JP4434711B2 - Resin composition for laser marking - Google Patents

Description

  The present invention relates to a resin composition for laser marking capable of forming characters, symbols, and the like on the surface of a molded article by irradiation with a laser beam, and a laser marking method using the same.

  As a method for printing characters, symbols, figures, etc. on the surface of a resin molded product or an article coated with a resin, printing with ink is generally performed. However, the ink stamping method requires complicated processing steps, and it is necessary to clean the surface of the molded article with a solvent such as chlorofluorocarbon or trichloroethane which is harmful to the environment in order to improve the ink fixing property. Furthermore, the above-mentioned stamping method cannot form a clear image with high adhesion on the surface of the crystalline plastic. Therefore, a laser marking method for marking the surface of a resin by irradiation with a laser beam has been proposed as an alternative to the ink stamping method. The laser marking method is a method capable of performing good marking even on a crystalline plastic by a simple process.

  For example, in JP-A-5-295274 (Patent Document 1), it is selected from (A) a thermoplastic resin and (B) a tetrazole compound, an azo compound having a decomposition temperature of 210 ° C. or higher, a nitroso compound, and a sulfonyl hydrazide compound. A resin composition for laser marking containing at least one kind of compound is disclosed. However, this composition does not have sufficient marking effects such as sharpness and fastness. In addition, the resin composition is colored by a nitrogen compound such as an azo compound, and the burden on the environment is large.

  Japanese Patent No. 3352481 (Patent Document 2) discloses a resin composition for laser marking containing (A) a thermoplastic resin and (B) zinc borate hydrate. In this document, zinc borate hydrate is used as an inorganic compound that releases water. However, even with this composition, the marking effect is not sufficient, and the zinc borate compound is a compound with a large environmental load.

Japanese Patent Application Laid-Open No. 2002-513062 (Patent Document 3) discloses polyester-based thermoplastic resins, bright pigments, boron phosphate, zinc oxide, zinc stannate, zinc hydroxystannate, tin oxalate (II) and these. A laser marking composition comprising a marking agent selected from a mixture of these is disclosed. However, the marking effect is not sufficient even with this composition, and the environmental load is large.
JP-A-5-295274 Japanese Patent No. 3352481 JP 2002-513062 A

  Accordingly, an object of the present invention is to provide a resin composition for laser marking capable of forming a clear and firm marking on the surface of a molded product, a molded product thereof, and a laser marking method using the same.

  Another object of the present invention is to provide a resin composition for laser marking, a molded product thereof, and a laser marking method using them, which have a low environmental impact.

  Still another object of the present invention is to provide a resin composition for laser marking that can be marked by a simple method even for fine and precise marking, a molded product thereof, and a laser marking method using them. .

The present inventors, as a result of intensive investigations to achieve the above objects, found that by using a specific organic compound as a marking agent, to form a clear and robust marking on the surface of the resin molded product, completion of the present invention did.

That is, the laser marking resin composition of the present invention is a resin composition composed of a base resin and a marking agent, the marking agent is a salt of a particular amino group-containing triazines and certain hydrazine compound, It is comprised with at least 1 type selected from. The base resin may be composed of, for example, a polyacetal resin, a (liquid crystal) polyester resin, a polyphenylene sulfide resin, a polyamide resin, or the like. The ratio of the marking agent is about 0.01 to 300 parts by weight with respect to 100 parts by weight of the base resin. The composition may further contain a pigment such as a black pigment or a non-black pigment. The composition further contains a marking aid such as a halogen-based compound, an inorganic metal compound (such as a compound containing a periodic table 6A, 2B, 4B, or 5B group metal), a boron-containing compound, or an aromatic resin. Also good.

  The present invention also includes a laser markable molded article composed of the composition. Furthermore, the present invention also includes a method of marking the molded product by irradiating it with a laser beam.

  In the present invention, a marking agent selected from alumina hydrate, alkaline earth metal hydrogen phosphate, Group 3B metal salt of (phosphorous) phosphoric acid, salt of amino group-containing triazine, and hydrazine compound is used. Therefore, a clear and firm marking can be formed on the surface of the resin molded product by irradiating with a laser beam. In addition, these marking agents have a small load on the environment. Furthermore, even if the molded product formed with the resin composition containing this marking agent is a fine marking, it can be marked by a simple method.

[Base resin]
The base resin is not particularly limited and includes various thermoplastic resins and thermosetting resins.

  The thermoplastic resin constituting the base resin includes polyester resin (including liquid crystal polyester), polyacetal resin, polyamide resin (including liquid crystal polyester amide and liquid crystal polyamide), polycarbonate resin, polyester amide resin, and polyester carbonate. Resin, polyphenylene oxide resin, polyphenylene sulfide resin, olefin resin (including cyclic olefin resin), acrylic resin, styrene resin, vinyl resin, polyurethane resin, polysulfone resin, polyethersulfone resin Examples thereof include resins, polyketone resins (including aliphatic polyketones and aromatic polyether ketones), polyimide resins (including polyetherimides), fluorine resins, and silicone resins. Examples of the thermosetting resin include phenol resin, amino resin, thermosetting polyester resin, epoxy resin, silicone resin, vinyl ester resin, polyurethane resin, and the like. These base resins can be used alone or in combination of two or more.

  Among these, polyacetal resins, (liquid crystal) polyester resins, polyphenylene sulfide resins, polyamide resins, or polymer alloys containing these resins (polycarbonate resin alloys, polyphenylene oxide resin alloys, olefin resin alloys, acrylics) Based resin alloys, styrene resin alloys, polyurethane resin alloys, etc.) are preferred.

(Polyacetal resin)
The polyacetal resin includes a polyacetal homopolymer having an oxymethylene group (—CH ₂ O—) as a constituent unit and a polyacetal copolymer containing other comonomer units in addition to the oxymethylene group. In the copolymer, comonomer units include oxy C _2-6 alkylene units (for example, oxy C _2-4 alkylene units such as oxyethylene group (—CH ₂ CH ₂ O—), oxypropylene group, oxytetramethylene group). included. The content of the comonomer unit is selected from a range of, for example, 0.01 to 30 mol%, preferably 0.03 to 20 mol%, more preferably about 0.03 to 15 mol%, with respect to the entire polyacetal resin. it can.

  The polyacetal copolymer may be a copolymer composed of two components, a terpolymer composed of three components, or the like. The polyacetal copolymer may be a random copolymer, a block copolymer, a graft copolymer, or the like. Moreover, the polyacetal resin may have a branched structure as well as a linear structure, and may have a crosslinked structure. Furthermore, the terminal of the polyacetal resin may be stabilized by esterification with a carboxylic acid such as acetic acid or propionic acid or an anhydride thereof.

  Examples of the polyacetal resin include aldehydes such as formaldehyde, paraformaldehyde, and acetaldehyde, trioxane, ethylene oxide, propylene oxide, 1,3-dioxolane, 1,3-dioxane, diethylene glycol formal, and 1,4-butanediol formal. It can be produced by polymerizing cyclic ether or cyclic formal.

(Polyester resin)
The polyester-based resin is a homopolyester or a copolyester obtained by polycondensation of a dicarboxylic acid component and a diol component, polycondensation of oxycarboxylic acid or lactone, or polycondensation of these components. Preferred polyester resins usually include saturated polyester resins, particularly aromatic saturated polyester resins.

  Examples of the dicarboxylic acid component include aliphatic dicarboxylic acids (for example, dicarboxylic acids having about 4 to 40 carbon atoms such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and dimer acid. , Preferably a dicarboxylic acid having about 4 to 14 carbon atoms), an alicyclic dicarboxylic acid (for example, a dicarboxylic acid having about 8 to 12 carbon atoms such as hexahydrophthalic acid), an aromatic dicarboxylic acid (about 8 to 16 carbon atoms). Dicarboxylic acids such as arene dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, etc.), bisphenyl-dicarboxylic acids (4,4'-biphenyldicarboxylic acid, diphenyl ether-4,4 ' -Dicarboxylic acid, diphenylalkanedicarboxylic acid (4,4'-diphenylmethane Such as carboxylic acid), 4,4'-diphenyl ketone dicarboxylic acid)], or derivatives thereof (e.g., lower alkyl esters, aryl esters, esters formable derivative such as an acid anhydride) and the like. These dicarboxylic acid components may be used alone or in combination of two or more. Furthermore, you may use together polyvalent carboxylic acids, such as trimellitic acid and a pyromellitic acid, as needed.

