JPS60226554A - Synthetic resin composition with good stamping properties - Google Patents

Abstract

PURPOSE:A synthetic resin composition that is obtained by adding an inorganic filler having hydroxyls bonding to metals of group IIa or IIIb in the periodic table, thus showing good stamping properties when it is carved with heat at high temperatures, especially with laser beams. CONSTITUTION:The objective composition is obtained by adding, to a synthetic resin, more than 1wt%, preferably more than 5wt% of a substance, preferably in the fine particle form, selected from inorganic fillers bearing hydroxyls bonding to metals of group IIIa or IIIb in the periodic table, hydrates aluminum-silicon salts such as talc, hydrated silicates such as amphibole, hydroxides of metals of group IIa and IIIb, preferably caolinite or aluminum hydroxide. The resultant composition is formed into articles to be directly stamped or made into a liquid or powder coating, which is applied to the substrates to be stamped or made into a laminate, which is adhered to parts to be stamped.

Description

[Detailed Description of the Invention] [Field of Application of the Invention] The present invention relates to a synthetic resin composition with excellent printing properties, and more particularly to a synthetic resin composition that can provide clear designs or characters by engraving with a laser beam or other high heat. It is something.

[Background of the Invention] Various electronic components such as hybrid IC1 resistor networks, film capacitors, tantalum capacitors, ceramic capacitors, varistors, coils, connectors, transistors, etc. have letters or letters indicating their characteristic value identification symbols, product numbers, etc. The pattern is engraved.

Traditionally, when stamping such characters and designs on electronic components, stamping inks containing heat-curable or ultraviolet-curable epoxy resins, phenonyl resins, alkyd resins, and acrylic resins have been used, but in recent years In order to automate and save labor in the stamping process, laser beam marking methods have begun to be adopted. The laser beam engraving method uses high heat from laser beams to thermally decompose or change synthetic resins, organic pigments, etc. on or near the surface of the object to be engraved, thereby engraving designs or letters. The marking method using a laser beam has the advantage of being able to print clear markings in a short time, regardless of the shape or size of the object to be engraved, and to be able to engrave even if the surface of the object is slightly uneven. Has characteristics. Moreover, in the field of electronic components, miniaturization has recently been promoted, and along with this, the letters and designs engraved on the surface of these components have also become smaller. Even when desired,
It has the advantage that it is possible to easily make markings large enough to be read only by using a magnifying glass.

However, with the materials currently used for engraving with laser beams, the sharpness of the engraved designs and characters is not sufficient, and it is difficult to identify the characters and designs compared to when stamping ink is used. 6 [Object of the Invention] The present invention has been made in view of the above-mentioned circumstances, and its purpose is to provide extremely clear markings when inscribed with a laser beam or other high heat source. It is an object of the present invention to provide a synthetic resin composition with excellent printability, which can provide easily distinguishable characters and designs.

[Structure of the Invention] In order to achieve this object, the present inventors have developed a resin composition for use in various electronic parts, laminates, marking paints, etc. whose surface is changed using laser beams or other high heat sources. As a result of intensive study to find a material that can clearly distinguish the difference from the surrounding area, we found that an inorganic filler that contains a hydroxyl group when expressed by a specific formula or a composition formula is blended into a resin composition. The present inventors have discovered that this identification can be facilitated by placing the wafer in place.

That is, the present invention provides a synthetic resin composition with excellent printability, characterized in that it contains 1% by weight or more of an inorganic filler having a hydroxyl group bonded to a metal of group TIa or group mb of the periodic table, The main points are as follows.

Hereinafter, the present invention will be explained in detail.

The inorganic filler blended into the synthetic resin composition in the present invention has a hydroxyl group bonded to a metal of group 11a or group mb of the periodic table. Examples of inorganic fillers that fall under this category include: ■ Hydrous aluminum silicate materials ■ Hydrous silicate materials ■ Hydroxides of metals in group 1Ia of the periodic table ■ Hydroxides of metals in group mb of the periodic table, etc. .

