Ｍｗで、傾きの値より平均二乗半径＜Ｒｇ²＞を求めた。
また、分岐パラメーター（Ｓｈｒｉｎｋ Ｐａｒａｍｅｔｅｒ）：ｇ₀、Ｇ₀は、下式（１０）及び（１１）により求めた。

The extrapolation point of θ → 0 was 1 / Mw, and the mean square radius <Rg ² > was determined from the slope value.
Further, the branch parameters (Shrink Parameter): g ₀ and G ₀ were obtained by the following formulas (10) and (11).

＜Ｒｇ²＞_b、＜Ｒｇ²＞_lは、それぞれ直鎖ポリマー、分岐ポリマーの平均二乗半径を表す。
［η₀］_b、［η₀］_lは、それぞれ直鎖ポリマー、分岐ポリマーの固有粘度を表す。
ｇ₀とＧ₀は、下式（１２）の関係を満たす。
Ｇ₀＝ｇ₀ ^ε （１２）
ε＝２−α（α：マーク・ホーウインク・桜田の式の指数）
分岐パラメーターｇ₀は、三官能性分岐、かつ、分子量分布の狭いポリマーの場合、下式（１２）で表される。

_{^{<Rg 2> b, <Rg}} 2> l is a straight chain polymer, respectively, represent the mean square radius of the branched polymer.
[Η ₀ ] _b and [η ₀ ] _l represent the intrinsic viscosities of the linear polymer and the branched polymer, respectively.
g ₀ and G ₀ satisfy the relationship of the following expression (12).
G ₀ = g ₀ ^ε (12)
ε = 2-α (α: Exponent of Mark-Hawink-Sakurada formula)
The branch parameter g ₀ is represented by the following formula (12) in the case of a trifunctional branch and a polymer having a narrow molecular weight distribution.

ｎ_3M：三官能性分岐で分子量分布の狭いポリマー１分子あたりの分岐度
また、固有粘度［η］は下式（１３）で表され、
［η］＝Ｋ・Ｍ^α・ｇ^ε （１３）
Ｋ：マーク・ホーウインク・桜田の式の定数
Ｍ：ポリマーの（相対）分子量
さらに、三官能性分岐、かつ、分子量分布の狭いポリマーの場合、下式（１４）で表される。

n _3M : Branching degree per molecule of polymer having trifunctional branching and narrow molecular weight distribution In addition, the intrinsic viscosity [η] is represented by the following formula (13):
[Η] = K · M ^α · g ^ε (13)
K: Constant of the formula of Mark Hawk, Sakurada M: (Relative) molecular weight of polymer Furthermore, in the case of a polymer having a trifunctional branch and a narrow molecular weight distribution, it is represented by the following formula (14).

λ：１ダルトンあたりの分岐度
λは、下式（１５）を満たす。
ｎ_3M＝λ・Ｍ^β （１５）
β＝ｋ・λ（ｋ：定数）

λ: The degree of branching λ per dalton satisfies the following equation (15).
n _3M = λ · M ^β (15)
β = k · λ (k: constant)

From the above formulas (7) to (15), the degree of branching ni per molecule in each fraction _i was determined.
The degree of branching λ _i per 1,000 units of the aromatic dihydroxy compound in each fraction i was determined by the following formula (16).
λ _i = 1,000 × n _i × M _i / M ₀ (16)
M _i : Weight average molecular weight of the polymer in each fraction i M ₀ : Weight average molecular weight of the monomer of the aromatic dihydroxy compound The branching degree λ _w per 1,000 units of the monomer of the aromatic dihydroxy compound is obtained by the following formula (17). It was.
λ _w = Σ (λ _i × w _i ) / Σw _i (17)
w _i : mass of polymer in each fraction i

(Thermoplastic resin that forms a polymer alloy with an aromatic polycarbonate (E))
Typical examples of thermoplastic resins that can be applied to the present invention and that form a polymer alloy with an aromatic polycarbonate are styrene resins, polyolefins, and polyesters. These resins are described in detail below.

[Styrene resin]
The styrene resin is a styrene resin obtained by polymerizing at least one selected from styrene monomers and other vinyl monomers and rubbery polymers that can be copolymerized with these as required. . These styrenic resins may be used alone or in combination of two or more.

