JP2014159542A - Game machine member, partition, touch panel, sheet for card, keyboard component, button component, switch component, building window or vehicle window - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a game machine member, a partition, a touch panel, a sheet for cards, a keyboard component, a button component, a switch component, a building window or a vehicle window, which has high surface hardness and excellent impact resistance.SOLUTION: The game machine member, the partition, the touch panel, the sheet for cards, the keyboard component, the button component, the switch component, the building window or the vehicle window comprises a polycarbonate resin composition which contains, at the least, a polycarbonate resin (i) having a specific structural unit and another polycarbonate resin (ii) having another specific structural unit by 90/10 to 10/90 of a mass ratio of the polycarbonate resin (i) to the polycarbonate resin (ii).

Description

  The present invention relates to gaming machine members, partitions, touch panels, card sheets, keyboard parts, button parts, switch parts, building windows or vehicle windows, and in particular, high surface hardness, scratch resistance and impact resistance. The present invention relates to a gaming machine member, a partition, a touch panel, a card sheet, a keyboard part, a button part, a switch part, a building window, or a vehicle window using a polycarbonate resin composition excellent in balance.

  Polycarbonate resins are excellent in mechanical strength, electrical properties, transparency, and the like, and are widely used as engineering plastics in various fields such as the electrical / electronic equipment field and the automotive field.

However, since the surface hardness of polycarbonate resin is lower than that of glass, it is inferior in scratch resistance, and when it is wiped with a cloth or handled roughly, the surface is easily scratched, and it is desired to have scratch resistance.
Conventionally, in order to improve the scratch resistance, various coatings have been applied to the surface of the polycarbonate resin molded product. However, in the processing such as coating, since processing costs and labor are required, It is desired to impart scratch resistance to the polycarbonate resin molded article itself by improving the composition of the polycarbonate resin composition.

Further, as techniques for increasing the hardness of the polycarbonate resin composition itself, polycarbonate resin blended with silicone oil (Patent Document 1), silicone compound or other slidable filler blended (Patent Document 2), biphenyl A compound, anti-plasticizer such as terphenyl compound, polycaprolactone, etc. (Patent Document 3) has been proposed, but the surface hardness is improved to some extent and the transparency is good, but the impact resistance is not sufficient There wasn't.
Patent Document 4 proposes a method of improving impact resistance by blending an acrylic elastomer and a polyester resin with an aromatic polycarbonate resin. However, although this resin composition has improved hardness and chemical resistance to some extent, transparency is lowered and both hardness and impact resistance are not satisfactory.

For example, there is a gaming machine such as a pachinko machine that requires high scratch resistance and impact resistance. For gaming machines, polycarbonate balls are used because many parts, such as game ball storage dishes, supply dishes, mechanism plates, etc., are made of resin molded products and have excellent resistance to impact forces from game balls. . However, in applications that are constantly exposed to such object collisions, handled in a messy manner, or rubbed with objects, conventional polycarbonate resin materials have surface hardness, scratch resistance, and impact resistance. Is not enough.
Also, in applications such as touch panels, partitions, windows for buildings, and vehicles, polycarbonate resin materials having high surface hardness and excellent scratch resistance and impact resistance are required, as in gaming machines. For these applications, it is difficult to say that the performance of the conventional polycarbonate resin material is sufficient.
Furthermore, materials having high surface hardness and scratch resistance are required for keyboard parts, button parts, switch parts, etc. provided in electrical and electronic equipment, OA equipment, information terminal equipment, machine parts, control equipment, home appliances, etc. is there. In the case of these parts, human nails are often directly touched, and higher scratch resistance is required.

  On the other hand, in the use of plastic cards such as magnetic stripe cards, contact type with IC chips, and non-contact type IC cards used in the fields of credit cards, transportation cards, ID cards, bank cards, embossed cards, etc. There is a problem of surface damage due to impact and rubbing, a material having a high surface hardness and hardly scratched, and a material excellent in impact resistance. Conventionally, polyvinyl chloride resin is used as a card material, and polycarbonate resin and polycarbonate resin alloy are also used for the purpose of improving the heat resistance and materials of polystyrene resin and polyester resin. . However, these conventional materials are not sufficient in scratch resistance and impact resistance, and materials excellent in all of surface hardness, scratch resistance and impact resistance have been desired.

JP 2004-210889 A JP 2007-51233 A JP 2007-326938 A Japanese Examined Patent Publication No. 62-37671

  In view of the above problems, the present invention provides a gaming machine using a polycarbonate resin material that has high surface hardness and has both high scratch resistance and excellent impact resistance without losing the excellent mechanical properties of the polycarbonate resin. The object is to obtain a member, partition, touch panel, card sheet, keyboard part, button part, switch part, building window or vehicle window.

As a result of intensive studies on the hardness and scratch resistance of the polycarbonate resin in order to achieve the above-mentioned problems, the present inventors have surprisingly found that those having a high surface hardness do not immediately develop a high degree of scratch resistance. The present inventors have found that a resin material composed of a specific polycarbonate resin and a specific polycarbonate resin solves the above problems, and has completed the present invention.
The present invention provides the following gaming machine members, partitions, touch panels, card sheets, keyboard parts, button parts, switch parts, building windows, or vehicle windows.

（一般式（１）中、Ｒ^１はメチル基、Ｒ^２及びＲ^３はそれぞれ独立に水素原子またはメチル基を示し、Ｘは、

のいずれかを示し、Ｒ^４及びＲ^５はそれぞれ独立に水素原子またはメチル基を示し、Ｚは、炭素原子（Ｃ）と結合し、置換基を有していてもよい炭素数６〜１２の脂環式炭素水素を形成する基を示す。）
ポリカーボネート樹脂（ｉｉ）
下記一般式（２）で表される構造単位を有する粘度平均分子量（Ｍｖ）が１６，０００〜２８，０００のポリカーボネート樹脂

（一般式（２）のＸは、前記一般式（１）と同義である。） [1] A polycarbonate resin composition containing at least the following polycarbonate resin (i) and the following polycarbonate resin (ii), wherein the mass ratio of the polycarbonate resin (i) and the polycarbonate resin (ii) is 90/10 to 10/90. Game machine parts, partitions, touch panels, card sheets, keyboard parts, button parts, switch parts, building windows or vehicle windows.
Polycarbonate resin (i)
Polycarbonate resin having a viscosity average molecular weight (Mv) of 20,000 to 35,000 having a structural unit represented by the following general formula (1)

(In the general formula (1), R ¹ represents a methyl group, R ² and R ³ each independently represents a hydrogen atom or a methyl group, and X represents

R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group, Z is bonded to a carbon atom (C), and may have a substituent and has 6 to 12 carbon atoms. The group which forms alicyclic carbon hydrogen is shown. )
Polycarbonate resin (ii)
Polycarbonate resin having a structural unit represented by the following general formula (2) and having a viscosity average molecular weight (Mv) of 16,000 to 28,000

(X in the general formula (2) has the same meaning as the general formula (1).)