  Preferred dicarboxylic acid components include aromatic dicarboxylic acids such as terephthalic acid and naphthalenedicarboxylic acid.

  Examples of the diol component include aliphatic alkylene diols (for example, aliphatic glycols having about 2 to 12 carbon atoms such as ethylene glycol, trimethylene glycol, propylene glycol, 1,4-butanediol, preferably 2 to 10 carbon atoms). An aliphatic glycol), a polyoxyalkylene glycol (a glycol having an alkylene group of about 2 to 4 carbon atoms and having a plurality of oxyalkylene units, such as diethylene glycol, dipropylene glycol, etc.), an alicyclic diol (for example, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.). Moreover, you may use together aromatic diols, such as hydroquinone, a biphenol, and 2, 2-bis (4-hydroxyphenyl) propane. These diol components may be used alone or in combination of two or more. Furthermore, you may use together polyols, such as glycerol, a trimethylol propane, a trimethylol ethane, a pentaerythritol, as needed.

Preferred diol components include C _2-6 alkylene glycol (linear alkylene glycol such as ethylene glycol, trimethylene glycol, propylene glycol, 1,4-butanediol), and oxyalkylene units having about 2 to 4 repetitions. Polyoxyalkylene glycols [glycols containing poly (oxy-C _2-4 alkylene) units such as diethylene glycol], 1,4-cyclohexanedimethanol and the like.

  Examples of the oxycarboxylic acid include oxybenzoic acid, oxynaphthoic acid, 4-carboxy-4'-hydroxybiphenyl, hydroxyphenylacetic acid, glycolic acid, D-, L- or D / L-lactic acid, oxycaproic acid, and the like. Oxycarboxylic acids or their derivatives are included.

Lactones include C _3-12 lactones such as propiolactone, butyrolactone, valerolactone, caprolactone (eg, ε-caprolactone).

Preferred polyester resins include homopolyesters or copolyesters having an alkylene arylate such as alkylene terephthalate or alkylene naphthalate as a main component (for example, about 50 to 100% by weight, preferably about 75 to 100% by weight) [for example, polyalkylene Terephthalate (for example, poly (1,4-cyclohexanedimethylene terephthalate) (PCT), polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT) and other poly C _2-4 alkylene terephthalates), polyalkylene naphthalate (e.g., polyethylene naphthalate, poly C _2-4 alkylene naphthalate and polybutylene naphthalate) homopolymer polyesters such as, alkylene terephthalate and Or mainly of alkylene naphthalate unit (e.g., more than 50% by weight) include copolyesters] containing as. Particularly preferred polyester resins include polybutylene terephthalate resins containing butylene terephthalate units as a main component (for example, polybutylene terephthalate, polybutylene terephthalate copolyester), polypropylene terephthalate resins containing propylene terephthalate units as main components ( For example, polypropylene terephthalate, polypropylene terephthalate copolyester) and polyethylene terephthalate resin (for example, polyethylene terephthalate, polyethylene terephthalate copolyester) containing ethylene terephthalate units as main components are included. In addition, these polyester-type resin can be used individually or in combination of 2 or more types.

In the copolyester, the copolymerizable monomer includes C _2-6 alkylene glycol (such as linear alkylene glycol such as ethylene glycol, propylene glycol, 1,4-butanediol), and a repeating number of 2 to 2. Polyoxyalkylene glycols having about 4 oxyalkylene units (such as diethylene glycol, glycols containing poly (oxy-C _2-4 alkylene) units such as polytetramethylene glycol), C _4-12 aliphatic dicarboxylic acids (succinic acid, Glutaric acid, adipic acid, suberic acid, sebacic acid, etc.), alicyclic diol (1,4-cyclohexanedimethanol etc.), aromatic diol [2,2-bis (4- (2-hydroxyethoxy) phenyl) propane Etc.], aromatic dicarboxylic acids (phthalic acid, isophthalic acid, 5- And sulfoisophthalic acid monosodium salt). The polyester resin may be not only linear but also branched or crosslinked as long as the melt moldability is not impaired. Furthermore, the polyester-based resin is an amino group-containing monomer (for example, 3- or 4-aminophenol, 3- or 4-aminobenzoic acid, tetramethylenediamine, hexamethylenediamine, nonamethylenediamine, m-xylylenediamine. Etc.) may be used.

  Polyester resins have mesogenic groups (groups having liquid crystal forming ability) such as p-substituted aromatic rings, linear biphenyl groups, and substituted naphthyl groups as structural units, and have liquid crystallinity (particularly thermotropic liquid crystallinity). The polyester-type resin shown may be sufficient.

  As the liquid crystalline polyester resin, for example, the aromatic polyester resin may be an aromatic oxycarboxylic acid (oxybenzoic acid such as p-hydroxybenzoic acid, oxynaphthoic acid such as 2-oxy-6-naphthoic acid, 4 -Carboxy-4'-hydroxybiphenyl, hydroxyphenylacetic acid, etc.) modified polyester resin, aromatic dicarboxylic acid and aromatic diol [hydroquinone, resorcinol, biphenol, 2,2-bis (4-hydroxyphenyl) A wholly aromatic polyester resin obtained from propane, 2,2-bis- (4- (2-hydroxyethoxy) phenyl) propane, xylylene glycol, and the like] and, if necessary, the aromatic oxycarboxylic acid. Can be mentioned. Specifically, a copolymer of p-hydroxybenzoic acid, 4,4′-dihydroxybiphenyl and terephthalic acid, a copolymer of p-hydroxybenzoic acid and 2-oxy-6-naphthoic acid, or the like. These liquid crystal polyester resins can be used alone or in combination of two or more. Further, the liquid crystal polyester resin includes a liquid crystal polyester amide resin modified with an amino group-containing monomer (for example, 3- or 4-aminophenol, 3- or 4-aminobenzoic acid, etc.).

  The polyester resin can be produced by a conventional method such as transesterification or direct esterification.

(Polyphenylene sulfide resin)
The polyphenylene sulfide resin (polyphenylene thioether resin) includes a homopolymer and a copolymer having a polyphenylene sulfide skeleton — (Ar—S —) — [wherein Ar represents a phenylene group]. The phenylene group (—Ar—) is, for example, a substituted phenylene group (for example, an alkylphenylene group having a substituent such as a C _1-5 alkyl group, or an arylphenyl group having a substituent such as a phenyl group). Or a group represented by the formula —Ar—X—Ar— (wherein Ar represents a phenylene group, and X represents O, SO ₂ , CO, or a direct bond). The polyphenylene sulfide resin may be a homopolymer using the same repeating unit among the phenylene sulfide groups composed of such phenylene groups, and includes different repeating units from the viewpoint of processability of the composition. It may be a copolymer.

  As the homopolymer, a substantially linear polymer having a p-phenylene sulfide group as a repeating unit is preferably used. Copolymers can be used in combination of two or more different phenylene sulfide groups. Of these, the copolymer is preferably a combination containing a p-phenylene sulfide group as a main repeating unit and an m-phenylene sulfide group. From the viewpoint of physical properties such as heat resistance, moldability and mechanical properties, p-phenylene is preferred. A substantially linear copolymer containing 60 mol% (preferably 70 mol%) or more of sulfide groups is particularly preferable.

  The polyphenylene sulfide resin may be a polymer having a relatively low molecular weight linear polymer whose melt viscosity is increased by oxidative crosslinking or thermal crosslinking to improve molding processability, and is reduced from a monomer mainly composed of a bifunctional monomer. It may be a high molecular weight polymer having a substantially linear structure obtained by polymerization. From the viewpoint of physical properties of the obtained molded product, a substantially linear structure polymer obtained by condensation polymerization is preferred. The polyphenylene sulfide resin includes a branched or crosslinked polyphenylene sulfide resin obtained by polymerizing a monomer having three or more functional groups in addition to the polymer, and a resin composition obtained by blending the resin with the linear polymer. Things can also be used.

  As polyphenylene sulfide resin, polyphenylene sulfide ketone (PPSK), polybiphenylene sulfide sulfone (PPSS), etc. can be used in addition to polyphenylene sulfide (poly-1,4-phenylene sulfide, etc.) and polybiphenylene sulfide (PBPS). Polyphenylene sulfide resins can be used alone or in combination of two or more.