Examples of the styrene monomer used in the styrene resin component include styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, vinyl xylene, ethyl styrene, dimethyl styrene, p-tert-butyl styrene, vinyl naphthalene. , Styrene derivatives such as methoxystyrene, monobromostyrene, dibromostyrene, fluorostyrene, and tribromostyrene, with styrene being particularly preferable. These may be used alone or in combination of two or more.
Other vinyl monomers copolymerizable with the styrenic monomer include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, aryl esters of acrylic acid such as phenyl acrylate benzyl acrylate, methyl acrylate, ethyl acrylate, Alkyl esters of acrylic acid such as propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, cyclohexyl acrylate and dodecyl acrylate, aryl methacrylates such as phenyl methacrylate and benzyl methacrylate, methyl methacrylate, ethyl methacrylate , Propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate 1, 2-ethylhexyl methacrylate, octyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate and other methacrylic acid alkyl esters, glycidyl methacrylate and other epoxy group-containing methacrylic acid esters, maleimide, N-methylmaleimide, N-phenylmaleimide and other maleimide monomers And α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid, and itaconic acid, and anhydrides thereof. Preferably, alkyl acrylates and alkyl methacrylates are used.
As the monomer copolymerizable with the styrene monomer and (meth) acrylonitrile, the same monomers as those copolymerizable with the styrene monomer can be used.

On the other hand, rubber having a glass transition temperature of 10 ° C. or less is suitable as the rubbery polymer copolymerizable with the styrene monomer. Specific examples of rubber include diene rubber, acrylic rubber, ethylene / propylene rubber, silicon rubber, polyorganosiloxane rubber component and polyalkyl (meth) acrylate rubber component so that they cannot be separated from each other. Composite rubber (IPN type rubber) and the like, preferably diene rubber, acrylic rubber and the like.
Examples of the diene rubber include polybutadiene, styrene / butadiene random copolymer and block copolymer, acrylonitrile / butadiene copolymer, polyisoprene, butadiene / isoprene copolymer, and ethylene / propylene / hexadiene copolymer. Examples thereof include ethylene, propylene and non-conjugated diene terpolymers, lower alkyl ester copolymers of butadiene / (meth) acrylic acid, lower alkyl ester copolymers of butadiene / styrene / (meth) acrylic acid, and the like.
Examples of the lower alkyl ester of (meth) acrylic acid include methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate.
The proportion of the lower alkyl ester of (meth) acrylic acid in the lower alkyl ester copolymer of butadiene / (meth) acrylic acid or the lower alkyl ester copolymer of butadiene / styrene / (meth) acrylic acid is 30% by weight of the rubber. % Or less is preferable.

  Examples of the acrylic rubber include acrylic acid alkyl ester rubber, and the alkyl group preferably has 1 to 8 carbon atoms. Specific examples of the alkyl acrylate include ethyl acrylate, butyl acrylate, ethyl hexyl acrylate, and the like. An ethylenically unsaturated monomer may optionally be used in the acrylic acid alkyl ester rubber. Specific examples of such compounds include di (meth) acrylate, divinylbenzene, trivinylbenzene, triallyl cyanurate, allyl (meth) acrylate, butadiene, isoprene and the like. Examples of the acrylic rubber include a core-shell type polymer having a crosslinked diene rubber as a core.

Examples of the styrene resin used in the present invention include a homopolymer of styrene, a copolymer of styrene and (meth) acrylonitrile, a copolymer of styrene and (meth) acrylic acid alkyl ester, and styrene and (meth ) Copolymers of acrylonitrile and other copolymerizable monomers, graft copolymers formed by polymerizing styrene in the presence of rubber, and graft polymers of styrene and (meth) acrylonitrile in the presence of rubber Examples thereof include a graft copolymer. Specifically, polystyrene, styrene / butadiene / styrene copolymer (SBS resin), hydrogenated styrene / butadiene / styrene copolymer (hydrogenated SBS), hydrogenated styrene / isoprene / styrene copolymer (SEPS). ), High impact polystyrene (HIPS), acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / butadiene / styrene copolymer (MBS resin), methyl methacrylate・ Acrylonitrile / butadiene / styrene copolymer (MABS resin), acrylonitrile / acrylic rubber / styrene copolymer (AAS resin), acrylonitrile / ethylene propylene rubber / styrene copolymer (AES resin), and styrene / IPN rubber copolymer Heavy Resin body and the like, or, mixtures thereof. Further, it may have stereoregularity such as syndiotactic polystyrene.
In addition, aromatic vinyl monomers can be widely used in place of the above styrene. Among these, acrylonitrile / butadiene / vinyl aromatic copolymer (ABS resin), acrylonitrile / vinyl aromatic copolymer (AS resin), acrylonitrile / ethylene propylene copolymer / vinyl aromatic copolymer (AES resin) Polybutadiene-containing vinyl aromatic copolymers are preferred.
Examples of the method for producing these styrene resins include known methods such as an emulsion polymerization method, a solution polymerization method, a suspension polymerization method, and a bulk polymerization method.

