JP4522204B2 - Thermoplastic polymer composition for multicolor laser marking and laser marking method - Google Patents

Description

  The present invention relates to a thermoplastic polymer composition for multicolor laser marking and a laser marking method. More specifically, the present invention relates to a nacreous appearance while maintaining excellent impact resistance by using a polycarbonate resin and an acrylic resin together. Multicolor development that can mark two or more different colors by irradiating the surface of a molded product of black or dark ground color with laser light having two or more different energies The present invention relates to a thermoplastic polymer composition for laser marking and a laser marking method.

  It is known that when a thermoplastic resin composition containing a polycarbonate resin and an acrylic resin such as polymethyl methacrylate is used, a molded article having a nacreous appearance can be easily obtained. Moreover, since this molded product contains the above-mentioned components, it is also known that the molded product is excellent in impact resistance, heat resistance, hardness, and the like (Patent Documents 1, 2 and the like).

On the other hand, a laser marking method is known as a technique for imparting markings of characters, symbols, designs, etc. of a desired color on the surface of a molded article made of a composition containing a resin (Patent Document 3 etc.). In recent years, a thermoplastic polymer composition and a laser marking method for diversifying the color of the marking to be used in a wide field have been disclosed (Patent Document 4). In Patent Document 4, an organic pigment / dye that is not easily affected by laser light as a colored colorant, and a resin such as a polyolefin resin, a polyester resin, a polyacetal resin, or an acrylic resin as a thermoplastic polymer. A resin composition is disclosed.
Further, a thermoplastic polymer composition for providing a chromatic marking derived from a colorant concealed in a black or dark ground color is disclosed (Patent Document 5).

JP-A-8-48863 Japanese Patent Laid-Open No. 11-60878 JP-A-5-92657 JP-A-6-297828 JP-A-8-127175

  The present invention maintains the excellent impact resistance by using a polycarbonate resin and an acrylic resin in combination, does not exhibit a pearly luster appearance, and is applied to the surface of a black or dark-colored ground color molded product. It is an object of the present invention to provide a thermoplastic polymer composition for multicolor laser marking and a laser marking method capable of marking in two or more different colors by irradiating with laser light having different energy. This multicolor laser marking includes two or more different tones including a chromatic color derived from a colorant, which is formed on the surface of a molded article exhibiting a black or dark ground color, for example, derived from a colorant Includes chromatic and white.

〔一般式（１）中、Ｒ ^Ａ 、Ｒ ^Ｂ 、Ｒ ^Ｃ 、Ｒ ^Ｄ 及びＲ ^Ｅ は、水素原子、アルキル基、アルケニル基、ベンゼン環を含む基又はヘテロ原子を含む基であり、各々、同一であっても異なってもよい。また、一般式（２）中、Ｒ ^Ｆ は、アルケニル基、アルキル基、ベンゼン環を含む基又はヘテロ原子を含む基であり、Ｙはアルキレン基であり、ｋは正の整数である。〕
上記重合体成分〔Ａ〕に含まれる上記ポリカーボネート樹脂（Ａ１）及び上記アクリル系樹脂（Ａ２）の含有割合は、これらの合計を１００質量％とした場合にそれぞれ１〜９９質量％及び９９〜１質量％であり、上記リン酸エステル系化合物〔Ｂ〕の含有量は、上記ポリカーボネート樹脂（Ａ１）及び上記アクリル系樹脂（Ａ２）の合計を１００質量部とした場合に０．１〜５０質量部であり、上記有彩色着色剤〔Ｃ〕の含有量は、上記重合体成分〔Ａ〕を１００質量部とした場合に０．００１〜３質量部であり、且つ、上記黒色物質〔Ｄ〕の含有量は、上記重合体成分〔Ａ〕を１００質量部とした場合に０．０１〜２質量部であることを特徴とする多色発色レーザーマーキング用熱可塑性樹脂組成物。
２．上記アクリル系樹脂（Ａ２）は、ゴム質重合体（ａ１）の存在下に、（メタ）アクリル酸エステル化合物を含む単量体（ａ２）を重合して得られるゴム強化アクリル系樹脂（Ａ２−１）、及び／又は、（メタ）アクリル酸エステル化合物を含む単量体の（共）重合体（Ａ２−２）を含む上記１に記載の多色発色レーザーマーキング用熱可塑性樹脂組成物。
３．上記芳香族基は、下記一般式（ＩＩＩ）で表される基である上記１又は２に記載の多色発色レーザーマーキング用熱可塑性樹脂組成物。

〔式中、Ｒ ^Ｇ 及びＲ ^Ｈ は、水素原子、アルキル基、アルケニル基、ベンゼン環を含む基又はヘテロ原子を含む基であり、各々、同一であっても異なってもよい。〕
４．上記有彩色着色剤〔Ｃ〕は、示差熱分析において、３６０℃以上５９０℃以下の範囲に発熱ピークを有する上記１乃至３のいずれかに記載の多色発色レーザーマーキング用熱可塑性樹脂組成物。
５．上記黒色物質〔Ｄ〕は、カーボンブラック、チタンブラック及び黒色酸化鉄から選ばれる少なくとも１種である上記１乃至４のいずれかに記載の多色発色レーザーマーキング用熱可塑性樹脂組成物。
６．上記重合体成分〔Ａ〕は、更に、ポリエステル系樹脂（Ｅ１）、ゴム強化スチレン系樹脂（Ｅ２）及びポリオレフィン系樹脂（Ｅ３）から選ばれる少なくとも１種の熱可塑性樹脂〔Ｅ〕を含み、上記重合体成分〔Ａ〕に含まれるこの熱可塑性樹脂〔Ｅ〕の含有量は、上記重合体成分〔Ａ〕の全量に対し、９８質量％以下である上記１乃至５のいずれかに記載の多色発色レーザーマーキング用熱可塑性樹脂組成物。
７．２以上の異なるエネルギーを有するレーザー光を、上記１乃至６のいずれかに記載の多色発色レーザーマーキング用熱可塑性樹脂組成物を含む成形品に照射して、２以上の異なる色調にマーキングすることを特徴とするレーザーマーキング方法。 The present invention is shown below.
1. [A] Polymer component containing polycarbonate resin (A1) and acrylic resin (A2), [B] phosphate ester compound, [C] chromatic colorant, [D] A thermoplastic resin composition for multicolor laser marking, which contains a black substance that disappears or discolors itself, and is marked in two or more different colors by irradiating laser light having two or more different energies The phosphate ester compound [B] is a phosphate ester compound (B1) having an aromatic group and an ester bond-containing group, and the aromatic group is represented by the following general formula (1). The ester bond-containing group is a group represented by the following general formula (2),

[In the general formula (1), R ^A , R ^B , R ^C , R ^D and R ^E are a hydrogen atom, an alkyl group, an alkenyl group, a group containing a benzene ring or a group containing a hetero atom, and each is the same. Or different. In general formula (2), R ^F is an alkenyl group, an alkyl group, a group containing a benzene ring or a group containing a hetero atom, Y is an alkylene group, and k is a positive integer. ]
The content ratios of the polycarbonate resin (A1) and the acrylic resin (A2) contained in the polymer component [A] are 1 to 99% by mass and 99 to 1 respectively when the total of these is 100% by mass. The content of the phosphate ester compound [B] is 0.1 to 50 parts by mass when the total of the polycarbonate resin (A1) and the acrylic resin (A2) is 100 parts by mass. The content of the chromatic colorant [C] is 0.001 to 3 parts by mass when the polymer component [A] is 100 parts by mass, and the black substance [D] Content is 0.01-2 mass parts when said polymer component [A] is 100 mass parts, The thermoplastic resin composition for multicolor coloring laser marking characterized by the above-mentioned.
2. The acrylic resin (A2) is a rubber-reinforced acrylic resin (A2-) obtained by polymerizing a monomer (a2) containing a (meth) acrylic acid ester compound in the presence of the rubber polymer (a1). 1) and / or the thermoplastic resin composition for multicolor laser marking according to 1 above , comprising a (co) polymer (A2-2) of a monomer containing a (meth) acrylic acid ester compound.
3. 3. The thermoplastic resin composition for multicolor laser marking according to 1 or 2 above, wherein the aromatic group is a group represented by the following general formula (III) .

[Wherein R ^G and R ^H are a hydrogen atom, an alkyl group, an alkenyl group, a group containing a benzene ring or a group containing a hetero atom, and may be the same or different. ]
4). 4. The thermoplastic resin composition for multicolor laser marking according to any one of 1 to 3, wherein the chromatic colorant [C] has an exothermic peak in a range of 360 ° C. or higher and 590 ° C. or lower in differential thermal analysis.
5). 5. The thermoplastic resin composition for multicolor laser marking according to any one of 1 to 4, wherein the black substance [D] is at least one selected from carbon black, titanium black, and black iron oxide.
6). The polymer component [A] further includes at least one thermoplastic resin [E] selected from a polyester resin (E1), a rubber-reinforced styrene resin (E2), and a polyolefin resin (E3). The content of the thermoplastic resin [E] contained in the polymer component [A] is 98% by mass or less based on the total amount of the polymer component [A]. Thermoplastic resin composition for color development laser marking.
7. Irradiating a molded article containing the thermoplastic resin composition for multicolored laser marking according to any one of 1 to 6 above with a laser beam having two or more different energies to mark two or more different colors A laser marking method characterized by:

According to the thermoplastic resin composition for multicolor laser marking of the present invention, the pearly luster appearance is not developed while maintaining excellent impact resistance by using a polycarbonate resin and an acrylic resin in combination, and black. Alternatively, it is possible to mark two or more different colors by irradiating the surface of a dark-colored ground-colored molded article with laser light having two or more different energies. That is, when a laser beam having two or more different energies is irradiated, the chromatic color derived from the chromatic colorant [C] (the color of the colorant itself, a color with a small degree of density change, or a color tone due to discoloration) Can be marked in two or more different tones, including different colors.
When the aromatic group and ester bond-containing group possessed by the phosphate ester compound [B] are each a predetermined functional group, the pearly luster appearance on the surface of the molded article is high, so that multicolor coloring The marking becomes clearer.
When the chromatic colorant [C] has an exothermic peak temperature in a predetermined temperature range, a clear marking can be formed.
When the black material [D] is at least one selected from carbon black, titanium black, and black iron oxide, these do not remain in a colored state on the marking portion formed by irradiation with laser light. A clear marking such as a color derived from the chromatic colorant [C] and white can be obtained.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the invention.
The thermoplastic polymer composition for multicolor laser marking of the present invention comprises: [A] a polymer component containing a polycarbonate resin (A1) and an acrylic resin (A2); [B] a phosphate ester compound; C] a chromatic colorant and [D] a black substance that itself disappears or changes color by receiving laser light, and is irradiated with laser light having two or more different energies, so that two or more different A thermoplastic resin composition for multicolor laser marking that is marked in color tone, wherein the phosphate ester compound [B] is a phosphate ester compound (B1) having an aromatic group and an ester bond-containing group, And / or a combination of a phosphate ester compound having an aromatic group and a phosphate ester compound having an ester bond-containing group (B2), The content ratios of the polycarbonate resin (A1) and the acrylic resin (A2) contained in the polymer component [A] are 1 to 99% by mass and 99 to 1 respectively when the total of these is 100% by mass. The content of the phosphate ester compound [B] is 0.1 to 50 parts by mass when the polymer component [A] is 100 parts by mass, and the chromatic colorant [ The content of C] is 0.001 to 3 parts by mass when the polymer component [A] is 100 parts by mass, and the content of the black substance [D] is the polymer component [A] When A] is 100 parts by mass, it is 0.01 to 2 parts by mass.

1. Polymer component [A]
The polymer component [A] according to the present invention includes a polycarbonate resin (A1) and an acrylic resin (A2).

1-1. Polycarbonate resin (A1)
The polycarbonate resin (A1) is not particularly limited as long as it has a carbonate bond in the main chain.
The polycarbonate resin (A1) may be an aromatic polycarbonate or an aliphatic polycarbonate. Moreover, you may use combining these. In the present invention, an aromatic polycarbonate is preferable from the viewpoint of compatibility with the acrylic resin (A2) used in combination, and further, impact resistance and heat resistance in the case of a molded product.

  Aromatic polycarbonates include those obtained by melting transesterification (transesterification reaction) of aromatic dihydroxy compounds and carbonic acid diesters, those obtained by interfacial polycondensation using phosgene, and the reaction between pyridine and phosgene. Those obtained by the pyridine method using the product can be used.

  As said aromatic dihydroxy compound, what is necessary is just a compound which has two hydroxyl groups in a molecule | numerator, dihydroxybenzene, such as hydroquinone and resorcinol, 4,4'- biphenol, 2,2-bis (4-hydroxyphenyl) propane. (Hereinafter simply referred to as “bisphenol A”), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 2 , 2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1- Bis (p-hydroxyphenyl) ethane, 2,2-bis (p-hydroxyphenyl) butane, 2,2-bis p-hydroxyphenyl) pentane, 1,1-bis (p-hydroxyphenyl) cyclohexane, 1,1-bis (p-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (p-hydroxyphenyl) -3 , 3,5-trimethylcyclohexane, 1,1-bis (p-hydroxyphenyl) -1-phenylethane, 9,9-bis (p-hydroxyphenyl) fluorene, 9,9-bis (p-hydroxy-3- Methylphenyl) fluorene, 4,4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisopropylidene) diphenol, bis (p-hydroxyphenyl) oxide, bis (p- Hydroxyphenyl) ketone, bis (p-hydroxyphenyl) ether, bis (p-hydro) Siphenyl) ester, bis (p-hydroxyphenyl) sulfide, bis (p-hydroxy-3-methylphenyl) sulfide, bis (p-hydroxyphenyl) sulfone, bis (3,5-dibromo-4-hydroxyphenyl) sulfone, Examples thereof include bis (p-hydroxyphenyl) sulfoxide. These can be used alone or in combination of two or more.

  Of the aromatic dihydroxy compounds, compounds having a hydrocarbon group between two benzene rings are preferred. In this compound, the hydrocarbon group may be a halogen-substituted hydrocarbon group. Further, the benzene ring may be one in which a hydrogen atom contained in the benzene ring is substituted with a halogen atom. Therefore, the above compounds include bisphenol A, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 2,2 -Bis (3-t-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis ( p-hydroxyphenyl) ethane, 2,2-bis (p-hydroxyphenyl) butane and the like. Of these, bisphenol A is particularly preferable.

  Examples of the carbonic acid diester used for obtaining the aromatic polycarbonate by transesterification include dimethyl carbonate, diethyl carbonate, di-t-butyl carbonate, diphenyl carbonate, and ditolyl carbonate. These can be used alone or in combination of two or more.

  The viscosity average molecular weight of the polycarbonate resin (A1) is preferably 13,000 to 32,000, more preferably 17,000 to 31,000, and particularly preferably 18,000 to 30,000.

  The polycarbonate resin (A1) contained in the polymer component [A] has a content ratio with the acrylic resin (A2) in a predetermined range. That is, the content of the polycarbonate resin (A1) is 1 to 99% by mass, preferably 3 to 97% by mass, when the total of the polycarbonate resin (A1) and the acrylic resin (A2) is 100% by mass. %, More preferably 5 to 95% by mass. If it is this range, it will be especially excellent in the impact resistance of the molded article obtained using this composition, heat resistance, a molded external appearance, etc.

1-2. Acrylic resin (A2)
This acrylic resin (A2) is preferably a resin containing (i) a specific rubber-reinforced acrylic resin and (ii) a monomer (co) polymer containing a (meth) acrylic acid ester compound. is there. Each of these may be used alone or in combination.

  As said (i), rubber-reinforced acrylic resin (A2-1) obtained by superposing | polymerizing the monomer (a2) containing a (meth) acrylic acid ester compound in presence of rubber-like polymer (a1). It is. The rubber-reinforced acrylic resin (A2-1) may be a resin composed only of a grafted rubbery polymer obtained by graft polymerization of the monomer (a2) to the rubbery polymer (a1). A resin composed of a mixture of a grafted rubbery polymer and a (co) polymer of the monomer (a2) may be used.

  Examples of the rubber polymer (a1) include a diene rubber polymer using a conjugated diene compound and a non-diene rubber polymer using a monomer other than the conjugated diene compound. These can be used alone or in combination.

