JP-2026075751-A - Thermoplastic resin composition for laser-cut products and its manufacturing method, molded body for laser-cut products, and laser-cut products and their manufacturing method.

Abstract

[Problem] To provide a thermoplastic resin composition for laser-cut products that contains a thermoplastic resin containing bonded sulfur atoms and can reduce off-odors during laser cutting. [Solution] The thermoplastic resin composition of the present disclosure comprises a thermoplastic resin (T) having a bonded sulfur atom content of 0.001 to 0.1 mmol/g and a phosphorus-based antioxidant (AO-P) containing a chemical structure represented by formula (1) in one molecule, wherein the content of the phosphorus-based antioxidant (AO-P) is 0.01 to 3.0 parts by mass per 100 parts by mass of the thermoplastic resin (T), and is for use in laser-cut products. PR 1 (-R 2 ) (-R 3 )...(1) ( R1 , R2 , and R3 are each independently organic groups, and two or more of these groups may be bonded together to form one or more rings.) [Selection Diagram] None

Inventors

• 高橋 享
• 菊川 侑亮

Assignees

• 株式会社クラレ

Dates

Publication Date

20260511

Application Date

20241023

Claims (12)

1. A thermoplastic resin (T) having a bonded sulfur atom weight of 0.001 to 0.1 mmol/g, It contains a phosphorus-based antioxidant (AO-P) with a chemical structure represented by the following formula (1) in one molecule, The content of phosphorus-based antioxidant (AO-P) is 0.01 to 3.0 parts by mass per 100 parts by mass of thermoplastic resin (T). A thermoplastic resin composition for use in laser-cut products. PR 1 (-R 2 ) (-R 3 )...(1) (In the above formula, R1 , R2 , and R3 are each independently organic groups, and two or more of these groups may be bonded together to form one or more rings.)
2. The thermoplastic resin composition according to claim 1, wherein the organic group is a group represented by the general formula R or OR (where R is an alkyl group having 1 to 22 carbon atoms or an aryl group which may have a substituent).
3. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (T) comprises one or more thermoplastic resins selected from the group consisting of methacrylic resins (M) and styrene resins (S).
4. The thermoplastic resin composition according to claim 1, comprising a phosphorus-based antioxidant (AO-P) having a structure in which two or more groups from R1 , R2 , and R3 are bonded to form one or more rings within a single molecule, a spiro structure, or a biphenyl structure.
5. The thermoplastic resin composition according to claim 4, wherein the phosphorus-based antioxidant (AO-P) comprises a phosphorus-based antioxidant having a spiro structure and an aryl group within a single molecule.
6. A single-layer or laminated molded article for laser cutting, comprising the thermoplastic resin composition described in claim 1.
7. A molded body for laser cutting according to claim 6, which is an extruded sheet.
8. A molded body for laser cutting according to claim 6, having a printed layer on at least a portion of its surface.
9. A laser-cut product comprising a molded body for laser cutting according to any one of claims 6 to 8.
10. A laser-cut product as described in claim 9, which is a novelty item.
11. A step (S1) to produce a thermoplastic resin (T) having a bonded sulfur atom content of 0.001 to 0.1 mmol/g by radical polymerization of a polymerization raw material containing a vinyl monomer in the presence of a thiol chain transfer agent, A method for producing a thermoplastic resin composition according to any one of claims 1 to 5, comprising the step (S2) of adding a phosphorus-based antioxidant (AO-P) to a thermoplastic resin (T).
12. A method for manufacturing a laser-cut product, comprising laser-cutting a molded body for laser cutting according to any one of claims 6 to 8.

