CN114634695A

CN114634695A - Resin composition and method for producing resin composition

Info

Publication number: CN114634695A
Application number: CN202210249663.1A
Authority: CN
Inventors: 栗山晃人; 大江贵裕; 上田贤司; 清水浩平; 稲垣靖史; 川手靖俊; 一瀬新吾; 泽田真一; 森永尚人
Original assignee: Sony Corp
Current assignee: Sony Corp
Priority date: 2017-04-07
Filing date: 2018-01-25
Publication date: 2022-06-17
Also published as: CN110506078B; JP7060013B2; WO2018186002A1; JPWO2018186002A1; CN110506078A

Abstract

The present invention provides a resin composition having excellent physical properties of resin. Provided is a resin composition comprising: 100 parts by mass of an aromatic polycarbonate resin; and 0.01 to 5.0 parts by mass of a crosslinked polyurethane resin, wherein the polyurethane resin is a curable resin.

Description

Resin composition and method for producing resin composition

The present application is a divisional application of an invention patent application having an application date of 2018, month 1 and 25, application number of 201880023460.2, entitled "resin composition and method for producing resin composition".

Technical Field

The present technology relates to resin compositions and methods of making resin compositions.

Background

Resin compositions including polycarbonate resins are widely used in fields such as appearance, electronic and electrical applications, optical disk substrates, and the like.

However, in order to expand the application range thereof to the fields of office automation equipment/copiers, vehicles, medical materials, and the like in the future, further improvement in the characteristics of a resin composition comprising a polycarbonate resin is desired.

For example, a transparent panel for outdoor use has been proposed (see patent document 1). The transparent panel includes 60 to 80 parts by mass of a polyester resin and 40 to 20 parts by mass of a polycarbonate resin. The polyester resin is obtained by polycondensation of a dicarboxylic acid polycondensation component and an ethylene glycol polycondensation component. The dicarboxylic acid polycondensation component is comprised of one or more terephthalic acid-based components selected from the group consisting of terephthalic acid derivatives and terephthalic acid. The ethylene glycol polycondensation component comprises 40 mole percent or greater of 1, 4-cyclohexanedimethanol.

Further, for example, a polycarbonate resin curable coating has been proposed (see patent document 2). The curable coating comprises: a compound (A) having two or more (meth) acryloyl groups in one molecule, conductive particles (B), and an organic solvent (C), wherein the curable coating material comprises a resin having at least 8.0 to 10.0 (cal/cm)³)^1/2The compound (C-1) having a solubility parameter of (1) as the organic solvent (C).

Reference list

Patent document

Patent document 1: JP 2000-

Patent document 2: JP 2011-

Disclosure of Invention

Technical problem

However, according to the techniques proposed in patent documents 1 and 2, the physical properties of the resin may not be further improved.

Accordingly, a primary object of the present technology is to provide a resin composition having excellent physical properties of a resin, and a method for preparing the resin composition having excellent physical properties of a resin.

Technical scheme

As a result of extensive studies to achieve the above object, the present inventors have succeeded surprisingly in significantly improving the physical properties of resins by using an aromatic polycarbonate resin and a crosslinked polyurethane resin in a predetermined composition ratio, and have completed the present technology.

In other words, according to the present technology, there is provided a resin composition comprising: 100 parts by mass of an aromatic polycarbonate resin; and 0.01 to 5.0 parts by mass of a crosslinked polyurethane resin, wherein the polyurethane resin is a curable resin.

The powder of the crosslinked polyurethane resin may have an average particle diameter of 0.5mm to 1.5 mm.

The ratio of the powder of the crosslinked polyurethane resin having a particle diameter of 0.5mm to 1.5mm to the total powder of the crosslinked polyurethane resin may be 70% or more.

The crosslinked polyurethane resin can be obtained by reacting a polyester polyol and a polyisocyanate with each other.

The mass ratio of the polyester polyol and the polyisocyanate may be 100:50 to 100: 200.

The polyester polyol can have a hydroxyl number of 30 to 300.

The weight average molecular weight of the polyester polyol in terms of polystyrene equivalents may be 10,000 or more and 500,000 or less.

The polyisocyanate may have two or more isocyanate groups.

The resin composition may further include 0.01 to 3.0 parts by mass of an organic sulfonic acid and/or metal organic sulfonate compound with respect to 100 parts by mass of the aromatic polycarbonate resin.

The weight average molecular weight of the metal organic sulfonate compound in terms of polystyrene equivalent may be 30,000 or more.

The metal organic sulfonate compound may include a metal sulfonate group, and the content of the metal sulfonate group may be 0.1 mol% to 10 mol%.

The aromatic polycarbonate resin may include a recyclable polycarbonate resin, and the content of the recyclable polycarbonate resin may be less than 1% by mass to 100% by mass relative to the total mass of the aromatic polycarbonate resin.

The resin composition according to the present technology can be obtained by: 0.01 to 5.0 parts by mass of a crosslinked polyurethane resin is added to 100 parts by mass of an aromatic polycarbonate resin, and the aromatic polycarbonate resin and the crosslinked polyurethane resin are kneaded.

Further, according to the present technology, there is provided a method of preparing a resin composition, the method comprising: adding 0.01 to 5.0 parts by mass of a crosslinked polyurethane resin to 100 parts by mass of an aromatic polycarbonate resin; and kneading the aromatic polycarbonate resin and the crosslinked polyurethane resin.

A method of preparing a resin composition according to the present technology may comprise: the crosslinked polyurethane resin is prepared by the reaction of a polyester polyol and a polyisocyanate.

Advantageous effects

According to the present technology, the physical properties of the resin can be improved. It should be noted that the effect described herein is not necessarily limited, but may be any effect described in the present technology.

Detailed Description

Suitable embodiments for implementing the present techniques will be described below. It should be understood that the embodiments described below are exemplary embodiments of the present technology and should not be construed as limiting the scope of the present technology.

Note that description will be made in the following order.

1. Summary of the present technology

2. First embodiment (example of resin composition)

2-1. resin composition

2-2. aromatic polycarbonate resin

2-3. polyurethane resin

2-4. polyester polyols

2-5. polyisocyanates

2-6. organic sulfonic acid and metal organic sulfonate compound

2-7, antidrip agent

2-8. other components

3. Second embodiment (example of method for producing resin composition)

3-1. method for producing resin composition

4. Third embodiment (example of resin molded article)

4-1. resin molded article

4-2. method for producing resin molded article

<1. summary of the present technology >

First, an overview of the present technology will be described.

The present technology relates to a resin composition having improved physical properties of the resin. The resin composition includes an aromatic polycarbonate resin and a crosslinked polyurethane resin. More particularly, the present technology relates to a resin composition having improved surface physical properties such as solvent resistance, chemical resistance and abrasion resistance without coating the surface thereof with a coating material. Further, the resin composition has improved flowability without lowering inherent mechanical properties of the aromatic polycarbonate resin, such as excellent impact resistance and the like. Further, the present technology relates to a method of preparing the resin composition.

A resin composition comprising a polycarbonate resin (such as an aromatic polycarbonate resin) is excellent in heat resistance, impact resistance, transparency, and the like. However, some resin compositions including a polycarbonate resin (such as an aromatic polycarbonate resin) have low flowability, which results in low moldability. In addition, surface physical properties such as solvent resistance and chemical resistance are sometimes deteriorated. It is desired to improve surface physical properties such as flowability, solvent resistance and chemical resistance of a resin composition comprising a polycarbonate resin such as an aromatic polycarbonate resin.

Examples of the method for improving the flowability and chemical resistance of the polycarbonate resin include a technique of melting and kneading a polycarbonate resin and a polyester-based resin such as a polyethylene terephthalate resin (PET) or a polybutylene terephthalate resin (PBT). However, polyethylene terephthalate resin (PET) and polybutylene terephthalate resin (PBT) have low compatibility with polycarbonate resin. Therefore, when they are melted and kneaded with polycarbonate resins, the characteristic mechanical properties of the polycarbonate resins become seriously impaired. In addition, polyethylene terephthalate resin (PET) and polybutylene terephthalate resin (PBT) have low glass transition temperatures, which results in a great decrease in heat resistance.

Further, examples of techniques for methods of improving chemical resistance, abrasion resistance, and the like include a method of coating a molded polycarbonate resin with a coating and improving chemical resistance. However, sometimes the mechanical properties of the polycarbonate resin may be seriously deteriorated by the attack of a solvent or a material. Therefore, even with this coating method, it is difficult to obtain both the surface physical properties and the mechanical properties.

In view of the above, the present inventors have made diligent studies and, as a result, have achieved the present technology. According to the present technology, there is provided a resin composition comprising: 100 parts by mass of an aromatic polycarbonate resin; and 0.01 to 5.0 parts by mass of a crosslinked polyurethane resin. The polyurethane resin is a curable resin. Further, according to the present technology, there is provided a method of preparing a resin composition, the method comprising: adding 0.01 to 5.0 parts by mass of a crosslinked polyurethane resin to 100 parts by mass of an aromatic polycarbonate resin; and kneading the aromatic polycarbonate resin and the crosslinked polyurethane resin. Further, according to the present technology, there is provided a resin molded body obtained by molding the resin composition relating to the present technology.

According to the present technology, there is provided a resin composition having improved flowability and improved surface physical properties such as solvent resistance, chemical resistance and abrasion resistance without lowering its mechanical properties such as impact resistance. Further, according to the present technology, if the resin composition additionally includes a flame retardant (such as an organic sulfonic acid or a metal organic sulfonate compound), a resin composition further having flame retardant properties is also provided.

Further, the present technology may use an aromatic polycarbonate resin including a recycled polycarbonate resin, such as a waste optical disc. Therefore, the recovered polycarbonate resin obtained from the discarded optical disc or the like can be effectively used as a raw material, which contributes to saving of the aromatic polycarbonate resin.

<2. first embodiment (example of resin composition) >

[2-1. resin composition ]

Details of the resin composition (an example of the resin composition) according to the first embodiment of the present technology will be described below.