Diene rubbery polymers include polybutadiene, styrene / butadiene copolymer, styrene / isoprene copolymer, butadiene / acrylonitrile copolymer, butadiene / (meth) acrylic acid ester copolymer, styrene / butadiene block copolymer And a styrene / isoprene block copolymer. Of these, polybutadiene, styrene / butadiene copolymer and the like are preferable. These can be used alone or in combination of two or more.
Non-diene rubber polymers include ethylene / α-olefin copolymers, ethylene / α-olefin rubber polymers such as ethylene / α-olefin / non-conjugated diene copolymers; styrene / butadiene copolymers. Hydrogenated polymer, Hydrogenated styrene / butadiene block copolymer, Hydrogenated styrene / isoprene copolymer, Hydrogenated styrene / isoprene block copolymer, Hydrogenated butadiene / acrylonitrile copolymer Diene polymers such as additives, hydrogenated butadiene / (meth) acrylate copolymer, hydrogenated butadiene (co) polymer, hydrogenated styrene / butadiene random copolymer And hydrogenated products; silicone rubbers; acrylic rubbers and the like. Of these, ethylene / α-olefin rubbery polymers, hydrogenated styrene / butadiene copolymers, hydrogenated styrene / butadiene block copolymers, silicone rubbers, acrylic rubbers and the like are preferable. These can be used alone or in combination of two or more.

  The rubber polymer (a1) has a spherical shape, but is not particularly limited, and may have various shapes. The average particle size is preferably 0.1 to 2 μm, more preferably 0.12 to 0.8 μm. If it is this range, the impact resistance of the molded product obtained, rigidity, and external appearance property will become especially favorable.

Next, the monomer (a2) polymerized in the presence of the rubbery polymer (a1) will be described. This monomer (a2) contains a (meth) acrylic acid ester compound.
Examples of the (meth) acrylate compound include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, and t-butyl acrylate. Acrylates such as n-amyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate; Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, n-amino methacrylate , Methacrylic acid n- hexyl methacrylate n- octyl, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, methacrylic acid esters of benzyl methacrylate. These can be used alone or in combination of two or more.
Among the compounds exemplified above, methyl methacrylate, n-butyl methacrylate, n-butyl acrylate and the like are preferable, and methyl methacrylate is particularly preferable.
The content rate of the said (meth) acrylic acid ester compound contained in the said monomer (a2) is 10 mass% or more normally, Preferably it is 15 mass% or more, More preferably, it is 20-100 mass%.

  The monomer (a2) may contain another monomer copolymerizable with the (meth) acrylic acid ester compound. Examples of other monomers include aromatic vinyl compounds, vinyl cyanide compounds, maleimide compounds, and the like. Also, (meth) acrylic acid ester compounds having functional groups such as hydroxyl group, amino group, amide group, epoxy group and oxazoline group, functional groups such as hydroxyl group, carboxyl group, amino group, amide group, epoxy group and oxazoline group An aromatic vinyl compound having a group can also be used. These can be used alone or in combination of two or more.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, ethylstyrene, vinyltoluene, vinylxylene, methyl-α-methylstyrene, t-butylstyrene, divinylbenzene, 1 , 1-diphenylstyrene, vinylnaphthalene and the like. These can be used alone or in combination of two or more.
Of the compounds exemplified above, styrene, α-methylstyrene, p-methylstyrene and the like are preferable.
When using the said aromatic vinyl compound, Preferably it is 1-90 mass% with respect to the whole quantity of the said monomer (a2), More preferably, it is 5-85 mass%, More preferably, it is 10-80 mass%. .

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. These can be used alone or in combination of two or more. Of these, acrylonitrile is preferred.
When the vinyl cyanide compound is used, it is preferably 1 to 60% by mass, more preferably 2 to 55% by mass, and still more preferably 5 to 55% by mass with respect to the total amount of the monomer (a2). .

Examples of the maleimide compound include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N-cyclohexylmaleimide, α , Β-unsaturated dicarboxylic acid imide compounds and the like. These can be used alone or in combination of two or more. Of these, N-phenylmaleimide, N-cyclohexylmaleimide and the like are preferable. In addition, as another method of introducing a monomer unit composed of a maleimide compound into a polymer without using a maleimide compound, for example, a method of copolymerizing maleic anhydride and then imidizing can be mentioned. .
When using the said maleimide type compound, Preferably it is 1-60 mass% with respect to the whole quantity of the said monomer (a2), More preferably, it is 2-55 mass%, More preferably, it is 5-55 mass%.

Examples of the (meth) acrylic acid ester having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and the like. Examples of the (meth) acrylic acid ester having an amino group include dimethylaminoethyl methacrylate. Examples of the (meth) acrylic acid ester having an amide group include acrylamide and methacrylamide. Examples of the (meth) acrylic acid ester having an epoxy group include glycidyl acrylate and glycidyl methacrylate.
Examples of the aromatic vinyl compound having an amino group include N, N-diethyl-p-aminomethylstyrene and N, N-diethyl-p-aminoethylstyrene.
In addition to the other monomers exemplified above, vinyl compounds such as acrylic acid, methacrylic acid, vinyl oxazoline, vinyl pyridine and the like can also be used.
The said compound can be used individually by 1 type or in combination of 2 or more types.
When the rubber-reinforced acrylic resin (A2-1) obtained by copolymerizing the above-mentioned compound having various functional groups and a (meth) acrylic acid ester compound is used, other heat is added to the composition. When the plastic resin is contained, the compatibility with the resin component can be adjusted.
When using the compound which has the said functional group, Preferably it is 0.01-30 mass% with respect to the whole quantity of the said monomer (a2), More preferably, it is 0.1-20 mass%, More preferably, it is 0.00. 1 to 15% by mass. If it exists in the said range, provision of the preferable performance which the compound to be used has can be adjusted.

  The rubber-reinforced acrylic resin (A2-1) can be obtained from the monomer (a2) by emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization or the like in the presence of the rubbery polymer (a1). . Of these, emulsion polymerization is preferred.

In emulsion polymerization, a polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water and the like are usually used.
As a method of using the monomer (a2) at the time of polymerization, polymerization may be carried out after adding the whole amount of the monomer (b2) in the presence of the whole amount of the rubbery polymer (a1). Or you may superpose | polymerize, adding continuously, and may superpose | polymerize by the method of combining these. Moreover, you may add the whole quantity or one part of usage-amount also about the rubber-like polymer (a1) in the middle of superposition | polymerization.

As the polymerization initiator, organic hydroperoxides typified by cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, etc. Redox based on combination with agents, or persulfates such as potassium persulfate, peroxides such as benzoyl peroxide (BPO), lauroyl peroxide, t-butyl peroxylaurate, t-butyl peroxymonocarbonate, etc. Is mentioned. These can be used alone or in combination of two or more. The amount of the polymerization initiator used is usually 0.1 to 1.5% by mass, preferably 0.2 to 0.7% by mass, based on the total amount of the monomer (a2).
The polymerization initiator at the time of polymerization can be added to the reaction system all at once or continuously.

  Examples of the chain transfer agent include mercaptans such as n-hexyl mercaptan, octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan, terpinolene, α -A dimer of methylstyrene or the like. These can be used alone or in combination of two or more. The amount of the chain transfer agent used is usually 0.05 to 2.0% by mass with respect to the total amount of the monomer (a2).

  Examples of the emulsifiers include higher alcohol sulfates, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, aliphatic sulfonates such as sodium lauryl sulfate, higher aliphatic carboxylates, and anionic surface activity such as rosinate. And nonionic surfactants such as an alkyl ester type and an alkyl ether type of polyethylene glycol. These can be used alone or in combination of two or more. The usage-amount of this emulsifier is 0.3 to 5.0 mass% normally with respect to the whole quantity of a monomer (a2).

Latex obtained by emulsion polymerization is usually purified by coagulating with a coagulant to form a polymer component in powder form, and then washing and drying. As the coagulant, inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride, and sodium chloride, inorganic acids such as sulfuric acid and hydrochloric acid, and organic acids such as acetic acid and lactic acid are used.
In addition, in the case of suspension polymerization, solution polymerization, bulk polymerization, etc., known methods can be applied to each.

The graft ratio of the graft polymer contained in the rubber-reinforced acrylic resin (A2-1) is not particularly limited, but is preferably 10 to 200%, more preferably 15 to 150%, and particularly preferably 20 to 100%. . If it is this range, the impact strength of the molded product obtained will be excellent, and also the appearance will be good. Moreover, it is excellent in workability.
Here, the graft ratio refers to x grams of the rubber component in 1 gram of the rubber-reinforced acrylic resin (A2-1) and 1 gram of the rubber-reinforced acrylic resin (A2-1) in acetone (however, the acrylic rubber) In the case of a rubber-reinforced acrylic resin obtained by using as a rubber polymer (a1), acetonitrile is used. It is.
Graft rate (%) = {(y−x) / x} × 100
The graft ratio (%) is the kind and amount of a polymerization initiator, a chain transfer agent, an emulsifier, a solvent, etc. when producing the rubber-reinforced acrylic resin (A2-1), and further, a polymerization time, It can be easily controlled by changing the polymerization temperature or the like.

  Acetone-soluble content of the rubber-reinforced acrylic resin (A2-1) (however, in the case of a rubber-reinforced acrylic resin obtained by using acrylic rubber as the rubbery polymer (a1), acetonitrile-soluble content and The intrinsic viscosity (measured in methyl ethyl ketone at 30 ° C.) is preferably 0.1 to 1.2 dl / g, more preferably 0.2 to 1.0 dl / g, particularly preferably 0.2 to 0. .8 dl / g.

The average particle diameter of the grafted rubbery polymer contained in the rubber-reinforced acrylic resin (A2-1) can be measured with an electron microscope, preferably 0.1 to 2 μm, more preferably 0.12 to 0.12. 0.8 μm. If it is this range, the impact resistance of the molded product obtained, rigidity, and external appearance property will become especially favorable.
The rubber-reinforced acrylic resin (A2-1) can be used alone or in combination of two or more.

  When the rubber-reinforced acrylic resin (A2-1) is used alone as the acrylic resin (A2), it contains the rubber-reinforced acrylic resin (A2-1) and a (meth) acrylic acid ester compound described later. When the (co) polymer (A2-2) obtained by polymerizing monomers is used in combination, the content of the rubbery polymer (a1) is relative to the entire acrylic resin (A2). Preferably it is 2-70 mass%, More preferably, it is 3-65 mass%, More preferably, it is 5-65 mass%. If it is this range, the impact resistance and rigidity of the molded product obtained will become especially favorable.

Moreover, said (ii) is the (co) polymer (A2-2) obtained by superposing | polymerizing the monomer containing a (meth) acrylic acid ester compound.
As a monomer used for making the said (co) polymer (A2-2), what was illustrated as a monomer (a2) which can be used when forming said (A2-1) as it is. Can be used. In addition, the usage-amount of each monomer may be the same as the said monomer (a2), and may differ.

The (co) polymer (A2-2) can be obtained by a known method such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization.
Moreover, as a usage method of the monomer containing a (meth) acrylic acid ester compound, it may polymerize after adding the whole quantity of this monomer collectively, and it may superpose | polymerize, dividing | segmenting or adding continuously. Alternatively, polymerization may be performed by a combination of these methods.

The intrinsic viscosity (measured in methyl ethyl ketone at 30 ° C.) of the acetone-soluble component of the (co) polymer (A2-2) is preferably 0.1 to 1.2 dl / g, more preferably 0.2 to 1. 0.0 dl / g, particularly preferably 0.2 to 0.8 dl / g.
The said (co) polymer (A2-2) can be used individually by 1 type or in combination of 2 or more types.

  The content of the acrylic resin (A2) contained in the polymer component [A] is 1 to 99% by mass when the total of the polycarbonate resin (A1) and the acrylic resin (A2) is 100% by mass. Yes, preferably 3-97 mass%, more preferably 5-95 mass%. If it is this range, it will be especially excellent in the impact resistance of the molded article obtained using this composition, heat resistance, a molded external appearance, etc.

  The polymer component [A] may be composed of a polycarbonate resin (A1) and an acrylic resin (A2), a polycarbonate resin (A1), an acrylic resin (A2), and another polymer. It may consist of:

Other polymers are not limited in properties such as thermoplasticity, thermosetting property, photocuring property (visible light, ultraviolet ray, electron beam, etc.), and room temperature curing property, but a thermoplastic polymer is preferable. The “curable” polymer includes an oligomer that becomes a polymer after curing. The “curable” polymer and other polymers may be cured at any time, and may be cured at the time of kneading, molding, or laser light irradiation.
Examples of the thermoplastic polymer include resins, alloys, and elastomers, and these can be used alone or in combination. Of these, thermoplastic resins are preferred.
Examples of the thermoplastic resin include polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate; styrene resins such as styrene / acrylonitrile copolymer and styrene / maleic anhydride copolymer; rubber Reinforced styrene resin (a resin containing a copolymer resin obtained by polymerizing a monomer containing styrene in the presence of a rubbery polymer); polyethylene, polypropylene, ionomer, ethylene / vinyl acetate copolymer, Olefin resins containing α-olefin units such as ethylene-vinyl alcohol copolymer, cyclic olefin copolymer, chlorinated polyethylene; polyvinyl chloride resins such as polyvinyl chloride, ethylene-vinyl chloride polymer, polyvinylidene chloride; Polyamide 6, polyamide 6,6, poly Polyamide resins (PA) such as amides 6 and 12; Polyacetal resins (POM); Polyarylate resins; Polyphenylene ethers; Polyphenylene sulfides; Fluorine resins such as polytetrafluoroethylene and polyvinylidene fluoride; Liquid crystal polymers; Imide resins such as polyetherimide; Ketone resins such as polyetherketone and polyetheretherketone; Sulfone resins such as polysulfone and polyethersulfone; and polyvinyl acetate, polyethylene oxide, polyvinyl alcohol, polyvinyl ether, polyvinyl Examples include butyral, phenoxy resin, photosensitive resin, and biodegradable plastic. Of these, polyester resins, rubber reinforced styrene resins and polyolefin resins are preferred.

Examples of thermoplastic alloys include PA / rubber reinforced thermoplastic resins (such as rubber reinforced styrene resins), PBT / rubber reinforced thermoplastic resins (such as rubber reinforced styrene resins), and the like.
Examples of thermoplastic elastomers include olefin elastomers; styrene elastomers such as styrene / butadiene / styrene block copolymers; polyester elastomers; urethane elastomers; vinyl chloride elastomers; polyamide elastomers; It is done.

  When the polymer component [A] contains the other polymer, the content is preferably 98% by mass or less, more preferably 1 to 98% by mass with respect to the total amount of the polymer component [A]. More preferably, it is 1-94 mass%, Most preferably, it is 1-90 mass%. Further, depending on the purpose and application, it may be 1 to 80% by mass, further 1 to 50% by mass, further 1 to 25% by mass, particularly 1 to 25% by mass.

2. Phosphate ester compound [B]
This phosphate ester compound [B] is a phosphate ester compound (B1) having an aromatic group and an ester bond-containing group, and / or a phosphate ester compound having an aromatic group and an ester bond-containing group. It is a combination (B2) of the phosphoric ester compound which has.
The phosphate ester compound [B] related to the present invention is a compound containing at least a phosphate ester skeleton, that is, -O-P-O-, and is a phosphate ester compound, a phosphite compound, or a polyphosphate compound. Etc. are widely included.
In the case where the phosphate ester compound [B] is (B1), the aromatic group and the ester bond-containing group are each independently directly on the oxygen atom in the phosphate ester skeleton, or It is a compound bonded through a divalent group. In the present invention, it is preferable that the aromatic group and the ester bond-containing group are each independently bonded directly to an oxygen atom in the phosphate ester skeleton.
When the phosphate ester compound [B] is the above (B2), the phosphate ester compound having an aromatic group and the phosphate ester compound having an ester bond-containing group are both aromatic. The group in which the group group and the ester bond-containing group are bonded to the oxygen atom in the phosphate ester skeleton directly or via a divalent group.

〔式中、Ｒ^Ａ、Ｒ^Ｂ、Ｒ^Ｃ、Ｒ^Ｄ及びＲ^Ｅは、水素原子、アルキル基、アルケニル基、ベンゼン環を含む基又はヘテロ原子を含む基であり、各々、同一であっても異なってもよい。〕 The aromatic group is a group that is not directly bonded to an ester bond-containing group described later. This aromatic group is any of a monocyclic aromatic group (a group containing a benzene ring), a bicyclic aromatic group (a group containing a naphthalene ring) and a tricyclic aromatic group (a group containing an anthracene ring). It may be any other aromatic group. Among these, a monocyclic aromatic group, that is, a group represented by the following general formula (I) is preferable.