  The styrene / (meth) acrylonitrile copolymer is preferably a graft copolymer obtained by graft polymerization of at least a styrene monomer and (meth) acrylonitrile in the presence of rubber, and at least a styrene copolymer in the presence of rubber. Examples thereof include a graft copolymer obtained by polymerizing a monomer and (meth) acrylonitrile, and a copolymer composition comprising a copolymer obtained by polymerizing at least a styrene monomer and (meth) acrylonitrile. .

[Polyolefin]
Polyolefins include polypropylene, polyethylene, polybutene, polyhexene, poly-3-methyl-1-butene, poly-4-methyl-1-pentene, ethylene / propylene copolymer, ethylene / butene copolymer, and ethylene / octene copolymer. Polymer, propylene / butene copolymer, propylene / octene copolymer, ethylene / propylene / butene copolymer, ethylene / propylene / diene copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer Etc.

〔polyester〕
Examples of the polyester include polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).

(Recovery method)
Below, the method to collect | recover polycarbonate (polymer alloy) from the molded article which consists of polycarbonate (polymer alloy) of this invention is demonstrated.
The polycarbonate (polymer alloy) recovery method to which the molding method of the present invention is applied includes a crushing step for crushing a molded product to make a crushed product, and removing a foreign layer from the thermoplastic resin substrate in the crushed product in a washing tank. A recovery step for removing and recovering the thermoplastic resin, and, if necessary, a fine particle removal step for controlling the crushed material or the recovered thermoplastic resin so as not to substantially contain fine particles having a size of 0.71 mm or less. Consists of. Moreover, the drying process may be included at the end of all the processes.
It is preferable to include a step of controlling the crushed material so as not to substantially contain fine particles in the recovery step, and a step of controlling so that the recovered thermoplastic resin does not substantially contain fine particles. “Substantially no fine particles are included in the crushed material in the recovery step” means that even if fine particles are mixed, the alkali cleaning time does not become 10% or longer than when no fine particles are present. “The thermoplastic resin is substantially free of fine particles” means that even if fine particles are mixed, a homogeneous molded product can be obtained as in the case of molding the thermoplastic resin having no fine particles. To do.
The step of controlling the content of fine particles may be controlled so as not to contain fine particles in the crushing step, or may be a step of removing fine particles by various classification means outside the washing tank after crushing. In the tank, it may be a step of removing fine particles in accordance with a draining operation such as a surfactant aqueous solution, an alkaline aqueous solution, a peroxide aqueous solution, or washing water. An operation of removing fine particles from the thermoplastic resin may be performed.

[Heterogeneous layer]
The “heterogeneous layer” provided on a base material made of a thermoplastic resin to be collected (hereinafter also simply referred to as “resin base material”) is a layer having a different chemical composition from the resin base material. . In many cases, the “heterogeneous layer” provided on the substrate is often a functional layer having a specific function. Examples of functional layers include recording materials, particularly coating layers or vapor deposition layers for digital recording that are useful as optical recording materials, including dye-containing layers, metal reflective layers, photosensitive layers, protective layers and subbing layers. Examples of other functional layers include coating layers, hard coat layers, antireflection layers, antiglare layers, viewing angle widening layers, ultraviolet ray prevention layers, heat ray absorption layers, heat ray reflection layers, electromagnetic wave absorption layers, and electromagnetic wave reflection layers. Examples thereof include a layer, an adhesive layer, a pressure-sensitive adhesive layer, and a cellulose derivative layer.

Cyanine dyes and the like are widely used for the dye-containing layer, and gold, silver, or inexpensive aluminum vapor deposition layers having excellent reflection characteristics are frequently used for the metal reflective layer. As the photosensitive layer, a silver halide emulsion layer or a non-silver salt photosensitive layer such as a photopolymer layer or a photosensitive diazo compound layer is used.
For the protective layer, the undercoat layer, and the like, a copolymer such as a thermoplastic acrylic ester, an acrylic ester monomer or a methacrylic ester monomer having excellent optical properties is used. Furthermore, a salicylic acid-based compound such as benzophenone-based, benzotriazole-based or phenyl salicylate is used for the protective layer, and an ultraviolet curing agent is also used. As the undercoat layer, hardened gelatin, thermosetting resin, or the like can be used.
The thickness of the heterogeneous layer varies depending on its function, but it is preferably 150 μm or less, more preferably 0.5 to 100 μm or less.