(Polyamide resin)
Polyamide resins include: polyamides derived from diamines and dicarboxylic acids; aminocarboxylic acids, polyamides obtained by using diamines and / or dicarboxylic acids in combination; lactams; diamines and / or dicarboxylics as required Polyamides derived by combination with acids are included. Polyamide also includes copolyamides formed by at least two different polyamide-forming components.

  Examples of the diamine include aliphatic diamines such as trimethylenediamine, hexamethylenediamine, and 2,2,4-trimethylhexamethylenediamine; alicyclic diamines such as bis (4-aminocyclohexyl) methane; metaxylylenediamine, and the like. Of the aromatic diamine. These diamines can be used alone or in combination of two or more.

Examples of the dicarboxylic acid include C _4-20 aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, suberic acid, and sebacic acid; dimerized fatty acids (dimer acid); and alicyclic such as cyclohexanedicarboxylic acid. Dicarboxylic acids; aromatic dicarboxylic acids such as phthalic acid and naphthalenedicarboxylic acid.

Examples of aminocarboxylic acids include C _4-20 aminocarboxylic acids such as aminononanoic acid and aminoundecanoic acid. Aminocarboxylic acids can be used alone or in combination of two or more.

Examples of the lactam include C _4-20 lactams such as caprolactam, capryl lactam, and dodecaractam. These lactams can also be used alone or in combination of two or more.

  Polyamide resins include aliphatic polyamides such as polyamide 46, polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 11 and polyamide 12, aromatic dicarboxylic acids (for example, terephthalic acid and / or isophthalic acid) and aliphatic. Obtained from polyamides obtained from diamines (eg hexamethylenediamine, nonamethylenediamine, etc.), aromatic and aliphatic dicarboxylic acids (eg terephthalic acid and adipic acid) and aliphatic diamines (eg hexamethylenediamine) Examples thereof include polyamide. These polyamides can be used alone or in combination of two or more.

  Preferred polyamides include aliphatic polyamides (polyamide 6, polyamide 66, polyamide 610, polyamide 612, etc.), polyamides having at least a diamine component as an aliphatic compound (polyamide 6T, polyamide 6T copolymer, polyamide 9T, etc.), semi-aromatic Group (copolymerization) polyamide (polyamide MXD6, polyamide 6T / 6, polyamide 6T / 66, polyamide 6T / 12, polyamide 6I / 6, polyamide 6I / 66, polyamide 6T / 6I, polyamide 6T / 6I / 6, polyamide 6T / 6I / 66, polyamide 6T / MST, etc.). Polyamide resins can be used alone or in combination of two or more.

The number average molecular weight of the base resin is not particularly limited and is appropriately selected depending on the type and use of the resin, for example, 5 × 10 ³ to 200 × 10 ⁴ , preferably 1 × 10 ^{4 to} 150 × 10 ⁴ , Preferably, it can be selected from the range of about 1 × 10 ^{4 to} 100 × 10 ⁴ . When the base resin is a polyester resin, the number average molecular weight is, for example, 5 × 10 ^{3 to} 100 × 10 ⁴ , preferably 1 × 10 ⁴ to 70 × 10 ⁴ , and more preferably 1.2 × 10 ⁴ to. It may be about 30 × 10 ⁴ .

[Marking agent]
In the present invention, alumina hydrate, hydrogen phosphate metal salt, (phosphite) metal phosphate salt, amino group-containing triazine salt, and hydrazine compound are used as the marking agent. These marking agents can be used alone or in combination of two or more.

(Alumina hydrate)
Alumina hydrate is a compound represented by the composition formula Al ₂ O ₃ .nH ₂ O (where 0 <n <3). In the above formula, n is usually a number exceeding 0 and less than 3 (preferably about 0.5 to 2, more preferably about 0.7 to 1.5). Examples of the alumina hydrate include alumina monohydrate (aluminum hydroxide oxide) such as boehmite and diaspore, and alumina hydrate such as pseudoboehmite. These alumina hydrates contain alumina trihydrate (aluminum hydroxide) such as gibbsite and bayerite, or are combined by hydrothermal treatment or the like (for example, 1 to 99% by weight, preferably 5 to 5% by weight). Boehmite in which 95% by weight of aluminum hydroxide is combined may be used. These alumina hydrates can be used alone or in combination of two or more.

  Of these alumina compounds, alumina monohydrate, pseudoboehmite, and aluminum hydroxide composite boehmite, particularly boehmite, are preferred because of their high dehydration temperature and excellent flame retardancy. Boehmite is a kind of mineral constituting bauxite, and is usually obtained by heating or hydrothermally treating aluminum hydroxide such as gibbsite or bayerite. Boehmite also includes hydrates in which n is less than 3 in the above formula, and in particular, alumina hydrate containing at least a monohydrate substantially having n = 1, or with aluminum hydroxide A composite (aluminum hydroxide composite boehmite) is preferred.

  The shape of the boehmite is not particularly limited, and may be granular (spherical, elliptical, rectangular, needle, strip, etc.) or plate (disc, elliptical, square, hexagonal, etc.) Polygonal plate shape, irregular plate shape such as scale shape, etc.). The average diameter of the granular or plate boehmite is, for example, about 0.1 to 50 μm, preferably about 0.3 to 30 μm, and more preferably about 0.5 to 20 μm (particularly 1 to 10 μm). The aspect ratio (ratio of average diameter to thickness) of the plate-like boehmite is, for example, 5 or more, preferably 10 to 500, and more preferably about 30 to 400. In the resin composition (particularly, a molded product), boehmite may be nano-dispersed at 0.1 μm or less (for example, 0.0001 to 0.1 μm).

The boehmite may be a layered laminate, and an inorganic component or an organic component may be contained or bonded between the layers. Binding of inorganic components and organic components, for example, in the formula _{AlO (OH) x (O (} CH 2) n OH) 1-x ( wherein, x is a number less than 1, n is the number of 2 to 10 It may be an aluminum glycoxide bond represented by Examples of the inorganic component include alkali metal compounds (such as compounds containing sodium and potassium), alkaline earth metal compounds (such as compounds containing magnesium, calcium, strontium, barium, etc.), inorganic acids (such as phosphoric acid and phosphoric acid). Phosphate, etc.). Examples of the organic component include organic acids or salts thereof (organic acid alkaline earth metal salts such as magnesium acetate), alcohol compounds (ethylene glycol, 1,2- or 1,3-propanediol, 1,3- or 1,4-butanediol, 1,6-hexanediol, diols such as 1,4-cyclohexanedimethanol), amine compounds (such as alkanolamines such as triethanolamine), resins (polyvinyl alcohol, polyethylene glycol, hydroxy) And hydroxyl group-containing resins such as propylcellulose).

The specific surface area of boehmite is, for example, 0.5 m ² / g or more, preferably 1 m ² / g or more (for example, 1 to ²⁰⁰ m ² / g), more preferably 3 m ² / g, from the viewpoint of the ability to release hydrated water. g or more (especially 5 to 150 m ² / g).

  Boehmite preferably releases water of hydration at a high temperature (for example, a temperature higher than the molding temperature of the base resin), for example, 240 ° C. or higher, preferably 330 to 700 ° C., more preferably 350 to 650 ° C. It is preferable to release water of hydration at about 400-600 ° C.

  As boehmite, specifically, JP-A-60-46923, JP-A-6-263437, JP-A-6-329411, JP-A-11-21125, JP-A-2000-86235, JP 2000-239014, JP-A-2001-261331, JP-A-2001-261976, JP-A-2001-302236, JP-A-2003-2641, JP-A-2003-2642, JP-A-2003. Examples of the boehmite described in JP-A-176126, JP-A 2003-221227, JP-A 2003-238150, and JP-A 2003-292819. Moreover, as a commercial item of boehmite, for example, the trade name “Cerasure” series of Kawai Lime Industry Co., Ltd. [for example, BMB, BMT, BMB (33), BMT (33), BMM, BMF, BMI, etc.), Nabaltec GmbH's trade name “Apyral” series [eg, AOH180DE, AOH180DS, etc.], Sasol North America Inc. The product name “DISPAL” series of the company, the product name “nanoalumina” series [for example, CAM9010, etc.] of the Saint-Gobain Ceramic Materials, etc. may be mentioned.

(Metal hydrogen phosphate)
Examples of phosphoric acid of metal hydrogen phosphate include non-condensed phosphoric acid such as peroxophosphoric acid, orthophosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid; hypophosphoric acid, pyrophosphoric acid, polyphosphoric acid (triphosphate, Tetraphosphoric acid, etc.), polymetaphosphoric acid (Ca ₃ (P ₃ O ₉ ) ₂ etc.), phosphoric anhydride (Ca ₂ (P ₄ O ₁₂ ), Ca ₅ (P ₃ O ₁₀ ) ₂ etc.) In particular, non-condensed phosphoric acid is preferred.