[Wherein, R ^A , R ^B , R ^C , R ^D and R ^E are a hydrogen atom, an alkyl group, an alkenyl group, a group containing a benzene ring or a group containing a hetero atom, and each may be the same. May be different. ]

In the above general formula (I), when R ^A , R ^B , R ^C , R ^D or R ^E is an alkyl group, the alkyl group is an aliphatic group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. An alkyl group (which may be linear or branched), an alicyclic alkyl group (which may have a substituent), and the like can be used. Therefore, as this alkyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-amyl group, n-hexyl group, Examples include n-octyl group, 2-ethylhexyl group, nonyl group, decyl group, cyclopropyl group, cyclohexyl group and the like. Of these, a methyl group and an ethyl group are preferred.

In the said general formula (I), when R ^<A> , R <^B> , R <^C> , R ^<D> or R ^<E > is an alkenyl group, it is preferable that these are ^C2- C20.
In addition, when R ^A , R ^B , R ^C , R ^D or R ^E is a group containing a benzene ring, a phenyl group, a benzyl group, an α, α-dimethylbenzyl group, and the like can be given. Of these, α, α-dimethylbenzyl group is preferred. The group containing a benzene ring may be a group in which a hydrogen atom bonded to the benzene ring is substituted with a halogen atom or a substituent.
Further, when R ^A , R ^B , R ^C , R ^D or R ^E is a group containing a hetero atom, hydroxyl group, alkoxysilyl group, epoxy group, carboxyl group, carbonyl group, oxycarbonyl group, sulfide group, disulfide Group, sulfonyl group, sulfinyl group, thiocarbonyl group, imino group, amino group, nitrile group, ammonium group, imide group, amide group, hydrazo group, azo group, diazo group and the like.

In the above general formula (I), when R ^A , R ^B , R ^C , R ^D and R ^E are all hydrogen atoms, the group represented by the general formula (I) is a phenyl group.
^Further, when ^{R A, R B, R C} , at least one of ^{R D} and ^{R E} is a substituent other than hydrogen ^{atom, R A, R B, R C} , ^{R D} and ^{R E} are each, A group selected from an alkyl group and a group containing a benzene ring is preferable. In this case, the alkyl group is more preferably an alkyl group having 1 to 10 carbon atoms, and the group containing a benzene ring is more preferably an α, α-dimethylbenzyl group. Furthermore, an alkyl group having 1 to 3 carbon atoms or an α, α-dimethylbenzyl group is preferable.
Accordingly, in the general formula (I), R ^A , R ^B , R ^C , R ^D and R ^E are each a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or α, α-dimethylbenzyl. Particularly preferred is a group.

〔式中、Ｒ^Ｇ及びＲ^Ｈは、水素原子、アルキル基、アルケニル基、ベンゼン環を含む基又はヘテロ原子を含む基であり、各々、同一であっても異なってもよい。〕 The aromatic group represented by the general formula (I) is preferably a group having any two substituents among R ^A , R ^B , R ^C , R ^D and R ^E. Is represented by the following general formula (III).

[Wherein R ^G and R ^H are a hydrogen atom, an alkyl group, an alkenyl group, a group containing a benzene ring or a group containing a hetero atom, and may be the same or different. ]

In the general formula (III), the types of R ^G and R ^H are the same as R ^A , R ^B , R ^C , R ^D and R ^E. Further, the substitution positions of ^RG and ^RH are not particularly limited, and the 2-position and 4-position when the most adjacent carbon atom is the 1st position when directly bonded to the oxygen atom in the phosphate ester skeleton. It is preferably located at the 3rd and 5th positions, or the 2nd and 6th positions, and particularly preferably located at the 2nd and 4th positions.
Therefore, the aromatic group is preferably a phenyl group or a dimethylphenyl group.

〔式中、Ｒ^Ｆは、アルケニル基、アルキル基、ベンゼン環を含む基又はヘテロ原子を含む基であり、Ｙはアルキレン基であり、ｋは正の整数である。〕 Next, the ester bond-containing group is not particularly limited as long as it is a group including an ester bond site. This ester bond site may be in the main chain of the group or in the side chain. As said ester bond containing group, group represented by the following general formula (II) is preferable.

[Wherein, R ^F is an alkenyl group, an alkyl group, a group containing a benzene ring or a group containing a hetero atom, Y is an alkylene group, and k is a positive integer. ]

In the said general formula (II), when R < ^F > is an alkenyl group, the carbon number becomes like this. Preferably it is 2-5, More preferably, it is 2-4, Most preferably, it is 2-3.
In addition, when R ^F is an alkyl group, an aliphatic alkyl group (which may be linear or branched) is preferable, and the carbon number thereof is preferably 1 to 5, more preferably 1 to 4, and particularly preferably. Is 2-3.
Furthermore, when R ^F is a group containing a benzene ring, a phenyl group, a benzyl group and the like can be mentioned. The group containing a benzene ring may be one in which a hydrogen atom bonded to the benzene ring is substituted with a halogen atom or a substituent.

  In the general formula (II), the alkylene group Y preferably has 1 to 5 carbon atoms, more preferably 2 to 5 carbon atoms, and particularly preferably 2 to 4 carbon atoms. Further, k is preferably 1 to 20, more preferably 1 to 10, particularly preferably 1 to 3.

〔式中、Ｒ^Ｊは、水素原子又は炭素数１〜３のアルキル基であり、Ｙはアルキレン基であり、ｌは正の整数である。〕 R ^F in the general formula (II) is preferably an alkenyl group or an alkyl group, and particularly preferably an alkenyl group. The ester bond-containing group in the case where R ^F is an alkenyl group is represented by the following general formula (IV).

[Wherein R ^J represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Y represents an alkylene group, and l represents a positive integer. ]

In the general formula (IV), R ^J is a hydrogen atom, a methyl group, an ethyl group or a propyl group, and among these, a hydrogen atom and a methyl group are preferable. Carbon number of alkylene group Y becomes like this. Preferably it is 1-5, More preferably, it is 2-5, Most preferably, it is 2-4.
Moreover, in the said general formula (IV), l becomes like this. Preferably it is 1-20, More preferably, it is 1-10, Most preferably, it is 1-3.

  When the phosphate ester compound [B] is a phosphate ester compound (B1) having an aromatic group and an ester bond-containing group, it may be a compound containing one of each of these groups. However, it may be a compound containing two of either one. An example of the former is a phosphate ester-based compound containing one aromatic group, one ester bond-containing group, and one hydroxyl group bonded to a phosphorus atom in the phosphate ester skeleton. An example of the latter is a phosphate ester-based compound containing one aromatic group and two ester bond-containing groups. Moreover, this phosphate ester type compound (B1) can be used individually by 1 type or in combination of 2 or more types.

Further, the phosphate ester compound [B] may be a combination (B2) of a phosphate ester compound having an aromatic group and a phosphate ester compound having an ester bond-containing group, In this case, the former phosphoric ester compound having an aromatic group may contain one or more aromatic groups. The latter phosphoric ester compounds having an ester bond-containing group may also contain one or more ester bond-containing groups.
The phosphoric acid ester compound having an aromatic group and the phosphoric acid ester compound having an ester bond-containing group constituting the phosphoric acid ester compound (B2) are each singly or in combination of two or more. They can be used in combination.
Furthermore, the content ratio of the phosphoric ester compound having an aromatic group and the phosphoric ester compound having an ester bond-containing group is preferably 20 to 80% by mass / 100% when these totals are taken as 100% by mass. It is 80-20 mass%, More preferably, it is 30-70 mass% / 70-30 mass%.

  In the present invention, as the phosphoric ester compound [B], a phosphoric ester compound (B1) having an aromatic group and an ester bond-containing group, and a phosphoric ester compound having an aromatic group and an ester bond are contained. Each of the combinations (B2) of the phosphate ester compounds having a group may be used alone or in combination.

Although the manufacturing method of the said phosphate ester type compound [B] is not specifically limited, The manufacturing example of the said phosphate ester type compound (B1) is shown below.
The phosphate ester compound (B1) includes, for example, phenols (b1) represented by the following general formula (V) and carboxylic acid esters having a hydroxyl group represented by the following general formula (VI) ( It can be obtained by reacting b2) with diphosphorus pentoxide (b3).

〔式中、Ｒ^Ｋ、Ｒ^Ｌ、Ｒ^Ｍ、Ｒ^Ｎ及びＲ^Ｐは、水素原子、アルキル基、アルケニル基、ベンゼン環を含む基又はヘテロ原子を含む基であり、各々、同一であっても異なってもよい。〕

[Wherein, R ^K , R ^L , R ^M , R ^N and R ^P are a hydrogen atom, an alkyl group, an alkenyl group, a group containing a benzene ring or a group containing a hetero atom, and each may be the same. May be different. ]

〔式中、Ｒ^Ｔは、アルケニル基、アルキル基、ベンゼン環を含む基又はヘテロ原子を含む基であり、Ｙはアルキレン基であり、ｍは正の整数である。〕

[Wherein, R ^T is an alkenyl group, an alkyl group, a group containing a benzene ring or a group containing a hetero atom, Y is an alkylene group, and m is a positive integer. ]

In the phenols (b1) represented by the general formula (V), when R ^K , R ^L , R ^M , R ^N or R ^P is an alkyl group, the alkyl group has 1 to 20 carbon atoms, An aliphatic alkyl group (which may be linear or branched) and an alicyclic alkyl group (which may have a substituent) which are preferably 1 to 10 may be used. Therefore, as this alkyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-amyl group, n-hexyl group, Examples include n-octyl group, 2-ethylhexyl group, nonyl group, decyl group, cyclopropyl group, cyclohexyl group and the like. Of these, a methyl group and an ethyl group are preferred.

The general formula ^(V), if ^{R K, R L, R M} , R N or ^{R P} is an alkenyl group, which preferably has a carbon number of 2-20.
In addition, when R ^K , R ^L , R ^M , R ^N or R ^P is a group containing a benzene ring, a phenyl group, a benzyl group, an α, α-dimethylbenzyl group, and the like can be given. Of these, α, α-dimethylbenzyl group is preferred. The group containing a benzene ring may be a group in which a hydrogen atom bonded to the benzene ring is substituted with a halogen atom or a substituent.
Further, when R ^A , R ^B , R ^C , R ^D or R ^E is a group containing a hetero atom, hydroxyl group, alkoxysilyl group, epoxy group, carboxyl group, carbonyl group, oxycarbonyl group, sulfide group, disulfide Group, sulfonyl group, sulfinyl group, thiocarbonyl group, imino group, amino group, nitrile group, ammonium group, imide group, amide group, hydrazo group, azo group, diazo group and the like.

In the above general formula (V), when R ^K , R ^L , R ^M , R ^N and R ^P are all hydrogen atoms, the compound represented by the general formula (V) is phenol.
^Further, when ^{R K, R L, R M} , at least one of ^{R N} and ^{R P} is a substituent other than a hydrogen ^{atom, R K, R L, R M} , ^{R N} and ^{R P} are each A group selected from an alkyl group and a group containing a benzene ring is preferable. In this case, the alkyl group is more preferably an alkyl group having 1 to 10 carbon atoms, and the group containing a benzene ring is more preferably an α, α-dimethylbenzyl group. Furthermore, an alkyl group having 1 to 3 carbon atoms or an α, α-dimethylbenzyl group is preferable.
Therefore, in the general formula (V), R ^K , R ^L , R ^M , R ^N and R ^P are each a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or α, α-dimethylbenzyl. Particularly preferred is a group.

〔式中、Ｒ^Ｑ及びＲ^Ｒは、水素原子、アルキル基、アルケニル基、ベンゼン環を含む基又はヘテロ原子を含む基であり、各々、同一であっても異なってもよい。〕 The phenols (b1) represented by the general formula (V) are preferably compounds having any two substituents among R ^K , R ^L , R ^M , R ^N and R ^P , This compound is represented by the following general formula (VII).

[Wherein, R ^Q and R ^R are a hydrogen atom, an alkyl group, an alkenyl group, a group containing a benzene ring or a group containing a hetero atom, and each may be the same or different. ]

The general formula (VII), for the type of ^{R Q} and ^{R R,} the ^{R K, R L, R M} , is the same as ^{R N} and ^{R P.} The substitution position of ^{R Q} and ^{R R} are not particularly limited. It is preferably located at the 2-position and 4-position, the 3-position and the 5-position, or the 2-position and the 6-position when it is bonded to the phosphate skeleton and the closest carbon atom is the 1-position. It is particularly preferred to be located at the 4th and 4th positions.

  Therefore, as the phenols (b1) represented by the general formula (V), phenol, cresol (o-cresol, m-cresol, p-cresol), ethylphenol (o-ethylphenol, m-ethylphenol, p-ethylphenol) dimethylphenol (2,4-dimethylphenol, 3,5-dimethylphenol, 2,6-dimethylphenol, etc.), diethylphenol, benzylphenol, 4-α-cumylphenol and the like. Of these, phenol, 2,4-dimethylphenol, 3,5-dimethylphenol, and 4-α-cumylphenol are preferred.

Next, in the carboxylic acid ester (b2) having a hydroxyl group represented by the general formula (VI), when ^RT is an alkenyl group, the carbon number is preferably 2 to 5, more preferably 2 to 4, particularly preferably 2 to 3.
Further, when ^RT is an alkyl group, an aliphatic alkyl group (which may be linear or branched) is preferable, and the carbon number thereof is preferably 1 to 5, more preferably 1 to 4, and particularly preferably. Is 2-3.
Furthermore, when ^RT is a group containing a benzene ring, a phenyl group, a benzyl group, and the like can be given. The group containing a benzene ring may be one in which a hydrogen atom bonded to the benzene ring is substituted with a halogen atom or a substituent.

  In the general formula (VI), the alkylene group Y preferably has 1 to 5 carbon atoms, more preferably 2 to 5 carbon atoms, and particularly preferably 2 to 4 carbon atoms. Further, m is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 3.

〔式中、Ｒ^Ｕは、水素原子又は炭素数１〜３のアルキル基であり、Ｙはアルキレン基であり、ｎは正の整数である。〕 ^RT in the general formula (VI) is preferably an alkenyl group or an alkyl group, and particularly preferably an alkenyl group. The carboxylic acid ester (b2) having a hydroxyl group when R ^T is an alkenyl group is represented by the following general formula (VIII).

[In formula, ^RU is a hydrogen atom or a C1-C3 alkyl group, Y is an alkylene group, and n is a positive integer. ]

In the general formula (VIII), R ^U is hydrogen atom, a methyl group, and ethyl group or propyl group, among these, hydrogen atom and methyl group are preferable. Carbon number of alkylene group Y becomes like this. Preferably it is 1-5, More preferably, it is 2-5, Most preferably, it is 2-4.
Moreover, in the said general formula (VIII), n becomes like this. Preferably it is 1-20, More preferably, it is 1-10, Most preferably, it is 1-3.

  Therefore, as the carboxylic acid ester (c2) having a hydroxyl group represented by the general formula (VI), hydroxymethyl acrylate, 2-hydroxylethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, hydroxy Methyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, polyethylene glycol monomethacrylate, polyethylene glycol monoacrylate, polypropylene glycol monomethacrylate, polypropylene glycol monoacrylate, polyethylene glycol-polypropylene glycol monomethacrylate, polyethylene Glycol-polypropylene glycol monoa Relate and the like.

The “diphosphorus pentoxide (b3)” is usually a compound represented by P ₂ O ₅ , but includes P ₂ O _5, P ₄ O _{10 and the} like.

  The method (reaction procedure) of reacting the above phenols (b1), the carboxylic acid ester (b2) having a hydroxyl group, and diphosphorus pentoxide (b3) is not particularly limited. That is, for example, it may be obtained by a two-stage reaction or by a one-stage reaction. In the case of a two-stage reaction, a reaction product obtained by reacting phenols (b1) with diphosphorus pentoxide (b3) and a hydroxyl group-containing carboxylic acid ester (b2) are reacted. The phosphoric acid ester compound (B1) may be produced, and the reaction product obtained by reacting the hydroxyl group-containing carboxylic acid ester (b2) with diphosphorus pentoxide (b3), and phenols The phosphate ester compound (B1) may be produced by reacting with (b1). Further, in the case of a one-step reaction, a phosphate ester compound (B1) is obtained by reacting a mixture of phenols (b1) and hydroxyl group-containing carboxylic acid esters (b2) with diphosphorus pentoxide (b3). ) Can be manufactured.

