Crack inhibitor for organic polymer material, resin composition, molded article, optical member, and method for inhibiting occurrence of crack in molded article

Abstract

To suppress the occurrence of cracks in a molded article containing an organic polymer material under a high temperature and high humidity environment.SOLUTION: A crack suppressant for organic polymer materials, comprising an organic boron compound represented by the following formula (1): wherein R1 and R2 each independently represent an alkyl group optionally substituted with an alkanoyloxy group or a hydroxy group, a molecular compound formed from an organic boron compound and an amine compound having a tertiary amino group, or both of them.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a crack inhibitor for organic polymer materials, a resin composition, a molded article, an optical member, and a method for suppressing crack generation in a molded article. [Background technology]

[0002] Molded articles made of resin compositions containing organic polymer materials are often required to have high durability in high-temperature, high-humidity environments. For example, it has been proposed that the use of a compound having a carboxyl group in a cyclic olefin resin composition can suppress the occurrence of cracks in high-temperature, high-humidity environments (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2022-108649 Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure relates to suppressing the occurrence of cracks in molded articles containing organic polymer materials under high-temperature and high-humidity environments. [Means for solving the problem]

[0005] The present disclosure includes at least the following aspects. [1] The following formula (1): [ka] and R 1 and R 2 each independently represent an alkyl group which may be substituted with an alkanoyloxy group or a hydroxy group; a molecular compound formed from the organic boron compound and an amine compound having a tertiary amino group, or both of them, Crack inhibitor for organic polymer materials. [2] an organic polymer material; [1] The crack inhibitor for organic polymer materials, A resin composition comprising: [3] The resin composition according to [2], wherein the organic polymer material comprises at least one selected from a cyclic olefin resin, a polyester resin, an acrylic resin, and a polycarbonate resin. [4] The resin composition according to [2], wherein the organic polymer material contains a cyclic olefin resin. [5] The resin composition according to [2], wherein the organic polymer material contains a polyester resin. [6] A molded article comprising the resin composition according to any one of [2] to [5]. [7] An optical member comprising the molded article according to [6]. [8] The present invention includes blending an organic boron compound represented by the above formula (1), a molecular compound formed from the organic boron compound and an amine compound having a tertiary amino group, or both of them, into a resin composition containing an organic polymer material. A method for suppressing the occurrence of cracks in a molded article formed from a resin composition under a high-temperature, high-humidity environment. [Effects of the Invention]

[0006] The present invention provides a molded article formed from a resin composition containing an organic polymer material, and the molded article is prevented from developing cracks under high-temperature and high-humidity conditions. The prevention of cracks under high-temperature and high-humidity conditions is particularly important for optical components, for example. [Brief explanation of the drawings]

[0007] [Figure 1] This is an enlarged photograph of the surface of a molded product after it was left in a high-temperature, high-humidity environment. [Figure 2] This is an enlarged photograph of the surface of a molded product after it was left in a high-temperature, high-humidity environment. [Figure 3] This is an enlarged photograph of the surface of a molded product after it was left in a high-temperature, high-humidity environment. [Figure 4] This is an enlarged photograph of the surface of a molded product after it was left in a high-temperature, high-humidity environment. [Figure 5] This is an enlarged photograph of the surface of a molded product after it was left in a high-temperature, high-humidity environment. [Figure 6] 1 is a graph showing the relationship between the weight change rate of a molded product and the time it is left in a high-temperature, high-humidity environment. DETAILED DESCRIPTION OF THE INVENTION

[0008] The present invention is not limited to the following examples.

[0009] An example of a crack inhibitor is represented by the following formula (1): [ka] or a molecular compound formed from this organoboron compound and an amine compound having a tertiary amino group, or both of these.

[0010] In formula (1), R 1 and R 2 R each independently represents an alkyl group which may be substituted with an alkanoyloxy group, or an alkyl group which may be substituted with a hydroxy group. 1 and R 2 are each independently, R 11 -CO-O-CH2-(R 11 represents an alkyl group, or HO-CH2-, and R 1 or R 2 At least one of them is R 11 It may also be -CO-O-CH2-. 11 is an alkyl group having 1 to 20 carbon atoms (e.g., CH3(CH2) 16 - or CH3(CH2) 20-) may also be used.