■Specifically, the hydrated aluminum silicate substances include ■talc■, pyrophyllite (waxite)
sericite, illite, etc.) ■ Montmorillonite group (montmorillonite, nontronite, sabonite, vermiculite, etc.) ■ Ryokudeite group ■ Jamonite group (chrysotile (warm asbestos), antibolite) ■ Kaolin group (hallosite, kaolinite, etc.) Night.

(Ditzkite, nacrite) @Mixed-layer clay mineral■ Examples include clay minerals in a broad sense such as allophane. This clay mineral may be natural or synthetic.

Examples of the hydrated silicate material (2) include natural or synthetic amphibole minerals, specifically, orthogonite, tremolite, aprotite, and the like.

Magnesium hydroxide is suitable as the hydroxide of a metal belonging to Group 11a of the periodic table.

Aluminum hydroxide is suitable as the hydroxide of a metal belonging to group mb of the periodic table.

Among these inorganic fillers, the following are particularly suitable. That is, Kaolinite [(DH) AI (OH) Si205]
2 Muscovite [K (AIS+ 0 ) (OH) AI (OH
) (AIS13010)K]310242 Phlogopite [K (a 1s + 3o,.) (OH)2
Mg8(OH)2(AISi30..)K] Biotite [K
(Mg, Fe2+)6(Si3Al)202o(OH)
, ] Sugilite Mica sericite (Sericite) Magnesium hydroxide Mg(OH)2 Aluminum hydroxide Al(OH)3 Otuite [SI O(OH)AI (OH)SI2051
25 2 Talc [SI 0 (OH) Mg (OH)
S1205125 3 Chlorite [Mg Al(OH) (AISi30,.Month 8 Warm asbestos (chrysotile) [Mg(B(OH)6Si, O
□BiH,,O] Anthophyllite [(Mg, Fe)7(OH)2(Si40.1)21 Tremorite [Ca2Mg5(OH)2(Si401□)2
1 Actinolite ICa ug, Fe) 5 (on) 2 (s+ao11) 2
], etc., and kudzu is, of course, not limited to these.

These inorganic fillers having hydroxyl groups bonded to metals in group IA or group MB of the periodic table may be used alone or in combination of two or more, and may be used in combination with other inorganic fillers that do not have hydroxyl groups. It is also possible to use it in combination with a filler.

The blending ratio of the inorganic filler having a hydroxyl group is 1% by weight or more based on the total synthetic resin composition. Even if the amount of the collector filler is small, it will have some effect, but in general, the larger the amount of the inorganic filler having a hydroxyl group, the more the sharpness of the engraving tends to increase. In order to obtain particularly clear markings, it is preferable that the blending ratio of the inorganic filler having hydroxyl groups is 5% by weight or more.

If the amount of inorganic filler to be mixed is the same, those with a finer particle size tend to have a clearer engraving than those with a coarser particle size. It is preferable to use

There are no particular restrictions on the resin materials used in the resin composition of the present invention, and examples include epoxy resins, phenol resins, polyester resins, diallyl phthalate, A7,17□O, and the like. Ye 4. A, ・) resins and commonly used resins such as hybrid resins thereof can be employed.

In addition to the above-mentioned resin materials, the resin composition of the present invention may optionally contain a flow control agent, a flame retardant, a pigment, a dye, a mold release agent,
Inorganic fillers with hydroxyl groups, which may contain curing agents, curing accelerators, etc., are generally white in color and the letters and designs will appear white when engraved, so organic pigments or dyes may be added to the resin composition. However, by coloring the surrounding resin, a sharp contrast is created and the marking becomes easier to identify, which is extremely advantageous.

The synthetic resin composition of the present invention can be used to manufacture resin molded products and directly use them as stamped objects, to produce liquid or powder coatings and to apply this to parts, etc. that are stamped objects, and to produce laminated products. An object to be engraved is obtained by pasting it on a part or the like that is an object to be engraved. These manufacturing methods are not particularly limited, and when manufacturing molded products, injection molding, transfer molding, roll molding, press molding, potting, etc. are employed. Application methods for liquid paints include brushing, spray painting, electrostatic painting, and dipping, and methods for applying powder paints include electrostatic painting, electrostatic dynamic dipping, and
Cascade coating, rolling coating, fluidized dipping coating, spray coating, etc. are used. In the case of pasting a laminated product, a press manufacturing method, a laminator manufacturing method, etc. can be employed.