When diphosphorus pentoxide (b3) is used, if the phenols (b1) and the hydroxyl group-containing carboxylic acid esters (b2) each have a melting point, it is used at a temperature equal to or higher than the melting point of the compound having a high melting point (further, The melting point is preferably 120 to 120 ° C., more preferably 100 to 100 ° C.
Further, in the case of using the above-mentioned two-stage reaction, when the phenols (b1) or the hydroxyl group-containing carboxylic acid esters (b2) are added (such as dropwise addition), the first-stage reaction product is not solidified. It is preferably carried out at a temperature, more preferably at a temperature at which it does not solidify to 120 ° C, and particularly preferably at a temperature at which it does not solidify to 100 ° C.

  The amount of phenols (b1), hydroxyl group-containing carboxylic acid esters (b2) and diphosphorus pentoxide (b3) used is not particularly limited, but the phenols (b1) and the amount of diphosphorus pentoxide (b3) used The total amount with the hydroxyl group-containing carboxylic acid ester (b2) is preferably 1: 1 to 1:10, more preferably 1: 2 to 1: 5. Moreover, it is preferable that the hydroxyl group contained in phenols (b1) and hydroxyl-group containing carboxylic acid ester (b2) is 1-10 mol with respect to 1 mol of diphosphorus pentoxide (b3) (P2O5). 2 to 5 mol is preferable. Further, the phenols (b1) and the hydroxyl group-containing carboxylic acid esters (b2) can be used in combination so as to be in this range.

  Moreover, when it is set as said (B2) as said phosphate ester type compound [B], using the manufacturing method of said (B1), the phosphate ester type compound which has an aromatic group, and ester bond containing What is necessary is just to mix in a predetermined ratio, after manufacturing separately the phosphate ester type compound which has group. That is, the phosphoric ester compound having an aromatic group is obtained by reacting the phenols (b1) represented by the general formula (V) with diphosphorus pentoxide (b3), The phosphate ester-based compound having a bond-containing group can be obtained by reacting a carboxylic acid ester (b2) having a hydroxyl group and diphosphorus pentoxide (b3). In each of these reactions, the molar ratio is adjusted according to the purpose.

  In addition, according to the manufacturing method of the said phosphate ester type compound (B1), since a reaction system contains phenols (b1), hydroxyl-group containing carboxylate ester (b2), and diphosphorus pentoxide (b3), it is a small amount. However, the phosphate ester compounds having an aromatic group and the phosphate ester compounds having an ester bond-containing group listed as (B2) above may be by-produced in the reaction product. In this invention, the reaction product obtained by the manufacturing method of the said phosphate ester type compound (B1) can be used as a raw material of a composition as it is.

  The content of the phosphate ester compound [B] contained in the multicolor laser marking thermoplastic resin composition of the present invention is 100 parts by mass of the total of the polycarbonate resin (A1) and the acrylic resin (A2). In this case, it is 0.1 to 50 parts by mass, preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass. When there is too little content of this phosphate ester type compound [B], when it is set as a molded article, a nacreous appearance is expressed. On the other hand, if the content is too large, the heat resistance, hardness, appearance, etc. may deteriorate.

3. Chromatic colorant [C]
The chromatic colorant [C] may be any colorant such as red, yellow, blue, purple, green, etc., as long as it is other than black and white, and other than black and white. Good. That is, it may be a pigment or a dye. A thing with an exothermic peak in the range of 360 degreeC or more and 590 degrees C or less is preferable by a differential thermal analysis. A preferred temperature is 380 ° C. or more and 585 ° C. or less, more preferably 400 ° C. or more and 585 ° C. or less. If the temperature showing the exothermic peak is too low, the chromatic marking tends to be defective when irradiated with low energy laser light. On the other hand, if the temperature is too high, the marking of white or a color having a reduced color density derived from this chromatic colorant tends to be defective when irradiated with high-energy laser light. Measurement conditions by differential thermal analysis are as described in the examples.

If the temperature which shows an exothermic peak exists in the said preferable temperature range, the said chromatic colorant [C] can also be used in combination of 2 or more types of chromatic colorants.
The chromatic colorant having an exothermic peak in the above range has a pigment or dye having a phthalocyanine skeleton (blue to green), a pigment or dye having a diketopyrrolopyrrole skeleton (orange to red), or a dioxazine skeleton. Pigment or dye (purple), pigment or dye having a quinacridone skeleton (orange to purple), pigment or dye having a quinophthalone skeleton (yellow to red), pigment or dye having an anthraquinone skeleton (yellow to blue), perylene skeleton Pigments or dyes (red to purple), pigments or dyes having a perinone skeleton (orange to red), pigments or dyes having a metal complex skeleton (yellow to purple), indanthrone pigments (blue to green), triallyl Carbonium pigments (blue), monoazo pigments (yellow to green), disazo pigments (yellow to green), isoindolinone pigments (yellow to purple) Thioindigo pigments (red to violet), include anthrapyridone dye (yellow) and the like. In addition, although the color of the coloring agent is described in parentheses, it is an example.
Among the above, preferred chromatic colorants have at least one skeleton selected from a phthalocyanine skeleton, a diketopyrrolopyrrole skeleton, a dioxazine skeleton, a quinacridone skeleton, a quinophthalone skeleton, an anthraquinone skeleton, a perylene skeleton, a metal complex skeleton, and the like. It is a colorant and is specifically exemplified below.

〔式中、Ｍは、配位金属原子又は２つの水素原子であり、Ｒ^１〜Ｒ^１６は、各々、独立して任意の官能基である。〕
上記フタロシアニン骨格を有する有彩色着色剤は、顔料又は染料である。
上記一般式（ＩＸ）において、Ｍは、銅（Ｃｕ）、アルミニウム（Ａｌ）、亜鉛（Ｚｎ）、スズ（Ｓｎ）又は２つの水素原子であることが好ましく、銅（Ｃｕ）、アルミニウム（Ａｌ）又は亜鉛（Ｚｎ）が更に好ましく、銅（Ｃｕ）又はアルミニウム（Ａｌ）が特に好ましい。尚、Ｍが金属の場合、ハロゲン原子、ＯＨ等の配位子を有してもよい。
また、上記一般式（ＩＸ）において、Ｒ^１〜Ｒ^１６は、無置換の水素原子；フッ素、塩素、臭素、ヨウ素等のハロゲン原子；スルホン酸アミド基（−ＳＯ_２ＮＨＲ）、−ＳＯ_３ ⁻・ＮＨ_３Ｒ^＋等の置換基（式中、Ｒは、炭素数１〜２０のアルキル基である。）が好ましく、Ｒ^１〜Ｒ^１６のうちの複数の隣接するＲが連結して芳香環を形成した基も好ましい。特に好ましくは、無置換の水素原子又はスルホン酸アミド基である。 Examples of the chromatic colorant having the phthalocyanine skeleton include compounds represented by the following general formula (IX).

[Wherein, M is a coordination metal atom or two hydrogen atoms, and R ^{1 to} R ¹⁶ are each independently an arbitrary functional group. ]
The chromatic colorant having the phthalocyanine skeleton is a pigment or a dye.
In the above general formula (IX), M is preferably copper (Cu), aluminum (Al), zinc (Zn), tin (Sn) or two hydrogen atoms, copper (Cu), aluminum (Al). Alternatively, zinc (Zn) is more preferable, and copper (Cu) or aluminum (Al) is particularly preferable. In addition, when M is a metal, you may have ligands, such as a halogen atom and OH.
In the general formula (IX), R ^{1 to} R ¹⁶ represent an unsubstituted hydrogen atom; a halogen atom such as fluorine, chlorine, bromine, or iodine; a sulfonic acid amide group (—SO ₂ NHR), —SO ₃ ^—. -A substituent such as NH ₃ R ⁺ (wherein R is an alkyl group having 1 to 20 carbon atoms) is preferable, and a plurality of adjacent Rs out of R ^{1 to} R ¹⁶ are linked to form an aromatic ring. Also preferred are groups that have formed Particularly preferred is an unsubstituted hydrogen atom or a sulfonic acid amide group.

上記銅フタロシアニン顔料の結晶はα型であっても、β型であってもよい。β型銅フタロシアニン顔料の平均二次粒子径は、一般的に、２０μｍを超え３０μｍ以下であるが、本発明においては、その上限が好ましくは２０μｍ、より好ましくは１０μｍであり、下限が１μｍである。尚、平均二次粒子径は、レーザー散乱法粒径分布測定装置等により確認することができる。
（２）上記一般式（ＩＸ）におけるＭがＣｕであり、Ｒ^１〜Ｒ^１６が、各々、独立して無置換の水素原子又はハロゲン原子であるハロゲン含有銅フタロシアニン顔料。尚、ハロゲン原子は、塩素原子、臭素原子が好ましい。
（３）上記一般式（ＩＸ）におけるＭがＣｕであり、Ｒ^１〜Ｒ^１６のうちの４〜８個、好ましくは４個が、上記スルホン酸アミド基又は−ＳＯ_３ ⁻・ＮＨ_３Ｒ^＋、好ましくはスルホン酸アミドである溶剤可溶型銅フタロシアニン染料。特に好ましい溶剤可溶型銅フタロシアニン染料の構造を、下記一般式（Ｘ）に示す。

〔式中、各Ｒは、各々、独立して炭素数１〜２０のアルキル基である。〕
上記一般式（Ｘ）において、各Ｒは、各々、独立して炭素数４〜８のアルキル基であることが特に好ましい。
（４）上記一般式（ＩＸ）におけるＭがＡｌであり、且つ、Ｒ^１〜Ｒ^１６が無置換の水素原子であるアルミニウムフタロシアニン顔料。Ａｌは、配位子として−ＯＨ又は−Ｃｌを有しているものが好ましく、−ＯＨを有しているものが更に好ましい。特に好ましいアルミニウムフタロシアニン顔料の構造を、以下に示す。

（５）上記一般式（ＩＸ）におけるＭがＳｎであり、且つ、Ｒ^１〜Ｒ^１６が、各々、独立して無置換の水素原子又はハロゲン原子であるスズフタロシアニン顔料。
（６）上記一般式（ＩＸ）におけるＭがＺｎであり、且つ、Ｒ^１〜Ｒ^１６が、各々、独立して無置換の水素原子又はハロゲン原子である亜鉛フタロシアニン顔料。
この亜鉛フタロシアニン顔料の構造を、下記一般式（ＸＩ）に示す。

〔式中、Ｒ^１〜Ｒ^１６は、各々、独立して無置換の水素原子又はハロゲン原子である。〕
亜鉛フタロシアニン顔料としては、上記一般式（ＸＩ）におけるＲ^１〜Ｒ^１６がすべて水素原子である亜鉛フタロシアニン顔料が特に好ましい。 As the chromatic colorant having the phthalocyanine skeleton, preferred specific structures are listed in the following (1) to (6). Of these, (1), (3) and (4) are particularly preferred.
(1) is M in the above general formula (IX) is Cu, and ^copper phthalocyanine pigments R 1 ^{to R 16} is an unsubstituted hydrogen atom.

The crystal of the copper phthalocyanine pigment may be α type or β type. The average secondary particle diameter of the β-type copper phthalocyanine pigment is generally more than 20 μm and not more than 30 μm. In the present invention, the upper limit is preferably 20 μm, more preferably 10 μm, and the lower limit is 1 μm. . The average secondary particle size can be confirmed with a laser scattering particle size distribution measuring device or the like.
(2) A halogen-containing copper phthalocyanine pigment in which M in the general formula (IX) is Cu, and R ^{1 to} R ¹⁶ are each independently an unsubstituted hydrogen atom or a halogen atom. The halogen atom is preferably a chlorine atom or a bromine atom.
(3) M in the general formula (IX) is Cu, and 4 to 8, preferably 4 of R ^{1 to} R ¹⁶ are the sulfonic acid amide group or —SO ₃ ^— · NH ₃ R ^+. A solvent-soluble copper phthalocyanine dye, preferably a sulfonic acid amide. The structure of a particularly preferred solvent-soluble copper phthalocyanine dye is shown in the following general formula (X).

[Wherein, each R is independently an alkyl group having 1 to 20 carbon atoms. ]
In the general formula (X), it is particularly preferable that each R is independently an alkyl group having 4 to 8 carbon atoms.
(4) An aluminum phthalocyanine pigment in which M in the general formula (IX) is Al, and R ^{1 to} R ¹⁶ are unsubstituted hydrogen atoms. Al preferably has —OH or —Cl as a ligand, and more preferably has —OH. A particularly preferred aluminum phthalocyanine pigment structure is shown below.

(5) A tin phthalocyanine pigment in which M in the general formula (IX) is Sn, and R ^{1 to} R ¹⁶ are each independently an unsubstituted hydrogen atom or a halogen atom.
(6) A zinc phthalocyanine pigment wherein M in the general formula (IX) is Zn, and R ^{1 to} R ¹⁶ are each independently an unsubstituted hydrogen atom or a halogen atom.
The structure of this zinc phthalocyanine pigment is shown in the following general formula (XI).

[Wherein, R ^{1 to} R ¹⁶ each independently represent an unsubstituted hydrogen atom or a halogen atom. ]
As the zinc phthalocyanine pigment, a zinc phthalocyanine pigment in which R ^{1 to} R ¹⁶ in the general formula (XI) are all hydrogen atoms is particularly preferable.

〔式中、Ａｒ及びＡｒ’は、各々、独立して置換基を有してもよい芳香族環である。〕
Ａｒ及びＡｒ’を構成する芳香族環は、芳香族性を有すれば、どのような環でもよいが、通常、５又は６員環の、単環又は２〜６縮合環からなる芳香環であり、Ｏ、Ｓ、Ｎ等のヘテロ原子を含んでいてもよい。具体的には、ベンゼン環、ナフタレン環、アンスラセン環、フェナントレン環、フルオレン環、ピリジン環、チオフェン環、ピロール環、フラン環、ベンゾチオフェン環、ベンゾフラン環、ベンゾピロール環、イミダゾール環、キノリン環、イソキノリン環、カルバゾール環、チアゾール環、ジベンゾチオフェン環等が挙げられ、これらのうち、６員環が好ましく、６員環の単環が更に好ましく、ベンゼン環が特に好ましい。
上記芳香族環は置換基を有している方が好ましく、好ましい置換基としては、ハロゲン原子、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシル基、アミノ基、−ＮＨＣＯＲ’、−ＣＯＲ’及び−ＣＯＯＲ’〔但し、Ｒ’は、炭素数１〜１２のアルキル基又は炭素数１２以下の（ヘテロ）アリール基である。〕が挙げられ、このうち、ハロゲン原子、特に塩素原子が好ましい。 Examples of the chromatic colorant having the diketopyrrolopyrrole skeleton include compounds represented by the following general formula (XII), and this colorant is usually a pigment.

[In the formula, Ar and Ar ′ each independently represent an aromatic ring which may have a substituent. ]
The aromatic ring constituting Ar and Ar ′ may be any ring as long as it has aromaticity, but is usually an aromatic ring consisting of a 5- or 6-membered monocyclic ring or a 2-6 condensed ring. Yes, it may contain heteroatoms such as O, S, N and the like. Specifically, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, pyridine ring, thiophene ring, pyrrole ring, furan ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, imidazole ring, quinoline ring, isoquinoline A ring, a carbazole ring, a thiazole ring, a dibenzothiophene ring, and the like. Among these, a 6-membered ring is preferable, a 6-membered single ring is more preferable, and a benzene ring is particularly preferable.
The aromatic ring preferably has a substituent, and preferred substituents include a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, an amino group, —NHCOR ′, -COR 'and -COOR' [wherein R 'is an alkyl group having 1 to 12 carbon atoms or a (hetero) aryl group having 12 or less carbon atoms. Of these, halogen atoms, particularly chlorine atoms are preferred.

この骨格を含む着色剤は、置換基を有する化合物であっても、有しない化合物であってもよいが、置換基を有する化合物であることが好ましい。置換基を有する化合物の構造は、例えば、下記一般式（ＸＩＩＩ）で表される。

〔式中、Ｒ^１７〜Ｒ^２２は、各々、独立して、ハロゲン原子、−ＮＨＣＯＲ’（但し、Ｒ’は、炭素数１〜１２のアルキル基又は炭素数１２以下の（ヘテロ）アリール基である。）、炭素数１〜１２のアルキル基又は炭素数１〜１２のアルコキシル基である。〕
上記ジオキサジン骨格を有する有彩色着色剤としては、上記一般式（ＸＩＩＩ）において、置換基Ｒ^１７及びＲ^１８を有することが特に好ましい。Ｒ^１７及びＲ^１８は、ハロゲン原子又は−ＮＨＣＯＲ’が好ましく、−ＮＨＣＯＲ’が更に好ましい。また、Ｒ^１９〜Ｒ^２２は、ハロゲン原子、−ＮＨＣＯＲ’、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシル基等が好ましく、炭素数１〜１２のアルコキシル基又は−ＮＨＣＯＲ’が更に好ましい。 Examples of the chromatic colorant having the dioxazine skeleton include compounds having the following skeleton, and this colorant is usually a pigment.