[2] R ² and R ³ in formula (1) are hydrogen atom, a game machine member according to the above [1] X is an isopropylidene group, partitions, a touch panel, a sheet for card, keyboard parts, Button parts, switch parts, building windows or vehicle windows.
[3] The gaming machine member, partition, touch panel, card sheet, keyboard part, button part, switch part, building according to [1] or [2], wherein X in the general formula (2) is an isopropylidene group Window or vehicle window.
[4] A card formed using the card sheet according to any one of [1] to [3].

  According to the present invention, gaming machine members, partitions, touch panels, card sheets, keyboard parts, button parts, switch parts, which are made of a polycarbonate resin composition having a high balance between high surface hardness and scratch resistance and impact resistance, Building windows or vehicle windows can be provided.

Hereinafter, the present invention will be described in detail with reference to embodiments and examples.
In addition, in this-application specification, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit unless there is particular notice.

[Overview]
As described above, the gaming machine member, partition, touch panel, card sheet, keyboard part, button part, switch part, building window or vehicle window of the present invention is made of the polycarbonate resin (i) and the polycarbonate resin (ii). It comprises at least a polycarbonate resin composition having a mass ratio of the polycarbonate resin (i) and the polycarbonate resin (ii) of 90/10 to 10/90.
Hereafter, each component etc. which comprise the polycarbonate resin composition used for this invention are demonstrated in detail.

[Polycarbonate resin]
The polycarbonate resins used in the polycarbonate resin composition are polycarbonate resin (i) and polycarbonate resin (ii).

（一般式（１）中、Ｒ^１はメチル基、Ｒ^２及びＲ^３はそれぞれ独立に水素原子またはメチル基を示し、Ｘは、

を示し、Ｒ^４及びＲ^５はそれぞれ独立に水素原子またはメチル基を示し、Ｚは、Ｃと結合して炭素数６〜１２の、置換基を有していてもよい脂環式炭素水素を形成する基を示す。） [Polycarbonate resin (i)]
The polycarbonate resin (i) is a polycarbonate resin having at least a structural unit represented by the following general formula (1) in the molecule.

(In the general formula (1), R ¹ represents a methyl group, R ² and R ³ each independently represents a hydrogen atom or a methyl group, and X represents

R ⁴ and R ⁵ each independently represents a hydrogen atom or a methyl group, and Z represents an alicyclic carbon hydrogen having 6 to 12 carbon atoms and optionally having a substituent by bonding to C. The group to be formed is shown. )

In the general formula (1), R ¹ is a methyl group, and R ² and R ³ are each independently a hydrogen atom or a methyl group, but R ² and R ³ are particularly preferably a hydrogen atom.

である場合、Ｒ^４及びＲ^５の両方がメチル基であるイソプロピリデン基であることが好ましく、また、Ｘが、

の場合、Ｚは、上記一般式（１）中の２個のフェニル基と結合する炭素Ｃと結合して、炭素数６〜１２の二価の脂環式炭化水素基を形成するが、二価の脂環式炭素水素基としては、例えば、シキロヘキシリデン基、シクロヘプチリデン基、シクロドデシリデン基、アダマンチリデン基、シクロドデシリデン基等のシクロアルキリデン基が挙げられる。置換されたものとしては、これらのメチル置換基、エチル置換基を有するもの等が挙げられる。これらの中でも、シクロヘキシリデン基、シキロヘキシリデン基のメチル置換体（好ましくは３，３，５−トリメチル置換体）、シクロドデシリデン基が好ましい。 X is

Is preferably an isopropylidene group in which both R ⁴ and R ⁵ are methyl groups, and X is

In this case, Z is bonded to carbon C bonded to the two phenyl groups in the general formula (1) to form a bivalent alicyclic hydrocarbon group having 6 to 12 carbon atoms. Examples of the valent alicyclic carbon hydrogen group include cycloalkylidene groups such as a cyclohexylidene group, a cycloheptylidene group, a cyclododecylidene group, an adamantylidene group, and a cyclododecylidene group. . Examples of the substituted ones include those having these methyl substituents and ethyl substituents. Among these, a cyclohexylidene group, a methyl-substituted cyclohexylidene group (preferably 3,3,5-trimethyl-substituted), and a cyclododecylidene group are preferable.

Preferable specific examples of the polycarbonate resin (i) include the following polycarbonate resins (a) to (d).
A) having a 2,2-bis (3-methyl-4-hydroxyphenyl) propane structural unit, that is, a structural unit in which R ¹ is a methyl group, R ² and R ³ are hydrogen atoms, and X is an isopropylidene group What you have,
B) a 2,2-bis (3-methyl-4-hydroxyphenyl) cyclododecane structural unit, that is, a structural unit in which R ¹ is a methyl group, R ² and R ³ are hydrogen atoms, and X is a cyclododecylidene group. What you have.
C) 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane structural unit, that is, a structural unit in which R ¹ is a methyl group, R ² and R ³ are methyl groups, and X is an isopropylidene group thing,
D) 2,2-bis (3-methyl-4-hydroxyphenyl) cyclohexane structural unit, that is, having a structural unit in which R ¹ is a methyl group, R ² and R ³ are hydrogen atoms, and X is a cyclohexylidene group ,
Among these, the polycarbonate resin of the above a), b) or c), more preferably the above b) or b), and particularly b) above is preferred.

  These polycarbonate resins (i) are respectively 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) cyclododecane, and 2,2-bis. (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) cyclohexane can be used as the dihydroxy compound.