[Crushing process]
Said crushing process is a process of crushing the molded article which provides a heterogeneous layer in a thermoplastic resin, and making it a crushing thing.
By crushing the molded product into a pulverized product of an appropriate size in advance by this crushing step, the cleaning efficiency can be improved. Further, by recovering the resin from the crushed material having an appropriate size, the recovered thermoplastic resin fragments can be easily reused. That is, the recovered resin can be easily re-pelletized, and can be thermoformed without going through the re-pelletizing step.
If the pulverized product contains fine particles of 0.71 mm or less, the washing process becomes inefficient and is not preferable for thermoforming the recovered resin.

[Washing process]
Said washing | cleaning is a process of wash | cleaning the said molded product which was crushed. Here, “cleaning” means washing and cleaning the resin base material, but it is not limited to removing foreign substances (contaminants) on the resin base material, but removing a foreign layer provided on the resin base material. It is meant to include.

Hereinafter, a method for recovering polycarbonate (polymer alloy) from a molded product having a heterogeneous layer on a resin substrate will be described.
The above recovery method employs a washing step in which a heterogeneous layer, usually a functional layer having a specific function, provided on a resin substrate of a molded product that has been crushed in advance, is preferably removed in an alkaline aqueous solution. Usually, it includes a step for removing the used alkaline aqueous solution from the resin substrate or the like (usually referred to as “water washing step” for washing off with water) and a drying step.

  Caustic alkali can be used for the preparation of an aqueous alkali solution preferably used in the washing step, where “caustic alkali” means an alkali metal hydroxide or carbonate, such as lithium hydroxide. Sodium hydroxide, sodium carbonate, potassium carbonate and the like. In addition to caustic, a surfactant and a peroxide may be used in combination as necessary.

In the washing step using the alkaline aqueous solution, an alkaline solution having a pH of 10 to 14 is preferably used. The pH can be adjusted by using a pH meter, or by using a conductivity meter in place of the pH meter.
The concentration of sodium hydroxide is generally 0.1% by weight or more, but is preferably 0.1 to 30% by weight, more preferably 0.4 to 20% by weight.
The concentration of sodium hydroxide used depends on the type of resin substrate to be recovered, the washing temperature, and the like. For example, in the washing treatment of a polycarbonate substrate, generally 0.1 to 20% by weight of sodium hydroxide is preferable, and 0.1 to 10% by weight of sodium hydroxide is more preferable. Moreover, in the washing | cleaning process of a polyester base material, 0.1 to 4 weight% is preferable and 0.1 to 3 weight% is more preferable.
In the washing treatment of the polyolefin substrate, 1 to 20% by weight of sodium hydroxide can be preferably used. In the washing treatment of the polyamide base material, 1 to 20% by weight of sodium hydroxide is preferable. In the washing treatment of the styrene resin substrate, 1 to 10% by weight of sodium hydroxide is preferable.
It is preferable to use a caustic alkali having a low ionic strength if it can be adjusted to the same pH value.

  The step of removing the heterogeneous layer from the thermoplastic resin in the aqueous alkali solution is preferably performed at 75 ° C. or higher, usually 75 to 180 ° C., preferably 105 ° C. or higher, usually 105 to 160 ° C. It is particularly preferred to use

  A surfactant may be used for removing the foreign layer (film). Surfactants include nonionic surfactants, anionic surfactants and cationic surfactants, and the surfactants used are preferably nonionic surfactants and anionic surfactants. As the nonionic surfactant, for example, polyethylene glycol ethers, in particular, polyethylene glycol ethers of higher alcohols, polyethylene glycol ethers of alkylphenols, and the like are preferably used. Moreover, examples of the anionic surfactant include sodium alkylbenzene sulfonate, and preferably used in combination with a nonionic surfactant. The concentration of the surfactant is preferably 0.001 to 10% by weight, more preferably 0.001 to 5% by weight, and particularly preferably 0.01 to 1% by weight. The surfactant is useful for removing pigments and fine foreign substances adhering to the waste as a collected raw material or removed and reattached in the treatment liquid.