The colorant containing this skeleton may be a compound having a substituent or a compound having no substituent, but is preferably a compound having a substituent. The structure of the compound having a substituent is represented, for example, by the following general formula (XIII).

[Wherein, R ^{17 to} R ²² are each independently a halogen atom, —NHCOR ′ (where R ′ is an alkyl group having 1 to 12 carbon atoms or a (hetero) aryl group having 12 or less carbon atoms] And an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. ]
The chromatic colorant having the dioxazine skeleton particularly preferably has substituents R ¹⁷ and R ¹⁸ in the general formula (XIII). R ¹⁷ and R ¹⁸ are preferably a halogen atom or —NHCOR ′, more preferably —NHCOR ′. R ^{19 to} R ²² are preferably a halogen atom, —NHCOR ′, an alkyl group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, or the like, wherein an alkoxyl group having 1 to 12 carbon atoms or —NHCOR ′ is Further preferred.

この骨格を含む着色剤は、置換基を有する化合物であっても、有しない化合物であってもよいが、置換基を有する化合物の構造は、例えば、下記一般式（ＸＩＶ）で表される。

上記一般式（ＸＩＶ）において、置換基は、Ｒ^２３〜Ｒ^２６の位置に結合していることが好ましい。好ましい置換基としては、ハロゲン原子又は炭素数１〜１２のアルキル基が挙げられる。 Examples of the chromatic colorant having the quinacridone skeleton include compounds containing the following skeleton, and this colorant is usually a pigment.

The colorant containing this skeleton may be a compound having a substituent or a compound having no substituent, but the structure of the compound having a substituent is represented by, for example, the following general formula (XIV).

In the general formula (XIV), the substituent is preferably bonded to the positions of R ^{23 to} R ²⁶ . Preferable substituents include halogen atoms or alkyl groups having 1 to 12 carbon atoms.

この骨格を含む着色剤は、置換基を有する化合物であっても、有しない化合物であってもよいが、置換基を有する化合物の構造は、例えば、下記一般式（ＸＶ）で表される。

〔式中、Ｒ^２７〜Ｒ^３０は、各々、独立して無置換の水素原子、ハロゲン原子、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシル基又は環構造を含む基であり、Ｒ^３１は、無置換の水素原子、ハロゲン原子、炭素数１〜１２のアルコキシル基、炭素数５〜１２のアリールオキシ基、炭素数１〜１２のヘテロアリールオキシ基、炭素数１〜１２のアルキルチオ基、炭素数５〜１２のアリールチオ基又は炭素数１〜１２のヘテロアリールチオ基であり、Ｒ^３２は、無置換の水素原子又はヒドロキシル基であり、Ｒ^３３〜Ｒ^３６は、各々、独立して無置換の水素原子、ハロゲン原子、カルボキシル基、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシル基、−ＣＯＯＲ’、−ＣＯＮＲ’_２（但し、Ｒ’は、炭素数１〜１２のアルキル基又は炭素数１２以下の（ヘテロ）アリール基である。）である。尚、Ｒ^２８及びＲ^２９、Ｒ^３１及びＲ^３２、Ｒ^３３及びＲ^３４、Ｒ^３４及びＲ^３５、並びに、Ｒ^３５及びＲ^３６は、各々、互いに連結して環を形成してもよい。〕 Examples of the chromatic colorant having the quinophthalone skeleton include compounds containing the following skeleton, and the colorant is a pigment or a dye.

The colorant containing this skeleton may be a compound having a substituent or a compound having no substituent, but the structure of the compound having a substituent is represented, for example, by the following general formula (XV).

[Wherein R ^{27 to} R ³⁰ are each independently an unsubstituted hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms or a group containing a ring structure. , R ³¹ is an unsubstituted hydrogen atom, a halogen atom, an alkoxyl group having 1 to 12 carbon atoms, an aryloxy group having 5 to 12 carbon atoms, a heteroaryloxy group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms. An alkylthio group, an arylthio group having 5 to 12 carbon atoms, or a heteroarylthio group having 1 to 12 carbon atoms, R ³² is an unsubstituted hydrogen atom or a hydroxyl group, and R ^{33 to} R ³⁶ are each independently An unsubstituted hydrogen atom, a halogen atom, a carboxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, -COOR ', -CONR' ₂ (where R 'is a carbon number of 1 ~ 12 Or a (hetero) aryl group having 12 or less carbon atoms. ^{Incidentally, R 28} and ^{R 29, R 31} and ^{R 32, R 33} and ^{R 34, R} 34 and ^{R 35, and, R 35} and ^{R 36} each may form a ring. ]

〔式中、Ｘ^１〜Ｘ^４は、各々、独立して無置換の水素原子又はハロゲン原子である。〕 In the said general formula (XV), when R < ²⁷ > -R < ³⁰ > is group containing a ring structure, the substituent represented by the following general formula (XVI) is mentioned.

[Wherein, X ^{1 to} X ⁴ are each independently an unsubstituted hydrogen atom or a halogen atom. ]

〔式中、Ｒ^２８〜Ｒ^３６は、前記と同様であり、Ｘ^５〜Ｘ^８は、各々、独立して無置換の水素原子又はハロゲン原子である。〕
上記一般式（ＸＶＩＩ）で表される、キノフタロン骨格を有する有彩色着色剤としては、Ｒ^２８〜Ｒ^３０が無置換の水素原子、ハロゲン原子、炭素数１〜１２のアルキル基又は炭素数１〜１２のアルコキシル基であり、Ｒ^３１及びＲ^３２が無置換の水素原子であり、且つ、Ｒ^３３〜Ｒ^３６がハロゲン原子である化合物が好ましい。
より好ましい着色剤は、Ｒ^２８及びＲ^２９が無置換の水素原子又はハロゲン原子であり、Ｒ^３０〜Ｒ^３２が無置換の水素原子であり、Ｒ^３３〜Ｒ^３６がハロゲン原子であり、且つ、Ｘ^５〜Ｘ^８がハロゲン原子である化合物である。この着色剤は、通常、顔料である。
特に好ましい着色剤は、Ｒ^２８及びＲ^２９が無置換の水素原子であり、Ｒ^３０〜Ｒ^３２が無置換の水素原子であり、Ｒ^３３〜Ｒ^３６がハロゲン原子（Ｘ^９〜Ｘ^１２）であり、且つ、Ｘ^５〜Ｘ^８がハロゲン原子である化合物（下記一般式（ＸＶＩＩＩ）参照）である。

〔式中、Ｘ^５〜Ｘ^１２は、各々、独立してハロゲン原子である。〕 The structure of the colorant when R ²⁷ in the general formula (XV) is a substituent represented by the general formula (XVI) is shown below as a general formula (XVII).

[Wherein R ^{28 to} R ³⁶ are the same as defined above, and X ^{5 to} X ⁸ each independently represent an unsubstituted hydrogen atom or a halogen atom. ]
As the chromatic colorant having a quinophthalone skeleton represented by the general formula (XVII), R ^{28 to} R ³⁰ are an unsubstituted hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, or 1 to 1 carbon atom. a 12 alkoxyl ^{group, R 31} and ^{R 32} is an unsubstituted hydrogen atom, and ^a compound R 33 ^{to R 36} is a halogen atom.
More preferred colorants are R ²⁸ and R ²⁹ are unsubstituted hydrogen atoms or halogen atoms, R ^{30 to} R ³² are unsubstituted hydrogen atoms, R ^{33 to} R ³⁶ are halogen atoms, and A compound in which X ^{5 to} X ⁸ are halogen atoms. This colorant is usually a pigment.
Particularly preferred colorants are R ²⁸ and R ²⁹ are unsubstituted hydrogen atoms, R ^{30 to} R ³² are unsubstituted hydrogen atoms, and R ^{33 to} R ³⁶ are halogen atoms (X ^{9 to} X ¹² ). And X ^{5 to} X ⁸ are halogen atoms (see the following general formula (XVIII)).

[Wherein, X ^{5 to} X ¹² each independently represent a halogen atom. ]

〔式中、Ｒ^２８及びＲ^２９は、各々、独立してハロゲン原子、炭素数１〜１２のアルキル基又は炭素数１〜１２のアルコキシル基であり、Ｒ^３１は、無置換の水素原子、ハロゲン原子、炭素数１〜１２のアルコキシル基、炭素数５〜１２のアリールオキシ基、炭素数１〜１２のヘテロアリールオキシ基、炭素数１〜１２のアルキルチオ基、炭素数５〜１２のアリールチオ基又は炭素数１〜１２のヘテロアリールチオ基であり、Ｒ^３２は、無置換の水素原子又はヒドロキシル基であり、Ｒ^３３〜Ｒ^３６は、各々、独立して無置換の水素原子、ハロゲン原子、カルボキシル基、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシル基、−ＣＯＯＲ’、−ＣＯＮＲ’_２（但し、Ｒ’は、炭素数１〜１２のアルキル基又は炭素数１２以下の（ヘテロ）アリール基である。）である。尚、Ｒ^２８及びＲ^２９、Ｒ^３１及びＲ^３２、Ｒ^３３及びＲ^３４、Ｒ^３４及びＲ^３５、並びに、Ｒ^３５及びＲ^３６は、各々、互いに連結して環を形成してもよい。〕 In the general formula (XV), R ²⁷ and R ³⁰ are unsubstituted hydrogen atoms, R ²⁸ and R ²⁹ are halogen atoms, alkyl groups having 1 to 12 carbon atoms, or alkoxyl groups having 1 to 12 carbon atoms. The compound (see the general formula (XIX) below) is usually a dye.

[Wherein R ²⁸ and R ²⁹ each independently represent a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms, and R ³¹ represents an unsubstituted hydrogen atom or a halogen atom. An atom, an alkoxyl group having 1 to 12 carbon atoms, an aryloxy group having 5 to 12 carbon atoms, a heteroaryloxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, an arylthio group having 5 to 12 carbon atoms, or A heteroarylthio group having 1 to 12 carbon atoms, R ³² is an unsubstituted hydrogen atom or a hydroxyl group, and R ^{33 to} R ³⁶ are each independently an unsubstituted hydrogen atom, a halogen atom, or a carboxyl group. group, an alkyl group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 12 carbon _{atoms, -COOR ', - CONR' 2} ( where, R 'is an alkyl group or having 12 or less carbon having 1 to 12 carbon atoms It is a hetero) aryl group.). ^{Incidentally, R 28} and ^{R 29, R 31} and ^{R 32, R 33} and ^{R 34, R} 34 and ^{R 35, and, R 35} and ^{R 36} each may form a ring. ]

この骨格を含む着色剤としては、下記一般式（ＸＸ）で表される化合物、上記骨格を複数含む化合物、及び、アミノ基を有する化合物が好ましく、２つのアンスラキノン骨格及び２つのアミノ基を有する化合物が特に好ましい。

〔式中、Ｒ^３７〜Ｒ^４４は、各々、独立して無置換の水素原子、ハロゲン原子、アミノ基、ヒドロキシル基、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシル基、炭素数５〜１２のアリール基、炭素数１〜１２のヘテロアリール基、−ＮＨＲ’、−ＮＲ’_２、−ＯＲ’、−ＳＲ’、−ＣＯＯＲ’又は−ＮＨＣＯＲ’（但し、Ｒ’は、炭素数１〜１２のアルキル基又は炭素数１２以下の（ヘテロ）アリール基である。）である。〕
上記一般式（ＸＸ）で表される化合物は、通常、黄〜青色の染料である。 Examples of the chromatic colorant having the anthraquinone skeleton include compounds containing the following skeleton. This colorant may be a compound containing only one of the following skeletons or a compound containing two or more.

As the colorant containing this skeleton, a compound represented by the following general formula (XX), a compound containing a plurality of the skeletons, and a compound having an amino group are preferable, and it has two anthraquinone skeletons and two amino groups. Compounds are particularly preferred.

[Wherein, R ^{37 to} R ⁴⁴ are each independently an unsubstituted hydrogen atom, a halogen atom, an amino group, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, carbon number 5-12 aryl group, a heteroaryl group having 1 to 12 carbon _{atoms, -NHR ', - NR' 2} , -OR ', - SR', - COOR ' or -NHCOR' (where, R 'is a carbon An alkyl group having 1 to 12 carbon atoms or a (hetero) aryl group having 12 or less carbon atoms). ]
The compound represented by the general formula (XX) is usually a yellow to blue dye.

〔式中、Ｒ^４５及びＲ^４６は、各々、独立して無置換の水素原子、炭素数１〜１２のアルキル基、炭素数５〜１２のアリール基、炭素数１〜１２のヘテロアリール基、炭素数２〜１３のアルキルカルボニル基、炭素数６〜１３のアリールカルボニル基又は炭素数２〜１３のヘテロアリールカルボニル基である。〕

尚、構造式（ＸＸＩＩ）で表される化合物は、芳香族環に結合する水素原子がハロゲン原子等に置換されていてもよい。 Examples of the compound having two anthraquinone skeletons and two amino groups include compounds represented by the following general formula (XXI) and structural formula (XXII). These compounds are usually blue pigments.

[Wherein, R ⁴⁵ and R ⁴⁶ are each independently an unsubstituted hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 5 to 12 carbon atoms, a heteroaryl group having 1 to 12 carbon atoms, An alkylcarbonyl group having 2 to 13 carbon atoms, an arylcarbonyl group having 6 to 13 carbon atoms, or a heteroarylcarbonyl group having 2 to 13 carbon atoms. ]

Note that in the compound represented by the structural formula (XXII), a hydrogen atom bonded to the aromatic ring may be substituted with a halogen atom or the like.

〔式中、Ｒ^４７及びＲ^４８は、各々、独立して水素原子、炭素数１〜１２のアルキル基、炭素数５〜１２のアリール基、炭素数１〜１２のヘテロアリール基、−ＣＯＲ’又は−ＣＯＯＲ’（但し、Ｒ’は、炭素数１〜１２のアルキル基、炭素数１２以下の（ヘテロ）アリール基である。）である。〕
上記一般式（ＸＸＩＩＩ）で表される、ペリレン骨格を有する有彩色着色剤としては、Ｒ^４７及びＲ^４８が炭素数１〜１２のアルキル基である着色剤が好ましく、炭素数１〜３のアルキル基である着色剤が更に好ましい。 Examples of the chromatic colorant having the perylene skeleton include a compound represented by the following general formula (XXIII), and this colorant is usually a pigment.

[Wherein, R ⁴⁷ and R ⁴⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 5 to 12 carbon atoms, a heteroaryl group having 1 to 12 carbon atoms, or —COR ′. Or —COOR ′ (wherein R ′ is an alkyl group having 1 to 12 carbon atoms and a (hetero) aryl group having 12 or less carbon atoms). ]
Represented by the general formula (XXIII), as the chromatic coloring agent having a perylene ^skeleton, colorants ^{R 47} and ^{R 48} is an alkyl group having 1 to 12 carbon atoms are preferred, alkyl of 1 to 3 carbon atoms More preferred is a colorant as a group.

  Examples of the chromatic colorant having the metal complex skeleton include compounds in which metal ions are coordinated to an organic dye skeleton. Examples of the organic dye skeleton include those having an azo group, those having an azomethine group, and the like, and may have a hydroxyl group, an amino group, an imino group, or the like at the ortho or peri position of the azo group or azomethine group. Examples of metal ions include copper, nickel, cobalt, and zinc ions.

  The content of the chromatic colorant [C] is 0.001 to 3 parts by mass, preferably 0.002 to 1 part by mass, when the polymer component [A] is 100 parts by mass. Is 0.005 to 0.8 parts by mass. If the content of the chromatic colorant [C] is too large, white marking may not be obtained by irradiation with laser light having a short wavelength such as 532 nm. On the other hand, if the content is too small, the energy is low. For example, in some cases, the marking of the color derived from the chromatic colorant [C] may not be obtained by irradiation with laser light having a long wavelength such as 1,064 nm.

