Injection molded body, and method and device for manufacturing injection molded body

Abstract

The injection-molded body 10 comprises a matrix resin and a thermoplastic elastomer dispersed in the matrix resin, comprising: a first portion 1 remote from a surface 4 of the injection-molded body, and a second portion 2 between the first portion 1 and the surface 4, and the ratio of the elastomer to the matrix resin in the area range of 102 [mu] m2 or more and 1302 [mu] m2 or less in the second portion 2 is 1.3 times or more of the ratio of the elastomer to the matrix resin in the area range of 102 [mu] m2 or more and 1302 [mu] m2 or less in the first portion 1.

Description

Technical Field

[0001] This disclosure relates to injection molded articles, methods for manufacturing injection molded articles, and apparatus. Background Technology

[0002] It is known that resin compositions obtained by adding thermoplastic elastomers to resins improve mechanical properties such as impact strength. Furthermore, as shown in Patent Document 1, the compatibility between the resin and elastomer is improved by adding a compatibility agent. This prevents interfacial delamination that occurs in simple blends of resin and elastomer and improves impact strength.

[0003] Citation List

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Publication No. 2011-231165 Summary of the Invention

[0006] Technical issues

[0007] However, adding elastomers and compatibilizers to the resin significantly reduces the flexural modulus of the resin composition. Therefore, many problems remain in achieving mechanical properties such as flexural modulus and impact strength. In the resin composition described in Patent Document 1, there is still room for improvement in mechanical properties, particularly the flexural modulus. Therefore, one aspect of this embodiment aims to provide an injection-molded article with excellent mechanical properties.

[0008] Solution to the problem

[0009] An injection-molded article according to this disclosure, comprising a matrix resin and a thermoplastic elastomer dispersed in the matrix resin, includes a first portion remote from a surface of the injection-molded article and a second portion located between the first portion and the surface, wherein the second portion contains 10 2 μm 2 Above and 130 2 μm 2 The elastomer to matrix resin ratio in the following area range is the same as that in Part 1 at 10. 2 μm 2 Above and 130 2 μm 2 The ratio of elastomer to matrix resin in the following area ranges is more than 1.3 times.

[0010] Beneficial effects of the invention

[0011] According to this embodiment, injection-molded parts with excellent mechanical properties can be provided. Attached Figure Description

[0012] Figure 1This is a conceptual diagram illustrating an example of an injection-molded article according to this embodiment.

[0013] Figure 2A The image is a cross-sectional scanning electron microscope (SEM) image of the injection-molded body according to Example 1.

[0014] Figure 2B The image is a cross-sectional scanning electron microscope (SEM) image of the injection-molded body according to Example 1.

[0015] Figure 3 This is a schematic diagram illustrating the apparatus according to this embodiment. Detailed Implementation

[0016] The following describes in detail the implementation schemes for carrying out this disclosure. The following implementation schemes are illustrative examples for describing this disclosure, and this disclosure is not limited to the following.

[0017] <<Injection Molded Body>>

[0018] The injection-molded article according to this embodiment is an injection-molded article comprising a matrix resin and a thermoplastic elastomer dispersed in the matrix resin.

[0019] Figure 1 A conceptual diagram illustrating an example of an injection-molded body 10 according to this embodiment is shown. The cross-section 5 (indicated by a section line) of the injection-molded body 10 is a transverse section of the central portion of the plate-shaped injection-molded body 10. However, the shape of the injection-molded body 10, as well as the position and shape of the cross-section, are not particularly limited. For example, the thickness T of the injection-molded body 10 according to this embodiment can be in the range of 1 mm to 5 mm, but is not limited thereto. The dimension of the injection-molded body 10 in the direction perpendicular to the thickness direction can be greater than the thickness T, and can, for example, be in the range of 10 mm to 1000 mm, but is not limited thereto.