According to a first embodiment of the present technique, a resin composition comprises: 100 parts by mass of an aromatic polycarbonate resin; and 0.01 to 5.0 parts by mass of a crosslinked polyurethane resin. The polyurethane resin is a curable resin. The crosslinked urethane resin may be a photo-curable resin obtained by curing the curable urethane-based resin composition by light (e.g., ultraviolet light) or a thermosetting resin obtained by curing the curable urethane-based resin composition by heating.

According to a first embodiment of the present technology, the resin composition has improved flowability and improved surface physical properties, such as solvent resistance, chemical resistance, and abrasion resistance, while maintaining its mechanical properties, such as impact resistance. Note that the improvement in fluidity leads to an improvement in processing suitability (such as moldability) of the resin composition.

In the resin composition, the content of the crosslinked polyurethane resin is 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. In view of further improvement of mechanical properties, the content of the crosslinked polyurethane resin is preferably 0.05 to 3.0 parts by mass.

[2-2. aromatic polycarbonate resin ]

According to a first embodiment of the present technology, a resin composition includes an aromatic polycarbonate resin. Although the resin composition may include any amount of the aromatic polycarbonate resin, the content of the aromatic polycarbonate resin is preferably 94.5 to 99.5 mass% with respect to the total mass of the resin composition. The content of the aromatic polycarbonate resin is more preferably 96 to 98 mass%.

The aromatic polycarbonate resin is used as a raw material for producing a molded part of the resin composition according to the first embodiment of the present technology, and is used as a material for a housing of a home appliance or an optical disk. An aromatic polycarbonate resin prepared by a reaction between a dihydric phenol and a carbonate precursor may be generally used. Examples of the reaction include interfacial polycondensation, melt transesterification, solid-phase transesterification of a carbonate prepolymer, and ring-opening polymerization of a cyclic carbonate compound. These dihydric phenols and carbonate precursors are not particularly limited. Various of these dihydric phenols and carbonate precursors may be used.

The aromatic polycarbonate resin may be a polyester carbonate obtained by copolymerizing an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, or derivatives thereof, as long as it falls within the scope of the present technology without departing from the spirit of the present technology. In addition, a thermoplastic resin other than the aromatic polycarbonate resin may be blended as long as it does not deteriorate the resin physical properties of the resin composition according to the first embodiment of the present technology. In general, the content of the mixed thermoplastic resin, which varies depending on the type and purpose, is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. Further, the content of the mixed thermoplastic resin is more preferably 2 to 20 parts by mass. Examples of the thermoplastic resin include general-purpose plastics represented by polyethylene resins, polypropylene resins, and polyalkylmethacrylate resins; engineering plastics typified by polyphenylene ether resins, polyacetal resins, polyamide resins, cyclic polyolefin resins, polyarylate resins (amorphous polyarylate, liquid crystal polyarylate), and the like; and so-called super engineering plastics such as polyetheretherketone, polyetherimide, polysulfone, polyethersulfone, polyphenylene sulfide. In addition, thermoplastic elastomers such as olefin-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers may also be used.

Next, the aromatic polycarbonate resin will be described in more detail.

(aromatic polycarbonate resin having branched structure)

According to the first embodiment of the present technology, the aromatic polycarbonate resin included in the resin composition may include an aromatic polycarbonate resin having a branched structure (sometimes referred to as a branched aromatic polycarbonate resin).

Although the branched aromatic Polycarbonate (PC) resin is not particularly limited as long as it is a branched aromatic polycarbonate resin, the following branched aromatic polycarbonate resins are given as examples thereof. The branched aromatic polycarbonate resin has a branched core structure derived from a branching agent represented by the following general formula (I), and has a viscosity average molecular weight of 15,000 to 40,000, preferably 17,000 to 30,000, and more preferably 17,000 to 27,000, and the branching agent is used preferably in an amount of 0.01 to 3 mol%, more preferably 0.1 to 2.0 mol%, relative to the dihydric phenol compound.

[ chemical formula 1]

R represents hydrogen or an alkyl group having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl or n-pentyl. Furthermore, R¹To R⁶Each independently represents hydrogen, an alkyl group having 1 to 5 carbon atoms (such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or an n-pentyl group), or a halogen atom (such as a chlorine atom, a bromine atom, or a fluorine atom).

More specifically, the branching agent represented by the general formula (I) is, for example, a compound having three or more functional groups, such as 1,1, 1-tris (4-hydroxyphenyl) -methane; 1,1, 1-tris (4-hydroxyphenyl) -ethane; 1,1, 1-tris (4-hydroxyphenyl) -propane; 1,1, 1-tris (2-methyl-4-hydroxyphenyl) -methane; 1,1, 1-tris (2-methyl-4-hydroxyphenyl) -ethane; 1,1, 1-tris (3-methyl-4-hydroxyphenyl) -methane; 1,1, 1-tris (3-methyl-4-hydroxyphenyl) -ethane; 1,1, 1-tris (3, 5-dimethyl-4-hydroxyphenyl) -methane; 1,1, 1-tris (3, 5-dimethyl-4-hydroxyphenyl) ethane; 1,1, 1-tris (3-chloro-4-hydroxyphenyl) -methane; 1,1, 1-tris (3-chloro-4-hydroxyphenyl) -ethane; 1,1, 1-tris (3, 5-dichloro-4-hydroxyphenyl) -methane; 1,1, 1-tris (3, 5-dichloro-4-hydroxyphenyl) -ethane; 1,1, 1-tris (3-bromo-4-hydroxyphenyl) -methane; 1,1, 1-tris (3-bromo-4-hydroxyphenyl) -ethane; 1,1, 1-tris (3, 5-dibromo-4-hydroxyphenyl) -methane; 1,1, 1-tris (3, 5-dibromo-4-hydroxyphenyl) -ethane; 4, 4' - [1- [4- [1- (4-hydroxyphenyl) -1-methylethyl ] phenyl ] ethylidene ] bisphenol; α, α', α ″ -tris (4-hydroxyphenyl) -1,3, 5-triisopropylbenzene; 1- [ α -methyl- α - (4 "-hydroxyphenyl) ethyl ] -4- [ α', α" -bis (4 "-hydroxyphenyl) ethyl ] benzene; phloroglucinol; trimellitic acid or isatinbis (o-cresol). Among these compounds, 1,1, 1-tris (4-hydroxyphenyl) ethane is preferably used from the viewpoints of availability, reactivity and economy.

Each of these branching agents may be used alone, or two or more of them may be used as a mixture. Further, in the case of using 1,1, 1-tris (4-hydroxyphenyl) ethane as the branching agent, the amount thereof is preferably 0.2 to 2.0 mol%, more preferably 0.3 to 2.0 mol%, and particularly preferably 0.4 to 1.9 mol%, relative to the dihydric phenol compound. When the amount is 0.2 mol% or more, the degree of freedom of mixing increases. When the amount is 2.0 mol% or less, gelation hardly occurs during the polymerization reaction, and thus the aromatic polycarbonate resin is easily produced.

The branched aromatic polycarbonate resin has a branched core structure derived from a branching agent represented by the general formula (I), and specifically represented by the following formula.

[ chemical formula 2]

Here, in the above formula, a, b and c each represent an integer, and PC represents a polycarbonate unit.

For example, in the case where bisphenol a is used as a raw material component, PC represents a repeating unit represented by the following formula.

[ chemical formula 3]

The amount (ratio) of the branched aromatic polycarbonate resin in 100 parts by mass of the aromatic polycarbonate resin is preferably 10 parts by mass to 100 parts by mass, more preferably 50 parts by mass to 100 parts by mass. For example, unless the amount of the branched aromatic polycarbonate resin is 10 parts by mass or more, the effect of thin-walled flame retardant property may not be obtained.

(unbranched aromatic polycarbonate resin)

The aromatic polycarbonate resin may include an unbranched aromatic polycarbonate resin not containing any halogen in its molecular structure. The unbranched polycarbonate resin is preferably a polymer having a structural unit represented by the following formula (II).

[ chemical formula 4]

In formula (II), each X represents a hydrogen atom, or an alkyl group having 1 to 8 carbon atoms (such as a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, a pentyl group, an isopentyl group, or a hexyl group). In the case where a plurality of X's are present, X's may be the same as or different from each other, a and b each represent an integer of 1 to 4, Y represents a single bond, an alkylene group having 1 to 8 carbon atoms or an alkylidene group having 2 to 8 carbon atoms (such as methylene, ethylene, propylene, butylene, pentylene, hexylene, ethylidene or isopropylidene), a cycloalkylidene group having 5 to 15 carbon atomsOr a cycloalkylidene group having 5 to 15 carbon atoms (such as cyclopentylidene, cyclohexylidene, cyclopentylidene, or cyclohexylidene), or-S-, -SO-, -SO₂a-O-, or-CO-bond, or a bond represented by the following formula (III) or (III'). X is preferably a hydrogen atom, and Y is preferably an ethylene group or a propylene group.

[ chemical formula 5]

The aromatic polycarbonate resin can be easily prepared by reacting a dihydric phenol represented by the following formula (IV) with phosgene or a carbonic acid diester compound. That is, the aromatic polycarbonate resin is prepared, for example, by: by a reaction between a dihydric phenol and a carbonate precursor such as phosgene or by a transesterification reaction of a dihydric phenol and a carbonate precursor such as diphenyl carbonate in a solvent such as methylene chloride in the presence of a known acid acceptor or viscosity average molecular weight modifier.

[ chemical formula 6]

In formula (IV), X, Y, a and b each have the same meaning as described above.