  In order to remove paints and dyes, an organic solvent, for example, a poor solvent for the substrate such as methanol, ethanol, isopropyl alcohol, glycerin and methyl solosolve can be used in combination.

  Further, the method for removing the coating on the resin substrate includes a vertical cylindrical body, a liquid draining plate having a narrow angle of 10 to 30 degrees and a plane perpendicular to the center axis of the body provided below the body. A resin base material having a coating on the surface is placed in a cleaning container having a stirring blade provided in the vicinity of the liquid cutting board above the liquid cutting board, and the resin base material deposited in the cleaning container A coating removal step of stirring the alkaline aqueous solution in an amount that makes the liquid level higher than the upper part and the resin base material at a rotational speed of 2 to 100 m / sec at the tip of the stirring blade at 75 to 180 ° C., and from the resin base material It is preferable to set it as the process of removing alkaline aqueous solution.

  In the cleaning treatment, substantially removing the functional layer means removing the functional layer from the substrate by 50% by weight or more, preferably 80% by weight or more, more preferably 95% by weight or more.

In order to heat the cleaning liquid to 100 ° C. or higher, preferably 105 ° C. or higher, it is usually heated by steam or hot water of 1 atm or higher, a burner or electric heat. In this case, it is preferable to use a pressure type cleaning device, and it is preferable to use a high pressure resistant (0.2 to 0.5 MPa = ^{2 to 5} kgf / cm ² ) cleaning device. The washing time is 5 to 150 minutes (5 to 150 minutes), preferably 5 to 100 minutes, and more preferably 10 to 60 minutes.

Further, although it can be applied to a cleaning treatment of less than 100 ° C., the cleaning treatment with an alkaline aqueous solution of 105 ° C. or more can be carried out in two or more stages, preferably in two or three stages. You may use combining the alkali washing process of 105 degreeC or more, and the alkali washing process below 100 degreeC.
By adopting a two-stage alkaline cleaning process that removes the extraneous layer by another alkaline cleaning process following the first alkaline cleaning process, the reusable high-quality can be achieved with a relatively short total cleaning time. Synthetic resins and the like can be recovered. In the treatment of two or more stages of caustic, cleaning can be performed by changing the alkali concentration, temperature or chip density of the aqueous alkali solution in each stage. A liquid draining process or a water washing process can be performed between the plurality of alkali cleaning steps as required.

  In the above recovery method, it is preferable to wash the resin substrate with an aqueous solution containing a peroxide following the alkali washing. In this case, examples of the peroxide used for cleaning include an oxide having an —O—O— bond and a metal oxide having a polyvalent valence. Preferred are hydrogen peroxide and its salt, ozone, persulfuric acid and its salt, and the like. The concentration of the peroxide is preferably 0.1 to 10% by weight. Moreover, it is preferable that the temperature of peroxide aqueous solution is 65-95 degreeC, and it is more preferable that it is 80-90 degreeC. Peroxides are useful for complete removal of residual metals and dyes. A solution of 0.1 to 10% by weight of hydrogen peroxide has a pH of 2 to 5 (weakly acidic) and can be preferably used as a final cleaning solution for removing trace alkaline cleaning solution.

[Drying process]
It refers to a treatment in which a treated chip is heated to a temperature of 50 to 200 ° C., preferably 80 to 120 ° C., and dried until the moisture content is preferably 2% by mass or less, further 1% by mass or less. In order to re-melt and produce recycled pellets, it is better to vacuum dry to make the water content 0.2% by weight or less.

Although the above-mentioned recovery method is not provided with a heterogeneous layer on the thermoplastic resin substrate, it can also be applied to a molded product in which foreign matter adheres to the thermoplastic resin substrate.
Here, the foreign substance is a substance different from the thermoplastic resin substrate, and includes a substance that contaminates the substrate such as oil. In addition, alkaline cleaning is not always necessary to remove foreign substances, and cases where a treatment with an aqueous surfactant solution capable of dissolving or solubilizing contaminants is sufficient.

(Molding method)
As the molding method of the present invention, a molding method generally used for a thermoplastic resin composition can be applied. For example, injection molding, injection blow molding, injection compression molding, blow molding, extrusion molding, thermoforming, rotational molding, hollow Either molding or sheet molding can be applied. It is particularly suitable for applications such as injection molding, hollow molding, and sheet molding. Moreover, you may shape | mold by adding additives, such as a stabilizer, a ultraviolet absorber, a mold release agent, or a coloring agent, as needed.