[0020] Figure 1 The injection-molded body 10 shown includes a first portion 1 remote from the surface 4 of the injection-molded body 10 and a second portion 2 located between the first portion 1 and the surface 4. Although the first portion 1 and the second portion 2 can be observed in the cross-section 5 of the injection-molded body 10, the injection-molded body 10 includes the first portion 1 and the second portion 2 without cutting the injection-molded body 10. The second portion is located in section 10. 2 μm 2 Above and 130 2 μm 2 The ratio of elastomer to matrix resin in the area ranges 21 and 22 below is the same as that in Part 1 at 10. 2 μm 2 Above and 130 2 μm2 The ratio of elastomer to matrix resin in area ranges 11 and 12 is at least 1.3 times. Ideally, the ratio of elastomer to matrix resin in area ranges 21 and 22 is at least 1.5 times that in area ranges 11 and 12. As described above, the first part 1 and the second part 2 are defined by the relationship between the ratio of elastomer to matrix resin. Therefore, the first part 1, which has a relatively low ratio of elastomer to matrix resin, can be referred to as the "low ratio part." The second part 2, which has a relatively high ratio of elastomer to matrix resin, can be referred to as the "high ratio part."

[0021] In addition, such as Figure 1 As shown, the injection-molded body 10 according to this embodiment may include a third portion 3 located between the second portion 2 and the surface 4. The third portion 3 may constitute the surface 4. It is desirable that the third portion 3, within the 10... 2 μm 2 Above and 130 2 μm 2 The elastomer to matrix resin ratio in the following area range is lower than that in Part 1, which is 10. 2 μm 2 Above and 130 2 μm 2 The ratio of elastomer to matrix resin in the following area range. Therefore, the third part 3, which has a relatively low ratio of elastomer to matrix resin compared to the first part, which is a low ratio part, can be referred to as the "ultra-low ratio part".

[0022] In the following text, "in part n, in 10..." 2 μm 2 Above and 130 2 μm 2 The elastomer to matrix resin ratio within the following area range (n is an integer from 1 to 3) is sometimes simply referred to as the "elastomer ratio in the nth part". A fourth part (not shown) may exist between the first part and the second part, where the elastomer to matrix resin ratio is higher than that in the first part 1 and lower than that in the second part 2. The fourth part may be referred to as the "medium ratio part". The elastomer to matrix resin ratio in the medium ratio part may be greater than 1.0 and less than 1.3 times that in the first part 1 (low ratio part).

[0023] In the case where the surface in contact with the mold during injection molding is defined as surface 4, the first part 1 is the part that is further away from surface 4 from the inside than the second part 2 and the third part 3. Figure 1This illustrates the suitable range for the first portion 1 (low-ratio portion), which is the region enclosed by the boundary represented by the single-point chain line (inner chain line). For example, the first portion 1 can exist in a region at least 250 μm inward from surface 4, typically at least 500 μm. That is, Figure 1 The distance between the boundary represented by the single-point chain line and the surface 4 represented by the solid line can be greater than 250 μm or greater than 500 μm. This means that the first part 1 can exist in a region greater than 250 μm or greater than 500 μm inward from surface 4, and the entire region greater than 250 μm or greater than 500 μm inward from surface 4 does not need to be the first part 1. The first part 1 can exist in a region greater than 250 μm or greater than 500 μm inward from two surfaces (front surface and rear surface) in the thickness direction of surface 4. The distance between these two surfaces is the thickness T, so, for example, the first part 1 can exist in a region greater than 250 μm or greater than 500 μm inward from surface 4 and less than T-250 μm or less than T / 2 inward from surface 4. Considering that the typical thickness T is greater than 1 mm, the first part 1 can exist in a region greater than 250 μm or greater than 500 μm inward from one surface of surface 4 and less than 750 μm or less than 600 μm. The elastomer ratio in Part 1 is less than the elastomer ratio in Part 2. It is desirable that the elastomer ratio in Part 1 is greater than the elastomer ratio in Part 3. For example, the elastomer ratio in Part 1 can be measured in regions 250 μm or more or 500 μm or more inward from surface 4 and less than T-250 μm, less than T / 2, and less than 750 μm or less than 600 μm inward from surface 4. It is desirable that the elastomer ratio in Part 1 is the average of a plurality of area ranges 11 and 12 in Part 1, each area range having 10... 2 μm 2 Above and 130 2 μm 2 The following area. For example, the elastomer ratio in Part 1 is less than 50%. It is desirable that the elastomer ratio in Part 1 is less than 25%. More preferably, the elastomer ratio in Part 1 is less than 15%. For example, the elastomer ratio in Part 1 is more than 5%. It is desirable that the elastomer ratio in Part 1 is more than 10%.