4). Black material [D]
The black material [D] is not particularly limited as long as it is extinguished or discolored by receiving laser light. That is, the color of the irradiated portion of the laser beam in the composition and a molded product obtained using the composition is changed to the color of a substance other than the black substance by itself disappearing or changing color by the energy of the laser beam. Any black material may be used as long as it has a color that is strongly influenced by.
The black material [D] is, for example, a laser beam having an output of 31 A, a frequency of 5.5 kHz, and a wavelength of 1,064 nm for a black test piece consisting of 100 parts by weight of polymethyl methacrylate and 0.1 part by weight of the black material. When irradiating, what the irradiation part discolors to colors other than white or black is preferable.

  The black substance [D] may be an inorganic substance or an organic substance, and may be a pigment or a dye. Further, the black substance [D] may contain a compound, a mineral, or the like that is not included in these, as long as the excellent effects of the present invention are not impaired. . As said black substance [D], carbon black, titanium black, inorganic pigments, such as black iron oxide, graphite, activated carbon, etc. are mentioned. These may be used alone or in combination of two or more. Of these, carbon black, titanium black and black iron oxide are preferred, and those containing carbon black as the main component are particularly preferred.

Examples of carbon black include acetylene black, channel black, and furnace black. The lower limit of the average particle size of the carbon black is preferably 0.1 nm, more preferably 1 nm, particularly preferably 5 nm, most preferably 10 nm, and the upper limit is preferably 1,000 nm, more preferably 500 nm, especially Preferably it is 100 nm, most preferably 80 nm. The lower limit of the nitrogen adsorption specific surface area of the above carbon black is preferably from ^{1 m} 2 / g, more preferably ^{5 m} 2 / g, particularly preferably ^{10 m} 2 / g, and most preferably ^{20 m} 2 / g, the upper limit , preferably 10,000 m ² / g, more preferably 5,000 m ² / g, particularly preferably 2,000 m ² / g, and most preferably 1,500 m ² / g.
Titanium black is generally obtained by reducing titanium dioxide. The lower limit of the average particle diameter of the titanium black is preferably 0.01 μm, more preferably 0.05 μm, particularly preferably 0.1 μm, and the upper limit is preferably 2 μm, more preferably 1.5 μm, particularly preferably. Is 1.0 μm, most preferably 0.8 μm.
Black iron oxide is generally an oxide of iron represented by Fe ₃ O ₄ or FeO · Fe ₂ O ₃ . The lower limit of the average particle diameter of the black iron oxide is preferably 0.01 μm, more preferably 0.05 μm, particularly preferably 0.1 μm, most preferably 0.3 μm, and the upper limit is preferably 2 μm, The thickness is preferably 1.5 μm, particularly preferably 1.0 μm, and most preferably 0.8 μm.

  Content of the said black substance [D] is 0.01-2 mass parts when said polymer component [A] is 100 mass parts, Preferably it is 0.03-1 mass part, More preferably, it is 0. 0.05 to 0.8 parts by mass. If the content of the black material [D] is too large, the color derived from the chromatic colorant [C] may not be clear and darkened by laser light irradiation. In some cases, neither the color derived from the chromatic colorant [C], the white color, nor the color having a reduced color density derived from the chromatic colorant [C] can be obtained.

A thermoplastic polymer composition for multicolor laser marking of the present invention comprises a predetermined amount of the polymer component [A], a phosphate ester compound [B], a chromatic colorant [C], and a black substance [D]. Although the composition is contained one by one, the background color of the composition or molded product by this combination exhibits a black or dark color. In the present invention, in order to adjust the brightness of these colors, a white material such as a white material is used for the purpose of improving the whiteness when white is developed in the irradiated portion of the high energy laser beam. Further, it can be contained.
Examples of the white substance include titanium dioxide, zinc oxide, zinc sulfide, and barium sulfate. These can be used alone or in combination of two or more.

  The average particle size of the white substance is not particularly limited, but is usually 0.1 to 3.0 μm, preferably 0.1 to 2.0 μm, and more preferably 0.1 to 1.0 μm.

  The content of the white substance is preferably 0.001 to 1 part by mass, more preferably 0.001 to 0.5 part by mass, when the polymer component [A] is 100 parts by mass. More preferably, it is 0.001-0.1 mass part. If the content of this white material is too large, markings with good contrast may not be obtained, while if too small, the degree of freedom of the ground color of the molded product may be limited.

  The thermoplastic polymer composition for multicolor laser marking of the present invention is an ultraviolet absorber, antioxidant, anti-aging agent, antistatic agent, flame retardant, weathering agent, plasticizer, filling depending on the purpose and application You may contain additives, such as a material, a lubricant, an antibacterial agent, a hydrophilic property imparting agent, a decorating agent, and a light-colored colorant.

Examples of the ultraviolet absorber include benzophenones, benzotriazoles, salicylic acid esters, metal complex salts and the like. These can be used alone or in combination of two or more.
The content of the ultraviolet absorber is preferably 0.05 to 5 parts by mass when the polymer component [A] is 100 parts by mass.

Anti-aging agents include naphthylamine, diphenylamine, p-phenylenediamine, quinoline, hydroquinone derivatives, monophenol, bisphenol, trisphenol, polyphenol, thiobisphenol, hindered phenol, phosphorous acid Examples include ester compounds. These can be used alone or in combination of two or more.
The content of the anti-aging agent is preferably 0.1 to 5 parts by mass when the polymer component [A] is 100 parts by mass.

Examples of the antioxidant include hindered amines, hydroquinones, hindered phenols, and sulfur-containing compounds. These can be used alone or in combination of two or more.
The content of the antioxidant is preferably 0.1 to 5 parts by mass when the polymer component [A] is 100 parts by mass.

Examples of the antistatic agent include a low molecular weight antistatic agent and a high molecular weight antistatic agent. Moreover, these may be an ion conduction type or an electron conduction type.
The low molecular weight antistatic agent includes an anionic antistatic agent; a cationic antistatic agent; a nonionic antistatic agent; an amphoteric antistatic agent; a complex compound; a metal alkoxide such as alkoxysilane, alkoxytitanium, and alkoxyzirconium; Derivatives thereof: coated silica, phosphate, phosphate ester and the like. These can be used alone or in combination of two or more.
Examples of the polymer antistatic agent include a vinyl copolymer having a sulfonic acid metal salt in the molecule, an alkylsulfonic acid metal salt, an alkylbenzenesulfonic acid metal salt, and betaine. Furthermore, a polyamide elastomer, a polyester elastomer, etc. can also be used. These can be used alone or in combination of two or more.
The content of the antistatic agent is preferably 0.5 to 10 parts by mass when the polymer component [A] is 100 parts by mass.

As the flame retardant, an organic flame retardant, an inorganic flame retardant, a reaction flame retardant, or the like can be used.
Examples of the organic flame retardant include brominated bisphenol epoxy resin, brominated bisphenol phenoxy resin, brominated bisphenol polycarbonate resin, brominated polystyrene resin, brominated crosslinked polystyrene resin, brominated bisphenol cyanurate resin, brominated polyphenylene. Halogen-based flame retardants such as ether, decabromodiphenyl oxide, tetrabromobisphenol A and oligomers thereof, and brominated alkyltriazine compounds; trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, toxyl phosphate, tricyclohexyl Phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate Phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, etc., compounds obtained by modifying these with various substituents, various condensation types Phosphoric acid ester compounds, phosphorus-based flame retardants such as phosphazene derivatives containing phosphorus and nitrogen elements; polytetrafluoroethylene and the like. These can be used alone or in combination of two or more.

Examples of the inorganic flame retardant include aluminum hydroxide, antimony oxide, magnesium hydroxide, zinc borate, zirconium-based, molybdenum-based, zinc stannate, guanidine salt, silicone-based, and phosphazene-based compounds. These can be used alone or in combination of two or more.
Examples of the reactive flame retardant include tetrabromobisphenol A, dibromophenol glycidyl ether, brominated aromatic triazine, tribromophenol, tetrabromophthalate, tetrachlorophthalic anhydride, dibromoneopentyl glycol, poly (pentabromobenzyl polyacrylate) ), Chlorendic acid (hett acid), chlorendic anhydride (hett acid anhydride), brominated phenol glycidyl ether, dibromocresyl glycidyl ether, and the like. These can be used alone or in combination of two or more.
The content of the flame retardant is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, when the polymer component [A] is 100 parts by mass.

  In addition, when mix | blending a flame retardant with this composition, it is preferable to use a flame retardant adjuvant together. As this flame retardant auxiliary, antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, antimony tartrate, antimony compounds, zinc borate, barium metaborate, hydrated alumina, zirconium oxide, Examples include ammonium polyphosphate and tin oxide. These can be used alone or in combination of two or more.

Examples of the weathering agent include organic phosphorus compounds, organic sulfur compounds, and organic compounds containing a hydroxyl group. These can be used alone or in combination of two or more. These can be used alone or in combination of two or more.
The content of the weathering agent is preferably 0.1 to 5 parts by mass when the polymer component [A] is 100 parts by mass.

Fillers include glass fiber, carbon fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate whisker, wollastonite, and also stainless steel, aluminum, titanium Inorganic fibrous fillers of metals such as copper, brass, etc .; organic fibrous fillers; silica, quartz powder, glass beads, glass powder, calcium oxalate, aluminum oxalate, kaolin, clay, diatomaceous earth Particulate fillers such as oxalates such as alumina, metal oxides such as alumina, carbonates such as calcium carbonate and magnesium carbonate, sulfates such as calcium sulfate, silicon carbide, silicon nitride, boron nitride, etc .; talc, mica, Examples thereof include plate-like fillers such as glass flakes and metal foils. These can be used alone or in combination of two or more. These fillers can also be used as reinforcing materials.
The content of the filler is preferably 1 to 30 parts by mass, more preferably 1 to 25 parts by mass, and still more preferably 1 to 20 parts by mass, when the polymer component [A] is 100 parts by mass. is there.

As the lubricant, fatty acid ester, hydrocarbon resin, paraffin, higher fatty acid, oxy fatty acid, fatty acid amide, alkylene bis fatty acid amide, aliphatic ketone, fatty acid lower alcohol ester, fatty acid polyhydric alcohol ester, fatty acid polyglycol ester, aliphatic alcohol , Polyhydric alcohol, polyglycol, polyglycerol, metal soap, silicone, modified silicone and the like. These can be used alone or in combination of two or more.
The content of the lubricant is preferably 0.1 to 5 parts by mass when the polymer component [A] is 100 parts by mass.

Examples of the antibacterial agent include inorganic antibacterial agents, organic antibacterial agents, inorganic / organic hybrid antibacterial agents, and natural antibacterial agents. These may be used alone or in combination of two or more.
Examples of inorganic antibacterial agents include zeolite-based antibacterial agents such as silver zeolite and silver / zinc-based zeolite; silica gel-based antibacterial agents such as complexed silver and silica gel; glass-based antibacterial agents; calcium phosphate-based antibacterial agents; zirconium phosphate-based antibacterial agents Agents: silicate antibacterial agents such as silver and magnesium aluminate silicate; titanium-containing antibacterial agents; ceramic antibacterial agents; whisker antibacterial agents and the like.
Organic antibacterial agents include formaldehyde releasing agents, halogenated aromatic compounds, rhodopropargyl derivatives, thiocyanate compounds, isothiazolinone derivatives, trihalomethylthio compounds, quaternary ammonium salts, biguanide compounds, aldehydes, phenols, and benzimidazole derivatives. Pyridine oxide, carbanilide, diphenyl ether, carboxylic acid, organometallic compound and the like.
The content of the antibacterial agent is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, when the polymer component [A] is 100 parts by mass.

As the decorating agent, when a molded product is used, one that can form a metallic pattern such as metallic tone or metallic luster on its surface can be used.
In order to form a metallic pattern, a metallic pigment can be used. It is preferable to use particles having an average particle diameter in a predetermined range and having a metallic luster. The shape of the particle is not particularly limited, and examples thereof include a sphere, a substantially sphere, a square (cube, cuboid, polyhedron, etc.), a scaly shape, a star shape, a rod shape, and the like. preferable. The preferable average particle diameter of such a metallic pigment is 1 to 500 μm, more preferably 2 to 300 μm. By setting it as this range, the molded product with which the said pattern has the clear external appearance property can be obtained easily. When the metallic pigment is other than spherical, the “average particle size” means the maximum length.

The metal-like glossy particles are made of metals such as nickel, aluminum, silver, copper, tin, chromium, zinc, cobalt, iron, molybdenum, manganese, tungsten, gold, titanium, antimony, silicon, platinum, and magnesium. And those composed of alloys containing the above metals, those composed of metallic compounds with metal-like gloss (oxides, nitrides, sulfides, etc.), inorganic compounds of calcium carbonate glass, and the like. Of these, nickel, aluminum, silver, copper, tin, chromium, gold, titanium, platinum and zinc are preferred. Moreover, what consists of minerals, such as a mica, can also be used as said powder which has a metallic luster.
Further, a film made of the above metal, alloy, metal compound or the like by plating, vapor deposition or the like, or a film of glass or the like can be formed on the surface of a particulate material having no metallic luster, and used as a metallic pigment.
Each of these particles can be used alone or in combination of two or more.
Each particle may form a film made of an organic compound such as a fatty acid or a film containing an inorganic compound such as titanium oxide or silica in order to protect the glossy surface.
The content of the decorating agent depends on the purpose and application, but is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts when the polymer component [A] is 100 parts by mass. Part by mass.

The thermoplastic polymer composition for multicolor laser marking of the present invention can be obtained, for example, by putting the above raw material components into various extruders, Banbury mixers, kneaders, rolls, etc. and kneading them. . As a kneading method, each component may be added all at once or may be kneaded by a multistage addition method. The composition thus obtained is itself or further mixed with another polymer, and then injection molding, extrusion molding, hollow molding, compression molding, film extrusion, sheet extrusion, vacuum molding, foaming. A molded product having a predetermined shape can be obtained by molding, blow molding, or the like. The shape of the molded product can be selected from various shapes depending on the purpose, application, etc. If the laser beam can be irradiated, the marked part is a flat surface, curved surface, uneven surface with corners, etc. There may be.
The thermoplastic polymer composition for multicolor color laser marking and a molded product obtained by using the thermoplastic polymer composition include a polymer component [A] as a matrix, a phosphate ester compound [B], a chromatic colorant [C ], A black substance [D] and the like are dispersed. Therefore, the molded article or the like usually exhibits a black or dark ground color.

In the laser marking method of the present invention, two or more different colors are marked by irradiating a molded product containing the above-described thermoplastic resin composition for multicolor laser marking with laser light having two or more different energies. It is characterized by.
That is, the method of the present invention irradiates a thermoplastic polymer composition for multicolor laser marking or a molded article containing the same with laser light having two or more different energies, and two or more different color tones, for example, The marking can be formed on the color derived from the chromatic colorant [C] and the color having a reduced density of white or the color derived from the chromatic colorant [C].
Specifically, when laser light having two different energies is irradiated, the color derived from the chromatic colorant [C] is marked by irradiation with low energy laser light, and by irradiation with high energy laser light. It is possible to obtain a white color or a color marking having a reduced color density derived from the chromatic colorant [C].

  In general, the “energy” of a laser beam depends on the irradiation condition of the laser beam. Specifically, by changing the type, wavelength, pulse width, frequency, output, irradiation time, irradiation area, distance and angle from the light source to the molded product, irradiation method, etc. The laser light can be “having different energy” when irradiated with laser light. Specifically, not only when laser beams having different wavelengths are used, but also when other irradiation conditions such as irradiation time are different using laser beams having the same wavelength, different energies can be obtained. In addition, with the same irradiation conditions, the energy for the object to be irradiated is different in the case of one-time irradiation and in the case of two-time irradiation. In this case, the latter having a longer irradiation time is “higher energy”.

  In addition, the “laser beam having two or more different energies” in the present invention refers to two or more laser beams having different degrees of damage to the irradiated object. When all of the above-mentioned irradiation conditions are the same, the damage given to the irradiated object is different between the case where the irradiation is performed once and the case where the irradiation is performed in a plurality of times. Are included in the laser light having different energies. In other words, even if the total energy to be applied is the same, if the irradiated object receives more damage than irradiated twice, the former is set to “high energy”.