[0011] A molecular compound formed from an organoboron compound and an amine compound having a tertiary amino group is a donor-acceptor molecular compound in which the organoboron compound is the donor component and the amine compound is the acceptor component. The amine compound is, for example, a compound represented by the following formula (2): [ka] In formula (2), R 3 and R 4 each independently represents an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydroxy group, and R 5 represents an alkylene group, and R 6 represents an alkyl group.

[0012] R 3 or R 4 The alkyl group may have 1 to 3 carbon atoms. 3 and R 4 may each independently be CH3-, CH3CH2-, HO-CH2-, HO-(CH2)2-, or HO-CH2CH(CH3)-. 5 R may be an alkylene group having 1 to 3 carbon atoms. 5 may be -(CH2)2- or -(CH2)3-. 6 is an alkyl group having 1 to 20 carbon atoms (e.g., CH3(CH2) 16 -) may also be used. 3 , R 4 and R 5 Of these, one may be an alkyl group having 1 to 20 carbon atoms, and the other two may be alkyl groups having 1 to 3 carbon atoms.

[0013] It is also possible to use commercially available molecular compounds formed from an organoboron compound represented by formula (1) and an amine compound represented by formula (2). Examples of commercially available products include Biomicelle BN-110, Biomicelle BN-225, and Biomicelle BN-105 manufactured by Boron Laboratory Co., Ltd.

[0014] The crack inhibitor may contain only the above-exemplified organoboron compound or molecular compound, or may contain other components as necessary. The crack inhibitor may contain unavoidable trace components. By blending an organoboron compound, a molecular compound, or both, with a resin composition containing an organic polymer material, it is possible to suppress the occurrence of cracks in molded articles of the resin composition under high-temperature, high-humidity environments.

[0015] An example of a resin composition includes an organic polymer material and the crack inhibitor. By molding this resin composition, a molded article that is less likely to crack under high-temperature and high-humidity environments can be produced.

[0016] The organic polymer material may contain at least one resin selected from, for example, a cyclic olefin resin, a polyester resin, an acrylic resin, and a polycarbonate resin. When the crack inhibitor according to the present disclosure is added to these resins, the crack inhibitor is easily dispersed uniformly in the organic polymer material. Therefore, the occurrence of cracks in the molded article can be significantly suppressed.

[0017] The cyclic olefin resin may be a polymer containing a monomer unit (cyclic olefin unit) derived from a cyclic olefin having a cyclic hydrocarbon group containing an unsaturated bond. The cyclic olefin unit is, for example, a divalent group represented by the following formula (I), (II), or (III):

[0018] [ka]

[0019] [ka]

[0020] [ka]

[0021] In formula (I), m1 represents 0 or 1, m2 represents an integer of 0 to 4, and R 21 , R 22 , R 23 and R 24 R each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted with an aromatic hydrocarbon group having 6 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. 21 , R 22 , R 23 and R 24 Two groups selected from the following may be bonded to form a monocycle or polycycle. 21 , R 22 , R 23 and R 24 (excluding) may be substituted with a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms.

[0022] In formula (II), p represents an integer of 0 to 4, and R 25 , R 26 , R 27 and R 28 R each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted with an aromatic hydrocarbon group having 6 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. 25 , R 26 , R 27 and R 28 Two groups selected from the following may be bonded to form a monocycle or polycycle. 25 , R 26 , R 27 and R 28(excluding) may be substituted with a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms.

[0023] In formula (III), n represents an integer of 1 to 18. One or more hydrogen atoms bonded to the carbon atom in formula (III) may be substituted with a hydrocarbon group having 1 to 5 carbon atoms (for example, an alkyl group or an aromatic hydrocarbon group).