  Phosphoric acid having a plurality of salt-forming sites is a partial salt (partial salt of a condensed acid such as ammonium polyphosphate or urea polyphosphate; ortholine, at least part of which is a compound containing other amino group such as amine and urea) A partial salt of a non-condensed acid such as acid urea) may be formed.

  The metal forming the hydrogen phosphate is a polyvalent metal, such as an alkaline earth metal (Mg, Ca, etc.), a transition metal (Mn, Fe, Co, Ni, etc.), a periodic table 2B-3B metal (Zn, Cd etc.) can be exemplified. Of these metals, alkaline earth metals (eg, Ca) are preferred.

Among these metal phosphates, substantially anhydrous metal hydrogen phosphate is usually used, and calcium hydrogen phosphate is preferably used from the viewpoint of marking properties and safety. Examples of the calcium hydrogen phosphate salt include calcium phosphate salts composed of phosphoric acid and calcium, such as calcium hydrogen orthophosphate, calcium hydrogen pyrophosphate, calcium hydrogen polyphosphate, and the like. Calcium oxyhydrogen salt, calcium dihydrogen phosphate, dicalcium phosphate (CaHPO ₄ ) and the like are preferable. These calcium hydrogen phosphate salts have little environmental impact and are economically advantageous.

((Sub-) metal phosphate)
Examples of metal salts of (sub-) phosphate metal salts include alkaline earth metal salts (Mg, Ca salts), transition metal salts (Ti, Mn salts, etc.), periodic table 3B group metal (for example, aluminum) salts, and the like. Valent metal salts. Among these, (sub-) phosphoric acid periodic table group 3B metal salts, particularly (sub-) phosphorous metal salts mainly composed of (sub-) aluminum phosphate salts are preferable. The (sub) phosphate metal salt may be foamable.

  The (phosphite) aluminum phosphate salt includes an aluminum phosphite salt, an aluminum phosphite double salt, a basic aluminum phosphite double salt, or a double salt containing boric acid and / or silicic acid. Etc. are included. Furthermore, double salts containing these amine compounds and / or other metals (alkali metal, alkaline earth metal, transition metal, etc.) and oxygen acid are also included in the (phosphite) aluminum phosphate salt. These (phosphorous) aluminum phosphate salts can be used singly or in combination of two or more.

  A preferred (phosphorous) aluminum phosphate salt is a foamable (phosphorous) aluminum phosphate salt. Such foamable (phosphite) aluminum phosphate salt is obtained by reacting phosphoric acid or a phosphorous acid component, an aluminum compound, and, if necessary, another base component or a foaming aid. . Instead of the aluminum compound and the base component, a basic aluminum compound (such as aluminum hydroxide such as kibsite) may be used.

  Examples of the phosphoric acid or phosphorous acid component include phosphoric acid or phosphate (a salt of phosphoric acid and ammonium, alkali metal or alkaline earth metal; water-soluble phosphate of phosphoric acid and aluminum or zinc, etc. ), Phosphorous acid or phosphite (phosphorous acid and ammonium, alkali metal or alkaline earth metal salt; water-soluble phosphite of phosphorous acid and aluminum or zinc, etc.) it can. Such (phosphorous) phosphoric acid components can be used singly or in combination of two or more.

  Examples of the base component include ammonium, metal hydroxide (hydroxide such as alkali metal, alkaline earth metal, aluminum, and zinc), carbonate (carbonate such as alkali metal, alkaline earth metal, and zinc). Zinc oxide, sodium aluminate, alumina gel, gibbsite, boehmite and the like. Such base components can be used singly or in combination of two or more.

  Examples of the foaming aid include boric acid, borate (such as a salt of boric acid and ammonium, alkali metal or alkaline earth metal), silicic acid, silicate (silicic acid, ammonium, alkali). A salt with a metal or an alkaline earth metal, etc.), an amine compound (for example, ammonium phosphate, urea, etc.) can be used. A foaming adjuvant can be used by 1 type or in combination of 2 or more types.

  The (phosphite) aluminum phosphate salt can be obtained by the methods described in JP-A-57-95814, JP-A-4-89306, JP-A-8-198609, JP-A-2000-53406, and the like. it can. The foamable aluminum hypophosphite salt can be obtained from Taihei Chemical Industry Co., Ltd. under the trade name “APA series (for example, APA-80, APA-100, etc.)”.

  When the foamable aluminum hypophosphite salt contains a volatile component such as water, the surface appearance of the base resin may be deteriorated or the resin may be decomposed. It may be preferable to perform a heat treatment of about 10 minutes to 24 hours in a temperature range of ˜400 ° C. For example, when the base resin is a polyester-based resin, it is preferable to use a foamable (phosphite) aluminum phosphate salt having a volatile component at 200 ° C. of 10% or less, preferably 5% or less, more preferably 2% or less. .

  The aluminum content in the (phosphite) aluminum phosphate salt, which is one of the preferred (phosphite) metal phosphates, is, for example, about 5 to 25% by weight, preferably about 8 to 20% by weight. Moreover, phosphorus content is 15 to 35 weight%, for example, Preferably it is 16 to 35 weight%, More preferably, it is about 17 to 33 weight%.

The (phosphite) aluminum phosphate salt can usually be used in a granular form (powder). The average particle diameter of the particulate (phosphorous) aluminum phosphate salt is, for example, about 0.01 to 100 μm (for example, 0.1 to 70 μm), preferably about 0.1 to 50 μm (for example, 0.5 to 30 μm). is there. The DBP (dibutyl phthalate) oil absorption of the (phosphite) aluminum phosphate salt is, for example, about 15 to 50 ml / 100 g, preferably about 20 to 40 ml / 100 g, and preferably about 25 to 30 ml / 100 g. The BET specific surface area of the (phosphite) aluminum phosphate salt is about 0.3 to ² m ² / g, preferably 0.5 to 1.5 m ² / g, more preferably about 0.8 to 1.2 m ² / g. is there.

  Such metal (phosphite) phosphate is excellent in safety, has no environmental impact, and is economically advantageous.

(Salts of amino group-containing triazines)
In the salt of amino group-containing triazines, amino group-containing 1,3,5-triazines are usually used as amino group-containing triazines (triazines having an amino group). For example, melamine, substituted melamine (2 -Methylmelamine, guanylmelamine, etc.), melamine condensates (melam, melem, melon, etc.), melamine cocondensation resins (melamine-formaldehyde resin, etc.), cyanuric amides (ammelin, ammelide, etc.), guanamine or derivatives thereof (Guanamine, methylguanamine, acetoguanamine, benzoguanamine, succinoguanamine, adipoguanamine, phthaloguanamine, CTU-guanamine, etc.).

Examples of the salt include salts of the triazines with inorganic acids and organic acids. Inorganic acids include nitric acid, chloric acid (such as chloric acid and hypochlorous acid), phosphoric acid (such as phosphoric acid exemplified in the above-mentioned metal hydrogen phosphate section), sulfuric acid (non-condensed sulfuric acid such as sulfuric acid and sulfurous acid, And condensed sulfuric acid such as peroxodisulfuric acid and pyrosulfuric acid), boric acid, chromic acid, antimonic acid, molybdic acid, tungstic acid and the like. Of these, phosphoric acid and sulfuric acid are preferred. Organic acids include organic sulfonic acids (aliphatic sulfonic acids such as methanesulfonic acid, aromatic sulfonic acids such as toluenesulfonic acid and benzenesulfonic acid), cyclic ureas (uric acid, barbituric acid, cyanuric acid, acetylene urea, etc.) ) And the like. Of these, C _1-4 alkanesulfonic acids such as methanesulfonic acid, C _1-3 alkyl C _6-12 arene sulfonic acids such as toluene sulfonic acid, cyanuric acid.

  Examples of salts of amino group-containing triazines include melamine phosphates (melamine polyphosphate, melamine polyphosphate, melam, melem double salt, etc.), melamine sulfates (melamine sulfate, dimelamine sulfate, dimelam pyrosulfate), sulfone, etc. Melamines (Melamine methanesulfonate, melam methanesulfonate, melem methanesulfonate, melamine methanesulfonate, melam melem, double salt, melamine toluenesulfonate, melam toluenesulfonate, melamine toluene, melam memel double salt) Etc.). These salts of amino group-containing triazines can be used alone or in combination of two or more.