Here, various compounds are given as the dihydric phenol represented by the formula (IV). Examples thereof include:

dihydroxydiarylalkanes such as bis (4-hydroxyphenyl) methane; bis (4-hydroxyphenyl) phenylmethane; bis (4-hydroxyphenyl) naphthylmethane; bis (4-hydroxyphenyl) - (4-isopropylphenyl) methane; bis (3, 5-dichloro-4-hydroxyphenyl) methane; bis (3, 5-dimethyl-4-hydroxyphenyl) methane; 1, 1-bis (4-hydroxyphenyl) ethane; 1-naphthyl-1, 1-bis (4-hydroxyphenyl) ethane; 1-phenyl-1, 1-bis (4-hydroxyphenyl) ethane; 1, 2-bis (4-hydroxyphenyl) ethane; 2, 2-bis (4-hydroxyphenyl) propane (common name: bisphenol a); 2-methyl-1, 1-bis (4-hydroxyphenyl) propane; 2, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane; 1-ethyl-1, 1-bis (4-hydroxyphenyl) propane; 2, 2-bis (3-methyl-4-hydroxyphenyl) propane; 1, 1-bis (4-hydroxyphenyl) butane; 2, 2-bis (4-hydroxyphenyl) butane; 1, 4-bis (4-hydroxyphenyl) butane; 2, 2-bis (4-hydroxyphenyl) pentane; 4-methyl-2, 2-bis (4-hydroxyphenyl) pentane; 2, 2-bis (4-hydroxyphenyl) hexane; 4, 4-bis (4-hydroxyphenyl) heptane; 2, 2-bis (4-hydroxyphenyl) nonane; 1, 10-bis (4-hydroxyphenyl) decane; and 1, 1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane;

dihydroxydiarylcycloalkanes such as 1, 1-bis (4-hydroxyphenyl) cyclohexane and 1, 1-bis (4-hydroxyphenyl) cyclodecane;

dihydroxydiaryl sulfones such as bis (4-hydroxyphenyl) sulfone and bis (3, 5-dimethyl-4-hydroxyphenyl) sulfone;

dihydroxy diaryl ethers such as bis (4-hydroxyphenyl) ether and bis (3, 5-dimethyl-4-hydroxyphenyl) ether;

dihydroxydiaryl ketones such as 4,4 '-dihydroxybenzophenone and 3, 3', 5,5 '-tetramethyl-4, 4' -dihydroxybenzophenone;

dihydroxy diaryl sulfides such as bis (4-hydroxyphenyl) sulfide; bis (3-methyl-4-hydroxyphenyl) sulfide; and bis (3, 5-dimethyl-4-hydroxyphenyl) sulfide;

dihydroxy diaryl sulfoxides such as (4-hydroxyphenyl) sulfoxide;

dihydroxybiphenyls such as 4, 4' -dihydroxybiphenyl; and

dihydroxyarylfluorenes, such as 9, 9-bis (4-hydroxyphenyl) fluorene.

Among them, 2, 2-bis (4-hydroxyphenyl) propane (common name: bisphenol A) is suitable.

Examples of the dihydric phenols other than the dihydric phenol represented by formula (IV) include: dihydroxybenzenes such as hydroquinone, resorcinol, and methylhydroquinone; and dihydroxynaphthalenes such as 1, 5-dihydroxynaphthalene and 2, 6-dihydroxynaphthalene. These dihydric phenols may be used alone or in combination of two or more. Further, examples of the carbonic acid diester compound include diaryl carbonates such as diphenyl carbonate and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

Further, the molecular weight regulator may be a molecular weight regulator generally used for polymerization of polycarbonate, and various molecular weight regulators may be used. Specific examples thereof include monohydric phenols such as phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, and nonylphenol. The aromatic polycarbonate used in the present invention may be a mixture of two or more aromatic polycarbonates. Further, the viscosity average molecular weight of the aromatic polycarbonate is preferably from 10,000 to 100,000, particularly suitably from 20,000 to 40,000, in terms of mechanical strength and moldability.

(aromatic polycarbonate-polyorganosiloxane copolymer)

According to a first embodiment of the present technology, the aromatic polycarbonate resin included in the resin composition may include an aromatic polycarbonate-polyorganosiloxane copolymer.

The aromatic polycarbonate-polyorganosiloxane copolymer includes an aromatic polycarbonate unit and a polyorganosiloxane unit, and includes an aromatic polycarbonate structural unit represented by the following general formula (V) and a polyorganosiloxane structural unit represented by the following general formula (VI).

[ chemical formula 7]

In the formula (V), R⁵And R⁶Each represents a halogen atom, an alkyl group having 1 to 6 carbon atoms (preferably having 1 to 4 carbon atoms), or an optionally substituted phenyl group. In the presence of a plurality of R⁵And R⁶In the case of (1), R⁵And R⁶May be the same as or different from each other. Y represents a single bond, an alkylene or alkylidene group having 1 to 20 carbon atoms (preferably having 2 to 10 carbon atoms), a cycloalkylene or cycloalkylidene group having 5 to 20 carbon atoms (preferably having 5 to 12 carbon atoms), or-O-, -S-, -SO-, -SO₂-or-CO-linkage, preferably representing a methylisopropyl group. p and q each represent an integer of 0 to 4 (preferably 0). In the case where a plurality of p and q are present, p and q may be the same as or different from each other. m meterAn integer of 1 to 100 (preferably an integer of 5 to 90) is shown. Since m is 1 to 100, a suitable viscosity average molecular weight of the aromatic polycarbonate-polyorganosiloxane copolymer can be obtained.

[ chemical formula 8]

In the formula (VI), R⁷To R¹⁰Each represents an alkyl group having 1 to 6 carbon atoms, or an optionally substituted phenyl group. R⁷To R¹⁰May be the same as or different from each other. R⁷To R¹⁰Specific examples of (b) include alkyl groups such as methyl, ethyl, propyl, n-butyl, isobutyl, pentyl, isopentyl, or hexyl; and phenylaryl groups such as phenyl, tolyl, xylyl, and naphthyl. R¹¹Denotes an organic residue comprising an aliphatic group or an aromatic group, preferably a divalent organic compound residue such as an o-allylphenol residue, a p-hydroxystyrene residue, or a eugenol residue.

The aromatic polycarbonate-polyorganosiloxane copolymer can be prepared, for example, by: an aromatic polycarbonate oligomer and a polyorganosiloxane which constitutes a polyorganosiloxane unit and has a terminal reactive group are dissolved in a solvent such as methylene chloride, a dihydric phenol such as bisphenol A is added using a catalyst such as triethylamine, and interfacial polycondensation is performed. Aromatic polycarbonate-polyorganosiloxane copolymers have been disclosed in JP H3-292359A, JP H4-202465A, JP H8-81620A, JP H8-302178A, JP H10-7897A and the like.

The polymerization degree of the aromatic polycarbonate structural unit of the aromatic polycarbonate-polyorganosiloxane copolymer is preferably about 3 to 100, and the polymerization degree of the polyorganosiloxane structural unit is preferably about 2 to 500, more preferably about 2 to 300, and particularly preferably about 2 to 140. Further, the content of the polyorganosiloxane in the aromatic polycarbonate-polyorganosiloxane copolymer is usually about 0.1 to 10% by mass, preferably 0.3 to 6% by mass. The viscosity average molecular weight of the aromatic polycarbonate-polyorganosiloxane copolymer used in the resin composition according to the first embodiment of the present technology is generally about 5,000 to 10,000, preferably about 10,000 to 30,000, more preferably about 12,000 to 30,000. Here, such viscosity average molecular weight (Mv) can be measured in the same manner as the above polycarbonate resin.

(recyclable polycarbonate resin)

The above aromatic polycarbonate resin may be a raw material newly prepared, or may be scrap or scraps, gates and rejects obtained in a production process, or a recycled material (recyclable polycarbonate resin) made of a product (for example, an optical disc (substrate) such as a Digital Versatile Disc (DVD), an optical disc (CD), MO, MD, a blu-ray disc (BD)). The recyclable polycarbonate resin is preferably a recyclable polycarbonate resin recovered from the market.

Therefore, the aromatic polycarbonate resin may include or consist of a recyclable polycarbonate resin. Further, the content of the recyclable polycarbonate resin is preferably less than 1 to 100 mass% with respect to the total mass of the aromatic polycarbonate resin.

In the case of a recycled optical disc, various attachments such as a metal reflective layer, a plated layer, a recording material layer, an adhesive layer, and a label may be included in the optical disc. According to the present invention, such an optical disc may be used in a state where these attachments are attached to the optical disc, or may be used after these attachments are separated and removed through a known process.

Specific examples of attachments include, but are not limited to: metal reflective layers such as Al, Au, Ag, and Si; organic dyes, including cyanine dyes; recording material layers such as Te, Se, S, Ge, In, Sb, Fe, Tb, Co, Ag, Ce, Bi; an adhesive layer comprising at least one of an acrylic-based acrylate, an ether-based acrylate, a vinyl monomer, an oligomer, or a polymer; a label ink layer wherein a polymerization initiator, pigment or adjuvant is mixed with at least one of a UV curable monomer, oligomer or polymer; and the like. Examples of the adherent may also include film-forming materials and coating materials generally used for optical disks. Note that, from the viewpoint of recovery, since the cost of raw materials is desired to be low, it may be appropriate to reuse the resin in a state of containing various impurity materials. For example, the finely pulverized optical disk itself may be used as it is, or may be kneaded and melted with given additives to prepare a pellet and used as a PC resin raw material. Alternatively, with some configurations of the injection molding machine, it is also possible to directly put the recovered compact disc into a hopper or the like of the injection molding machine together with various additives to be described later. Thus, a molded article made of the resin composition can be obtained. It should be noted that in the case where the Polycarbonate (PC) resin used is a resin in a state not including the above-mentioned impurities, attachments such as a metal reflective layer, a recording material layer, an adhesive layer, a surface hardened layer, and a label can be removed by a mechanical or chemical method proposed in, for example, JP H6-223416A, H10-269634A, H10-249315A or the like.

Note that the weight average molecular weight of the aromatic polycarbonate resin can be measured in terms of polystyrene equivalent by Gel Permeation Chromatography (GPC) using a chloroform solvent based on polystyrene molecular weight standards (samples).