[0024] Part 2 is the part that is further away from surface 4 than Part 3. Figure 1The diagram shows the suitable range for the existence of the second part 2 (high-ratio portion), which is the region enclosed by the boundary represented by the single-point chain line and the boundary represented by the double-point chain line (outer chain line). For example, the second part 2 can exist in a region that is more than 50 μm inward from surface 4 and less than 500 μm or less than 250 μm inward from surface 4. That is, in Figure 1 The distance between the boundary represented by the double-dot chain line and the surface 4 represented by the solid line can be greater than 50 μm. Figure 1 The distance between the boundary represented by the single-point chain line and the surface 4 represented by the solid line can be less than 500 μm or less than 250 μm. This means that the second part 2 can exist in a region more than 50 μm inward from surface 4 and less than 500 μm or less than 250 μm inward from surface 4, and the entire region more than 50 μm inward from surface 4 and less than 500 μm or less than 250 μm inward from surface 4 does not need to be the second part 2. In a region more than 250 μm inward from surface 4 and less than 500 μm, either the first part 1 or the second part 2 can exist. The elastomer ratio in the second part 2 is more than 1.3 times the elastomer ratio in the first part 1. The elastomer ratio in the second part 2 is greater than the elastomer ratio in the third part 3. It is expected that the elastomer ratio in the second part 2 is the maximum value of the plurality of area ranges 21 and 22 in the second part 2, each of which has 10 2 μm 2 Above and 130 2 μm 2 The following area. For example, the elastomer ratio in Part 2 is 10% or more. It is desirable that the elastomer ratio in Part 2 is 15% or more. It is even more desirable that the elastomer ratio in Part 2 is 25% or more. For example, the elastomer ratio in Part 2 is less than 50%. It is desirable that the elastomer ratio in Part 2 is less than 40%.

[0025] The third part 3 is the portion between the second part 2 and surface 4, and may include surface 4. Figure 1 The diagram shows the suitable range for the existence of the third part 3 (ultra-low ratio portion), which is the region enclosed by the boundary represented by the double-dotted chain line and the surface 4 represented by the solid line. For example, the third part 3 can exist in a region less than 50 μm inward from the surface 4. That is, in Figure 1The distance between the boundary represented by the double-dot chain line and the surface 4 represented by the solid line can be less than 50 μm. This means that the third part 3 can exist in a region less than 50 μm inward from the surface 4, and the entire region less than 50 μm inward from the surface 4 does not need to be the third part 3. The third part 3 is the portion that cools and solidifies immediately upon contact between the resin composition and the metal mold. Therefore, if the melting point or glass transition point of the matrix resin is the highest among the materials constituting the resin composition, the matrix resin exists in a higher proportion than the overall resin composition and is hard.

[0026] Ideally, in the first part 1 and the second part 2, the matrix resin and the elastomer material form a phase-separated structure, and the elastomer particles are dispersed in the matrix resin. When an impact is applied to the molded article, the dispersed elastomer particles form cracks and absorb the impact, thereby exhibiting high impact strength. Due to the formation of the phase-separated structure, the hardness of the matrix resin is higher than that of the matrix resin in which the elastomer material is compatible. This prevents a decrease in flexural modulus. It is desirable that the average particle diameter of the elastomer particles in the second part 2 is greater than the average particle diameter of the elastomer particles in the first part 1. For example, the average particle diameter of the elastomer particles in the first part 1 is 1.0 μm or less. It is desirable that the average particle diameter of the elastomer particles in the first part 1 is 0.9 μm or less. It is even more desirable that the average particle diameter of the elastomer particles in the first part 1 is 0.8 μm or less. For example, the average particle diameter of the elastomer particles in the first part 1 is 0.1 μm or more. For example, the average particle diameter of the elastomer particles in the second part 2 is greater than 1.0 μm. It is desirable that the average particle diameter of the elastomer particles in the second part 2 is 1.2 μm or more. It is desirable that the average particle diameter of the elastomer particles in Part 2 is 1.5 μm or more. For example, the average particle diameter of the elastomer particles in Part 2 is 5 μm or less. For example, the difference between the average particle diameter of the elastomer particles in Part 1 and the average particle diameter of the elastomer particles in Part 2 is 0.8 μm or more. It is desirable that the difference between the average particle diameter of the elastomer particles in Part 1 and the average particle diameter of the elastomer particles in Part 2 is 1.0 μm or more. It is desirable that the difference between the average particle diameter of the elastomer particles in Part 1 and the average particle diameter of the elastomer particles in Part 2 is 1.2 μm or more. For example, the average particle diameter of the elastomer particles in Part 2 is more than twice the average particle diameter of the elastomer particles in Part 1. It is desirable that the average particle diameter of the elastomer particles in Part 2 is more than three times the average particle diameter of the elastomer particles in Part 1. For example, the average particle diameter of the elastomer particles in Part 2 is less than 20 times the average particle diameter of the elastomer particles in Part 1. It is desirable that the average particle diameter of the elastomer particles in Part 2 is less than 10 times that of the average particle diameter of the elastomer particles in Part 1. The average particle diameter of the elastomer particles in Part 2 may be less than 5 times that of the average particle diameter of the elastomer particles in Part 1.