[0024] The cyclic olefin resin may contain other monomer units in addition to the cyclic olefin units. The other monomer units may be monomer units derived from ethylene or α-olefins. Examples of α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

[0025] When the content of the organoboron compound and the molecular compound is high, the crack suppression effect is more likely to be obtained. When the content of the organoboron compound and the molecular compound is low, the transparency of the molded article can be improved. From these viewpoints, the content of the organoboron compound and the molecular compound in the resin composition may be 0.1 mass % or more and 20 mass % or less based on the total amount of the organic polymer material, the organoboron compound, and the molecular compound. The content of the organic boron compound and molecular compound in the resin composition may be 0.2% by mass or more, 0.3% by mass or more, 0.4% by mass or more, 0.5% by mass or more, 0.6% by mass or more, 0.7% by mass or more, 0.8% by mass or more, 0.9% by mass or more, 1.0% by mass or more, 1.1% by mass or more, 1.2% by mass or more, 1.3% by mass or more, 1.4% by mass or more, or 1.5% by mass or more, or 15% by mass or less, 10% by mass or less, 9.0% by mass or less, 8.0% by mass or less, 7.0% by mass or less, 6.0% by mass or less, 5.0% by mass or less, 4.0% by mass or less, 3.5% by mass or less, or 3.0% by mass or less, based on the total amount of the organic polymer material, the organic boron compound, and the molecular compound. When the resin composition contains both the organic boron compound and the molecular compound, the total content thereof may be within the above numerical range.

[0026] The resin composition may further contain other components in addition to the organic polymer material and the crack inhibitor. Examples of other components include antioxidants and ultraviolet absorbers. The content of the other components may be less than 50% by mass, 40% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, 10% by mass or less, 9.0% by mass or less, 8.0% by mass or less, 7.0% by mass or less, 6.0% by mass or less, 5.0% by mass or less, 4.0% by mass or less, 3.0% by mass or less, 2.0% by mass or less, or 1.0% by mass or less, or may be substantially 0% by mass, based on the total amount of the organic polymer material, the organoboron compound, and the molecular compound.

[0027] The resin composition can be obtained, for example, by a method including melt-kneading a mixture containing an organic polymer material, a crack inhibitor, and other components that may be added as needed.

[0028] A molded article of the resin composition can be obtained by molding the resin composition (e.g., pellets) using various molding methods such as injection molding. The molded article may be transparent. For example, the molded article may have a total light transmittance of 70% or more and 100% or less. The molded article can be used, for example, as an optical component. Examples of optical components include camera lenses, AR / VR terminals, and head-up displays. [Example]

[0029] The present invention is not limited to the following examples.

[0030] 1. Cyclic olefin resin composition 1-1. Crack inhibitor The following compounds were prepared as crack inhibitors: [Molecular compound formed from an organoboron compound represented by formula (1) and an amine compound represented by formula (2)] Biomicelle BN-110 (product name, Boron Laboratory Co., Ltd., R 1 =CH3(CH2) 16 CO-OCH2-, R 2 =CH3(CH2) 16 CO-OCH2-, R 3 =CH3-, R 4 =CH3-, R 5 =-(CH2)3-, R 6 =-(CH2)2OCH3) Biomicelle BN-225 (product name, Boron Laboratory Co., Ltd., R 1 =CH3(CH2) 20 CO-OCH2-, R 2 =CH3(CH2) 20 CO-OCH2-, R 3 =CH3-, R 4 =CH3-, R 5 =-(CH2)3-, R 6 =-(CH2)2OCH3) Biomicelle BN-105 (product name, Boron Laboratory Co., Ltd., R 1 =CH3(CH2) 16 CO-OCH2-, R 2 =CH3(CH2)16 CO-OCH2-, R 3 =CH3-, R 4 =CH3-, R 5 =-(CH2)3-, R 6 =-(CH2) 16 CH3) [Organoboron compound represented by formula (1)] Organoboron Compound A(R 1 =CH3(CH2) 16 CO-OCH2-, R 2 =CH3(CH2) 16 CO-OCH2-)

[0031] 1-2. Resin compositions and molded products A mixture containing a cyclic olefin resin (ZEONEX K26R (trade name), Zeon Corporation), a crack inhibitor, and an antioxidant was melt-kneaded using a twin-screw kneading extruder (TEM18SS, Toshiba Machine) to obtain pellets of the resin compositions of Examples 1 to 4 containing these. Pellets of the resin composition of Comparative Example 1 containing only the cyclic olefin resin and the antioxidant were also prepared. Transparent molded plates with thicknesses of 1 mm, 2 mm, or 3 mm were obtained by injection molding the pellets of each resin composition. Table 1 shows the compounding ratios (parts by mass) of each resin composition.