(Recovery method)
The molded product to which foreign matters such as oil adhered was crushed using a rotary crusher, then washed with a nonionic surfactant aqueous solution, and dried by heating to recover an aromatic polycarbonate (polymer alloy).

(Molding method)
Using Toshiba Machine Co., Ltd. injection molding machine IS100GN (clamping force 1010kN), using a square sheet mold whose thickness changes in three stages, the molding temperature is 280 ° C and the mold temperature is 80 ° C. Resin was molded.
The shape of the above-mentioned square sheet mold is 150 × 150 square as a whole, and the wall thickness in the flow direction is 3mm (back), 2mm (bottom), 1mm (buttock) at the front. It is the shape of thickness division.

(Evaluation methods)
The molded product obtained by injection molding was dried under reduced pressure at 120 ° C. for 3 hours, and then an aluminum film was directly deposited without a primer. For the deposition of aluminum, UEP manufactured by ULVAC was used. That is, aluminum (purity 99.99%) is heated by an electron beam method in a vacuum chamber maintained in a vacuum state of 8 × 10 ⁻⁵ Pa (Pascal), and vapor-deposited with a thickness of 100 μm on a molded product. I let you.
After the treatment, the mixture was allowed to stand at room temperature for 24 hours, and then a cross-cut tape method according to JIS K5400 was performed to evaluate the adhesion of the deposited film to the cloth. That is, after the surface was notched by 50 squares at intervals of 3 mm with a grid notch having razor teeth, an adhesive tape was applied, the tape was peeled off in the vertical direction, and the above evaluation was performed.

(Measuring method of melting relaxation time)
The measurement sample was preheated at 300 ° C. for 5 minutes using a dedicated spacer having a diameter of 50 mm, then pressed at 50 kg / mm ² for 3 minutes, and then cooled with a water-cooled press to form a sample pellet. The pellets were then dried for 5 hours at 120 ° C. under vacuum.
Subsequently, the sample pellet was measured using a mechanical spectrometer RMS800 type (manufactured by Rheometrics), parallel plate: diameter 50 mm, strain: 5%, frequency: 0.015 to 100 rad / sec, sample gap: 1.5 mm. Under the conditions, the temperature was maintained at 230 ° C., and the storage elastic modulus G ′ and the loss elastic modulus G ″ were measured.

  From the storage elastic modulus G ′, loss elastic modulus G ″ obtained by the above measuring method, and the frequency ω (rad / sec) used for the measurement, the melting relaxation time τ (sec / rad) is obtained by the following equation (6). It was.

(Measurement method of branching degree)
GPC-RI / Viscometer / MALLS (Aliance 2000CV: Nippon Waters Co., Ltd., DAWN-DSP: Wyatt Technology), mobile phase: chloroform, flow rate: 1.0 ml / min, temperature: 40 ° C., column: TSKgel GMH _{Under the conditions of HR-} H, injection amount: 0.332 ml, concentration: about 2 mg / ml, the weight average molecular weight, mean square radius, viscosity, and differential refractive index were measured for each fraction separated by molecular weight. The branching degree n _i per molecule and the branching degree λ _i per 1,000 units of the monomer of the aromatic dihydroxy compound were determined, and the branching degree λ _w per 1,000 units of the monomer of the aromatic dihydroxy compound was determined.

(Comparative Example 1: Sample 1)
A polycarbonate “Iupilon H3000R” (molecular weight: 19700, melting relaxation time: 0.034 rad / sec) manufactured by Mitsubishi Engineering Plastics was molded by the above molding method to obtain a molded product <1>.
Aluminum vapor deposition was performed on the molded product <1> under the above conditions, and the adhesion between the vapor deposition film and the fabric was evaluated.
As a result, in the case of the molded product <1>, zero peeling was observed at the former and the second part, and one peeling was observed at the buttocks.
As for the molecular weight at this time, the molecular weight of the molded product <1> is 19300 with respect to the molecular weight 19700 of the initial raw material, and it can be seen that the molecular weight deterioration due to molding occurs.

(Comparative Example 2: Sample 2)
Next, the recovered molded product <1> was subjected to injection molding in the same manner as in Comparative Example 1 to obtain a molded product <2>.
As a result, in the case of the molded product <2>, as in the molded product <1>, there were zero peelings in the upper part, but 5 peelings were observed in the second part and 20 peelings were observed in the buttocks. .
As for the molecular weight at this time, the molecular weight of the molded product <2> is 19100 with respect to the molecular weight 19700 of the initial raw material, and it can be seen that the molecular weight deterioration due to molding occurs as in the molded product <1>.