[0027] The second part 2 is flexible due to its high elastomer ratio. This flexibility, located near surface 4, prevents the development of cracks when impacted by the rigid third part 3 (if the matrix resin ratio is high) and more effectively mitigates impact. Therefore, high impact strength can be provided to the injection-molded body. While it is desirable to adjust the relative size relationship between the average particle diameters of the elastomer particles described above to control the elastomer ratio, this disclosure is not limited thereto. For example, even if the average particle diameter of the elastomer particles in the second part 2 is not greater than the average particle diameter of the elastomer particles in the first part 1, the elastomer ratio can be adjusted by changing the number density of the elastomer particles in the second part 2 and the number density of the elastomer particles in the first part 1.

[0028] The injection-molded article according to this embodiment has the above-described structure, thereby achieving excellent mechanical properties, such as excellent flexural modulus and excellent impact strength. Although the average particle diameter has been used as the typical particle diameter of the elastomer particles in the above description, the median particle diameter (median diameter) or modal particle diameter may also be used instead of the average particle diameter. The numerical value described as the average particle diameter can also be read as the value of the median particle diameter or modal particle diameter.

[0029] <Method for manufacturing injection molded parts>

[0030] <Resin Composition>

[0031] First, a resin composition suitable for manufacturing injection-molded articles according to this disclosure will be described. The resin composition according to this embodiment includes a resin as a matrix and a thermoplastic elastomer material. Furthermore, filler particles can be added to improve mechanical properties. Additionally, desired additives can be added to enhance other functions.

[0032] [Matrix resin]

[0033] As the matrix resin, injection-moldable thermoplastic resins are used. Among thermoplastic resins, polar polymers are preferred as the matrix resin. For example, polar polymers are polymers whose main chain includes polar groups, such as amide groups, imide groups, carbonyl (ketone) groups, ester bonds, etc. Polar polymers are resins commonly referred to as general-purpose engineering plastics or super-engineering plastics, and are used in applications requiring higher physical properties such as heat resistance and strength than general-purpose resins (such as polyethylene or polypropylene). If the values ​​of mechanical and physical properties can be improved, the molded products can be made thinner and lighter. Therefore, further improvements in physical properties can be expected.

[0034] Specific examples of polar polymers that include amide groups include polyamides and polyamide-imides. Examples of polar polymers that include imide groups include polyimides, polyamide-imides, and polyetherimides. Examples of polar polymers that include carbonyl (ketone) groups include polyetherketones and polyetheretherketones. Examples of polar polymers that include ester bonds include polyarylates, polycarbonates, and polyesters. Examples of polyesters include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate.

[0035] In thermoplastic resins, crystalline polymers are preferred as matrix resins. The advantages of crystalline polymers are that they exhibit superior hardness, elasticity, and stiffness compared to amorphous polymers. Examples of crystalline polymers among the aforementioned polar polymers include polyamides, polyetherketones, polyetheretherketones, polyethylene terephthalate (PET), polybutylene terephthalate (PET), polyethylene naphthalate (PET), and polybutylene naphthalate (PET). In polyesters, polyarylates and polycarbonates are amorphous polymers. Other examples of crystalline polymers include polyacetals. Polyesters are desirable as matrix resins, and polyethylene terephthalate (PET) is even more desirable. PET is excellent in terms of recyclability, and furthermore, the CO2 emissions from PET production are lower than those from polycarbonate production. Therefore, the use of PET helps reduce CO2 emissions. For example, the crystallinity of the matrix or crystalline polymer can range from 1% to 50%. The desired crystallinity of the matrix or crystalline polymer is 1% to 40%. The crystallinity can be controlled according to the molding conditions (temperature and pressure).