Although the molecular weight of the aromatic polycarbonate resin may be any value, a molecular weight of 36000 to 63000 is preferably taken as the weight average molecular weight (in terms of polystyrene equivalent). This is because, in the case where the weight average molecular weight of the aromatic polycarbonate resin exceeds 63000, the fluidity (processability) of the resin composition as a final product at the time of melting tends to be deteriorated. On the other hand, in the case where the weight average molecular weight is less than 36000, since solvent resistance may be reduced, solvent-based cracks (cracks caused by chemicals) may be more likely to occur, and impact resistance may be reduced.

In view of mechanical strength and moldability, the weight average molecular weight of the aromatic polycarbonate resin included in the resin composition is preferably 40000 to 59000, particularly suitably 44000 to 54000.

[2-3. polyurethane resin ]

According to the first embodiment of the present technology, the resin composition includes 0.01 to 5.0 parts by mass of a crosslinked polyurethane resin as a curable resin with respect to 100 parts by mass of an aromatic polycarbonate resin. Next, details of the crosslinked polyurethane resin will be described.

With respect to the resin composition according to the first embodiment of the present technology, the urethane resin is not particularly limited as long as it is a urethane resin that is a curable resin having a crosslinked structure. However, from the viewpoint of forming a coating film having excellent surface physical properties such as chemical resistance, a polyurethane resin having a three-dimensional crosslinked structure obtained by reacting a polyester polyol and a polyisocyanate with each other is preferable. The mass ratio of the polyester polyol and the polyisocyanate reacted with each other is any ratio, and is preferably 100:50 to 100: 200. Further, the polyurethane resin preferably includes a structural unit derived from a polyester polyol and a structural unit derived from a polyisocyanate.

For example, the crosslinked polyurethane resin can be obtained by mixing a polyester polyol and a polyisocyanate, and then initiating a heat curing reaction. By using a pelletized aromatic polycarbonate resin, mixing a polyester polyol and a polyisocyanate, and heating in the range of 60 to 200 ℃ for about several seconds to ten minutes, a polycarbonate resin coating film can be formed on the pellet surface of the aromatic polycarbonate resin. Subsequently, they are kneaded, for example, by a twin-screw extruder. Thus, a resin composition according to the first embodiment of the present technology, which includes an aromatic polycarbonate resin and a crosslinked polyurethane, may be prepared.

Alternatively, the resin composition according to the first embodiment of the present technology may also be prepared by: the polyester polyol and the polyisocyanate are coated on a color plate including an aromatic polycarbonate resin, and a resin composition coated with a polyurethane resin formed by heating is pulverized and re-pelletized.

Note that details of the production method of the resin composition according to the first embodiment of the present technology will be described later.

On the other hand, a coated product obtained by coating a carbonate resin (such as an aromatic polycarbonate resin) with a polyurethane resin is not particularly limited, and any known method may be used. For example, a method of coating a urethane resin onto a substrate of a carbonate resin (such as an aromatic carbonate resin) and then simultaneously baking the obtained two-layer film may be used. As a method of coating the resin, any known method may be appropriately selected in consideration of the form of the urethane resin used, the surface shape of the substrate of a carbonate resin (such as an aromatic carbonate resin), and the like. The method of coating the resin is not particularly limited. For example, the resin may be applied by general electrostatic coating by using air spray, airless spray, shower, curta coater, bell jar, or the like. After the coating, the obtained coated product may be subjected to natural drying or forced drying (such as hot air drying, near infrared drying, and electromagnetic wave drying). The baking method is not particularly limited. However, in view of the possibility that baking deteriorates the substrate of a carbonate resin (such as an aromatic carbonate resin), the baking temperature is preferably 70 ℃ to 110 ℃, more preferably 80 ℃ to 100 ℃. In general, in view of energy efficiency, it is sufficient to appropriately set the baking time according to the baking temperature. The baking time is preferably 10 minutes to 60 minutes, more preferably 15 minutes to 40 minutes.

The powder of the crosslinked polyurethane resin is sufficient to have any average particle diameter, preferably 0.5mm to 1.5 mm. When the average particle diameter of the crosslinked polyurethane resin is 0.5mm to 1.5mm, the polyurethane resin has better dispersibility and mixability in the aromatic polycarbonate resin. When the polyurethane resin has better dispersibility and mixability, the mechanical properties of the resin composition are kept good, and surface physical properties (such as chemical resistance) and flowability are further improved.

As for the crosslinked polyurethane resin, any ratio can be used as the ratio of the powder of the crosslinked polyurethane resin having a particle diameter of 0.5mm to 1.5mm to the total powder of the polyurethane resin. However, 70% or more is preferable. When the proportion is 70% or more, the polyurethane resin has better dispersibility and mixability in the aromatic polycarbonate resin. When the polyurethane resin has better dispersibility and mixability, the mechanical properties of the resin composition are kept good, and surface physical properties (such as chemical resistance) and flowability are further improved.

The particle size distribution of the polyurethane resin powder can be measured as follows. The Ro-Tap measurement is used to measure the particle size distribution. The Ro-Tap measurement is a selection method using a sieve mesh. In this measurement method, the mass of the sample remaining on the screen after screening is measured, the cumulative distribution is graphically recorded, and then the average particle size distribution is obtained.

The particle diameter of the powder of the crosslinked polyurethane resin can be changed by adjusting the pulverization conditions. The urethane resin can be prepared by pulverizing the urethane resin by freeze pulverization, wherein the proportion of the urethane resin powder having a particle diameter of 0.5mm to 1.5mm is 70% or more with respect to the total powder of the urethane resin.

It is advantageous to set the formulation ratio of the polyester polyol and the polyisocyanate so that the ratio of the hydroxyl equivalent weight in the polyester polyol to the isocyanate equivalent weight in the polyisocyanate (hydroxyl equivalent weight of the polyester polyol component: isocyanate equivalent weight of the polyisocyanate) is in the range of 100:50 to 100:200, more preferably in the range of 100:80 to 100: 180. When the hydroxyl equivalent weight in the polyester polyol is 100 and the isocyanate equivalent weight in the polyisocyanate is less than 50, the crosslinking reaction between the polyester polyol and the polyisocyanate becomes slightly insufficient, which may result in a slight decrease in the fast curability of the coating film, and a slight deterioration in the physical properties of the coating film such as abrasion resistance, hardness, weather resistance, water resistance, solvent resistance and chemical resistance. On the other hand, when the hydroxyl equivalent weight in the polyester polyol is 100 and the isocyanate equivalent weight in the polyisocyanate exceeds 200, physical properties may be slightly deteriorated due to the presence of an excessive amount of polyisocyanate.

The curable polyurethane-based resin composition may suitably include a solvent for dissolving or dispersing the polyester polyol and/or polyisocyanate. The solvent may be included in either one of the polyester polyol and the polyisocyanate, or may be included in both the polyester polyol and the polyisocyanate. Furthermore, a solvent may be used for dilution so that a suitable viscosity is obtained after mixing the polyester polyol and the polyisocyanate. Examples of the solvent include hydrocarbon solvents such as toluene, xylene, solvent naphtha, methylcyclohexane, and ethylcyclohexane; ester solvents such as ethyl acetate, butyl acetate, and ethylene glycol monomethyl ether acetate; and ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone. One solvent may be used, or two or more solvents may be used in combination. Further, the solvent for the polyol component and the solvent for the polyisocyanate component may be the same or may be different from each other.

If desired, the curable polyurethane-based resin composition may include a coloring component such as a natural colorant, an organic synthetic colorant, a pigment, an inorganic pigment or a glitter (a flake pigment imparting a glittering glossy feeling or optical interference to a coating film). Such a coloring component may be included in either one of the polyester polyol and the polyisocyanate, but it is preferable to include such a coloring component in the polyester polyol. One coloring component may be used, or two or more coloring components may be used in combination. Of course, clear coats without coloring components can also be used as the crosslinked polyurethane resin.

Examples of natural colorants include: carotenoid dyes such as carotene, carotenal, capsanthin, lycopene, carmine, crocin, canthaxanthin, or bixin; flavonoid dyes such as anthocyanins (e.g. viologen), raphanin, or anthocyanins, chalcones (e.g. carthamin or safflower dye), flavonols (e.g. rutin or quercetin), or flavonoids (e.g. cocoa pigment); flavin dyes such as riboflavin; quinoline dyes, such as succinic acid (e.g. tannic acid), carminic acid (cochineal), kermesic acid or rubia pigment, or naphthoquinones (e.g. violaxacin, alkannin or echinocandin pigment); porphyrin dyes, such as chlorophyll or hemoglobin; diketone dyes such as curcumin (turmeric); beta cyanin dyes, such as betanin; and the like.

Examples of the organic synthetic colorants and pigments include those specified in regulation No. 30 of japan health and welfare department. For example, Red No.202 (lithol rubine BCA), Red No.203 (gold Red C), Red No.204 (gold Red CBA), Red No.205 (lithol Red), Red No.206 (lithol Red CA), Red No.207 (lithol Red BA), Red No.208 (lithol Red SR), Red No.219 (bright lake Red R), Red No.220 (dark maroon), Red No.221 (toluidine Red), Red No.228 (perm Red), Orange No.203 (permanent Orange), Orange No.204 (benzidine Orange G), Yellow205 (benzidine Yellow G), Red No.404 (fast bright scarlet Red), Red No.405 (fast Red F5R), Orange No.401 (han Orange), Yellow No.401 (durable Yellow), Blue cyanine Blue, and the like are included.

Examples of the inorganic pigment include, for example, silicic anhydride, magnesium silicate, talc, kaolin, bentonite, zirconia, magnesium oxide, zinc oxide, titanium oxide, light calcium carbonate, heavy calcium carbonate, light magnesium carbonate, heavy magnesium carbonate, barium sulfate, yellow iron oxide, brownish red iron oxide (colcothar), black iron oxide, ultramarine, chromium oxide, chromium hydroxide, carbon black, and calamine. Examples of bright materials include flake aluminum, deposited aluminum, aluminum oxide, bismuth oxychloride, mica, titanium oxide coated mica, iron oxide coated mica, micaceous iron oxide, titanium oxide coated silica, titanium oxide coated alumina, iron oxide coated silica, iron oxide coated alumina, glass flakes, colored glass flakes, deposited glass flakes, holographic films, and the like. Although the size of the bright material is not particularly limited, it is preferable that the size of the bright material is in the range of 1 μm to 30 μm in the longitudinal direction and the thickness is in the range of 0.001 μm to 1 μm.