(Comparative Example 3: Sample 3)
50 parts of polycarbonate <Iupilon ML300> (molecular weight: 22000) manufactured by Mitsubishi Engineering Plastics Co., Ltd., which has a higher molecular weight than the molded product <1>, is blended with 50 parts of the collected molded product <1>. The molecular weight was adjusted to about 19700, which is the molecular weight of the initial raw material, and the same experiment as in Comparative Example 1 was performed. As a result, peeling was observed at zero in the upper part, 7 in the second part, and 15 in the buttock.

(Example 1: Sample 4)
50 parts of the recovered molded product <1> is blended with 50 parts of polycarbonate “Novalex M7022A” (molecular weight: 22000) manufactured by Mitsubishi Engineering Plastics as a raw material for adjusting the melting relaxation time, thereby forming a melting relaxation time. When the product was adjusted so as to have a product <1> and the above-described molding and evaluation were performed, the peeling at the former and the buttock was zero, and the peeling at the buttock was observed at three points.

(Example 2: Sample 5)
Melting relaxation time is molded by blending 25 parts of polycarbonate “Novalex M7027A” (molecular weight: 27000) made by Mitsubishi Engineering Plastics as a raw material for adjusting the melting relaxation time to 75 parts of the recovered molded product <1>. When it was adjusted so as to have a product <1> and the above molding and evaluation were performed, no peeling was observed in any of the former, the second and the buttocks.

(Example 3: Sample 6)
50 parts of the recovered molded product <1> is blended with 50 parts of polycarbonate “Novalex M7020A” (molecular weight: 16800) manufactured by Mitsubishi Engineering Plastics as a raw material for adjusting the melting relaxation time, thereby forming a melting relaxation time. When it was blended so as to be about product <1> and subjected to the above molding and evaluation, peeling at the upper and second parts was zero, and peeling at three parts was observed at the buttocks.

(Example 4: Sample 7)
25 parts of polycarbonate “SYK T6181” (molecular weight: 27500) manufactured by Mitsubishi Engineering Plastics Co., Ltd. as a raw material for adjusting the melting relaxation time is added to 75 parts of the recovered molded product <1>, so that the melting relaxation time is a molded product. When it mix | blends so that it may become about <1> and performs said shaping | molding and evaluation, peeling in the former and the buttock was zero place, and peeling of one place was observed in the buttocks.

(Comparative Example 4: Sample 8)
80 parts by weight of polycarbonate “Iupilon S2000” manufactured by Mitsubishi Engineering Plastics Co., Ltd. and 20 parts by weight of polybutylene phthalate “Novadur 5010” manufactured by Mitsubishi Engineering Plastics Co., Ltd. The mixture was kneaded at a temperature of 0 ° C., and a molded product <3> was obtained by the above molding method.
When the above-mentioned evaluation was performed on the molded product <3>, peeling was observed at 1 place on the upper part, 10 places on the back part, and 15 places on the buttocks part.

(Comparative Example 5: Sample 9)
The collected molded product <3> was crushed by the same method as in Comparative Example 2, and then molded product <4> was obtained by the above molding method.
When the above-mentioned evaluation was performed on the molded product <4>, peeling was observed at 3 places on the upper part, 27 places on the back part, and 33 places on the buttocks part.

(Example 5: Sample 10)
Next, 32 parts of branched polycarbonate “Novalex M7027A” and 8 parts by weight of polybutylene terephthalate “Novadur 5010” are blended and kneaded with 60 parts by weight of the collected molded article <4>, and the molded article <5> was obtained.
When the above-mentioned evaluation was performed on the molded product <5>, peeling was observed at 1 place on the upper part, 5 places on the back part, and 14 places on the buttocks part.

(Comparative Example 6: Sample 11)
A molded product <6> was obtained in the same manner as in Example 5 except that “NOVAREX M7027A” was changed to “S2000”.
When the above-mentioned evaluation was performed on the molded product <6>, peeling was observed at 3 places on the upper part, 20 places on the back part, and 25 places on the buttocks part.

  Hereinafter, Table 1 shows the results of Examples 1 to 5 and Comparative Examples 1 to 6 (Samples 1 to 11), and Table 2 shows the degree of branching of the raw materials used.