[0036] Alternatively, the matrix resin can be a polar polymer crosslinked using a crosslinking agent. Examples of crosslinking agents include compounds that perform the crosslinking reaction by heating, such as carbodiimide crosslinking agents, oxazoline crosslinking agents, epoxy crosslinking agents, isocyanate crosslinking agents, etc. For example, the polar polymer can be a regenerated polymer obtained by collecting used polymers with a reduced molecular weight, re-crosslinking the used polymers using a crosslinking agent, and increasing the molecular weight. Polyethylene terephthalate (PET) is suitable as both the used polymer and the regenerated polymer, and is produced and used in large quantities.

[0037] The carbodiimide crosslinking agent according to this embodiment refers to a compound comprising at least one carbodiimide group in its molecule, and can be manufactured, for example, by a decarboxylation reaction induced by heating an organic isocyanate in the presence of a suitable catalyst. The carbodiimide group is represented as (-N=C=N-). In the resin matrix using the carbodiimide crosslinking agent, the carbodiimide group derived from the crosslinking agent is present as part of the macromolecule.

[0038] Examples of carbodiimide crosslinking agents include single-carbodiimide or two-carbodiimide compounds such as diphenylcarbodiimide, dicyclohexylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, diisopropylcarbodiimide, dioctyldecylcarbodiimide, di-o-tolylcarbodiimide, di-p-tolylcarbodiimide, di-p-nitrophenylcarbodiimide, di-p-aminophenylcarbodiimide, di-p-hydroxyphenylcarbodiimide, di-p-chlorophenylcarbodiimide, di-o-chlorophenylcarbodiimide, di-3,4-dichlorophenylcarbodiimide, di-2,5-dichlorophenylcarbodiimide, p-phenylene-bis-o-tolylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, etc. p-Phenylidene-bis(di-p-chlorophenyl)carbodiimide, 2,6,2',6'-tetraisopropyldiphenylcarbodiimide, hexamethylene-bis(cyclohexyl)carbodiimide, ethylidene-bis(diphenyl)carbodiimide, ethylidene-bis(dicyclohexyl)carbodiimide, N,N'-di-o-tolylcarbodiimide, N,N'-diphenylcarbodiimide, N,N'-di-octyldecylcarbodiimide, N,N'-di-2,6-dimethylphenylcarbodiimide, N-tolyl-N'-cyclohexylcarbodiimide, N,N'-di-2,6-diisopropylphenylcarbodiimide, N,N'-di-2,6-di-tert-butylphenylcarbodiimide, N-tolyl-N'-phenylcarbodiimide Imine, N,N'-di-p-nitrophenylcarbodiimide, N,N'-di-p-aminophenylcarbodiimide, N,N'-di-p-hydroxyphenylcarbodiimide, N,N'-dicyclohexylcarbodiimide, N,N'-di-p-tolylcarbodiimide, N,N'-dibenzylcarbodiimide, N-octadecyl-N'-phenylcarbodiimide, N-benzyl-N'-phenylcarbodiimide, N-octadecyl-N'-tolylcarbodiimide, N-cyclohexyl-N'-tolylcarbodiimide, N-phenyl-N'-tolylcarbodiimide, N-benzyl-N'-tolylcarbodiimide, N,N'-di-o-ethylphenylcarbodiimide, N,N'-di-p-ethyl Phenylene carbodiimide, N,N'-di-o-isopropylphenyl carbodiimide, N,N'-di-p-isopropylphenyl carbodiimide, N,N'-di-o-isobutylphenyl carbodiimide, N,N'-di-p-isobutylphenyl carbodiimide, N,N'-di-2,6-diethylphenyl carbodiimide, N,N'-di-2-ethyl-6-isopropylphenyl carbodiimide, N,N'-di-2-isobutyl-6-isopropylphenyl carbodiimide, N,N'-di-2,4,6-trimethylphenyl carbodiimide, N,N'-di-2,4,6-triisopropylphenyl carbodiimide, N,N'-di-2,4,6-triisobutylphenyl carbodiimide, etc.;Polycarbodiimides such as poly(1,6-hexamethylenecarbodiimide), poly(4,4'-methylenebicyclohexylcarbodiimide), poly(1,3-cyclohexylcarbodiimide), poly(1,4-cyclohexylcarbodiimide), poly(4,4'-diphenylmethanecarbodiimide), poly(3,3'-dimethyl-4,4'-diphenylmethanecarbodiimide), poly(naphthylcarbodiimide), poly(p-phenylcarbodiimide), poly(m-phenylcarbodiimide), poly(tolylcarbodiimide), poly(diisopropylcarbodiimide), poly(methyl-diisopropylphenylcarbodiimide), poly(triethylphenylcarbodiimide), poly(triisopropylphenylcarbodiimide), etc.; and similar compounds.