The curable polyurethane-based resin composition may include other resins of natural origin, if desired. In this case, such a naturally-derived resin may be included in either one of the polyester polyol and the polyisocyanate, but it is preferable to include the naturally-derived resin in the polyester polyol. One kind of naturally derived resin may be used, or two or more kinds of naturally derived resins may be used in combination.

The other natural source resin is not particularly limited. Examples of the naturally-derived resin include vegetable fibers, cellulose resins, polyhydroxycarboxylic acids represented by polylactic acid, polycaprolactam, modified polyvinyl alcohol, biodegradable aliphatic polyesters represented by polycaprolactone, and the like. Specifically, a solvent-soluble resin is preferable as the resin of other natural origin, and a resin derived from cellulose is most suitable. For example, when one or more selected from cellulose, cellulose nitrate, cellulose acetate butyrate is included in a small amount, physical properties such as surface hardness of a curable coating film to be obtained can be improved. As cellulose nitrate, examples of commercial products suitable for use as other naturally derived resins include: "BNC-HIG-2" manufactured by Bergerac NC Co., France, "RS 1-4" manufactured by Korea CNC Co., Ltd., "SwanCel HM 1-4" manufactured by Hyuppeon Corporation, and "Sernova BTH 1-4" manufactured by Asahi Kasei Chemicals Corporation. As cellulose acetate butyrate, examples of commercial products suitable for use as other naturally derived resins include: "CAB 381-0.1", "CAB 381-0.5", "CAB 381-2", "CAB 531-1", "CAB 551-0.01", and "CAB 551-0.2", manufactured by Eastman Chemical Products, USA.

The curable polyurethane-based resin composition may suitably include various additives, if necessary, such as conventional surface modifiers (e.g., wax, moth-proofing agent, or antifoaming agent), plasticizers, ultraviolet stabilizers, antioxidants, fluidity modifiers, scale inhibitors, matting agents, polishes, and preservatives. Such additives may be included in either of the polyester polyol and the polyisocyanate, but it is preferable to include such additives in the polyester polyol.

The crosslinked polyurethane resin is a cured resin obtained by curing a curable polyurethane-based resin composition including at least a polyester polyol and a polyisocyanate. The resin is obtained by curing a polyester polyol using a polyisocyanate. For example, as described above, the crosslinked polyurethane resin is obtained by mixing a polyester polyol with a polyisocyanate. Subsequently, the obtained crosslinked polyurethane resin (dry-blended) was added to a polycarbonate resin, and they were kneaded. Thus, the resin composition according to the first embodiment of the present technology can be obtained.

[2-4. polyester polyol ]

A polyester polyol as a raw material of the crosslinked polyurethane resin will be described.

Although the hydroxyl value of the polyester polyol may be any value, it is preferably 30 to 300. When the hydroxyl value of the polyester polyol is less than 30, a polyurethane resin having a slightly low crosslinking density is sometimes obtained. As a result, the resin composition added to the aromatic polycarbonate resin and kneaded sometimes has somewhat inferior chemical resistance, abrasion resistance, weather resistance, water resistance and solvent resistance. On the other hand, when the hydroxyl value of the polyester polyol exceeds 300, crosslinking proceeds too much and the compatibility with the aromatic polycarbonate resin is slightly deteriorated. Therefore, mechanical properties and chemical resistance are sometimes slightly deteriorated. The hydroxyl value was determined by the method described in JIS K-1557-1.

Although the weight average molecular weight of the polyester polyol may be any value, it is preferably 10,000 to 500,000. When the weight average molecular weight of the polyester polyol is less than 10,000, a crosslinked polyurethane structure is formed. This results in a resin composition added to the polycarbonate resin and kneaded having somewhat inferior chemical resistance. On the other hand, when the weight average molecular weight of the polyester polyol exceeds 500,000, the viscosity becomes high. Further, if such a resin composition is added to a polycarbonate resin and kneaded, the dispersibility is slightly poor, which may cause a decrease in physical properties.

For example, the polyester polyol can be prepared by reacting a low molecular weight polyol and a polycarboxylic acid with each other, or by ring-opening polymerization of a cyclic ester compound (e.g., epsilon-caprolactone).

As the low molecular weight polyol, for example, ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 1, 8-octanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (having a molar amount of 300 to 6000), dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, bisphenol a, hydrogenated bisphenol a, hydroquinone, an alkylene oxide adduct thereof, or the like can be used.

Further, as the polycarboxylic acid, for example, succinic acid, adipic acid, azelaic acid, sebacic acid, tetradecanedioic acid, maleic acid, fumaric acid, 1, 3-cyclopentanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1, 4-naphthalenedicarboxylic acid, 2, 5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, naphthoic acid, biphenyldicarboxylic acid, 1, 2-bis (phenoxy) ethane-p, p' -dicarboxylic acid, an acid anhydride or an ester-forming derivative thereof, or the like can be used.

Further, the polyester polyol may be a polyester polyol obtained by using a material derived from a vegetable oil.

The vegetable oil-derived material is preferably one or more selected from the group consisting of vegetable oils, fatty acids thereof, carboxylic acids produced by using vegetable oils as a material, and materials having a hydroxyl value derived from vegetable oils. Examples of vegetable oils and vegetable oil fatty acids include, for example, chinese wood oil (fatty acid), linseed oil (fatty acid), dehydrated castor oil (fatty acid), tall oil fatty acid, cottonseed oil (fatty acid), soybean oil (fatty acid), olive oil (fatty acid), safflower oil (fatty acid), castor oil (fatty acid), rice bran oil, hydrogenated coconut oil (fatty acid), palm oil (fatty acid), and the like.

Examples of carboxylic acids prepared by using vegetable oils as materials include: 12-hydroxystearic acid, heptanoic acid, undecylenic acid, sebacic acid prepared from castor oil; dimer acid produced by drying vegetable fatty acid such as rosin obtained by refining pine resin, hydrogenated rosin as a hydrogenation product thereof, and polymerized rosin tall oil fatty acid as a polymer thereof, hydrogenated dimer acid as a hydrogenation product of dimer acid; isostearic acid, which is a by-product obtained in the preparation of dimer acid. Examples of materials having hydroxyl values derived from vegetable oils include heptanal, octanol, and 1, 10-decanediol prepared from castor oil; glycerin obtained by refining various vegetable oils; and the like.

The polyester polyol can be obtained by using the above-mentioned material derived from vegetable oil, and the preparation method thereof is not particularly limited. For example, the polyester polyol is obtained by esterification of a vegetable oil-derived material with an acid component and/or an alcohol component which are generally used for the esterification reaction, as needed.

Examples of the acid component for obtaining the polyester polyol include benzoic acid, p-tert-butylbenzoic acid, isophthalic acid, phthalic anhydride, terephthalic acid, phthalic acid, 2, 6-naphthalenedicarboxylic acid, azelaic acid, sebacic acid, isodecanoic acid, oxalic acid, trimellitic acid, (anhydrous) succinic acid, (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, dodecanoic acid, tetrahydro (anhydrous) phthalic acid, hexahydro-isophthalic acid, hexahydroterephthalic acid, tetrachlorophthalic acid (anhydride), hexachlorophthalic acid (anhydride), tetrabromophthalic acid (or anhydride), glutaric acid, adipic acid, pimelic acid, suberic acid, hydrogenated phthalic acid, and 1, 4-cyclohexanedicarboxylic acid. One acid component may be used, or two or more acid components may be used in combination.

Examples of the alcohol component for obtaining the polyester polyol include: glycol components such as ethylene glycol, neopentyl glycol, diethylene glycol, tetramethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 2,3, 4-trimethyl-1, 3-pentanediol, 3-methylpentene-1, 5-diol, 1, 4-cyclohexanedimethanol, ethylene oxide or propylene oxide of bisphenol A or hydrogenated bisphenol A, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, 2-dimethyl-1, 3-propanediol, 2-n-butyl-ethyl-1, 3-propanediol, tricyclodecane dimethanol, cyclohexane dicarboxylic acid, cyclohexane dimethanol, cyclohexanediol; triol components such as synthetic glycerin (not derived from vegetable oils), trimethylolpropane, and trimethylolethane; tetrahydric alcohols such as pentaerythritol; and the like. Note that one alcohol component may be used, or two or more alcohol components may be used in combination.

In order to obtain the polyester polyol, with respect to the use of the vegetable oil-derived material, although the content of the vegetable oil-derived material in the obtained polyester polyol may be any amount, it is preferably 30 to 100% by mass. When the content of the vegetable oil-derived material in the polyester polyol is less than 30% by mass, the effect of preventing global warming obtained by using a carbon neutral material tends to become smaller. Note that as the esterification reaction for obtaining the polyester polyol, a conventional esterification method, conditions, and the like can be appropriately used.

[2-5. polyisocyanates ]

Polyisocyanates as materials for the crosslinked polyurethane resin will be described.

The polyisocyanate comprises at least one isocyanate group, preferably two or more isocyanate groups.

Examples of polyisocyanates include: aromatic polyisocyanates, aliphatic polyisocyanates, cyclic aliphatic polyisocyanates, cycloaliphatic polyisocyanates, reaction products of such polyisocyanates with polyols, and the like. Among them, aromatic polyisocyanates such as Tolylene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polyphenylmethane polyisocyanate (crude MDI), modified diphenylmethane diisocyanate (modified MDI), Xylylene Diisocyanate (XDI), and hexamethylene diisocyanate (HMDI), trimer compounds of such polyisocyanates; or the reaction product of such a polyisocyanate with a polyol. As the polyisocyanate, one polyisocyanate may be used, or two or more polyisocyanates may be used for the resin composition according to the first embodiment of the present technology.