  In the laser marking method of the present invention, the laser beam applied to the molded article may be performed under any irradiation conditions as long as the excellent performance of the multicolor laser marking of the present invention is not significantly impaired. The irradiation method may be either a scanning method or a mask method, and two or more laser beams having different energies may be irradiated simultaneously or may be irradiated one by one. Moreover, as a laser beam irradiation device, a general laser marking device or the like can be used. This device is usually equipped with a laser oscillator, laser modulator, handling unit, controller, etc., and laser light oscillated from the laser oscillator is pulse-modulated by the laser modulator and irradiated to the surface of the molded product. Marking is formed. In laser marking, two or more laser beams having different energies may be irradiated with one device, or a plurality of devices may be used. As an apparatus capable of two-wavelength laser marking, for example, a laser marking system “RSM50D type”, “RSM30D type” manufactured by Roffin Basel, Inc. can be used.

The laser beam used in the multicolor laser marking of the present invention may be any of gas, solid, semiconductor, dye, excimer and free electron, but preferably has a wavelength in the range of 100 to 2,000 nm. In the present invention, for example, numerals indicating the “wavelength” of laser light, such as 1,064 nm and 532 nm, all mean the center wavelength, and normally include an error of ± 3%.
Examples of the gas laser include a helium / neon laser, a rare gas ion laser, a helium / cadmium laser, a metal vapor laser, and a carbon dioxide laser. Examples of the solid laser include a ruby laser, a neodymium laser, and a wavelength tunable solid laser. The semiconductor laser may be inorganic or organic, and examples of the inorganic semiconductor laser include GaAs / GaAlAs, InGaAs, and InP. A semiconductor laser-excited solid laser such as Nd: YAG, Nd: YVO ₄ , or Nd: YLF can also be used. The laser beams exemplified above may be used alone or in combination of two or more.

  A simple method for obtaining laser beams having different energies is to use laser beams having different wavelengths. For example, when the multicolor laser marking according to the present invention is clearly performed by irradiation with laser light having only different wavelengths, the difference in wavelength of each laser light is preferably 100 nm or more, more preferably 200 nm or more, and particularly preferably 500 nm. That's it. The upper limit is usually 1,500 nm. When the chromatic colorant [C], that is, a chromatic colorant having an exothermic peak by differential thermal analysis in a temperature range of 360 ° C. or higher and 590 ° C. or lower is used, the chromatic color is irradiated by two laser light irradiations having different wavelengths only. In order to clearly form the marking of the color derived from the colorant [C] and the marking of the color having a reduced color density derived from the white or chromatic colorant [C], the wavelength of 1,064 nm It is preferable to use laser light and laser light having a wavelength of 532 nm. That is, the density of the color derived from the chromatic colorant [C] is reduced by irradiation with the laser beam having a wavelength of 1,064 nm, and the density of the color derived from the white or chromatic colorant [C] is decreased by irradiation with the laser beam having the wavelength of 532 nm. It is suitable for forming a clear marking with a developed color.

An example of a coloring method using laser light irradiation will be briefly described with reference to the drawings. However, the multicolor coloring laser marking method according to the present invention is not limited to this.
The molded article 1 containing the thermoplastic polymer composition for multicolor laser marking of the present invention is irradiated with laser beams having two different energies at different positions ([I] in FIG. 1). At this time, laser beam irradiation may be performed simultaneously or separately. The irradiation part of the low energy laser light is marked with a color derived from the chromatic colorant [C] (3a in FIG. 1), while the irradiation part of the high energy laser light is white or chromatic coloring. The color of the color derived from the agent [C] is marked (3b in FIG. 1) with a lowered color density ([II] in FIG. 1). By the above procedure, a molded product (molded product with multicolor marking) 2 marked in two different color tones can be obtained.

The “color derived from the chromatic colorant” obtained by the laser marking method of the present invention mainly refers to a color obtained as a result of the black substance disappearing or changing color due to laser light irradiation. Specifically, (a) the color of the chromatic colorant of the present invention itself (hereinafter simply referred to as "the colorant of the present invention" (B) Color of the colorant of the present invention which is blackish (color of the colorant of the present invention + color of the black substance, color of the colorant of the present invention + color in which the black substance is discolored) ), (C) a color in which the color tone of the chromatic colorant of the present invention has changed, and (d) a color in which the above color (c) is blackish.
In addition, “a color having a reduced color density derived from a chromatic colorant” obtained by the laser marking method of the present invention refers to a “color having a reduced density of the“ color derived from a chromatic colorant ”. This color is mainly obtained as a result of the change of the chromatic colorant by laser light irradiation. Specifically, the color of the chromatic colorant is affected by the decomposition or scattering of the chromatic colorant. In addition to the color that appears when the color becomes smaller, the color or the like whose color tone has changed due to the color change of the chromatic colorant is also included. The “color having a reduced color density derived from the chromatic colorant” is more preferable as it is closer to white because it is easier to distinguish from the “color derived from the chromatic colorant” described above.

The “white” obtained by the laser marking method of the present invention is usually pure white mainly of the color of the polymer component [A] itself contained in the thermoplastic polymer composition for multicolor laser-marking of the present invention. Not limited to this, white colors mixed with other colors are also included. Furthermore, in addition to this color, when titanium black is contained as a black material [D] in the thermoplastic polymer composition for multicolored laser marking of the present invention, it is changed to titanium dioxide by irradiation with laser light. , A color derived from this titanium dioxide, or a mixed color of this color and the color of the polymer component [A], or a color derived from a white material blended as necessary, or this A mixed color of the color and the color of the polymer component [A]. When the polymer component [A] contained in the thermoplastic polymer composition for multicolor laser marking of the present invention is easily foamed by receiving laser light, the color development in the irradiated portion of the high energy laser light is: Whiteness is higher.
The whiteness of the “white” can be evaluated according to JIS K7105. This whiteness means the degree of whiteness of the color, and is evaluated by the reflectance when a certain amount of light is irradiated onto the object. The reflectance can be measured with a Hunter whiteness meter or the like. Here, the reflectance varies depending on the type of light to be irradiated (wavelength or the like). In the case of a hunter whiteness meter, measurement is performed with blue light that is the three primary colors of light. The whiteness (%) of the white marking obtained in the thermoplastic polymer composition for multicolor laser marking of the present invention and a molded article containing the same can be expressed as a ratio of the intensity of magnesium oxide to the reflected light. Although white by human vision and whiteness by a whiteness meter may not necessarily match, the white marking obtained in the composition of the present invention and a molded article containing the same does not show the human eye even if the whiteness is low. It only needs to look white. However, the standard of whiteness is preferably 55 to 100%, more preferably 60 to 100%, still more preferably 70 to 100%, and particularly preferably 80 to 100%.

  According to the multicolor laser marking according to the present invention, when the molded product is irradiated with laser light, the portion where the change (disappearance, discoloration, etc.) of the black substance [D] occurs is a substance other than the black substance [D]. The portion where the color appears strongly and the change (decomposition, scattering, etc.) of the chromatic colorant [C] occurs becomes a color in which the density of the color derived from the chromatic colorant [C] is reduced or white. When the energy of the laser beam is low, the black substance [D] is vaporized, volatilized, disappears by complete decomposition, etc .; or at least part or all of the black substance [D] stays there, The discoloration which becomes a different color occurs, and the laser beam irradiation section develops a color derived from the chromatic colorant [C]. When the energy of the laser beam is further increased, the change in the chromatic colorant [C] contained in the molded product occurs at a higher energy than the energy at which the black material [D] changes as described above. The light irradiating portion develops a white color or a color having a reduced color density derived from the chromatic colorant [C].

In the composition which does not contain the Lab value of the white marking part obtained by irradiating the laser beam with a wavelength of 532 nm to the thermoplastic polymer composition for multicolor laser marking of the present invention and the chromatic colorant [C]. The ΔE1 calculated from the Lab marking value obtained by irradiating a laser beam with a wavelength of 1064 nm is preferably 3 or less, more preferably 2.5 or less, and even more preferably 2 to 0. be able to. The smaller this ΔE1, the higher the whiteness.
Also, the Lab value of the white marking part obtained by irradiating the thermoplastic polymer composition for multicolor laser marking of the present invention with laser light having a wavelength of 532 nm, and a laser having a wavelength of 1064 nm applied to the present composition. ΔE2 calculated from the Lab value of the chromatic marking part obtained by irradiating light is preferably 3 or more, more preferably 3.5 or more, and further preferably 4 to 50. The larger this ΔE2, the clearer the color tone difference.
ΔE1 and ΔE2 can be obtained by the following method.

ΔE1 is a compound containing no white marking portion formed when the test piece made of the thermoplastic polymer composition for multicolored laser marking of the present invention is irradiated with a laser beam having a wavelength of 532 nm and the above colorant. Each Lab value (L: lightness, a: redness, b: yellowness) between the white marking portion formed when the test piece molded in step 1 is irradiated with laser light having a wavelength of 1,064 nm. Measure and calculate according to the following formula. As a measurement apparatus for Lab, “Color-Eye 7000A” manufactured by Gretag Macbeth, Inc. can be used.
ΔE1 = √ {(L ₁ −L ₂ ) ² + (a ₁ −a ₂ ) ² + (b ₁ −b ₂ ) ² }
In the above formula, L ₁ , a ₁ and b ₁ are the values of the white marking part formed when irradiating laser light with a wavelength of 532 nm, and L ₂ , a ₂ and b ₂ include the colorant. It is the value of the white marking part formed when the laser beam with a wavelength of 1,064 nm is irradiated to a test piece molded with no blending.
ΔE2 is a white marking portion formed when the laser beam with a wavelength of 532 nm is irradiated to the test piece, and a laser beam with a wavelength of 1064 nm to a different position of the same test piece. Each Lab value of the chromatic color marking portion formed in (2) is measured (the latter are L ₃ , a ₃ and b ₃ ), and can be calculated according to the following formula.
ΔE2 = √ {(L ₁ −L ₃ ) ² + (a ₁ −a ₃ ) ² + (b ₁ −b ₃ ) ² }

  In the molded product, it is preferable that at least one of the marking portions formed by laser light irradiation is foamed. Thereby, the coloring of a marking part can be made clearer. Although it depends on the kind and content of the polymer contained in the polymer component [A] contained in the molded article, the rubber-reinforced acrylic resin (A2-1) is particularly used as the acrylic resin (A2). And / or a monomer (co) polymer (A2-2) containing a (meth) acrylic acid ester compound is used, even if low energy laser light is received. Regardless of the type, content, etc., of the chromatic colorant [C] and the black substance [D], the marking portion foams, so that the coloring of the marking portion becomes clearer.

Moreover, in the said molded article, it is preferable that the marking part formed by irradiation of the laser beam exists in the foaming state colored in white. Thereby, white marking with high whiteness can be formed.
As described above, the “white” obtained by laser marking is often the color of the contained polymer itself, but depending on the type or the degree of foaming, the degree of whiteness High white color may be obtained.

It is known that the molded product contains carbon black as the black material [D], and when this molded product is irradiated with laser light, the carbon black existing in the irradiated part absorbs the laser light and vaporizes. Yes. When carbon black disappears, the degree of black or dark color in the irradiated area becomes small or almost colorless. Therefore, when the chromatic colorant [C] is contained in the molded product, the portion irradiated with the laser light is the color derived from the chromatic colorant [C] or the chromatic colorant [C]. As a result of decomposition, scattering, etc., the color of the color derived from the white or chromatic colorant [C] is marked with a lowered color.
When the wavelength of the laser beam is different, the energy of the laser beam is also generally different. Therefore, the carbon black is vaporized at a lower energy, and the color marking derived from the chromatic colorant [C] is higher. It is possible to form a color marking in which the density of the color derived from white or its chromatic colorant [C] is reduced in energy.

Here, when two types of laser beams having different energies are irradiated, these energies are assumed to be E1 and E2, respectively, and E1 <E2 and E1 is energy enough to vaporize carbon black. .
When the surface of a molded article containing the present composition is irradiated with laser beams having two different energies, carbon black is vaporized only by the thermal conversion of the laser light at the portion irradiated with the laser beam of energy E1. The portion marked with the color derived from the chromatic colorant [C] and irradiated with the laser beam of energy E2 vaporizes carbon black, and further, a part of the chromatic colorant [C] or A color different from the color of the original chromatic colorant [C], for example, white, a color having a reduced concentration of color derived from the chromatic colorant [C], It is considered that the color is changed and marked with a color completely different from the chromatic colorant [C].

Further, when a molded product containing titanium black as the black material [D] is irradiated with laser light, the titanium black present in the irradiated portion of the molded product changes to white titanium dioxide, and the black color in the irradiated portion is changed. The degree becomes smaller or colorless.
Further, when the molded product containing black iron oxide as the black material [D] is irradiated with laser light, the black iron oxide present in the irradiated portion of the molded product changes to reddish white, The degree of black becomes small or becomes colorless.
Therefore, if the molded product containing titanium black, black iron oxide or the like as the black material [D] further contains a colored colorant, the same marking as when carbon black is used can be made. . When laser beams having two different types of energy are irradiated, the same as in the case of carbon black, and laser markings having different colors can be formed.

  In this way, a desired color marking can be formed by irradiating laser beams having different energies. As described above, the energy of the laser beam usually depends on the wavelength, but the laser beam having the same wavelength is used, and the irradiation condition (time, pulse output, pulse width, etc.) is changed and the irradiation method is used. May have different energies or provide markings of different tones.

  In addition, as described above, the laser light irradiation part has different colors depending on the energy of the laser light, but the energy of the laser light is less than the energy that causes the black substance [D] to disappear or change color. Between high energies, shades can be added to the color developed from the chromatic colorant [C]. That is, in the above energy range, the degree of progress of the reaction (decomposition, etc.) of the chromatic colorant [C] varies depending on the penetration depth of the laser light, thereby forming a shade.

  As described above, since the chromatic colorant [C] can be used in combination of two or more kinds, a molded product containing a plurality of chromatic colorants [C] having different tones is used for laser light having different wavelengths. Can be formed to form markings having different color tones and markings having a reduced color density derived from white or chromatic colorant [C]. As described above, when a plurality of chromatic colorants [C] are used, for example, when a red colorant and a blue colorant are used, the energy of the laser light to be irradiated (E1, E2, and E3 are used, and E1 <E2 <E3), the following aspect can be obtained. The laser beam with energy E1 eliminates black (or dark color) and forms a purple marking that is a mixed color of red and blue, and one chromatic colorant [C], for example, a red colorant, with laser beam with energy E2 Only is decomposed, scattered, etc., and marked with a color mainly derived from the blue colorant. Furthermore, the blue colorant is decomposed and scattered by the laser beam of energy E3, so that marking is formed in a color in which the density of the color derived from white or the chromatic colorant is reduced.

  When the chromatic colorant [C] has an exothermic peak in a predetermined temperature range of 360 ° C. or higher and 590 ° C. or lower, the laser beam is irradiated in the presence of a black material [D] such as carbon black. Depending on the pulse energy of the laser beam having the above-mentioned wavelength (1,064 nm, 532 nm, etc.), the reaction (decomposition etc.) is made, and markings of different tones are clearly formed according to the above-described aspect. The

  In addition, by irradiating the molded product 1 containing the composition of the present invention with low energy laser light, a wide area, a color marking portion derived from the chromatic colorant [C] is formed, and then By further irradiating this marking portion with laser light, the irradiated portion can be marked with white or a color having a reduced color density derived from the chromatic colorant [C] (see FIG. 2). According to this method, the marking portion 3a of the color derived from the chromatic colorant [C] and the marking portion 3b of the color having a reduced color density derived from white or the chromatic colorant [C] are adjacent to each other. It can be set as the molded product 2a with the multicolor marking which appeared the matching laser marking. Incidentally, the energy of the laser light irradiated for the second time may be the same as or different from the first time, and is not particularly limited.

When the laser beam is irradiated onto the molded product, the irradiated portion becomes a convex portion, a concave portion, or is left as it is, depending on the type of the polymer component [A], the type of the black material [D], and the like. Or In particular, in the case where the polymer component [A] contains a resin that foams by receiving laser light, it may be a convex portion. There may be a recess.
In addition, the black substance [D], which itself disappears or discolors by laser light irradiation, exhibits the above behavior instantaneously after absorbing the heat of the laser light. For example, titanium black or the like When discolored by heat, it may accompany heat storage. Thereby, the irradiation part of a laser beam will have the said shape.

  The height when the convex portion is formed is usually 1 to 200 μm, preferably 1 to 100 μm, more preferably 1 to 80 μm. Moreover, the depth at the time of forming a recessed part is 1-200 micrometers normally, Preferably it is 1-100 micrometers. Each length can be adjusted by changing the irradiation condition of the laser beam. In particular, if the height of the convex part exceeds 200 μm, the visibility of the marking part is improved, while in applications that require contact with the marking part (keyboard, Braille, etc.), the characters are crushed along with the number of contacts, contact pressure, etc. There is a case.