(Hydrazine compounds)
Examples of hydrazine compounds include carboxylic acid hydrazide compounds, hydrazone compounds, biurea compounds, urazole compounds, and the like, and carboxylic acid hydrazide compounds, biurea compounds, and urazole compounds are preferred. For example, aliphatic carboxylic acid hydrazide compounds [monocarboxylic acid hydrazides (such as lauric acid hydrazide, stearic acid hydrazide, 12-hydroxystearic acid hydrazide, 1,2,3,4-butanetetracarboxylic acid hydrazide), polycarboxylic acid Hydrazides (succinic acid mono or dihydrazide, glutaric acid mono or dihydrazide, adipic acid mono or dihydrazide, pimelic acid mono or dihydrazide, suberic acid mono or dihydrazide, azelaic acid mono or dihydrazide, sebacic acid mono or dihydrazide, dodecanedioic acid mono or Dihydrazide, hexadecanedioic acid mono- or dihydrazide, eicosane diacid mono- or dihydrazide, 7,11-octadecadien-1,18-dicarbohydrazide etc.)], alicyclic carboxylic acid hydra Compound [monocarboxylic acid hydrazides (such as cyclohexanecarboxylic acid hydrazide), polycarboxylic acid hydrazides (dimer acid mono or dihydrazide, trimer acid mono to trihydrazide, 1,2-, 1,3- or 1,4- Cyclohexanedicarboxylic acid mono or dihydrazide, cyclohexanetricarboxylic acid mono to trihydrazide, etc.]], aromatic carboxylic acid hydrazide compounds [monocarboxylic acid hydrazides (benzoic acid hydrazide and its functional group (alkyl group, hydroxy group, acetoxy) Group, amino group, acetamino group, nitrile group, carboxy group, alkoxycarbonyl group, carbamoyl group, alkoxy group, phenyl group, benzyl group, cumyl group, hydroxyphenyl group and other functional groups such as phenyl residue of benzoguanamine 1 to 5 substituted derivatives: for example, o-, m- or p-methylbenzoic acid hydrazide, 2,4-, 3,4-, 3,5- or 2,5-dimethylbenzoic acid hydrazide, o-, m- or p-hydroxybenzoic acid hydrazide, o-, m- or p-acetoxybenzoic acid hydrazide, 4-hydroxy-3-phenylbenzoic acid hydrazide, 4-acetoxy-3-phenylbenzoic acid hydrazide, 4-phenylbenzoic acid Hydrazide, 4- (4′-phenyl) benzoic acid hydrazide, 4-hydroxy-3,5-dimethylbenzoic acid hydrazide, 4-hydroxy-3,5-di-t-butylbenzoic acid hydrazide, etc.), α- or β -Naphthoic acid hydrazides and their functional groups (for example, 3-hydroxy-2-naphthoic acid hydrazide, 6-hydroxy-2-naphthoic acid hydride) ), Polycarboxylic acid hydrazides (isophthalic acid mono or dihydrazide, terephthalic acid mono or dihydrazide, 1,4- or 2,6-naphthalenedicarboxylic acid mono or dihydrazide, 3,3′-, 3,4′- or 4,4 'diphenyldicarboxylic acid mono or dihydrazide, diphenyl ether dicarboxylic acid mono or dihydrazide, diphenylmethane dicarboxylic acid mono or dihydrazide, diphenylethane dicarboxylic acid mono or dihydrazide, diphenoxyethanedicarboxylic acid mono or dihydrazide, diphenylsulfone dicarboxylic acid mono or dihydrazide, Diphenyl ketone dicarboxylic acid mono- or dihydrazide, 4,4 ″ -terphenyl dicarboxylic acid mono- or dihydrazide, 4,4 ′ ″-quarterphenyl dicarboxylic acid mono- or dihydride Zido, 1,2,4-benzenetricarboxylic acid mono to trihydrazide, pyromellitic acid mono to tetrahydrazide, 1,4,5,8-naphthoic acid mono to tetrahydrazide, etc.)]], heteroatom-containing carboxylic acid hydrazide Compounds [dioxane ring-containing carboxylic acid hydrazides (mono- or dihydrazide of 5-methylol-5-ethyl-2- (1,1-dimethyl-2-carboxyethyl) -1,3-dioxane, etc.), tetraoxospiro ring Containing carboxylic acid hydrazides (3,9-bis (2-carboxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane mono- or dihydrazide, 3,9-bis (2-methoxycarbonyl) Ethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane mono- or dihydra 3,9-bis (1,1-dimethyl-1-carboxymethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane mono- or dihydrazide, 3,9-bis (1, 1-dimethyl-1-methoxycarbonylmethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane mono- or dihydrazide), isocyanuric ring-containing carboxylic acid hydrazides (1,3,5-tris) (2-carboxyethyl) isocyanurate mono to trihydrazide, 1,3,5-tris (3-carboxypropyl) isocyanurate mono to trihydrazide), hydantoin ring-containing carboxylic acid hydrazides (1,3-bis (2-hydrazinocarbonylethyl) -5-isopropylhydantoin), U.S. Pat. No. 4,465,830, U.S. Pat. No. 4,544,733, JP-A-3-193653, JP-A-58-131953, JP-A-59-24714, JP-A-59-67256, JP-A-60-178851 And carboxylic acid hydrazides described in JP-A No. 61-183316], polymer type carboxylic acid hydrazide compounds [poly (meth) acrylic acid hydrazide which may be branched or cross-linked, or a copolymer ( Olefin copolymer, vinyl monomer copolymer, styrene copolymer divinylbenzene cross-linked product, bis (meth) acrylic acid ester cross-linked product, etc.), JP-A-53-14296, JP-A-54-21493, JP-A-54-43254, JP-A-55-145529, JP-A-56-2306, JP-A-56- No. 05905, Japanese Patent Application Laid-Open No. 58-69232, Japanese Patent Application Laid-Open No. 63-49300, commercially available “aminopolyacrylamide APA”, Otsuka Chemical Co., Ltd., and US Pat. No. 3,574,786 And the like.

  Examples of the hydrazone compound include a reaction product of the carboxylic acid hydrazide or hydrazine and aldehydes (formaldehyde, acetaldehyde, etc.) or ketones (acetone, methyl ethyl ketone, acetophenone, benzophenone, etc.). For example, hydrazone derivatives of aliphatic carboxylic acid hydrazide compounds [acetone semicarbazone, acetone hydrazone of adipic acid monohydrazide, mono or diacetone hydrazone of adipic acid dihydrazide, mono or diacetone hydrazone of sebacic acid dihydrazide, dodecanedioic acid dihydrazide Mono- or diacetone hydrazone), hydrazone derivatives of alicyclic carboxylic acid hydrazide compounds (mono- or diacetone hydrazone of cyclohexanedicarboxylic acid dihydrazide, mono- or diacetone hydrazone of dimer acid dihydrazide), aromatic carboxylic acid hydrazide-based Hydrazone derivatives of compounds (monophthalic dihydrazide mono- or diacetone hydrazone, 1,4- or 2,6-naphthalenedicarboxylic acid dihydrazide mono- or diacetate) Hydrazone, etc.), hydrazone derivatives of heteroatom-containing carboxylic acid hydrazide compounds [mono- to triacetone hydrazone of 1,3,5-tris (2-hydrazinocarbonylethyl) isocyanurate, 1,3-bis (2-hydrazino) Carbonylethyl) -5-isopropylhydantoin mono- or diacetone hydrazone], hydrazone hydrazone derivatives (acetophenone hydrazone, benzophenone hydrazone, etc.) and the like.

  Examples of the biurea compound include biurea and N-substituted derivatives thereof, and biurea is particularly preferable.

  Examples of the urazole compound include urazole and its N-substituted derivative, and urazole and aminourazole are particularly preferable.

  Among these marking agents, alumina hydrate, alkaline earth metal hydrogen phosphate, Group 3B metal salt of (phosphorous) phosphoric acid, and salt of amino group-containing triazines improve moisture resistance. Therefore, the surface may be coated and used. In particular, the surface of these compounds may be coated with a resin (for example, a thermosetting resin or a thermoplastic resin) and / or an inorganic substance (for example, a glassy ceramic described in WO01 / 09234). . Examples of the thermosetting resin include phenol resin, melamine resin, urea resin, alkyd resin, unsaturated polyester resin, epoxy resin, and silicone resin. Examples of the thermoplastic resin include polyester. Resin, polyamide resin, acrylic resin, olefin resin and the like. These resins may be used alone or in combination of two or more.