[2-6. organic sulfonic acid metal organic sulfonate Compound ]

According to the first embodiment of the present technology, the resin composition may further include 0.01 to 3.0 parts by mass of an organic sulfonic acid and/or metal organic sulfonate compound with respect to 100 parts by mass of the aromatic polycarbonate resin. Next, details of the organic sulfonic acid and the metal organic sulfonate compound will be described.

Although the organic sulfonic acid is not particularly limited, aromatic organic sulfonic acids are preferable. Although the metal organic sulfonate compound is not particularly limited, an aromatic metal sulfonate compound is preferable. The aromatic metal sulfonate compound includes a metal sulfonate group. The content of the metal sulfonate group may be appropriately adjusted, and the content of the metal sulfonate group may be any value, but is preferably 0.1 to 10 mol%. With respect to the organic sulfonic acid and metal organic sulfonate compounds, examples of the low molecular weight compound include alkali metal salts and alkaline earth metal salts of perfluoroalkanesulfonic acid, alkylbenzenesulfonic acid, haloalkylbenzenesulfonic acid, alkylsulfonic acid, naphthalenesulfonic acid, and the like, and examples of the high molecular weight compound include polymers having an aromatic ring and including a predetermined amount of sulfonic acid and/or metal salts thereof. This has been described in JP4196862B and JP 4196861B. Examples of polymers having aromatic rings include Polystyrene (PS) sulfonic acid, metal salts of Polystyrene (PS) sulfonic acid, High Impact Polystyrene (HIPS) sulfonic acid, metal salts of High Impact Polystyrene (HIPS) sulfonic acid, and styrene-acrylonitrile copolymer resins (AS) including sulfonic acid and/or sulfonate groups.

There are various organic sulfonic acid and metal organic sulfonate compounds such as the above-mentioned low molecular weight compounds and high molecular weight compounds. Generally, a high molecular weight compound is preferable because it can obtain good dispersibility when kneaded with an aromatic polycarbonate resin and excellent storage stability under high temperature/high humidity conditions.

Among them, more preferable are a styrene-based polymer having a core/shell structure in which a sulfonic acid group is bonded to a surface portion of the particle, an alkali metal salt thereof, an alkaline earth metal salt thereof, and the like. Specifically, for example, polystyrene sulfonic acid and potassium salts thereof are desirable. One of them may be used, or two or more of them may be mixed in an appropriate ratio and the mixture may be used. Polystyrene sulfonic acid or its potassium salt is preferred because they can provide high flame retardant performance with very small additions. Further, it may be more desirable if the weight average molecular weight thereof (in terms of polystyrene equivalents) is 30000 or more. Further, the weight average molecular weight is 40000 or more and 300000 or less is more preferable because it can maintain a balance between solvent resistance and compatibility.

As described above, the content of the organic sulfonic acid or metal organic sulfonate compound is 0.01 to 3.0 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. 0.05 to 1.5 parts by mass is more preferable because it improves the flame retardant property, and 0.05 to 1 part by mass is particularly preferable because it further improves the flame retardant property. In the case where the content is less than 0.05 parts by mass, it is sometimes difficult to obtain flame retardancy. Further, in the case where the content exceeds 1.5 parts by mass, the compatibility with the aromatic polycarbonate resin sometimes becomes slightly poor, which may result in a negative effect on the flame retardancy, i.e., the flame retardancy level may become even lower than when the component is not included.

[2-7. antidrip agent ]

In accordance with a first embodiment of the present technique, the resin composition may further comprise an anti-drip agent. The content of the anti-dripping agent may be 0.8 parts by mass or less with respect to 100 parts by mass of the aromatic polycarbonate resin. In the case where the resin composition according to the first embodiment of the present technology is used as a flame-retardant resin composition, an anti-dripping agent may be included in addition to the organic sulfonic acid and the metal organic sulfonate compound, and dripping that may occur when the composition is burned is suppressed. Examples of the anti-dripping agent include fluoroolefin resins and the like.

Examples of the fluoroolefin resin capable of suppressing dripping include a vinylidene fluoride polymer, a tetrafluoroethylene-hexafluoropropylene copolymer, a copolymer of tetrafluoroethylene and an ethylene monomer, and the like. These may be used alone, or a plurality of such compounds may be used in combination.

In particular, a tetrafluoroethylene polymer or the like is preferably used among these fluoroolefin resins. The average molecular weight thereof is 50000 or more, preferably, in the range of 100000 to 20000000. Note that as the fluoroolefin resin, a resin having fibril-forming ability is more preferable.

As described above, the sufficient content of the anti-dripping agent such as the fluoroolefin resin may be 0.8 parts by mass or less with respect to 100 parts by mass of the aromatic polycarbonate resin. Further, a range of 0.001 parts by mass to 0.8 parts by mass is preferable, a range of 0.01 parts by mass to 0.5 parts by mass is more preferable, and a range of 0.05 parts by mass to 0.3 parts by mass is particularly preferable.

Sometimes, when the content of the anti-dripping agent such as the fluoroolefin resin is less than 0.001 parts by mass relative to 100 parts by mass of the aromatic polycarbonate resin, it is difficult to suppress dripping. On the other hand, when the content of the anti-dripping agent such as a fluoroolefin resin exceeds 0.8 parts by mass, a whitening product is sometimes obtained and the transparency is slightly lowered.

[2-8. other Components ]

For example, the resin composition according to the first embodiment of the present technology may further include, as another component (another additive), an antioxidant (hindered phenol, phosphorus or sulfur antioxidant), an antistatic agent, an ultraviolet absorber (benzophenone, benzotriazole, hydroxyphenyl triazine, cyclic imino ester or cyanoacrylate UV absorber), a light stabilizer, a plasticizer, a compatibilizer, a colorant (pigment or dye), a light stabilizer, a crystal nucleating agent, an antibacterial agent, a flow modifier, an infrared absorber, a fluorescent material, a hydrolysis inhibitor, a mold release agent, a silicone-based flame retardant, a surface treatment agent, or the like, in addition to the above-described components. This can enhance properties such as injection moldability, impact resistance, appearance, heat resistance, weather resistance, color and hardness. Specifically, examples of the silicone-based flame retardant include silicone compounds described below.

The silicone resin compound is used to impart flame retardant properties to the resin composition according to the first embodiment of the present technology. The addition amount of the silicone-based flame retardant in the resin composition is preferably 0.1 to 2 mass%, and the mass ratio of the silicone-based flame retardant to the resin composition is preferably 0.001 to 0.02. Sometimes, when the addition amount of the silicone-based flame retardant is less than 0.1% by mass, that is, when the mass ratio of the silicone-based flame retardant to the resin composition is less than 0.001, the effect of imparting flame retardancy to the resin composition becomes insufficient. On the other hand, when the addition amount exceeds 2 mass%, that is, when the ratio exceeds 0.02, sometimes the efficiency is lowered and the economic efficiency is lowered, the effect of providing flame retardant performance becomes saturated and the efficiency is lowered.

<3. second embodiment (example of method for producing resin composition) >

[3-1. method for producing resin composition ]

Details of a method for producing a resin composition according to a second embodiment of the present invention (examples of the method for producing a resin composition) will be described below.

A method for producing a resin composition according to a second embodiment of the present technology (example of the method for producing a resin composition) is a method for producing a resin composition, the method including: adding 0.01 to 5.0 parts by mass of a crosslinked polyurethane resin to 100 parts by mass of an aromatic polycarbonate resin; and kneading the aromatic polycarbonate resin and the crosslinked polyurethane resin. Although the crosslinked urethane resin is preferably a curable resin, it may be a photo-curable resin or a thermosetting resin. Note that, regarding the aromatic polycarbonate resin and the crosslinked polyurethane resin used in the method for producing a resin composition according to the second embodiment of the present technology, the contents of the aromatic polycarbonate resin and the crosslinked polyurethane resin included in the resin composition according to the first embodiment of the present technology may be applied to the aromatic polycarbonate resin and the crosslinked polyurethane resin used in the method for producing a resin composition according to the second embodiment of the present technology, except for the following description.

The resin composition prepared by the method of preparing a resin composition according to the second embodiment of the present technology has improved flowability and improved surface physical properties such as solvent resistance, chemical resistance and abrasion resistance, while maintaining its mechanical properties such as impact resistance. Note that the improvement in fluidity leads to good processability of the resin composition.

The amount of the crosslinked polyurethane resin added to 100 parts by mass of the aromatic polycarbonate resin is 0.01 to 5.0 parts by mass relative to 100 parts by mass of the aromatic polycarbonate resin. Further, the addition amount of the crosslinked polyurethane resin is preferably 0.05 to 3.0 parts by mass from the viewpoint of further improving mechanical properties.

For example, the method of preparing the resin composition according to the second embodiment of the present technology is as follows.

According to need (such as application of the resin composition), 0.01 to 5.0 parts by mass of the crosslinked polyurethane resin component and predetermined amounts of the respective components are added to 100 parts by mass of the aromatic polycarbonate resin component and mixed. The various components include the organic sulfonic acid and/or metal organic sulfonate compound, the anti-dripping agent, other components, and/or the silicone compound which have been described in <2 > first embodiment (example of resin composition) ". After mixing, the mixture is substantially uniformly dispersed, for example, by a Henschel mixer or tumbler. Thereafter, when the mixture is melted and kneaded by a single-screw or twin-screw extruder or the like, strands are obtained, and the strands are cut by a pelletizer to form pellets. Thereby, a resin composition was obtained. Note that the form of the resin composition prepared by the method for preparing a resin composition according to the second embodiment of the present technology is not limited to the processed form of pellets. Possible forms also include a state in which the components are mixed together (powder state or fluid state), and a processed form other than pellets (sheet-like, etc.).