Description

This disclosure relates to a thermoplastic resin composition for laser-cut products, a method for producing the same, a molded article for laser-cutting, and a laser-cut product and a method for producing the same. Inkjet printing has expanded to include a wider variety of printable media and is now used in various fields such as advertising media and signs/displays like posters, billboards, and stickers; events and amusement; architecture and interiors; and general merchandise. Besides paper, other printing media include thin molded articles, such as sheets or plates, made from transparent thermoplastic resins like acrylic and styrene resins. For example, Patent Documents 1 and 2 disclose a laminate having a base layer containing a methacrylic resin and a surface layer containing a styrene copolymer such as methyl methacrylate-styrene copolymer (MS resin), which has good ink adhesion and laser cutting properties (Claim 1 of Patent Document 1, Claim 1 of Patent Document 2). Thin molded bodies, such as sheets or plates, can be shaped into desired forms by inkjet printing images of anime characters and idols on at least one surface, followed by laser cutting. The resulting laser-cut products can be suitably used for novelty goods such as keychains, charms attached to mobile phone straps, figurines or figurine stands, and panels; as well as accessories such as pendants and badges. Japanese Patent Publication No. 2018-94843Japanese Patent Publication No. 2021-160119Japanese Patent Publication No. 2013-144786Japanese Patent Publication No. 2013-245344 This is a schematic cross-sectional view showing an example of a laminated structure molded body for laser cutting. Generally, thin molded articles are referred to as "film," "sheet," or "plate," depending on their thickness. However, there are no clear definitions of these terms, and no clear distinctions between them. In this specification, "plate" may include "sheet." In this specification, (meth)acrylic is a general term for acrylic and methacrylic, and the same applies to (meth)acrylic acid, (meth)acrylamide, and (meth)acrylonitrile, etc. In this specification, unless otherwise specified, "alkyl groups having three or more carbon atoms" may be linear or branched. Compounds that have isomers include all isomers. [Thermoplastic resin composition for laser-cut products] The thermoplastic resin composition for laser-cut products of this disclosure comprises one or more thermoplastic resins (T) having a bonded sulfur atom content of 0.001 to 0.1 mmol/g, and one or more antioxidants (AO) including a phosphorus-based antioxidant (AO-P) having a specific chemical structure. (Thermoplastic resin (T)) A thermoplastic resin (T) having a bonded sulfur atom weight of 0.001 to 0.1 mmol/g can be produced by radical polymerization of a polymerization raw material containing one or more vinyl monomers, such as acrylic monomers and styrene monomers, in the presence of one or more thiol-based chain transfer agents. Molecular weight can be suitably adjusted by using a thiol-based chain transfer agent with a large chain transfer constant. In the radical polymerization reaction mechanism using a thiol-based chain transfer agent, sulfur atoms contained in the chain transfer agent or groups containing them can be bonded to the ends of the polymer. Thiol-based chain transfer agents are organic compounds having a thiol group (-SH), and include alkyl mercaptans such as ethyl mercaptan, n-butyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, and n-dodecyl mercaptan; thiolphenols such as phenyl mercaptan and benzyl mercaptan; hydroxyl-containing mercaptans such as thioglycolic acid and 3-mercaptopropionic acid; and mercaptans having multiple thiol groups within a single molecule, such as pentaerythritol tetrakis(3-mercapto)propionate. The amount of bound sulfur atoms in the thermoplastic resin (T) can be adjusted by the type and amount of thiol-based chain transfer agent used during radical polymerization, polymerization temperature, polymerization time, and other polymerization conditions. The lower limit of the amount of bound sulfur atoms in the thermoplastic resin (T) can be 0.002 mmol/g or 0.003 mmol/g. The upper limit can be 0.090 mmol/g, 0.080 mmol/g, 0.070 mmol/g, 0.060 mmol/g, 0.050 mmol/g, 0.040 mmol/g, 0.030 mmol/g, 0.020 mmol/g, or 0.010 mmol/g. The amount of bound sulfur atoms in the thermoplastic resin (T) can be measured by the method described in the [Examples] section below. Examples of thermoplastic resins (T) include (meth)acrylic resins; styrene resins; polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; polycarbonate resins, polycarbonate-ABS resin alloys; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polyamide resins such as nylon 6, nylon 66, and polyamide elastomers; polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, pol