Additives for cycloolefin polymers that do not cause structural deterioration, fracture, or deterioration of transparency even under high-temperature continuous heat treatment, compositions containing the additives for cycloolefin polymers and cycloolefin polymers, and products thereof.

Abstract

To provide a hydrophobic cycloolefinic polymer additive that exhibits superior thermostability and interfacial activity.SOLUTION: An additive comprises a donor acceptor-based molecular compound represented by formula (1).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an additive that can protect the surface of cycloolefin-based polymer products, continuously and homogeneously exist inside, contribute to the structural stability, not cause structural damage, and retain transparency without hydrophilizing the surface when added to cycloolefin-based polymer materials. The present invention also relates to a cycloolefin-based polymer composition containing such an additive and its products.

Background Art

[0002] Cyclo-olefin Polymer (COP) is a polymer having high heat resistance, excellent dimensional stability, and high transparency, which was developed by Japan ahead of the world.

[0003] By taking advantage of various properties of cycloolefin-based polymers, cycloolefin-based polymers are applied in many fields. For example, by taking advantage of the optical properties of cycloolefin-based polymers, they are used in optical components such as cameras, printers, optical pickups, and mirrors (Patent Document 1). Also, by taking advantage of properties such as transparency, high barrier properties, and low impurities, they are used in medical and biological applications (Patent Document 2). At the same time, by taking advantage of properties such as low dielectric constant and low dielectric tangent, they are also developed for applications in electronic devices that require electrical insulation, such as high-frequency connectors and antenna substrates (Patent Document 3).

[0004] Non-Patent Document 1 published the performance test results that a donor-acceptor type molecular compound formed between an organic boron compound with a novel structure and a tertiary amine compound is compatible with various plastics and changes the electrical properties of the surface. Non-Patent Document 2 investigated that a test body formed by kneading a donor-acceptor type compound antistatic agent into a high-transparency plastic molded product made of cycloolefin-based polymer has an antistatic effect with almost no reduction in transparency.

[0005] As described above, with expectations for other applications of cycloolefin polymers increasing, there is a growing need to provide antistatic properties without altering the hydrophobicity of the cycloolefin polymer surface. Furthermore, there is a strong demand for the development of a new type of internally incorporated antistatic agent that exhibits antistatic effects over a long period while uniformly dispersed within the cycloolefin polymer. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2022-108649 [Patent Document 2] Japanese Patent Publication No. 2019-218118 [Patent Document 3] Japanese Patent Publication No. 2021-143247 [Non-patent literature]

[0007] [Non-Patent Document 1] Hiroyoshi Hamanaka, Application Development of a Newly Developed Donor-Acceptor Molecular Compound Type Antistatic Agent, Plastics Age, April 2018, pp. 47-52. [Non-Patent Document 2] Takuro Watanabe, Hiroyoshi Hamanaka, Tomoki Sano, Hiroshi Ito, Proceedings of the Symposium on Molding and Processing 2015, pp. 219-220. [Overview of the project] [Problems that the invention aims to solve]

[0008] However, in order to further expand the applications of products made from cycloolefin polymers, it was necessary to confirm through rigorous testing whether products in which donor-acceptor molecular compounds are compatible with cycloolefin polymer materials as antistatic agents can maintain good transparency over a long period of time, and furthermore, whether such products can maintain overall uniformity, do not crack or break, and maintain durability even when exposed to high temperatures. [Means for solving the problem]

[0009] As a result of various studies to solve the above problems, the inventors have selected a group of compounds from among donor-acceptor molecular compound type antistatic agents that have previously functioned as antistatic agents by a novel mechanism of being present inside the plastic structure and performing static electricity countermeasures, without limiting the target plastic material. They have confirmed that these compounds strengthen the interfacial adsorption force on the surface and inside of cycloolefin polymers, maintain a homogeneous dispersion state even under high-temperature treatment in the matrix of cycloolefin polymers, preserve transparency, and do not damage molded products, thus completing the present invention. The present invention is defined by the following specific features.

[0010] (1) An additive for hydrophobic cycloolefin polymers that has excellent thermal stability and surface activity, characterized by containing a donor-acceptor molecular compound represented by the following general formula (1). [ka] In the above formula, R1 and R2 are each independently CH3(CH2)nCO-OCH2-, where n is 14 or 16, and R3 is CH3(CH2) 14 - or CH3 (CH2) 16 - is (2) A cycloolefin polymer composition characterized by comprising a hydrophobic additive for cycloolefin polymers having excellent thermal stability and surface activity as described in (1), and a cycloolefin polymer. (3) A product comprising the cycloolefin polymer composition described in (2). [Effects of the Invention]

[0011] By using the donor-acceptor type molecular compound represented by the formula (1) as an additive (antistatic agent), the interfacial adsorption force on the surface and inside of the cycloolefin-based polymer is strengthened, and the dispersion state is maintained uniformly even under high-temperature treatment in the matrix of the cycloolefin-based polymer, thereby retaining transparency and not damaging the molded product. The fact that the molded product is not damaged by cracks or the like even under high-temperature treatment is particularly effective in the application of cycloolefin-based polymers to optical parts.