  These marking agents may be used after surface treatment with a surface treatment agent or the like in order to improve adhesion with the base resin. As such a surface treatment agent, a functional compound (for example, an epoxy compound, a silane compound, a titanate compound, etc.) can be used.

  Further, these marking agents may be blended during the polymerization of the resin in order to improve the dispersibility in the base resin. For example, boehmite or a layered laminate of boehmite may be blended during a polyester polycondensation reaction such as PET, PPT, PBT, etc. to form a nano-dispersed polymer.

  The ratio of the marking agent is 0.01 to 300 parts by weight, preferably 0.03 to 250 parts by weight, more preferably 0.05 to 200 parts by weight (particularly 0.1 to 100 parts by weight) with respect to 100 parts by weight of the base resin. Part by weight).

  The resin composition for laser marking may further contain a pigment, a marking aid, a stabilizer, a filler, a flame retardant, and the like. By combining a pigment or a marking aid with the marking agent, the marking characteristics can be further improved.

[Pigment]
The pigment includes a non-black pigment as well as a black pigment that is excellent in laser beam absorptivity and suitable for white marking. Examples of pigments include organic pigments (azo, azomethine, methine, indanthrone, anthraquinone, pyranthrone, flavanthrone, benzenethrone, phthalocyanine, quinophthalone, perylene, perinone, dioxazine, thioindigo. Organic pigments such as organic, isoindolinone, isoindoline, pyrrole pyrrole and quinacridone) or inorganic pigments can be used, but usually black or non-black inorganic pigments are used. These pigments can be used alone or in combination of two or more.

  Examples of the black pigment include carbon black (acetylene black, lamp black, thermal black, furnace black, channel black, ketjen black, gas black, oil black, etc.), graphite, titanium black, black iron oxide, and the like. Of these, carbon black is particularly desirable in terms of dispersibility, color developability, and cost. A black pigment can be used individually or in combination of 2 or more types.

  Examples of non-black pigments include white pigments (for example, calcium carbonate, titanium oxide, zinc oxide, zinc sulfide), yellow pigments (for example, cadmium yellow, yellow lead, titanium yellow, zinc chromate, ocher, yellow iron oxide, etc. ), Red pigment (eg, red mouth pigment, amber, red iron oxide, cadmium red, etc.), blue pigment (eg, bitumen, ultramarine blue, cobalt blue, etc.), green pigment (eg, chrome green, etc.). Of these, white pigments such as titanium dioxide and calcium carbonate are preferred. These non-black pigments can be used alone or in combination of two or more.

  In the present invention, the color of the marking can be adjusted by combining a black pigment and a non-black pigment. For example, by increasing the proportion of the black pigment, a composition suitable for white marking can be prepared. By increasing the proportion of the white pigment, it is possible to prepare a composition suitable for black marking.

  The average particle diameter of the pigment can be selected according to the use from the range of about 10 to 100 nm, for example, 10 to 90 nm, preferably 12 to 80 μm, and more preferably about 15 to 50 μm. The DBP oil absorption of the pigment is, for example, about 30 to 150 ml / 100 g, preferably about 35 to 130 ml / 100 g, and more preferably about 50 to 1115 ml / 100 g.

  The ratio of the pigment is, for example, about 0.001 to 5 parts by weight, preferably about 0.005 to 3 parts by weight, and more preferably about 0.01 to 2 parts by weight with respect to 100 parts by weight of the base resin.

  The ratio (weight ratio) between the pigment and the marking agent is pigment / marking agent = 10/1 to 1/10000, preferably 1/1 to 1/1000, more preferably 1/2 to 1/500 (particularly 1/5 to 1/100).

[Marking aid]
As the marking aid, for example, halogen compounds, inorganic metal compounds, aromatic resins and the like can be used.

(Halogen compounds)
Halogen compounds include halogenated hydrocarbons, halogenated oligomers, halogen-containing resins and the like.

  Examples of halogenated hydrocarbons include halogenated aliphatic hydrocarbons (chlorinated paraffin, brominated ethylene, etc.), halogenated alicyclic hydrocarbons (brominated cyclohexane, brominated cyclododecane, etc.), halogenated aromatic hydrocarbons. Examples thereof include hydrogen (brominated benzene, brominated phthalic anhydride, brominated bisphenol A, brominated biphenyl, brominated phenyl ether, brominated biphenylethane, brominated ethylene bisphthalimide, and the like).

  Examples of the halogenated oligomer include brominated carbonate oligomer and brominated bisphenol A type epoxy resin.

  Examples of the halogen-containing resin include brominated polystyrene, brominated polyphenylene oxide, and brominated polycarbonate.

  These halogen compounds can be used alone or in combination of two or more. Of these, brominated bisphenol A type epoxy resin, brominated polystyrene, and brominated ethylene bisphthalimide are preferred.

(Inorganic metal compound)
The inorganic metal compound may be a compound containing an alkali metal (sodium, potassium, etc.), but is usually a compound containing a polyvalent metal.

  As the inorganic metal compound, a compound containing an alkaline earth metal (metal hydroxide such as magnesium hydroxide), a compound containing a group 4A metal of the periodic table [metal oxide (such as titanium oxide or zirconium oxide), metal Hydroxides (zirconium hydroxide, etc.), compounds containing Group 6A metals of the periodic table [metal oxides (molybdenum oxide, tungsten oxide, etc.), molybdates (eg, (hydrous) ammonium molybdate, (hydrous) Lithium molybdate, (hydrated) calcium molybdate, (hydrated) zinc molybdate, (hydrated) calcium molybdate / zinc double salt, etc., tungstate (eg (hydrated) ammonium tungstate, (hydrated) lithium tungstate , (Hydrated) calcium tungstate, (hydrated) zinc tungstate, Hydrous calcium tungstate / zinc double salt, etc.), metal sulfides (molybdenum sulfide, tungsten sulfide, etc.)], compounds containing group 7A metals (metal oxides such as manganese oxide), periodic table group 8 Metal-containing compounds [metal oxides (iron oxide, nickel oxide, etc.), metal hydroxides (nickel-containing magnesium hydroxide, etc.), titanate metal salts (potassium titanate, barium titanate, etc.), periodic table A compound containing a Group 1B metal (metal oxide such as copper oxide), a periodic table 2A compound containing a Group B metal [metal oxide (such as zinc oxide), metal sulfide (such as zinc sulfide)], a periodic table Compounds containing Group 3B metals [metal oxides (such as aluminum oxide), metal hydroxides (such as aluminum hydroxide)], compounds containing Group 4B metals in the periodic table Compounds [metal oxides (such as tin oxide), metal hydroxides (such as tin hydroxide), metal stannates (such as (hydrous) zinc stannate), etc.], compounds containing a group 5B metal of the periodic table ( Metal oxides such as antimony trioxide, antimony tetraoxide, and antimony pentoxide, and metal antimonates such as sodium antimonate). These inorganic metal compounds can be used alone or in combination of two or more.

  Among these inorganic metal compounds, compounds containing Group 6A metals of the periodic table (for example, (hydrous) ammonium molybdate, (hydrous) lithium molybdate, (hydrous) calcium molybdate, (hydrous) zinc molybdate, and (hydrous) ) Zinc tungstate, etc.), compounds containing Group 2B metals of the periodic table (eg, zinc sulfide), compounds containing Group 4A metals of the periodic table (eg, titanium oxide), compounds containing Group 4B metals of the periodic table (E.g., (hydrated) zinc stannate), compounds containing Group 5B metal of the periodic table (e.g., antimony oxide such as antimony trioxide, antimony tetroxide, antimony pentoxide, metal antimonate such as sodium antimonate, etc.) ), A compound containing a Group 8 metal of the periodic table (for example, iron oxide or the like) is preferable.