  The polycarbonate resin (i) may have a carbonate structural unit other than the structural unit represented by the general formula (1). For example, the structural unit represented by the general formula (2) (for example, derived from bisphenol-A) (Structural unit) or a structural unit derived from another dihydroxy compound as described later. The copolymerization amount of structural units other than the structural unit represented by the general formula (1) is usually 60 mol% or less, preferably 50 mol% or less, more preferably 40 mol% or less, and further 30 mol% or less. Is most preferred.

The viscosity average molecular weight (Mv) of the polycarbonate resin (i) is 20,000 to 35,000. When the viscosity average molecular weight is within this range, a molded product having good moldability and high mechanical strength can be obtained. When the viscosity average molecular weight is less than 20,000, impact resistance is deteriorated, resulting in a problem in practical use. If it exceeds 1, the melt viscosity increases, and it becomes difficult to perform injection molding or extrusion molding. The minimum of the preferable molecular weight of polycarbonate resin (i) is 22,000, More preferably, 23,000, More preferably, it is 24,000, The upper limit becomes like this. Preferably it is 33,000, More preferably, it is 32,500. .
Here, the viscosity average molecular weight (Mv) is determined using the Schnell viscosity equation, using dichloromethane as a solvent, using an Ubbelohde viscometer, and determining the intrinsic viscosity ([η]) (unit dl / g) at a temperature of 20 ° C. : Means a value calculated from the equation of η = 1.23 × 10 ⁻⁴ M ^0.83 .

  The polycarbonate resin (i) may be used singly or in combination of two or more, and may be adjusted to the above viscosity average molecular weight by mixing two or more types of polycarbonate resins having different viscosity average molecular weights. Moreover, you may mix and use the polycarbonate resin whose viscosity average molecular weight is outside said suitable range as needed.

（一般式（２）のＸは、前記一般式（１）と同義である。） <Polycarbonate resin (ii)>
The polycarbonate resin (ii) used in combination with the polycarbonate resin (i) is a polycarbonate resin having a structural unit represented by the following general formula (2).

(X in the general formula (2) has the same meaning as the general formula (1).)

A preferred specific example of the polycarbonate structural unit represented by the general formula (2) is 2,2-bis (4-hydroxyphenyl) propane, that is, a carbonate structural unit derived from bisphenol-A.
The polycarbonate resin (ii) may have a carbonate structural unit other than the structural unit represented by the general formula (2), and may have a carbonate structural unit derived from another dihydroxy compound. The copolymerization amount of structural units other than the structural unit represented by the general formula (2) is usually preferably less than 50 mol%, more preferably 40 mol% or less, further 30 mol% or less, and particularly 20 mol% or less. 10 mol% or less, and most preferably 5 mol% or less.

Examples of other dihydroxy compounds include the following aromatic dihydroxy compounds.
Bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methyl Pentane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-) (1-methylethyl) phenyl) propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3- (1-methylpropyl) phenyl) propane 2,2-bis (4-hydroxy-3-cyclohexylphenyl) propane, 2,2-bis (4-hydroxy-3-phenylphenyl) propane 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) Phenylmethane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3) -(1-methylethyl) phenyl) cyclohexane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3- (1-methylpropyl) phenyl) Cyclohexane, 1,1-bis (4-hydroxy-3-cyclohexylphenyl) cyclohexane, 1,1- (4-hydroxy-3-phenylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) ) -1-phenylethane, 1,1-bis (4-hydroxy-3- (1-methylethyl) phenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3- (1-methylpropyl) phenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-cyclohexylphenyl) -1- Phenylethane, 1,1-bis (4-hydroxy-3-phenylphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclopent Tan, 1,1-bis (4-hydroxyphenyl) cyclooctane, 4,4 ′-(1,3-phenylenediisopropylidene) bisphenol, 4,4 ′-(1,4-phenylenediisopropylidene) bisphenol, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 4,4′-dihydroxybenzophenone, 4,4′-dihydroxyphenyl ether, 4,4 '-Dihydroxybiphenyl, 1,1-bis (4-hydroxyphenyl) -3,3-5-trimethylcyclohexane, 1,1-bis (4-hydroxy-6-methyl-3-tert-butylphenyl) butane, etc. Can be mentioned.

The viscosity average molecular weight (Mv) of the polycarbonate resin (ii) is 16,000 to 28,000. When the viscosity average molecular weight is within this range, a molded product having good moldability and high mechanical strength can be obtained. When the viscosity average molecular weight is less than 16,000, the surface impact resistance is remarkably lowered, so that the use becomes difficult. If it exceeds 28,000, the melt viscosity increases, making injection molding or extrusion molding difficult. The lower limit of the preferred molecular weight of the polycarbonate resin (ii) is 17,000, more preferably 18,000, and the upper limit thereof is preferably 27,000.
The definition of the viscosity average molecular weight (Mv) is as described above.

  The polycarbonate resin (ii) may be used alone or in combination of two or more, and may be adjusted to the above viscosity average molecular weight by mixing two or more types of polycarbonate resins having different viscosity average molecular weights. Moreover, you may mix and use the polycarbonate resin whose viscosity average molecular weight is outside said suitable range as needed.

<Production method of polycarbonate resin>
The method for producing the polycarbonate resin used in the present invention is not particularly limited, and any method can be adopted. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.
Hereinafter, a particularly preferable one of these methods will be specifically described.

-Interfacial polymerization method First, the case where a polycarbonate resin is manufactured by the interfacial polymerization method will be described.
In the interfacial polymerization method, in the presence of an organic solvent inert to the reaction and an alkaline aqueous solution, the pH is usually kept at 9 or more, and each dihydroxy compound and a carbonate precursor (preferably phosgene) are reacted, followed by polymerization. A polycarbonate resin is obtained by performing interfacial polymerization in the presence of a catalyst. In the reaction system, a molecular weight adjusting agent (terminal terminator) may be present if necessary, and an antioxidant may be present for the purpose of preventing oxidation of the dihydroxy compound.

  Examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene; It is done. In addition, 1 type may be used for an organic solvent and it may use 2 or more types together by arbitrary combinations and a ratio.

Examples of the alkali compound contained in the alkaline aqueous solution include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate. Among them, sodium hydroxide and Potassium hydroxide is preferred. In addition, an alkali compound may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
Although there is no restriction | limiting in the density | concentration of the alkali compound in alkaline aqueous solution, Usually, in order to control pH in the alkaline aqueous solution of reaction to 10-12, it is used at 5-10 mass%. For example, when phosgene is blown, the molar ratio of the bisphenol compound and the alkali compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. In particular, it is preferably set to 1: 2.0 or more, usually 1: 3.2 or less, and more preferably 1: 2.5 or less.

  Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic rings such as N, N′-dimethylcyclohexylamine and N, N′-diethylcyclohexylamine. Tertiary amines; aromatic tertiary amines such as N, N′-dimethylaniline and N, N′-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride and triethylbenzylammonium chloride Pyridine; guanine; guanidine salt; and the like. In addition, 1 type may be used for a polymerization catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

Examples of the molecular weight modifier include aromatic phenols having a monovalent phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides, and the like. Among them, aromatic phenols are preferable.
Specific examples of such aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. Examples thereof include substituted phenols; vinyl group-containing phenols such as isopropanyl phenol; epoxy group-containing phenols; carboxyl group-containing phenols such as o-oxinebenzoic acid and 2-methyl-6-hydroxyphenylacetic acid; In addition, a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The usage-amount of a molecular weight modifier is 0.5 mol or more normally with respect to 100 mol of dihydroxy compounds, Preferably it is 1 mol or more, and is 50 mol or less normally, Preferably it is 30 mol or less. By making the usage-amount of a molecular weight modifier into this range, the thermal stability and hydrolysis resistance of a polycarbonate resin composition can be improved.

In the reaction, the order of mixing the reaction substrate, reaction medium, catalyst, additive and the like is arbitrary as long as a desired polycarbonate resin is obtained, and an appropriate order may be arbitrarily set. For example, when phosgene is used as the carbonate precursor, the molecular weight modifier can be mixed at any time as long as it is from the time of the reaction (phosgenation) of the dihydroxy compound and phosgene to the start of the polymerization reaction.
In addition, reaction temperature is 0-40 degreeC normally, and reaction time is normally several minutes (for example, 10 minutes)-several hours (for example, 6 hours).

-Melt transesterification method Next, the case where polycarbonate resin is manufactured by the melt transesterification method is demonstrated. In the melt transesterification method, for example, a transesterification reaction between a carbonic acid diester and a dihydroxy compound is performed.

The dihydroxy compound is as described above.
On the other hand, examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diphenyl carbonate; substituted diphenyl carbonate such as ditolyl carbonate, and the like. Of these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable. In addition, 1 type may be used for carbonic acid diester, and it may use 2 or more types together by arbitrary combinations and a ratio.

  The ratio of the dihydroxy compound and the carbonic acid diester is arbitrary as long as the desired polycarbonate resin can be obtained, but it is preferable to use an equimolar amount or more of the carbonic acid diester with respect to 1 mol of the dihydroxy compound. It is more preferable. The upper limit is usually 1.30 mol or less. By setting it as such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.

  In the polycarbonate resin, the amount of terminal hydroxyl groups tends to have a great influence on thermal stability, hydrolysis stability, color tone, and the like. For this reason, you may adjust the amount of terminal hydroxyl groups as needed by a well-known arbitrary method. In the transesterification reaction, a polycarbonate resin in which the terminal hydroxyl group amount is adjusted can be usually obtained by adjusting the mixing ratio of the carbonic acid diester and the dihydroxy compound, the degree of vacuum during the transesterification reaction, and the like. In addition, the molecular weight of the polycarbonate resin usually obtained can also be adjusted by this operation.

When adjusting the amount of terminal hydroxyl groups by adjusting the mixing ratio of the carbonic acid diester and the dihydroxy compound, the mixing ratio is as described above.
Further, as a more aggressive adjustment method, there may be mentioned a method in which a terminal terminator is mixed separately during the reaction. Examples of the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, carbonic acid diesters, and the like. In addition, 1 type may be used for a terminal terminator and it may use 2 or more types together by arbitrary combinations and a ratio.

  When producing a polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among these, it is preferable to use an alkali metal compound and / or an alkaline earth metal compound. In addition, auxiliary compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. In addition, 1 type may be used for a transesterification catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  In the melt transesterification method, the reaction temperature is usually 100 to 320 ° C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, a melt polycondensation reaction may be performed under the conditions in this range while removing by-products such as hydroxy compounds.

  The melt polycondensation reaction can be performed by either a batch method or a continuous method. In the case of a batch system, the order of mixing the reaction substrate, reaction medium, catalyst, additive, etc. is arbitrary as long as the desired polycarbonate resin is obtained, and an appropriate order may be set arbitrarily. However, in view of the stability of the polycarbonate resin and the polycarbonate resin composition, the melt polycondensation reaction is preferably carried out continuously.

In the melt transesterification method, a catalyst deactivator may be used as necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. In addition, a catalyst deactivator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Furthermore, it is 1 mass ppm or more normally with respect to polycarbonate resin, and is 100 mass ppm or less normally, Preferably it is 20 mass ppm or less.

<Ratio of polycarbonate resin (i) and (ii)>
The mixing ratio of the polycarbonate resin (i) and the polycarbonate resin (ii) is polycarbonate resin (i) / polycarbonate resin (ii) = 90/10 to 10/90 in mass ratio of both. By using in such a mixing ratio, it becomes possible to achieve a polycarbonate resin composition excellent in the balance of high surface hardness, scratch resistance and impact resistance. When the mass ratio of the polycarbonate resin (i) is less than 10, the surface hardness of the molded product is reduced, and the surface is easily damaged when used as an actual product, and when it exceeds 90, the impact resistance of the molded product is reduced. However, it is easy to break when made into a real product.
A preferable mixing ratio is polycarbonate resin (i) / polycarbonate resin (ii) = 90 / 10-20 / 80, more preferably 90 / 10-30 / 70.

Moreover, 10 mass% or more of polycarbonate resin (i) and polycarbonate resin (ii) may be used as flaky powder in 100 mass% in total of polycarbonate resin (i) and polycarbonate resin (ii). The content ratio of the flaky powder is preferably 15% by mass or more, more preferably 20% by mass or more. By including the flaky powder at such a ratio, the additive components are prevented from being classified during the production of the composition when additives are added as necessary, as described below. It tends to be easy to obtain a molded product that suppresses agglomeration and the like and is excellent in flame retardancy, surface impact resistance and transparency. The average particle size of the flaky powder is preferably 2 mm or less, and more preferably 1.5 mm or less.
The polycarbonate resin other than the flaky powder is preferably a pellet. The pellet length is preferably 1 to 5 mm, more preferably 2 to 4 mm. When the cross section is elliptical, the major axis is 2 to 3.5 mm, the minor axis is 1 to 2.5 mm, and the section is circular. Those having a diameter of 2 to 3 mm are preferred. The length and cross-sectional shape of the pellet can be adjusted by the number of rotations of the blade of the strand cutter during the production of the polycarbonate resin, the winding speed, the discharge amount of the extruder, and the like.