The heat source for stamping the obtained stamped object may be any heat source that can decompose or change various organic additives such as resin materials, organic pigments, mold release agents, flow control agents, etc. Of course, it is possible to use a method other than a laser beam, but a laser beam is the most excellent method in terms of handling and the clarity of the engraving that can be obtained.

[Examples of the Invention] Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

Examples 1 to 5 and Comparative Examples 1 to 3: Production of epoxy resin composition for powder coating material Copolymerization of 5 parts by weight of dicyandiamide, 1 part by weight of phthalocyanine green, and acrylic ester per 100 parts by weight of solid epoxy resin 1 part by weight of Modaflow (manufactured by Monsando Chemical Co., Ltd.) and the inorganic fillers listed in Table 1 were added, followed by dry mixing, melt mixing using a twin-screw mixer, and pulverization to obtain a powder coating material. This was applied to an iron plate by a fluidized dipping method and cured by heating at 180° C. for 8 hours. The resulting painted surface was engraved using a carbon dioxide laser masking device, and the clarity of the resulting print was examined. The results are shown in Table 1.

*Order of clarity ■: Very clear and fine markings are clear.

O: Clear and easy to see.

Δ: Unclear and difficult to read.

X: Unclear and almost invisible.

As in Comparative Example 1.2, when an inorganic filler that does not have a hydroxyl group is blended with an inorganic filler such as crystalline silica or calcium carbonate, clear markings cannot be obtained.

Further, in the case where no inorganic filler was included as in Comparative Example 3, the presence or absence of the engraving was unclear and difficult to read. On the other hand, when an inorganic filler having a hydroxyl group is blended as in Examples 1 to 5, extremely clear markings can be obtained.

Examples 6 to 11: Production of polyester resin composition for powder coating material For 100 parts by weight of solid polyester resin, 10 parts by weight of watching red (Ba salt), benzophenone tetracarboxylic anhydride, and acrylic ester were added. Copolymer (
1 part by weight of Modaflow (manufactured by Monsando Chemical Co.) and the inorganic fillers listed in Table 2 were added, followed by dry mixing, melt mixing using a twin-screw kneader, and pulverization to obtain a powder coating material. This is applied to an aluminum plate using electrostatic coating method.
It was heat cured at 200°C for 1 hour. The resulting painted surface was engraved using a carbon dioxide laser masking device, and the clarity of the resulting print was examined. The results are shown in Table 2.

*1 The order of clarity is the same as in Table 1.

*2 Particle size 600 mesh or less.

*J Particle size 200 mesh or less.

It is clear from Tables 1 and 2 that extremely clear markings can be obtained using the synthetic resin composition of the present invention.

[Effects of the Invention] As detailed above, the synthetic resin composition of the present invention with excellent printability contains an inorganic filler having a hydroxyl group bonded to a metal of group 11a or group mb of the periodic table. It is possible to obtain extremely clear and easy-to-identify markings using an excellent marking method such as a laser beam.

Furthermore, it can be applied to various objects to be engraved, and is particularly advantageous for engraving small characters, designs, etc.

Agent: Patent attorney Tsuyoshi Shigeno

Claims (4)

[Claims] (1) A synthetic resin composition with excellent printability characterized by containing 1% by weight or more of an inorganic filler having a hydroxyl group bonded to a metal of group 11a or group mb of the periodic table. (2) The synthetic resin composition according to claim 1, which contains 5% by weight or more of an inorganic filler. (3) The synthetic resin composition according to claim 1 or 2, wherein the inorganic filler is a hydrated aluminum silicate material or a hydrated silicate material. (4) The synthetic resin composition according to claim 1 or 2, wherein the inorganic filler is a hydroxide of a metal of group 1 Ta or group mb of the periodic table.