Examples of a method of adding 0.01 to 5.0 parts by mass of the crosslinked polyurethane resin component or the like to 100 parts by mass of the aromatic polycarbonate resin component include: a method of adding 0.01 to 5.0 parts by mass of a urethane resin component or the like to 100 parts by mass of the particle surface of the aromatic polycarbonate resin component to form a coating film; and a method of adding 0.01 to 5.0 parts by mass of a urethane resin component or the like to a color plate including 100 parts by mass of an aromatic polycarbonate resin so that the color plate is coated with the urethane resin component or the like. In the case of using a method of adding a urethane resin component or the like to a color sheet including an aromatic polycarbonate resin so that the color sheet is coated with the urethane resin component or the like, it is sometimes necessary to pulverize the resin composition obtained after coating and regrind it.

The method of preparing the resin composition according to the second embodiment of the present technology preferably includes preparing a crosslinked polyurethane resin by reacting a polyester polyol and a polyisocyanate with each other. For example, a method of preparing a crosslinked resin composition by reacting a polyester polyol and a polyisocyanate with each other is a preparation method which comprises mixing a polyester polyol and a polyisocyanate and then carrying out a heat curing reaction or photocuring.

<4. third embodiment (example of resin molded article) >

[4-1. resin molded article ]

A resin molded body according to a third embodiment of the present technology is a resin molded body obtained by molding the resin composition according to the first embodiment of the present technology. Further, the resin molded body according to the third embodiment of the present technology may be a resin molded body including the resin composition according to the first embodiment of the present technology. Since the resin composition according to the first embodiment of the present technology does not lower mechanical properties, and improves fluidity, processability, and surface physical properties such as chemical resistance, a resin molded body suitable for office automation equipment/copying machines, vehicle-mounted equipment, and medical materials can be obtained.

[4-2. method for producing resin molded article ]

For example, the resin molded body according to the third embodiment of the present technology can be prepared as follows. The resin molded body can be obtained by: pellets or the like including the resin composition according to the first embodiment of the present technology, or pellets or the like including the resin composition prepared via the preparation method of the resin composition according to the second embodiment of the present technology are molded into a predetermined shape (for example, a housing or a part for various products such as home appliances, automobiles, information devices, office equipment, telephones, stationery, furniture, or fibers) by various methods such as injection molding, injection compression molding, extrusion molding, blow molding, vacuum molding, press molding, foam molding, and supercritical molding to obtain a transmission type resin molded article.

The present technology is not limited to the above-described embodiments, but various modifications may be made without departing from the gist of the present technology.

Note that the effects described in this specification are merely illustrative, and the present technology is not limited thereto. Other effects are possible.

Further, the present technology can also be configured as follows.

[1] A resin composition comprising:

100 parts by mass of an aromatic polycarbonate resin; and

0.01 to 5.0 parts by mass of a polyurethane resin having a crosslinked structure, wherein

The polyurethane resin is a cured resin.

[2] The resin composition according to [1],

wherein the average particle diameter of the powder of the polyurethane resin having a crosslinked structure is 0.5mm to 1.5 mm.

[3] The resin composition according to [1] or [2],

wherein a ratio of the powder of the polyurethane resin having a crosslinked structure with the particle diameter of 0.5mm to 1.5mm to the total powder of the polyurethane resin having a crosslinked structure is 70% or more.

[4] The resin composition according to any one of [1] to [3],

wherein the polyurethane resin having a crosslinked structure is obtained by a reaction of a polyester polyol and a polyisocyanate.

[5] The resin composition according to [4],

wherein the mass ratio of the polyester polyol to the polyisocyanate is from 100:50 to 100: 200.

[6] The resin composition according to [4] or [5],

wherein the polyester polyol has a hydroxyl number of 30 to 300.

[7] The resin composition according to any one of [4] to [6],

wherein the polyester polyol has a weight average molecular weight of 10,000 or more and 500,000 or less in terms of polystyrene.

[8] The resin composition according to any one of [4] to [7],

wherein the polyisocyanate has more than two isocyanate groups.

[9] The resin composition according to any one of [1] to [8],

further comprising 0.01 to 3.0 parts by mass of an organic sulfonic acid and/or a metal salt compound of an organic sulfonic acid, relative to 100 parts by mass of the aromatic polycarbonate resin.

[10] The resin composition according to [9],

wherein the weight average molecular weight of the metal salt of organic sulfonic acid compound in terms of polystyrene is 30,000 or more.

[11] The resin composition according to [9] or [10],

wherein the organic sulfonic acid metal salt compound contains a sulfonic acid metal salt group, and

the content of the sulfonic acid metal salt group is 0.1 to 10 mol%.

[12] The resin composition according to any one of [1] to [11],

wherein the aromatic polycarbonate resin comprises a recycled polycarbonate resin, and

the content of the recycled polycarbonate resin is 1 to less than 100% by mass relative to the total mass of the aromatic polycarbonate resin.

[13] The resin composition according to any one of [1] to [12],

wherein the resin composition is obtained by: adding 0.01 to 5.0 parts by mass of the polyurethane resin having a crosslinked structure to 100 parts by mass of the aromatic polycarbonate resin, and kneading the aromatic polycarbonate resin and the polyurethane resin having a crosslinked structure.

[14] A method of preparing a resin composition comprising:

adding 0.01 to 5.0 parts by mass of a polyurethane resin having a crosslinked structure to 100 parts by mass of an aromatic polycarbonate resin; and

kneading the aromatic polycarbonate resin and the polyurethane resin having a crosslinked structure.

[15] The method for producing a resin composition according to [14], comprising:

reacting a polyester polyol and a polyisocyanate to prepare the polyurethane resin having a crosslinked structure.

[ examples ]

Hereinafter, the effects of the present technology will be specifically described by the embodiments. Note that the scope of the present technology is not limited to the embodiments.

The resin compositions of examples 1-1 to 1-10 and examples 2-1 to 2-10 and the resin compositions of comparative examples 1-1 to 1-5 and comparative examples 2-1 to 2-4 were prepared, and each resin composition was evaluated. Note that comparative examples 1 to 5 relate to coated products, and the coated products were prepared as described below.

With respect to comparative examples 1 to 5 (coated products), the coating material was applied to the surface of the base material by a roll coating method, a spray coating method or a dipping method. After the coating is applied, a desired coating film is formed on the surface of the substrate by heating and drying in the range of 60 to 120 ℃ for about several seconds to 10 minutes, if necessary. The coating materials were two-component curable coating compositions obtained by combining a polyester polyol (Placcel PCL305 (manufactured by Daicel Corporation)) component with a polyisocyanate-based curing agent (Duranate TPA-100 (manufactured by Asahi Kasei Corporation)) so that their isocyanate equivalent weight was 100: 100.

Table 1 listed below shows the compositions (parts by mass) of the components of the resin compositions of examples 1-1 to 1-10, and the evaluation results of the flowability (g/10min), tensile strength (%), chemical resistance, and flexural strength thereof. Further, Table 2 listed below shows the compositions (parts by mass) of the respective components of the resin compositions of comparative examples 1-1 to 1-5, and the evaluation results of the flowability (g/10min), tensile strength (%), chemical resistance, and flexural strength thereof.

Table 3 listed below shows the compositions (parts by mass) of the components of the resin compositions of examples 2-1 to 2-10, and the evaluation results of the flowability (g/10min), tensile strength (%), chemical resistance, flame retardancy (UL94,1.6mm), and flexural strength thereof. Further, Table 4 listed below shows the compositions (parts by mass) of the respective components of the resin compositions of comparative examples 2-1 to 2-4, and the evaluation results of the flowability (g/10min), tensile strength (%), chemical resistance, flame retardancy (UL94,1.6mm), and flexural strength thereof.

[ configurations of the resin compositions of examples 1-1 to 1-10 and examples 2-1 to 2-10 and the resin compositions of comparative examples 1-1 to 1-5 and comparative examples 2-1 to 2-4 ]

The respective components included in the resin compositions of examples 1-1 to 1-10 and examples 2-1 to 2-10 and the resin compositions of comparative examples 1-1 to 1-5 and comparative examples 2-1 to 2-4 will be described. Note that the components (component a, component B, component C, component D, component E, and component F) respectively correspond to the aromatic polycarbonate resin, the crosslinked polyurethane resin, the polyester polyol, the polyisocyanate, the organic sulfonic acid and/or metal organic sulfonate compound, and the anti-dripping agent, which have been described with respect to the resin composition according to the first embodiment of the present technology.

(component A: aromatic polycarbonate resin)

As the aromatic polycarbonate resin of component A, the following components A-1 to A-4 were used.

A-1: commercially available medium molecular weight PC resin (L-1225L: produced by Teijin Chemicals Ltd.; Mw in PS equivalents 45000)

A-2: commercially available low molecular weight PC resin (L-1225 LLL: produced by Teijin Chemicals Ltd.; Mw in PS equivalent 33000)

A-3: PC resin (Mw in terms of PS equivalent: 46000) obtained by coarsely pulverizing used building Material pieces, melting and kneading the resulting material using a twin-screw extruder, and then making it into pellets

A-4: PC resin (Mw in terms of PS equivalent: 32000) obtained by subjecting used CDs to a pulverization treatment (2mm to 20mm), treating them in a hot alkaline aqueous solution to remove a coating film (recording material layer, label, adhesive layer, hardened layer, metal reflective layer, etc.), subsequently melting and kneading the resultant material using a twin-screw extruder, and then pelletizing it

(component B: crosslinked polyurethane resin)

The following components B-1 to B-3 as thermosetting resins were used as the crosslinked polyurethane resin of component B. Note that the component C-1 and the component D-1 for the component B-3 will be described later.

B-1: NEORABASAN N781 (manufactured by Musashi Paint Co., Ltd.)

B-2: NEORABASANSOFT NS781 (manufactured by Musashi Paint Co., Ltd.)

B-3: a crosslinked polyurethane resin obtained by mixing C-1 and D-1 in a ratio of 100 parts by mass to 100 parts by mass (C-1: D-1), heating at 80 ℃ for 10 minutes, and allowing them to react.

(component C: polyester polyol)

As the polyester polyol of component C, the following component C-1 was used.

C-1: placcel PCL305 (manufactured by Daicel Corporation)

(component D: polyisocyanate)

The following component D-1 was used as the polyisocyanate for component D.