The pencil hardness of the polycarbonate resin composition is preferably HB or higher. Here, the pencil hardness is measured according to JIS K5600-5-4.
When the pencil hardness is lower than HB, the surface hardness of the molded product is low, and the surface is easily damaged during use of the molded product. Among them, the pencil hardness of the polycarbonate resin composition is preferably F or higher, particularly H or higher.

  The glass transition temperature of the polycarbonate resin composition is preferably 100 to 150 ° C, and more preferably 110 to 140 ° C. When the glass transition temperature is less than 100 ° C., the heat resistance and rigidity of the molded product may be insufficient. When the glass transition temperature exceeds 150 ° C., the melt viscosity and reaction temperature when producing a polycarbonate resin by the melt transesterification method are low. It becomes higher, the impact resistance of the molded product decreases, it becomes easy to break during bending deformation, and when molding button parts etc. thickly, there is a problem of sink marks, or the card sheet or card is embossed When embossing is performed, the embossability tends to be unfavorable. The glass transition temperature refers to a glass transition temperature observed when the temperature is increased from 30 ° C. to 20 ° C./min by DSC measurement.

[Other ingredients]
The polycarbonate resin composition may contain other components other than those described above as necessary, as long as the desired physical properties are not significantly impaired. Examples of other components include resins other than polycarbonate resins and various resin additives. In addition, 1 type may contain other components and 2 or more types may contain them by arbitrary combinations and ratios.

Other resins Examples of other resins include thermoplastic polyesters such as acrylic resins such as polymethyl methacrylate and phenyl methacrylate-methyl methacrylate copolymer, polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin. Resin; polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer ( AES resin), styrene resin such as acrylonitrile-butadiene-styrene copolymer (ABS resin); polyolefin resin such as polyethylene resin and polypropylene resin; polyamide resin A polyimide resin; a polyetherimide resin; a polyurethane resin; a polyphenylene ether resin; a polyphenylene sulfide resin; and a polysulfone resin.
In addition, 1 type may contain other resin and 2 or more types may contain it by arbitrary combinations and ratios.
When other resins are contained, it is preferably 40% by mass or less, and preferably 30% by mass or less, based on the total of 100% by mass of the polycarbonate resin (i), the polycarbonate resin (ii) and the other resins. More preferably, it is more preferably 20% by mass or less. When other resins are used in a larger amount than the above range, surface hardness, scratch resistance, impact resistance, and transparency may be lowered.

Resin additives Examples of resin additives include heat stabilizers, antioxidants, mold release agents, UV absorbers, colorants, flame retardants, dyes and pigments, antistatic agents, antifogging agents, lubricants, and antiblocking agents. , Fluidity improvers, plasticizers, dispersants, antibacterial agents and the like. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.
Hereinafter, the example of an additive suitable for the polycarbonate resin composition used for this invention is demonstrated concretely.

.. Heat stabilizer Examples of the heat stabilizer include phosphorus compounds. Any known phosphorous compound can be used. Specific examples include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphoric acid Group 1 or Group 2B metal phosphates such as potassium, sodium phosphate, cesium phosphate and zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, etc. Particularly preferred.

Organic phosphite compounds include triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl Diphenyl phosphite, dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis (4,6-di- tert-butylphenyl) octyl phosphite and the like.
As such an organic phosphite compound, specifically, for example, “ADEKA STAB 1178”, “ADEKA STAB 2112”, “ADEKA STAB HP-10” manufactured by ADEKA Corporation, manufactured by Johoku Chemical Industry Co., Ltd. Examples thereof include “JP-351”, “JP-360”, “JP-3CP”, “Irgaphos 168” manufactured by BASF.
In addition, 1 type may contain the heat stabilizer and 2 or more types may contain it by arbitrary combinations and a ratio.

  Content of a heat stabilizer is 0.001 mass part or more normally with respect to a total of 100 mass parts of polycarbonate resin (i) and polycarbonate resin (ii), Preferably it is 0.01 mass part or more, More preferably, it is 0.00. It is 03 parts by mass or more, and is usually 1 part by mass or less, preferably 0.7 parts by mass or less, more preferably 0.5 parts by mass or less. If the content of the heat stabilizer is less than the lower limit value of the range, the heat stability effect may be insufficient, and if the content of the heat stabilizer exceeds the upper limit value of the range, the effect reaches a peak. And may become less economical.

.. Antioxidants Examples of antioxidants include hindered phenol antioxidants.
Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] Methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(me Citylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4- Hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis ( Octylthio) -1,3,5-triazin-2-ylamino) phenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-t rt- pentylphenyl acrylate.

Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable. As such a phenolic antioxidant, specifically, for example, “Irganox 1010”, “Irganox 1076” manufactured by BASF (trade name, the same applies hereinafter), “Adeka Stub AO-50” manufactured by ADEKA, "ADK STAB AO-60" etc. are mentioned.
In addition, 1 type may contain antioxidant and 2 or more types may contain it by arbitrary combinations and a ratio.

  Content of antioxidant is 0.001 mass part or more normally with respect to a total of 100 mass parts of polycarbonate resin (i) and polycarbonate resin (ii), Preferably it is 0.01 mass part or more, and usually 1 part by mass or less, preferably 0.5 part by mass or less. When the content of the antioxidant is less than the lower limit of the range, the effect as an antioxidant may be insufficient, and when the content of the antioxidant exceeds the upper limit of the range, There is a possibility that the effect reaches its peak and is not economical.

.. Release agent Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, polysiloxane silicone oil, and the like. Can be mentioned.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as the said aliphatic carboxylic acid can be used, for example. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable. In addition, an aliphatic includes an alicyclic compound here.

  Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. Is mentioned.

  In addition, said ester may contain aliphatic carboxylic acid and / or alcohol as an impurity. Moreover, although said ester may be a pure substance, it may be a mixture of a plurality of compounds. Furthermore, the aliphatic carboxylic acid and alcohol which combine to form one ester may be used alone or in combination of two or more in any combination and ratio.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons. Further, these hydrocarbons may be partially oxidized.

Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
The number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less.
The aliphatic hydrocarbon may be a single substance, but even a mixture of various constituent components and molecular weights can be used as long as the main component is within the above range.

In addition, 1 type may contain the mold release agent mentioned above, and 2 or more types may contain it by arbitrary combinations and a ratio.
The content of the release agent is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, and usually 100 parts by mass with respect to a total of 100 parts by mass of the polycarbonate resin (i) and the polycarbonate resin (ii). 2 parts by mass or less, preferably 1 part by mass or less. When the content of the release agent is less than the lower limit of the range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the range, hydrolysis resistance And mold contamination during injection molding may occur.

..Ultraviolet absorbers Examples of ultraviolet absorbers include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic acid ester compounds, Examples include organic ultraviolet absorbers such as hindered amine compounds. In these, an organic ultraviolet absorber is preferable and a benzotriazole compound is more preferable. By selecting the organic ultraviolet absorbent, the transparency and mechanical properties of the polycarbonate resin composition are improved.

  Specific examples of the benzotriazole compound include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl). ) Phenyl] -benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5 ′) -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2'-hydroxy-3 ', 5'-di-tert-amyl) -benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] and the like, among others, 2- (2′- Hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] And 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole is particularly preferable.

  Specific examples of such benzotriazole compounds include “Seesorb 701”, “Seesorb 702”, “Seesorb 703”, “Seesorb 704”, and “Seesorb 705” manufactured by Sipro Kasei Co., Ltd. (trade names, the same applies hereinafter). , “Seasorb 709”, “Biosorb 520”, “Biosorb 580”, “Biosorb 582”, “Biosorb 583” manufactured by Kyodo Yakuhin Co., Ltd. “Chemisorb 71”, “Chemisorb 72” manufactured by Chemipro Kasei Co., Ltd. "UV5411", ADEKA "LA-32", "LA-38", "LA-36", "LA-34", "LA-31", BASF "Tinubin P", "Tinubin 234", " Tinuvin 326 "," Tinuvin 327 "," Tinubin 328 ", etc.

The content of the ultraviolet absorber may be appropriately adjusted according to the target performance level, but is usually 0.001 part by mass or more with respect to 100 parts by mass in total of the polycarbonate resin (i) and the polycarbonate resin (ii). , Preferably it is 0.1 mass part or more, and is 1 mass part or less normally, Preferably it is 0.5 mass part or less. When the content of the UV absorber is less than the lower limit of the above range, the effect of improving the weather resistance is poor, and when the content of the UV absorber exceeds the upper limit of the above range, mold deposits or the like occur and mold contamination Easy to cause.
In addition, 1 type may contain the ultraviolet absorber and 2 or more types may contain it by arbitrary combinations and a ratio.

-Colorant Examples of the colorant include inorganic pigments, organic pigments, dyes, and the like.
Examples of inorganic pigments include carbon black, titanium oxide, barium sulfate, zinc sulfide, zinc oxide, iron oxide, lead titanate, potassium titanate, zircon oxide, antimony oxide, titanium yellow, titanium black, cobalt blue, and ultramarine blue. It is done.
Examples of the organic pigment include monoazo, condensed azo, anthraquinone, disazo, heterocycle, quinacridone, anthraquinone, perylene, monoazo, phthalocyanine and the like.
Further, examples of the dye include monoazo, anthraquinone, disazo, heterocycle, anthraquinone, perinone, thioindigo, disazo, anthraquinone and the like.

  Content of a coloring agent is 0.0001 mass part or more normally with respect to a total of 100 mass parts of polycarbonate resin (i) and polycarbonate resin (ii), Preferably it is 0.001 mass part or more, More preferably, it is 0.01. It is 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 1 part by mass or less. When the content of the colorant is less than the lower limit of the above range, it is difficult for the desired hue to be colored, and when laser marking is performed, the laser marking property may be lowered. Moreover, when exceeding the said upper limit, a mechanical physical property tends to fall and it is unpreferable.

[Production Method of Polycarbonate Resin Composition]
There is no restriction on the production method of the polycarbonate resin composition, and a production method of a known polycarbonate resin composition can be widely adopted. Polycarbonate resins (i) and (ii), and other components blended as necessary, for example, Examples thereof include a method of premixing using various mixers such as a tumbler and a Henschel mixer and then melt-kneading with a mixer such as a Banbury mixer, a roll, a Brabender, a single-screw kneading extruder, a twin-screw kneading extruder, and a kneader. The temperature for melt kneading is not particularly limited, but is usually in the range of 240 to 320 ° C.

[Molding]
The obtained polycarbonate resin composition is formed into a molded product by molding pellets obtained by pelletizing the above-described polycarbonate resin composition by various molding methods. Further, the resin melt-kneaded by an extruder can be directly molded into a molded product without going through the pellets.
The shape of the molded product is not particularly limited and can be appropriately selected according to the use and purpose of the molded product. For example, a plate shape, a plate shape, a rod shape, a sheet shape, a film shape, a cylindrical shape, an annular shape, Examples include a circular shape, an elliptical shape, a polygonal shape, an irregular shape, a hollow shape, a frame shape, a box shape, and a panel shape. Further, for example, the surface may be uneven or may have a three-dimensional curved surface. Moreover, when using as a sheet | seat, a film, plate shape, etc., the laminated body of the multilayer structure laminated | stacked with the other resin sheet may be sufficient.

  The method for molding a molded product is not particularly limited, and a conventionally known molding method can be employed.For example, an injection molding method, an injection compression molding method, an extrusion molding method, a profile extrusion method, a transfer molding method, a hollow molding method, Gas assisted hollow molding method, blow molding method, extrusion blow molding, IMC (in-mold coating molding) molding method, rotational molding method, multilayer molding method, two-color molding method, insert molding method, sandwich molding method, foam molding method , Pressure molding method, sheet molding method, thermoforming method, laminate molding method, press molding method and the like.

  Molded products have high surface hardness and excellent balance between scratch resistance and impact resistance, so that these characteristics are strictly required for gaming machine parts, partitions, touch panels, card sheets, keyboard parts, button parts, switch parts, Used as building window or vehicle window.