(Boron-containing compounds)
Boron-containing compounds include metal borate salts, boron phosphate, boron nitride and the like. Examples of the metal borate salts include non-condensate borates [non-condensed borate salts of alkaline earth metals such as calcium orthoborate and calcium metaborate; transition metal non-condensed borates such as manganese orthoborate and copper metaborate; Non-condensed borate (especially metaborate) of Group 2B metals such as zinc metaborate and cadmium metaborate], and condensed borate (trimagnesium tetraborate, calcium pyroborate, etc.) Condensed borate; transition metal condensate such as manganese tetraborate and nickel diborate; condensed borate of Group 2B metal of periodic table such as zinc tetraborate and cadmium tetraborate); basic boron Acid salts (such as basic borate salts of Group 2B metals of the periodic table such as basic zinc borate and basic cadmium borate). As the boric acid metal salt, hydrogen borate salts corresponding to these borates (for example, manganese hydrogenborate) can be used.

  These boron-containing compounds can be used alone or in combination of two or more. Of these, boric acid salts of Group 2B metals of the periodic table (for example, (hydrated) calcium borate, (hydrated) zinc borate) and boron phosphate are preferable.

(Aromatic resin)
The aromatic resin includes a resin having an aromatic ring having a hydroxyl group and / or an amino group, an aromatic vinyl resin, a polycarbonate resin, a polyarylate resin, an aromatic epoxy resin, an aromatic polyamide, and the like.

  Examples of the resin having an aromatic ring having a hydroxyl group and / or an amino group include novolak resins (phenol novolac resins obtained by reaction of phenols such as phenol and cresol and aldehydes such as formaldehyde, and aminotriazines. Modified novolac resins, etc.), aniline aldehyde resins (condensates of anilines such as aniline and naphthylamine and aldehydes), aralkyl resins (phenols or anilines and aralkyls such as xylylene glycol dimethyl ether) Phenyl aralkyl resins and aniline aralkyl resins, etc.) and (di) cyclopentadiene type phenol resins and the like, and unsaturated cyclic hydrocarbon compound-modified phenol resins.

  Examples of the aromatic vinyl resin include homopolymers of hydroxyl group-containing aromatic vinyl monomers such as vinylphenol, dihydroxystyrene and vinylnaphthol (polyvinylphenol resins such as p-vinylphenol homopolymer), and the aromatic Examples thereof include a copolymer of a vinyl monomer and a vinyl monomer (such as a polyvinylphenol-styrene copolymer).

Examples of the polycarbonate resin include a polymer obtained by a reaction between a dihydroxy compound and phosgene or a carbonate (such as diphenyl carbonate or dimethyl carbonate). Examples of the dihydroxy compound include bis (hydroxyaryl) C _1-6 alkane such as bisphenol A, bis (hydroxyaryl) C _4-10 cycloalkane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenylsulfone, 4 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, and the like.

  The polyarylate resin is obtained from a polyester obtained by the reaction of an aromatic polyol component and a polycarboxylic acid, for example, a bisphenol such as bisphenol A or bisphenol AD, and a benzenedicarboxylic acid such as isophthalic acid or terephthalic acid. And polyesters obtained from the above bisphenols and bis (arylcarboxylic acids) such as bis (carboxyphenyl) methane.

Examples of aromatic epoxy resins include biphenyl type epoxy resins, bisphenol type epoxy resins (such as glycidyl ethers of bis (hydroxyaryl) C _1-6 alkanes such as bisphenol A), novolac type epoxy resins, and unsaturated cyclic hydrocarbon compounds. Examples thereof include modified epoxy resins and stilbene type epoxy resins. The bisphenol-type epoxy resin also includes the bisphenol glycidyl ether (that is, phenoxy resin) having a large molecular weight.

As the aromatic polyamide, a polyamide obtained from an aromatic diamine and α, ω-C _2-12 dicarboxylic acid, for example, a polyamide (MXD6, PMD6, etc.) obtained from adipic acid and meta or paraxylylenediamine, adipine Polyamide obtained from acid and N, N'-dimethylmetaxylylenediamine, polyamide obtained from adipic acid and 1,3-phenylenediamine, copolymer obtained from adipic acid and metaxylylenediamine and paraxylylenediamine Examples thereof include polyamide.

  These aromatic resins can be used alone or in combination of two or more. Of these aromatic resins, phenol novolac resins, bisphenol A type epoxy resins, bisphenol A type polycarbonates and the like are preferable.

  The ratio of the marking aid is, for example, in the range of about 0.01 to 100 parts by weight, preferably 0.05 to 80 parts by weight, and more preferably about 0.1 to 40 parts by weight with respect to 100 parts by weight of the base resin. You can choose.

  The ratio (weight ratio) between the marking aid and the marking agent is marking aid / marking agent = 100/1 to 1/100, preferably 80/1 to 1/80, more preferably 50/1 to 1 /. It is about 50 (particularly 40/1 to 1/40).

[Additive]
The resin composition of the present invention contains conventional additives such as stabilizers [antioxidants (hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydroquinones]. Antioxidants, quinoline antioxidants, etc.), UV absorbers, weathering stabilizers, heat stabilizers (hydrotalcite, zeolite, etc.), processing stabilizers (long chain fatty acids and their derivatives, polyalkylene glycols, etc.)] , Anti-dripping agent (fluorine-based resin, etc.), filler (fiber filler such as glass fiber, carbon fiber, aluminum borate, etc., and powder particles such as glass beads, milled fiber, kaolin, talc, mica, glass flakes, etc. Or plate filler, etc.), mold release agent (wax etc.), lubricant, plasticizer, flame retardant aid, colorant (dye etc.), antistatic , Nucleating agents, impact modifiers, (low) gloss modifiers, Suridozai, dispersing agents, may also contain anti-microbial agents. Flame retardants other than the above-mentioned components, for example, organic phosphorus flame retardants (condensed phosphate ester, phosphate ester amide, phosphazene, organic phosphonate ester, organic phosphonate, organic phosphinate, organic phosphinate, etc.), silicone Flame retardants (linear or branched organic silicones such as polydimethylsiloxane and polymethylphenylsiloxane), organic sulfonic acid alkali metal salts, alcohol flame retardants [polyhydric alcohols, oligomeric polyhydric alcohols, esters Polyhydric alcohols, substituted alcohols, sugars (monosaccharides, polysaccharides, etc.)], radical flame retardants (benzyl radical generating compounds, nitroxide generating compounds, etc.), anti-dripping agents (polytetrafluoroethylene, etc.) ) And the like.

  These additives can be used alone or in combination of two or more. The content can be selected, for example, from the range of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, and particularly about 0.1 to 3 parts by weight with respect to 100 parts by weight of the base resin.

  When using a filler, the ratio of the filler in a resin composition is about 5 to 60 weight%, for example, Preferably it is about 5 to 50 weight%, More preferably, it is about 5 to 45 weight%.

  The marking agent used in the present invention not only has a small load on the environment, but also enables clear and firm marking. In particular, use of boehmite, calcium hydrogen phosphate, or aluminum (phosphorous) phosphate as the marking agent is effective for white marking.

  In addition, by combining these marking agents with the pigment, not only the color of the marking can be adjusted, but also the marking characteristics can be improved by the laser absorptivity of the pigment. Furthermore, marking characteristics can be further improved by combining with the marking aid having char forming ability.

[Laser Marking Products and Laser Marking Methods]
The resin composition of the present invention may be a powder mixture or a molten mixture, and by mixing a base resin, a marking agent, and, if necessary, the pigment and / or the marking aid by a conventional method. Can be prepared.

  The resin composition of the present invention can be kneaded and molded into various molded articles by a conventional method such as extrusion molding, injection molding or compression molding. The formed molded body can be subjected to color marking such as white, gray and black on the surface by irradiating with a laser beam. Moreover, a resin coating film can be formed using the resin composition which mix | blended resin for coating materials, and the marking agent, and a laser marking can also be given to this resin coating film.

As an apparatus for irradiating a laser beam, for example, a conventional laser such as a YAG laser, a CO ₂ laser, an Ar laser, or an excimer laser (KrF, XeCl, XeF excimer laser, etc.) can be used. Among these apparatuses, a YAG laser, particularly an Nd: YAG laser (fundamental wavelength: 1064 nm, second harmonic: 532 nm, third harmonic: 355 nm, fourth harmonic: 266 nm) is preferable. The marking method of laser marking may be a mask method or a scan method. The laser oscillation form may be a continuous system or a pulse system. For example, in the case of a polyacetal-based resin, a YAG laser is used, a scanning method is adopted, and marking can be performed with a high-speed pulse.