D-1: duranate TPA-100 (manufactured by Asahi Kasei Corporation)

(component E: organic sulfonic acid and metal organic sulfonate compound)

As the organic sulfonic acid and metal organic sulfonate compounds of the component E, the following components E-1 to E-2 were used.

E-1: products in which potassium sulfonate salt was introduced into surface portions of polystyrene and metal organic sulfonate compound (PSS-K: manufactured by Sony Corporation)

E-2: products in which sulfonic acid was introduced into the surface portions of polystyrene and organic sulfonic acid (PSS-H: manufactured by Sony Corporation)

(component F: antidrip agent)

As the antidrip agent for component F, the following component F-1 was used.

F-1: commercially available PTFE, which is polytetrafluoroethylene having fibril forming ability (Polyflon FA 500H: produced by Daikin Industries, Ltd.)

[ Molding of the resin compositions of examples 1-1 to 1-10 and examples 2-1 to 2-10 and the resin compositions of comparative examples 1-1 to 1-5 and comparative examples 2-1 to 2-4 ]

The above-mentioned respective components (components A-1 to A-4, components B-1 to B-3, components E-1 to E-2, and component F-1) were combined in the proportions shown in Table 1 (example 1-1 to example 1-10), in Table 2 (comparative example 1-1 to comparative example 1-5), in Table 3 (example 2-1 to example 2-10), and in Table 4 (comparative example 2-1 to comparative example 2-4), mixed using a tumbler, and then pelletized by melt-kneading in a co-rotating twin-screw extruder (manufactured by Toyo Seiki Seisaku-sho L.Ltd.: tdo Plaplastol using a Labo Plastomil). The extrusion conditions were a discharge rate of 4kg/h, a screw rotation speed of 48rpm, and an extrusion temperature of 270 ℃ from the first supply port to the die. After drying the resulting pellets by a hot air circulation dryer at 120 ℃ for 8 hours, the resulting material was molded at a cylinder temperature of 290 ℃ and a mold temperature of 70 ℃ using an injection molding machine to obtain a test piece to be subjected to the following test method.

Next, the prepared test pieces were evaluated for flowability (g/10min), tensile strength (%), chemical resistance and flame retardancy according to the following test methods.

[ method for measuring fluidity (g/10min) (MFR: melt flow Rate) ]

The fluidity of the resin composition when molten was measured under the conditions of a resin temperature of 280 ℃ and a load of 2.16Kg in accordance with JIS K7210. Tables 1 to 4 below show the evaluation results of fluidity (g/10 min).

[ method for measuring tensile Strength ]

Tensile test was conducted in accordance with JIS K7162 to measure the tensile strength of the test pieces. Tables 1 to 4 below show the results of evaluation of tensile strength (%).

[ test method for chemical resistance ]

A strain of 1.0% was applied to the test piece by a three-point bending test method, and then the test piece was covered with a cloth impregnated with a sunscreen cream (sunplac Super Block d (manufactured by Rohto Pharmaceutical co., ltd.) and left to stand at 23 ℃ for 72 hours. Thereafter, the change in appearance thereof was observed. Tables 1 to 4 below show the evaluation results of chemical resistance. Note that the evaluation was performed based on the following criteria.

(evaluation Standard of chemical resistance)

O: the appearance was unchanged.

And (delta): fine cracks were observed.

X: large cracks were observed which could lead to breakage.

[ test method for flame retardancy ]

A test piece having a thickness of 1.6mm was subjected to a vertical burning test in accordance with UL94 standard, and V-1 or more was determined as "good". Table 5 below shows the standards and decision criteria of UL 94V. Tables 3 to 4 below show the evaluation results of flame retardancy. Note that table 5 below shows the standards and decision criteria of UL 94V.

[ method for testing flexural Strength ]

The bending test is a test in which a prepared test piece (length of 110mm, width of 13mm, thickness of 1.0mm) is bent, the angle at which a fracture occurs is measured, and qualitative evaluation is made on impact resistance. According to the evaluation, O was used when the angle of the site at which the fracture occurred was 90 ℃ or more, and X was used when the angle of the site at which the fracture occurred was 90 ℃ or less.

Table 1 below shows the results of examples 1-1 to 1-10, and Table 2 shows the results of comparative examples 1-1 to 1-5.

As is apparent from tables 1 and 2, the resin compositions according to examples 1-1 to 1-10 are suitable for thin-walled molded products. Further, the resin compositions according to examples 1-1 to 1-10 had excellent moldability (flowability), mechanical properties (tensile strength and flexural strength), and surface physical properties (chemical resistance) as compared with the resin compositions according to comparative examples 1-1 to 1-5.

When examples are compared with comparative examples in consideration of the same molecular weight of aromatic polycarbonate resin, in other words, when examples 1-1 to 1-3 and examples 1-7 to 1-8 are compared with comparative example 1, examples 1-4 are compared with comparative example 1-2, examples 1-5 are compared with comparative example 1-3, and examples 1-6 are compared with comparative examples 1-4, examples have substantially similar mechanical properties (tensile strength) but better flowability, surface physical properties (chemical resistance) than comparative examples.

Examples 1-1 to 1-10 were compared with comparative examples 1-5. Comparative examples 1 to 5 relate to coating products obtained by coating a carbonate resin with a polyurethane resin to improve chemical resistance. The resin compositions according to examples 1-1 to 1-10 are superior to the resin compositions according to comparative examples 1-5 in that the resin compositions according to examples 1-1 to 1-10 can provide surface physical properties (chemical resistance) without lowering mechanical properties (tensile strength and flexural strength) as compared with the resin compositions of comparative examples 1-5. Further, the resin compositions according to examples 1-1 to 1-10 are also significantly superior to the resin compositions according to comparative examples 1-5, because the resin compositions according to examples 1-1 to 1-10 have improved degree of freedom of molding (flowability).

Table 3 below shows the results of examples 2-1 to 2-10, and Table 4 shows the results of comparative examples 2-1 to 2-4.

As is apparent from tables 3 and 4, the resin compositions according to examples 2-1 to 2-10 were suitable for thin-walled molded products. Further, the resin compositions according to examples 2-1 to 2-10, to which the organic sulfonic acid or metal organic sulfonate compound (flame retardant) was added, were excellent in moldability (flowability), mechanical properties (tensile strength and flexural strength), surface physical properties (chemical resistance), and flame retardant properties, as compared with the resin compositions according to comparative examples 2-1 to 2-4.

[ Table 1]

[ Table 2]

[ Table 3]

[ Table 4]

[ Table 5]

Table 5: standards and decision criteria for UL94V

Claims

1. A resin composition comprising:

100 parts by mass of an aromatic polycarbonate-polyorganosiloxane copolymer; and

The polyurethane resin is a cured resin, and

the polyurethane resin having a crosslinked structure has a three-dimensional crosslinked structure obtained by reacting a polyester polyol and a polyisocyanate with each other.

2. The resin composition according to claim 1, wherein

The average particle diameter of the powder of the polyurethane resin having a crosslinked structure is 0.5mm to 1.5 mm.

3. The resin composition according to claim 1, wherein

The ratio of the powder of the polyurethane resin having a crosslinked structure with the particle diameter of 0.5mm to 1.5mm to the total powder of the polyurethane resin having a crosslinked structure is 70% or more.

4. The resin composition according to claim 1, wherein

The mass ratio of the polyester polyol to the polyisocyanate is 100:50 to 100: 200.

5. The resin composition according to claim 1, wherein

The polyester polyol has a hydroxyl value of 30 to 300.

6. The resin composition according to claim 1, wherein

The polyester polyol has a weight average molecular weight of 10,000 to 500,000 in terms of polystyrene.

7. The resin composition of claim 1, wherein

The polyisocyanate has more than two isocyanate groups.

8. The resin composition according to claim 1, wherein

Further comprising 0.01 to 3.0 parts by mass of an organic sulfonic acid and/or a metal salt compound of an organic sulfonic acid, relative to 100 parts by mass of the aromatic polycarbonate-polyorganosiloxane copolymer.

9. The resin composition of claim 8, wherein

The weight average molecular weight of the metal salt of organic sulfonic acid compound in terms of polystyrene is 30,000 or more.

10. The resin composition of claim 8, wherein

The organic sulfonic acid metal salt compound contains a sulfonic acid metal salt group, and

the content of the sulfonic acid metal salt group is 0.1 to 10 mol%.

11. The resin composition according to claim 1, wherein

The aromatic polycarbonate-polyorganosiloxane copolymer further contains 0.8 parts by mass or less of an anti-dripping agent per 100 parts by mass of the aromatic polycarbonate-polyorganosiloxane copolymer.

12. The resin composition according to claim 1, wherein

The resin composition is obtained by: adding 0.01 to 5.0 parts by mass of the polyurethane resin having a crosslinked structure to 100 parts by mass of the aromatic polycarbonate-polyorganosiloxane copolymer, and kneading the aromatic polycarbonate-polyorganosiloxane copolymer and the polyurethane resin having a crosslinked structure.

13. The resin composition according to claim 1, wherein

The aromatic polycarbonate-polyorganosiloxane copolymer has an aromatic polycarbonate structural unit having a degree of polymerization of 3 to 100, and the aromatic polycarbonate-polyorganosiloxane copolymer has a polyorganosiloxane structural unit having a degree of polymerization of 2 to 500.

14. The resin composition according to claim 1, wherein

The content of polyorganosiloxane in the aromatic polycarbonate-polyorganosiloxane copolymer is 0.1 to 10% by mass.

15. A method of preparing a resin composition comprising:

adding 0.01 to 5.0 parts by mass of a polyurethane resin having a crosslinked structure to 100 parts by mass of an aromatic polycarbonate-polyorganosiloxane copolymer; and

kneading the aromatic polycarbonate-polyorganosiloxane copolymer and the polyurethane resin having a crosslinked structure,

wherein the polyurethane resin having a crosslinked structure has a three-dimensional crosslinked structure obtained by reacting a polyester polyol and a polyisocyanate with each other.

16. A resin molded body comprising the resin composition according to claim 1.