As gaming machine members, various members of commercial gaming machines such as pachinko machines and slot machines, such as prize ball tanks, supply dishes, storage dishes, alignment rails for arranging and flowing down prize balls, Examples include various parts installed in a ball passage such as a downflow passage through which a prize ball passes, a cover of a game board, a storage outer frame of the game machine board itself, and the like.
The partition is a partition such as a partition or a room partition as a building interior material.

  In addition, the touch panel is a touch panel as a display-integrated input device that is disposed on the front surface of the display, and examples thereof include a touch panel protective plate and a protective sheet that are pressed or touched with a finger or the like. Applications of the touch panel include, for example, car navigation systems, portable information terminals, bank ATMs, personal computer screens, touch panels for portable game machines, and the like.

  Examples of the keyboard parts, button parts, and switch parts include keyboard parts, button parts, and switch parts such as electrical and electronic equipment, OA equipment, information terminal equipment, machine parts, control equipment, and home appliances. For example, personal computers, tablet terminals, game machines, TVs, telephones, printers, copiers, scanners, fax machines, electronic notebooks and PDAs, electronic desk calculators, electronic dictionaries, cameras, video cameras, mobile phones, smartphones, recording media drives And reading devices, mouse, numeric keypad, CD player, MD player, DVD player, Blu-ray player, portable radio, portable audio player, washing machine, vacuum cleaner, microwave oven, refrigerator, various cooking appliances keyboard parts, button parts, switches Parts. In addition, navigation systems for automobiles, motorcycles, scooters, railway vehicles, aircraft, ships, etc., audio systems, vehicle control systems, control devices, keyboard parts for various operations such as cabin equipment, button parts, switch parts, and the like are also included.

The method for producing a card using the card sheet of the present invention is not particularly limited, and the card sheet may be produced by injection molding or extrusion molding, and it may be used as it is as a single layer, or these card sheets. A plurality of sheets may be stacked and punched into a card shape having a desired size. Examples of the method of stacking a plurality of card sheets include a co-extrusion molding method and a heat heat fusion method using a press machine.
The card thus obtained is easily scratched when its surface touches a human hand or comes into contact with a device. Therefore, the outermost sheet of the card has excellent surface hardness and scratch resistance. It is preferable to use the polycarbonate resin composition. In addition, from the viewpoint of impact resistance, toughness, etc., it is preferable to use polycarbonate resin (ii) for the inner layer sheet, and it is particularly preferable to use bisphenol A type polycarbonate resin.

  Since the card thickness is usually preferably 500 to 1000 μm, and preferably 700 to 900 μm, the thickness of each sheet is usually 10 to 400 μm, preferably 30 to 300 μm, and more preferably 60 to 250 μm. It is.

  The card sheet preferably has a 10-point average roughness of at least one surface (Rz measured according to 1994 version JIS B0601) of 1 to 30 μm, and more preferably 3 to 20 μm. When the 10-point average roughness is 1 μm or more, the sheet and another sheet are laminated and hot-press-fused, and when the card of the present invention is manufactured, Since the air between the sheets can be efficiently discharged, it is preferable that the card of the present invention does not contain voids or be deformed. In addition, since the slipperiness of the sheet is improved, handling properties such as winding during film formation tend to be improved. On the other hand, it is preferable that the 10-point average roughness be 30 μm or less, because the adhesion between the sheets after hot press fusion is likely to be sufficient. For example, by subjecting the surface of the sheet to mat processing, it is possible to impart a 10-point average roughness in such a range.

Examples of building windows include general buildings such as buildings and houses, and window glass such as greenhouses.
Furthermore, examples of vehicle windows include window glass and door glass for vehicles such as automobiles and buses, sunroofs, etc. Applicable to those that have been difficult to apply until now because they are easily damaged when rubbed during wiper or car wash. it can.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited to the following examples.
The raw materials used in the following examples and comparative examples are as follows.

[Polycarbonate resin]
As a polycarbonate resin corresponding to the polycarbonate resin (i), a polycarbonate resin (C-PC) according to the following production example was used.
<Manufacture of polycarbonate resin (i) (C-PC)>
2,2-bis (3-methyl-4-hydroxyphenyl) propane (hereinafter referred to as “BPC”) 26.14 mol (6.75 kg) and diphenyl carbonate 26.79 mol (5.74 kg) The reactor was placed in a SUS reactor (with an internal volume of 10 liters) equipped with a stirrer and a distillation condenser, and after the inside of the reactor was replaced with nitrogen gas, the temperature was raised to 220 ° C. over 30 minutes in a nitrogen gas atmosphere.
Next, the reaction solution in the reactor is stirred, and cesium carbonate (Cs ₂ CO ₃ ) is used as a transesterification reaction catalyst in the molten reaction solution so that the amount becomes 1.5 × 10 ⁻⁶ mol per 1 mol of BPC. In addition, the reaction solution was stirred and brewed at 220 ° C. for 30 minutes in a nitrogen gas atmosphere. Next, under the same temperature, the pressure in the reactor was reduced to 100 Torr over 40 minutes, and the reaction was further performed for 100 minutes to distill phenol.

Next, the temperature in the reactor was raised to 284 ° C. over 60 minutes and the pressure was reduced to 3 Torr, and phenol corresponding to almost the entire distillation amount was distilled. Next, the pressure in the reactor was kept below 1 Torr at the same temperature, and the reaction was further continued for 60 minutes to complete the polycondensation reaction. At this time, the stirring rotation speed of the stirrer was 38 rotations / minute, the reaction liquid temperature just before the completion of the reaction was 289 ° C., and the stirring power was 1.00 kW.
Next, the reaction solution in a molten state is fed into a twin screw extruder, and 4-fold molar amount of butyl p-toluenesulfonate is supplied from the first supply port of the twin screw extruder with respect to cesium carbonate, After kneading with the reaction solution, the reaction solution was extruded in a strand shape through a die of a twin screw extruder and cut with a cutter to obtain carbonate resin pellets.