  Since the resin composition of the present invention is excellent in laser marking properties, it can be used in a wide range of applications in which letters and designs are printed on the surface. For example, suitable for applications such as electrical / electronic parts (OA (office automation) equipment such as computers and word processor keyboards), mechanical mechanism parts, automobile parts, packaging materials, cases, household goods, building materials, paints and coating materials Can be used.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The base resins, marking agents, marking aids, pigments and additives used in the examples and comparative examples are as follows. Moreover, the conditions in the marking process performed by the Example and the comparative example and the evaluation method are also shown below.

[1. Base resin a]
(A-1): Polyacetal resin copolymer [manufactured by Polyplastics Co., Ltd., Duracon]
(A-2): Polybutylene terephthalate [manufactured by Polyplastics Co., Ltd., DURANEX]
(A-3): AS resin [manufactured by Daicel Chemical Industries, Ceviane N]
(A-4): Polyethylene terephthalate [Kanebo Gosei Co., Ltd., Belpet]
(A-5): Polytrimethylene terephthalate [Intrinsic viscosity = 1.0]
(A-6): Polyphenylene sulfide [KPS manufactured by Kureha Chemical Industry Co., Ltd.]
(A-7): Liquid crystalline polyester [Polyplastics, Vectra]
(A-8): Polycarbonate [manufactured by Teijin Chemicals Ltd., Panlite]
(A-9): Polyamide-6,6 [manufactured by Polyplastics Co., Ltd., Polyplastic Nylon 66].

[2. Marking agent b1]
(B1-1): adipic acid dihydrazide (b1-2): sebacic acid dihydrazide (b1-3): dodecanedioic acid dihydrazide (b1-4): isophthalic acid dihydrazide (b1-5): 2,6-naphthalenedicarboxylic acid Dihydrazide (b1-6): 8,12-eicosadienedioic acid dihydrazide [Ajinomoto Fine Techno Co., Ltd., Amicure UDH]
(B1-7): 1,3-bis (2-hydrazinocarbonylethyl) -5-isopropylhydantoin [Ajinomoto Fine Techno Co., Ltd., Amicure VDH]
(B1-8): Biurea (b1-9): Urazole (b1-10): Melamine cyanurate [manufactured by Nissan Chemical Industries, Ltd., MC610]
(B1-11): anhydrous calcium monohydrogen phosphate [average particle size = 3 μm]
(B1-12): Boehmite [manufactured by Kawai Lime Industry, Cerasur BMB (granular)]
(B1-13): Boehmite [manufactured by Kawai Lime Industry Co., Ltd., Cerasur BMT (plate-like)]
(B1-14): (phosphite) aluminum phosphate [manufactured by Taihei Chemical Industry Co., Ltd., APA-100]
(B1-15): Melamine polyphosphate, melam, melem double salt [manufactured by Nissan Chemical Industries, PMP200]
(B1-16): Dimelamine sulfate [manufactured by Sanwa Chemical Co., Ltd., APINON-901]
(B1-17): melam methanesulfonate [manufactured by Nissan Chemical Industries, Ltd., MMS200]
(B1-18): Aluminum hydroxide composite boehmite [ammonium hydroxide obtained by charging 1 liter of water and 230 g of ammonium hydroxide into an autoclave, hydrothermally treating at 170 ° C. for 6 hours, dehydrating, then drying And boehmite composite (aluminum hydroxide / boehmite = 40/60 (weight ratio))].

[Other types of marking agents b2]
(B2-1): 4,4'-oxybisbenzenesulfonylhydrazide (b2-2): azodicarbonamide (b2-3): azobistetrazole diaminoguanidine (b2-4): aluminum hydroxide (b2-5) : Magnesium hydroxide.

[3. Marking aid c]
(C-1): Potassium titanate (c-2): Ammonium molybdate (c-3): Calcium molybdate (c-4): Calcium borate [UB powder, manufactured by Kinsematic Co., Ltd.]
(C-5): Zinc sulfide (c-6): Brominated ethylene bisphthalimide [BT93, manufactured by Ethyl Corporation] 15 parts by weight and antimony trioxide 5 parts by weight (c-7): Brominated polystyrene [ Pyrochek 68PB, manufactured by Ferrochemicals] Mixture of 20 parts by weight and 7 parts by weight of antimony trioxide (c-8): Mixture of brominated polystyrene [Pyrochek 68PB, manufactured by Ferrochemicals, Inc.] 10 parts by weight and 10 parts by weight of antimony trioxide (C-9): Brominated epoxy resin [SRT5000, manufactured by Sakamoto Yakuhin Co., Ltd.] 20 parts by weight and antimony pentoxide 7 parts by weight (c-10): Bisphenol-A type epoxy resin [Epicoat 1004K, oil Made by Kasei Shell Epoxy Co., Ltd.].

[4. Pigment d]
(D-1): Titanium dioxide (rutile type)
(D-2): Carbon black (d-3): Phthalocyanine blue.

[5. Additive e]
(E-1): Glass fiber [a chopped strand having a diameter of 13 μm and a length of 3 mm]
(E-2): Glass fiber [chopped strand having a diameter of 10 μm and a length of 3 mm].

[Marking conditions]
Marking method: Scanning Number of marking characters: 40 characters (numbers, alphabets)
Marking character size: 20 characters with 2 mm height and 20 characters with 3 mm height Power at marking part: 1-10 W
Scanning speed: 100mm / sec Byte size: 30μm
Q switch frequency: 3 kHz
Processing time: about 3 seconds.

[Evaluation methods]
The sharpness of the marking was visually evaluated according to the following four criteria.

1: The sharpness is extremely excellent. 2: The sharpness is excellent. 3: The sharpness is slightly inferior. 4: The sharpness is inferior.

Example 1-29
After mixing a marking agent, a marking aid, a pigment, and an additive with 100 parts by weight of the base resin with the compositions shown in Tables 1 to 4 , the mixture is melt-mixed with a 30 mm diameter twin screw extruder to obtain a pellet-shaped resin composition. Prepared. This resin pellet was injection molded to obtain a flat plate of 50 mm × 70 mm × 3 mm. Using the Nd; YAG laser (basic wavelength of 1064 nm, second harmonic of wavelength 532 nm, third harmonic of wavelength 355 nm, or fourth harmonic of wavelength 266 nm) or excimer laser (wavelength 248 nm) on this flat plate Marking processing was performed under the conditions, and the sharpness of the marking was evaluated. The results are shown in Tables 1-4 .

Comparative Examples 1-11
After mixing with the composition shown in Table 6 without blending the marking agent, a flat plate was formed by injection molding from the resin composition obtained by melt mixing in the same manner as in the examples. Furthermore, the marking process similar to the Example was performed and the clearness of marking was evaluated. The results are shown in Table 6.

Comparative Examples 12-16
Using different types of marking agents [(b2-1) to (b2-5)] and mixing with the compositions shown in Table 6, an attempt was made to melt and mix in the same manner as in the examples. A composition could not be obtained. Moreover, in the comparative example 13 and the comparative example 14, it colored yellowish brown.

Claims (9)

A resin composition composed of a base resin and a marking agent, the marking agent, amino group salt-containing triazines, and the at least one laser marking resin composition which is composed of selected from hydrazine compound A thing ,
The amino group-containing triazine salt is at least one amino group-containing triazine selected from melamine, melam, melem, and melon, and sulfuric acid, boric acid, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, organic sulfonic acid, Composed of a salt with at least one acid selected from organic phosphonic acid, organic phosphinic acid, and cyanuric acid, and
A resin composition for laser marking, wherein the hydrazine compound is composed of at least one hydrazine compound selected from a carboxylic acid hydrazide compound, a biurea compound, and a urazole compound .   The composition according to claim 1, wherein the base resin is composed of at least one selected from a polyacetal resin, a (liquid crystal) polyester resin, a polyphenylene sulfide resin, and a polyamide resin.   The composition according to claim 1, wherein the ratio of the marking agent is 0.01 to 300 parts by weight with respect to 100 parts by weight of the base resin.   The composition according to claim 1, further comprising at least one pigment selected from black pigments and non-black pigments.   The composition according to claim 1, further comprising at least one marking aid selected from halogen compounds, inorganic metal compounds, boron-containing compounds, and aromatic resins. The composition according to claim 5 , wherein the inorganic metal compound is composed of a compound containing at least one metal selected from Group 6A, 2B, 4B, and 5B group metals.   The composition of claim 1, further comprising at least one additive selected from stabilizers, fillers, and flame retardants.   A molded article capable of laser marking, comprising the composition according to claim 1. A method for marking by irradiating the molded article according to claim 8 with a laser beam.