From the above results, the aromatic polycarbonate (A) as the initial raw material is determined by blending the branched aromatic polycarbonate with the polycarbonate recovered from the molded product or the polymer alloy thereof, and the melting relaxation time of the resulting mixed aromatic polycarbonate (polymer alloy). By adjusting the melt relaxation time to 0.7 times or more or 1.05 times or more of the melt relaxation time of the recovered polycarbonate (polymer alloy), the material of the deposited film in the molded product is formed. Adhesion with was improved.

Claims (10)

Aromatic polycarbonate (B) is recovered from a molded article having foreign matter or a foreign layer on a substrate made of aromatic polycarbonate (A),
The melting relaxation time of the mixed aromatic polycarbonate (D) obtained by blending the branched aromatic polycarbonate (C) with the aromatic polycarbonate (B) is 0.7 times or more the melting relaxation time of the aromatic polycarbonate (A). Or after adjusting to be at least 1.05 times the melting relaxation time of the aromatic polycarbonate (B),
A method for molding an aromatic polycarbonate, comprising molding. Foreign matter is present on a substrate made of a polymer alloy (F) containing 20 parts by weight or more and less than 100 parts by weight of the aromatic polycarbonate (A) and 80 parts by weight or less of a thermoplastic resin (E) other than the aromatic polycarbonate. Or the polymer alloy (G) is recovered from a molded article having a heterogeneous layer,
The melting relaxation time of the mixed polymer alloy (I) obtained by blending the branched aromatic polycarbonate (H) with the polymer alloy (G) is 0.7 times or more the melting relaxation time of the aromatic polycarbonate (A), or , After adjusting to be at least 1.05 times the melting relaxation time of the polymer alloy (G),
A method for molding an aromatic polycarbonate polymer alloy, comprising molding.   The molding method according to claim 1 or 2, wherein the branched aromatic polycarbonate (C or H) has a degree of branching of 1.5 to 10 per 1,000 units of the monomer of the aromatic dihydroxy compound.   The molding method according to any one of claims 1 to 3, wherein the branched aromatic polycarbonate (C or H) has a degree of branching of 2.5 to 5.0 per 1,000 units of the monomer of the aromatic dihydroxy compound.   The thermoplastic resin (E) is an acrylonitrile / butadiene / vinyl aromatic copolymer, an acrylonitrile / vinyl aromatic polymer, an acrylonitrile / ethylene propylene copolymer / vinyl aromatic polymer, or a polybutadiene-containing vinyl aromatic polymer. The molding method according to claim 2, wherein the molding method is at least one styrenic resin selected from the group consisting of:   Heterogeneous layer is dye-containing layer, metal reflective layer, photosensitive layer, protective layer, undercoat layer, paint layer, hard coat layer, antireflection layer, antiglare layer, viewing angle widening layer, ultraviolet ray prevention layer, heat ray absorption The shaping | molding method as described in any one of Claims 1-5 selected from the group which consists of a layer, a heat ray reflective layer, an electromagnetic wave absorption layer, an electromagnetic wave reflection layer, an adhesive bond layer, an adhesive layer, and a cellulose derivative layer. It is the shaping | molding method as described in any one of Claims 1-6,
A molding method characterized by injection molding.   The molded product formed by the shaping | molding method as described in any one of Claims 1-7. Aromatic polycarbonate (B) is recovered from a molded article having foreign matter or a foreign layer on a substrate made of aromatic polycarbonate (A),
A mixed aromatic polycarbonate (D) obtained by blending the aromatic polycarbonate (B) with a branched aromatic polycarbonate (C), the melting relaxation time of which is 0 of the melting relaxation time of the aromatic polycarbonate (A). Mixed aromatic polycarbonate (D) that is 7 times or more or 1.05 times or more of the melting relaxation time of the aromatic polycarbonate (B). Foreign matter is present on a substrate made of a polymer alloy (F) containing 20 parts by weight or more and less than 100 parts by weight of the aromatic polycarbonate (A) and 80 parts by weight or less of a thermoplastic resin (E) other than the aromatic polycarbonate. Or the polymer alloy (G) is recovered from a molded article having a heterogeneous layer,
A mixed polymer alloy (I) obtained by blending the branched aromatic polycarbonate (H) with the polymer alloy (G), the melting relaxation time of which is 0. 0 of the melting relaxation time of the aromatic polycarbonate (A). Mixed polymer alloy (I) which is 7 times or more, or 1.05 times or more of the melting relaxation time of the polymer alloy (G).