[0032] [Table 1]

[0033] 1-3.Evaluation The molded articles were left in an environment of 85°C and 85% relative humidity for 100, 200, or 500 hours. The appearance of each molded article was visually inspected before and after storage. Numerous cracks were observed in the molded article of the comparative example after 100 hours of storage. Almost no cracks were observed in the molded articles of each example after 500 hours of storage. Furthermore, the molded articles of each example maintained good transparency even after 500 hours of storage. Figures 1, 2, 3, 4, and 5 are photographs of molded articles (3 mm thick) from Comparative Example 1, Example 1, Example 2, Example 3, and Example 4 before storage (0 hours), after storage for 100 hours, after storage for 200 hours, and after storage for 500 hours, respectively.

[0034] Figure 6 is a graph showing the relationship between the weight change rate of each molded product and the time it was left standing. A tendency for the weight of the molded products to increase in each example to which the crack inhibitor was added was observed. This suggests that the crack inhibitor, which was uniformly dispersed in the molded product, adsorbed a certain amount of moisture. It is believed that the moisture adsorption imparted a moderate degree of hydrophilicity to the molded product, thereby suppressing the occurrence of cracks in a high-temperature, high-humidity environment.

[0035] 2. Polycarbonate resin composition, polyester resin composition 2-1. Crack inhibitor The following compounds were prepared as crack inhibitors: [Organoboron compound represented by formula (1)] Organoboron Compound A

[0036] 2-2. Resin compositions and molded products A mixture containing a polyester resin (copolyester resin, TRITAN TX1501HF (trade name), Eastman Chemical Company), a crack inhibitor, and an antioxidant was melt-kneaded using a twin-screw extruder (TEM18SS, Toshiba Machine) to obtain pellets of a resin composition containing these. Pellets of the resin composition of Comparative Example 2, containing only the copolyester resin and the antioxidant, were also prepared. Transparent molded plates with thicknesses of 1 to 3 mm were obtained by injection molding the pellets of each resin composition. Table 2 shows the compounding ratios (parts by mass) of each resin composition.

[0037] 2-3.Evaluation The molded articles produced were left in a high-temperature, high-humidity environment at a temperature of 85°C and a relative humidity of 85% for 100, 200, or 500 hours. The appearance of each molded article was visually inspected before and after leaving it. Almost no cracking was observed in the molded articles of each Example up to 500 hours of leaving it in a high-temperature, high-humidity environment. Table 2 also shows the weight change rate of each molded article after leaving it in a high-temperature, high-humidity environment. A tendency for the weight of the molded articles of each Example to which a crack inhibitor was added was observed. The weight increase suggests moisture adsorption, which is thought to contribute to the suppression of cracking in a high-temperature, high-humidity environment.

[0038] [Table 2]

Claims

1. The following formula (1): 【Chemistry 1】 and R １ and R ２ each independently represents an alkyl group which may be substituted with an alkanoyloxy group or a hydroxy group; a molecular compound formed from the organic boron compound and an amine compound having a tertiary amino group, or both of them, Crack inhibitor for organic polymer materials.

2. an organic polymer material; The crack inhibitor for organic polymer materials according to claim 1, A resin composition comprising:

3. The resin composition according to claim 2 , wherein the organic polymer material comprises at least one selected from a cyclic olefin resin, a polyester resin, an acrylic resin, and a polycarbonate resin.

4. The resin composition according to claim 2 , wherein the organic polymer material comprises a cyclic olefin resin.

5. The resin composition according to claim 2 , wherein the organic polymeric material comprises a polyester resin.

6. A molded article comprising the resin composition according to any one of claims 2 to 5.

7. An optical member comprising the molded article according to claim 6 .

8. A resin composition containing an organic polymer material is added to a compound of the following formula (1): 【Chemistry 2】 and R １ and R ２ each independently represent an alkyl group which may be substituted with an alkanoyloxy group or a hydroxy group; a molecular compound formed from the organic boron compound and an amine compound having a tertiary amino group, or both of them, A method for suppressing the occurrence of cracks in a molded article formed from a resin composition under a high-temperature, high-humidity environment.

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