The physical properties of the obtained polycarbonate resin (C-PC) were as follows.
Pencil hardness: 2H
Viscosity average molecular weight (Mv): 26,000

Moreover, the following polycarbonate resin (A-PC) was used as a polycarbonate resin applicable to polycarbonate resin (ii).
<Polycarbonate resin (ii) (A-PC)>
Polycarbonate resin by the interfacial method using bisphenol-A as a starting material. Product name “Iupilon S-3000” manufactured by Mitsubishi Engineering Plastics.
Pencil hardness: 2B
Viscosity average molecular weight (Mv): 21,000

In addition, the following acrylic resins were used as other resins.
<Polymethyl methacrylate resin (VH-001)>
Product name "Acrypet VH-001" manufactured by Mitsubishi Rayon Co., Ltd.
Pencil hardness: 3H
<Phenyl methacrylate / methyl methacrylate copolymer (H-880)>
Product name "Acrypet H-880" manufactured by Mitsubishi Rayon Co., Ltd.
Pencil hardness: 3H

The viscosity average molecular weight (Mv) of the polycarbonate resin was determined by dissolving the polycarbonate resin in dichloromethane (concentration 6.0 g / L) and measuring the specific viscosity (η _sp ) at 20 ° C. using an Ubbelohde viscosity tube. The viscosity average molecular weight (Mv) was calculated from the formula.
η _sp /C=[η](1+0.28η _sp)
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83

(Examples 1-2, Comparative Examples 1-4, Reference Examples 1-2)
[Production of polycarbonate resin composition pellets]
Each resin described above is blended and mixed in the composition (parts by mass) shown in Table 1 below, and kneaded at a barrel temperature of 280 ° C. by a twin-screw extruder (“TEX30XCT” manufactured by Nippon Steel Works), and pellets of a polycarbonate resin composition Got.

[Preparation of test specimen for measuring pencil hardness and scratch resistance]
After drying the above pellets at 80 ° C. for 5 hours, using an injection molding machine (“J55-60H” manufactured by Nippon Steel Co., Ltd.), conditions of cylinder set temperature of 260 to 280 ° C., mold temperature of 80 ° C., screw rotation speed of 100 rpm Below, a 90 mm × 50 mm × 3 mm thick flat test piece was injection molded. C-PC, A-PC, VH-001, and H-880 test pieces for pencil hardness measurement were also prepared in the same manner as described above.

[Creation of test pieces for impact resistance measurement]
After drying the above pellets at 80 ° C. for 5 hours, using an injection molding machine (“J55-60H” manufactured by Nippon Steel Co., Ltd.), conditions of cylinder set temperature of 260 to 280 ° C., mold temperature of 80 ° C., screw rotation speed of 100 rpm Below, an ISO multipurpose test piece (thickness 3 mm) was molded under conditions of an injection time of 2.0 sec and a molding cycle of 40 sec.

[Pencil hardness]
About the flat test piece obtained by the method described above, the pencil hardness measured with a 750 g load was determined using a pencil hardness tester (manufactured by Toyo Seiki Co., Ltd.) in accordance with JIS K5600-5-4. .

[Shock resistance]
Based on ISO179, the ISO multipurpose test piece (3 mm thickness) produced above was notched, and the Charpy impact strength with notch (unit: kJ / m ² ) was measured at 23 ° C.

[Abrasion resistance]
Using a surface abrasion tester “PA-300A” manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd., a cotton cloth was reciprocated 2000 times with an 800 g load on the surface of the flat test piece obtained above, and then subjected to an abrasion test. The haze (%) after the measurement was measured, and a value ΔHaze (%) obtained by subtracting the haze before the test was measured.
The haze was measured with an NDH6000 type haze meter manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K7136.
The above evaluation results are shown in Table 1 below.

As can be seen from Table 1, in Examples 1 and 2, the surface hardness, impact strength, and scratch resistance are all excellent in a well-balanced manner. On the other hand, in Comparative Examples 1 to 3, although the surface hardness is high, the impact resistance is poor, and all of the surface hardness, impact resistance strength, and scratch resistance cannot be satisfied. As for Comparative Example 2, it can be seen that although the acrylic resin having high pencil hardness is blended, the scratch resistance is lowered. In addition, it can be seen from Reference Examples 1 and 2 that even when an acrylic resin having a high pencil hardness is blended in an amount of 25% by mass in the resin composition, the scratch resistance is not significantly improved. That is, a resin having a high surface hardness such as an acrylic resin does not immediately exhibit a high degree of scratch resistance, but by using a specific amount of the polycarbonate resin (i) and the polycarbonate resin (ii) of the present invention, It can be seen that all of high surface hardness, impact resistance and scratch resistance can be satisfied.
Therefore, according to the resin composition having both high surface hardness, scratch resistance and impact resistance of the present invention, gaming machine members, partitions, touch panels, card sheets, keyboard parts, button parts, switch parts, building windows or It can be seen that the object of providing a vehicle window is achieved for the first time.

  The gaming machine member, partition, touch panel, card sheet, keyboard part, button part, switch part, building window or vehicle window of the present invention is excellent in balance between high surface hardness and scratch resistance and impact resistance. Therefore, industrial applicability is very high.

Claims (4)

A gaming machine member comprising a polycarbonate resin composition comprising at least the following polycarbonate resin (i) and the following polycarbonate resin (ii), wherein the mass ratio of the polycarbonate resin (i) and the polycarbonate resin (ii) is 90/10 to 10/90 Partition, touch panel, card sheet, keyboard part, button part, switch part, building window or vehicle window.
Polycarbonate resin (i)
Polycarbonate resin having a viscosity average molecular weight (Mv) of 20,000 to 35,000 having a structural unit represented by the following general formula (1)

(In the general formula (1), R ¹ represents a methyl group, R ² and R ³ each independently represents a hydrogen atom or a methyl group, and X represents

R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group, Z is bonded to a carbon atom (C), and may have a substituent and has 6 to 12 carbon atoms. The group which forms alicyclic carbon hydrogen is shown. )
Polycarbonate resin (ii)
Polycarbonate resin having a structural unit represented by the following general formula (2) and having a viscosity average molecular weight (Mv) of 16,000 to 28,000

(X in the general formula (2) has the same meaning as the general formula (1).) The gaming machine member, partition, touch panel, card sheet, keyboard component, button component, switch according to claim 1, wherein R ² and R ³ in the general formula (1) are hydrogen atoms and X is an isopropylidene group. Parts, building windows or vehicle windows.   The gaming machine member, partition, touch panel, card sheet, keyboard part, button part, switch part, building window or vehicle window according to claim 1 or 2, wherein X in the general formula (2) is an isopropylidene group. .   The card | curd formed using the sheet | seat for cards of any one of Claims 1-3.