In the embodiment in which the polymer component [A] contains a thermosetting polymer, the size (volume) of the thermosetting polymer changes and is cured when irradiated with laser light and cured. In some cases, the resin may be cured with a small rate of change in size.
As an example of the former, there is a case where the laser beam is instantly dissolved and deformed from the original size, for example, becomes larger by irradiation with laser light. In this case, the strength of the marking portion is further improved. In particular, when the marking portion is a convex portion, the durability is more excellent. The thermosetting polymer exhibiting such an effect may be granular or may have other shapes.

  Therefore, even when the polymer component [A] is irradiated with laser light on a molded article containing a resin that is foamed by receiving laser light and a thermosetting polymer, the peripheral part of the foamed part ( Since the components derived from the thermosetting polymer are present in the wall or the like, the effect as a reinforcing material is exhibited, and the durability in terms of strength is further improved as the entire marking portion. Further, depending on the type and content ratio of the thermosetting polymer, a component derived from the thermosetting polymer may be present in the void formed by foaming. In an embodiment in which the laser light irradiation conditions are adjusted, the foamed portion is made smaller, and the component derived from the thermosetting polymer enters the voids, particularly excellent color developability and impact resistance can be obtained.

The laser light non-irradiated part in the molded article is composed of a polymer component [A], a phosphate ester compound [B], a chromatic colorant [C], a black substance [D] and the like. Yes.
Further, in a molded article with multicolor marking formed by irradiation with laser light, the black material [D] disappears (vaporization, etc.) in the irradiated portion of lower energy laser light (for example, laser light having a wavelength of 1064 nm). Or it is discolored (whitening etc.) and the chromatic colorant [C] remains as it is. The irradiated portion of the higher energy laser light (for example, laser light having a wavelength of 532 nm) exhibits a color in which the density of the color derived from white or its chromatic colorant [C] is reduced. The substance [D] is extinguished (vaporization etc.) or discolored (whitening etc.), and the chromatic colorant [C] may remain partially, but hardly exists. This is because the chromatic colorant [C] is decomposed or scattered by laser light. In the molded product with multi-color marking, as described above, the multi-color marking is, as described above, a portion that is colored by irradiating laser light to different positions on the surface of the molded product, and a color derived from the chromatic colorant [C], You may have the part which developed the color adjacent to the color which the density of the color derived from white or a chromatic colorant [C] fell.
In addition, since the said molded article contains acrylic resin (A2), a laser beam irradiation part tends to foam. Therefore, when the laser light irradiated part becomes a foamed part, depending on the behavior of the chromatic colorant [C] at the time of laser light irradiation, the difference in refractive index between the laser light irradiated part (foamed part) and the surrounding unirradiated part may be It may become larger and the markings may become clearer. In particular, when the chromatic colorant [C] is decomposed or scattered by higher energy, resulting in a white color or a color with a reduced color density, the laser beam irradiation part (foaming) Part) and the surrounding non-irradiated part have a large difference in refractive index, so that a molded product with multicolor markings with clearer markings can be obtained.

The molded product with multicolor marking may include a protective layer on the surface having the marking portion. The material constituting the protective layer may be selected depending on the purpose and application, and is not particularly limited, but is preferably a transparent material for protecting the marking portion, maintaining the visibility of the marking, or the like. . The above protective layer is preferably disposed on at least the entire surface of the marking portion, and may be disposed on the entire surface of the molded product.
By providing the above-described protective layer, the surface smoothness of the molded product can be improved in addition to the purpose of protecting the marking portion. In addition, the formation method of the above-mentioned protective layer is not specifically limited.

  Hereinafter, the present invention will be specifically described with reference to examples. In addition, this invention is not restrict | limited at all by these Examples. Further, “%” and “part” in the examples are based on mass unless otherwise specified.

1. Production of molded part 1-1. Raw material component of composition [X] (1) Polymer (A)
(1) Polycarbonate resin (A1)
A polycarbonate “NOVAREX 7022PJ” (trade name) manufactured by Mitsubishi Engineering Plastics was used. The viscosity average molecular weight is 22,000.

(2) Acrylic resin (A2)
A rubber-reinforced acrylic resin obtained by the following production method was used as (A2-1), and polymethyl methacrylate “Acrypet VH001” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. was used as (A2-2). .

<Method for producing rubber-reinforced acrylic resin (A2-1)>
In a glass flask equipped with a stirrer, 100 parts of ion-exchange water, 1.5 parts of sodium dodecylbenzenesulfonate, 0.1 part of t-dodecyl mercaptan, polybutadiene latex (weight average particle size 240 nm, gel content 85%) 30 parts (in terms of solid content), 12.25 parts of methyl methacrylate, 4 parts of styrene and 1.25 parts of acrylonitrile were added, and the temperature was increased while stirring. When the internal temperature reaches 45 ° C., it consists of 0.1 part of sodium ethylenediaminetetraacetate, 0.003 part of ferrous sulfate, 0.2 part of sodium formaldehyde sulfoxylate dihydrate and 15 parts of ion-exchanged water. An aqueous activator solution and 0.1 part of diisopropylbenzene hydroperoxide were added and allowed to react for 1 hour.
Thereafter, 50 parts of ion-exchanged water, 1 part of sodium dodecylbenzenesulfonate, 0.1 part of t-dodecyl mercaptan, 0.2 part of diisopropylbenzene hydroperoxide, 36.75 parts of methyl methacrylate, 12 parts of styrene and acrylonitrile 3. 75 parts of the polymerization component was continuously added over 3 hours to continue the polymerization. After adding all the polymerization components and stirring for another hour, 0.2 part of 2,2-methylene-bis (4-ethyl-6-t-butylphenol) was added to terminate the polymerization. The reaction product latex was coagulated with 2 parts of calcium chloride and washed with water. Thereafter, the polymer was taken out and dried to obtain a white powdery rubber-reinforced acrylic resin (A2-1). The polymerization conversion obtained was 98.5%, the grafting rate was 40%, and the intrinsic viscosity [η] of the acetone-soluble component was 0.3 dl / g.

(3) Thermoplastic resin (A3)
The following two types were used as other polymer components.
Polyethylene terephthalate “NOVADUR 5007” manufactured by Mitsubishi Engineering Plastics Co., Ltd. as (A3-2) and polyethylene terephthalate “Unipet RT523C” (trade name) manufactured by Nippon Unipet Co., Ltd. as the thermoplastic resin (A3-1). (Trade name) was used.

1-2. Phosphate ester compound [B]
122.2 g (1.00 mol) of 2,4-dimethylphenol was placed in a four-necked flask having a volume of 300 ml, which was equipped with a Liebig condenser, a stirrer, and a thermometer. Thereafter, this four-necked flask was connected to a round bottom flask having a volume of 100 ml containing 71 g (0.50 mol) of diphosphorus pentoxide via a connecting joint. After the internal temperature of the four-necked flask was set to 40 ° C., diphosphorus pentoxide was gradually added. After reaching 65 ± 5 ° C. due to an increase in internal temperature due to exotherm, diphosphorus pentoxide was further added at this temperature. After the total amount of diphosphorus pentoxide was added, the internal temperature was raised to 90 ° C., and the reaction was carried out for 2 hours while the internal temperature was 90 ± 5 ° C.
Next, the internal temperature is cooled to 75 ± 5 ° C., 72.1 g (0.50 mol) of 4-hydroxybutyl acrylate is added dropwise, and the mixture is reacted at this temperature for 2 hours. The brown containing the phosphate ester compound [B] There were obtained 265.4 g of a liquid phosphate ester reaction product. The acid value was 300 mgKOH / g. The infrared absorption spectrum of the resulting phosphate ester reaction product is shown in FIG. This phosphate ester reaction product was used as a phosphate ester compound [B].

（２）着色剤（ｂ）
下記の構造を有するジケトピロロピロール系顔料（赤色）を用いた。発熱ピーク温度は５５０℃である。

（３）着色剤（ｃ）
下記の構造を有するアルミニウムフタロシアニン顔料（緑色）を用いた。発熱ピーク温度は５８１℃である。

（４）着色剤（ｄ）
下記の構造を有するペリノン系染料（赤色）を用いた。発熱ピーク温度はなかった。

（５）着色剤（ｅ）
下記の構造を有するアンスラキノン系染料（青色）を用いた。発熱ピーク温度はなかった。

1-3. Chromatic colorant [C]
The following colorants were used. The exothermic peak temperature measured by differential thermal analysis is also shown. The measuring device is “TG-DTA320 type (horizontal furnace)” manufactured by Seiko Denshi. About 3 mg of the sample was uniformly and densely packed into a dish-shaped container made of aluminum having a diameter of 5 mm and a height of 2.5 mm, and the temperature rising rate was 10 ° C./min. Note that the temperature calibration in the measuring apparatus was performed using indium and tin. The weight was calibrated using a weight at room temperature, and further using calcium oxalate. The exothermic peak temperature was determined by the peak top in the temperature rise curve.
(1) Colorant (a)
A dioxazine pigment (purple) having the following structure was used. The exothermic peak temperature is 402 ° C.

(2) Colorant (b)
A diketopyrrolopyrrole pigment (red) having the following structure was used. The exothermic peak temperature is 550 ° C.

(3) Colorant (c)
An aluminum phthalocyanine pigment (green) having the following structure was used. The exothermic peak temperature is 581 ° C.

(4) Colorant (d)
A perinone dye (red) having the following structure was used. There was no exothermic peak temperature.

(5) Colorant (e)
An anthraquinone dye (blue) having the following structure was used. There was no exothermic peak temperature.

1-4. Black material [D]
Carbon black “Mitsubishi Carbon # 45” (trade name) manufactured by Mitsubishi Chemical Corporation was used.

2. Preparation and evaluation of thermoplastic resin composition (Examples 1-6 and Comparative Examples 1-7)
Each thermoplastic resin composition was prepared according to the formulation of Table 1 and Table 2, using the raw material components. That is, after each raw material component was mixed for 5 minutes by a mixer, it was melt kneaded and extruded at a cylinder set temperature of 180 to 220 ° C. with a 50 mmφ extruder to obtain pellets. The obtained pellets were sufficiently dried, and a test piece for evaluation of laser marking properties and molding appearance (length 80 mm, width 55 mm, thickness) with an injection molding machine (model name “EC-60”, manufactured by Toshiba Machine Co., Ltd.). 2.5 mm) and a test piece for evaluating impact resistance.

Using each of the above test pieces, laser marking properties, impact resistance, and molded appearance were evaluated by the following methods, and are also shown in Tables 1 and 2.
(1) Laser Marking Properties Using the Lofine Basel Lofine power line “E / SHG type” and the company's laser marker “RSM30D type”, the wavelength of the laser beam is set to 532 nm and 1,064 nm, respectively, as shown in Table 3. According to the irradiation conditions, laser light was irradiated to different positions on the surface of the test piece, and the color of the irradiated portion was observed.

(2) Impact resistance It evaluated with Charpy impact strength. This Charpy impact strength was measured according to ISO179. The unit is kJ / m. In Tables 1 and 2, when the test piece was not broken, it was indicated as “NB”.
(3) Molding appearance property The surface of the test piece was visually observed to determine whether pearl luster was observed. In Tables 1 and 2, “pearly tone” was indicated for those in which pearly luster was observed, and “good” was indicated for those in which pearly luster was not observed.

  From Table 2, the comparative example 1 is an example using the composition which does not contain a chromatic colorant [C], and even if it irradiated the laser beam, the chromatic marking was not obtained. Comparative Example 2 is an example that does not contain the phosphate ester compound [B], and a pearly luster appearance was developed on the surface of the test piece, and chromatic and white markings were not obtained. Comparative Examples 3 to 5 are examples using a colorant that does not have an exothermic peak by differential thermal analysis, and only a color derived from each colorant was obtained even when irradiated with laser light. In Comparative Example 6, when laser light having a wavelength of 1,064 nm for applying low energy was irradiated, color development was not confirmed, and the original black (ground color) remained. In Comparative Example 7, the color developability was good, but the impact resistance was not sufficient. On the other hand, in all of Examples 1 to 6, a pearly luster appearance was not recognized at all on the surface of the test piece, marking by irradiation with laser light was clear, and impact resistance was sufficient. In particular, in Examples 5 and 6 using the thermoplastic resins (A3-1) and (A3-2), the impact resistance was improved by 50% or more compared to Examples 1-3.

  The thermoplastic polymer composition for multicolor laser marking of the present invention can be easily formed into a molded product that exhibits a black or dark ground color, and the molded product is irradiated with laser light having different energy. Therefore, it is suitable for clearly forming markings having two or more different colors. Therefore, housings such as personal computers, keyboards, printers, facsimiles, telephones, mobile phones, etc., home appliances such as refrigerators and washing machines, various containers, coating materials such as electric wires, printed wiring boards, and precision parts such as electronic components mounted on them. It is useful for molded parts such as automobile interior parts, various pipes, films for building materials, cards such as credit cards and IC cards, exterior materials such as signboards and signs.

It is explanatory drawing which shows the laser marking method of this invention. It is a schematic sectional drawing which shows the molded article with a multicolor marking obtained by the other laser marking method of this invention. It is a figure which shows the infrared absorption spectrum of a phosphate ester type reaction product.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1; Molded article, 2 and 2a; Molded article with multicolor marking, 3a; Chromatic marking part, 3b; White marking part.

Claims (7)

[A] Polymer component containing polycarbonate resin (A1) and acrylic resin (A2), [B] phosphate ester compound, [C] chromatic colorant, [D] A thermoplastic resin composition for multicolor laser marking, which contains a black substance that disappears or discolors itself, and is marked in two or more different colors by irradiating laser light having two or more different energies There,
The phosphate ester compound [B] is a phosphate ester compound (B1) having an aromatic group represented by the following general formula (1) and an ester bond-containing group represented by the following general formula (2 ). Yes,

[In the general formula (1), R ^A , R ^B , R ^C , R ^D and R ^E are a hydrogen atom, an alkyl group, an alkenyl group, a group containing a benzene ring or a group containing a hetero atom, and each is the same. Or different. ]

[In General Formula (2), R ^F is an alkenyl group, an alkyl group, a group containing a benzene ring or a group containing a hetero atom, Y is an alkylene group, and k is a positive integer. ]
The content ratios of the polycarbonate resin (A1) and the acrylic resin (A2) contained in the polymer component [A] are 1 to 99% by mass and 99 to 1 respectively when the total of these is 100% by mass. Mass%,
Content of the said phosphate ester type compound [B] is 0.1-50 mass parts when the sum total of the said polycarbonate resin (A1) and the said acrylic resin (A2) is 100 mass parts,
The content of the chromatic colorant [C] is 0.001 to 3 parts by mass when the polymer component [A] is 100 parts by mass, and
The content of the black substance [D] is 0.01 to 2 parts by mass when the polymer component [A] is 100 parts by mass. object.   The acrylic resin (A2) is a rubber-reinforced acrylic resin (A2-) obtained by polymerizing a monomer (a2) containing a (meth) acrylic acid ester compound in the presence of the rubber polymer (a1). The thermoplastic resin composition for multicolor laser marking according to claim 1, comprising (1) and / or a monomeric (co) polymer (A2-2) containing a (meth) acrylic acid ester compound. The thermoplastic resin composition for multicolor laser marking according to claim 1 or 2, wherein the aromatic group is a group represented by the following general formula (III) .

[Wherein R ^G and R ^H are a hydrogen atom, an alkyl group, an alkenyl group, a group containing a benzene ring or a group containing a hetero atom, and may be the same or different. ]   The thermoplastic resin composition for multicolor laser marking according to any one of claims 1 to 3, wherein the chromatic colorant [C] has an exothermic peak in a range of 360 ° C or higher and 590 ° C or lower in differential thermal analysis. .   5. The thermoplastic resin composition for multicolor laser marking according to claim 1, wherein the black substance [D] is at least one selected from carbon black, titanium black, and black iron oxide.   The polymer component [A] further includes at least one thermoplastic resin [E] selected from polyester resins, rubber-reinforced styrene resins, and polyolefin resins, and is included in the polymer component [A]. The thermoplastic resin for multicolor laser marking according to any one of claims 1 to 5, wherein the content of the thermoplastic resin [E] is 98% by mass or less based on the total amount of the polymer component [A]. Composition.   A laser beam having two or more different energies is irradiated on a molded article containing the thermoplastic resin composition for multicolor laser marking according to any one of claims 1 to 6 to mark two or more different colors. Laser marking method characterized by the above.

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