Mode for Carrying Out the Invention

[0012] [Donor-Acceptor Type Molecular Compound] The donor-acceptor type molecular compound according to the present invention is a compound having the following chemical formula.

Chemical formula

[0013] [Additive for Cycloolefin-Based Polymer] As the additive for the cycloolefin-based polymer, it is essential that the donor-acceptor type molecular compound according to the present invention is included, and one or more donor-acceptor type molecular compounds are included. Conventional components used as the additive for the cycloolefin-based polymer can be included as long as the effects of the present invention are not impaired. The shape of the additive for the cycloolefin-based polymer according to the present invention is solid, and the addition amount is not particularly limited as long as the effects are exhibited.

[0014] [Cycloolefin-Based Polymer] Cycloolefin-based polymers are polymers synthesized using cycloolefins as monomers and having an alicyclic structure in the polymer. There are no particular restrictions on the cycloolefin-based polymer constituting the cycloolefin-based polymer composition according to the present invention, and commercially available cycloolefin-based polymers can be used.

[0015] Examples and comparative examples are shown below to explain specific forms including the best mode for carrying out the present invention, but the present invention is not limited in any way by these examples and the like. In the examples and comparative examples, “%” represents “% by weight” unless otherwise specified.

Examples

[0016] As donor-acceptor-based molecular compounds, examples and comparative examples were conducted using compounds included in the scope of the present invention and compounds outside the scope of the present invention, and the high-temperature stability, change in transparency, and degree of destruction of the molded product were measured.

[0017] In the examples and comparative examples, as the cycloolefin-based polymer (hereinafter referred to as “COP” in Table 1), Zeonex E48R manufactured by Nippon Zeon Co., Ltd. was used. Also, as the donor-acceptor-based molecular compound, compounds in which n in formula (1) is 14 and 16 were used in the examples, and compounds in which n in formula (1) is 20 and 10 were used in the comparative examples. The donor-acceptor-based molecular compound was added at 2.5% to the cycloolefin-based polymer, and after being dissolved, precision injection molding was performed at 280° C. to obtain test specimens. The obtained test specimens were subjected to a long-term high-temperature test by the 8585 test (high-temperature and high-humidity test) defined in ED-4701 / 300.

[0018] After 1000 hours, changes in the test specimens, such as changes in light transmittance, colorability, dust adsorption, and changes in appearance, were measured. The results are shown in Table 1.

[0019]

Table 1

[0020] As shown in Table 1, injection-molded articles of cycloolefin polymers produced using the specific donor-acceptor molecular compound according to the present invention as an additive exhibited light transmittance and heat resistance equivalent to injection-molded articles of cycloolefin polymers without the additive. Furthermore, these properties were confirmed to have the advantage of maintaining a uniform and stable state even under high-temperature conditions. In addition, their significance is considered to be extremely great because they enable static electricity countermeasures without altering the hydrophobicity of the surface of products made of cycloolefin polymers, which was previously considered difficult to achieve. [Industrial applicability]

[0021] By using the donor-acceptor molecular compound according to the present invention as an additive, products made of cycloolefin polymers maintain transparency and do not break due to cracks or other damage even under high-temperature processing, thus further expanding the application of cycloolefin polymers to optical components. In addition, in the present invention, copolymers can be derived by coexisting, for example, an acyclic olefin monomer as a copolymer with the starting material cycloolefin monomer, as long as the unique properties of the cycloolefin polymer are not impaired.

Claims

1. An additive for hydrophobic cycloolefin polymers exhibiting excellent thermal stability and surface activity, characterized by containing a donor-acceptor molecular compound represented by the following general formula (1). 【Chemistry 1】 In the above formula, R １ , R ２ are each independently CH ３ (CH ２ )nCO - OCH ２ -, where n is 14 or 16, and R ３ is CH ３ (CH ２ ) １４ - or CH ３ (CH ２ ) １６ -.

2. A cycloolefin polymer composition characterized by comprising a hydrophobic additive for cycloolefin polymers having excellent thermal stability and surface activity as described in claim 1, and a cycloolefin polymer.

3. A product comprising the cycloolefin polymer composition described in claim 2.

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