[0039] According to this embodiment, an oxazoline crosslinking agent refers to a compound that includes an oxazoline group in its molecule. In particular, polymers synthesized using monomers comprising oxazoline compounds as raw material monomers are desirable. Examples of oxazoline compounds include 2-oxazoline, 3-oxazoline, and 4-oxazoline compounds, and any one of them may be used. In particular, 2-oxazoline compounds are highly reactive and are also put into practical industrial use. Examples of oxazoline compounds include 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4,4-oxazoline, 4,4-dimethyl-2-vinyl-5,6-dihydro-4H-1,-oxazine, 4,4,6-trimethyl-2-vinyl-5,6-dihydro-4H-1,3-oxazine, 2-isopropenyl-2-oxazoline, 4,4-dimethyl-2-isopropenyl-2-oxazoline, and 4-acryloyl-oxy Methyl-2,4-dimethyl-2-oxazoline, 4-methacryloyl-oxymethyl-2,4-dimethyl-2-oxazoline, 4-methacryloyl-oxymethyl-2-phenyl-4-methyl-2-oxazoline, 2-(4-vinylphenyl)-4,4-dimethyl-2-oxazoline, 4-ethyl-4-hydroxymethyl-2-isopropenyl-2-oxazoline, 4-ethyl-4-ethoxycarbonylmethyl-2-isopropenyl-2-oxazoline, etc. However, this disclosure is not limited to these.

[0040] As an epoxy crosslinking agent according to this embodiment, for example, glycidyl ether compounds, glycidyl ester compounds, glycidyl amine compounds, glycidyl imide compounds, alicyclic epoxy compounds, etc., may be used desirablely.

[0041] Examples of glycidyl ether compounds may include bisphenol A diglycidyl ether type epoxy resins, bisphenol F diglycidyl ether type epoxy resins, bisphenol S diglycidyl ether type epoxy resins, etc., which are obtained through the condensation reaction between bisphenols and epichlorohydrin, such as butyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, o-phenylphenyl glycidyl ether, ethylene oxide lauryl glycidyl ether, ethylene oxide phenol glycidyl ether, etc. Glyceryl ether diol, polyethylene glycol diglyceryl ether, propylene glycol diglyceryl ether, polypropylene glycol diglyceryl ether, neopentyl glycol diglyceryl ether, polytetramethylene glycol diglyceryl ether, cyclohexanediol diglyceryl ether, glycerol triglyceryl ether, trimethylolpropane triglyceryl ether, pentaerythritol polyglyceryl ether, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)sulfone, etc. Among these, bisphenol A diglyceryl ether type epoxy resin is desirable.

[0042] Examples of glycidyl ester compounds may include glycidyl benzoate, glycidyl p-toluene, glycidyl cyclohexanecarboxylic acid, glycidyl stearate, glycidyl laurate, glycidyl palmitate, glycidyl tert-carbonate, glycidyl oleate, glycidyl linoleate, glycidyl linolenic acid, diglycidyl terephthalate, diglycidyl isophthalate, diglycidyl phthalate, and diglycidyl naphthalate. Glyceryl benzoate, diglycidyl vinylbenzoate, diglycidyl methyl terephthalate, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, diglycidyl cyclohexanedicarboxylate, diglycidyl adipic acid, diglycidyl succinate, diglycidyl sebacate, diglycidyl dodecanoate, diglycidyl octadecanoate, triglycidyl trimellitate, and tetraglycidyl pyromellitic acid, etc. Among these compounds, glycidyl benzoate and glycidyl tert-carbonate are desirable.

[0043] Examples of glycidylamine compounds may include tetraglycidylaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidyl-m-phenylenediamine, diglycidyltribromoaniline, tetraglycidylbis(aminomethyl)cyclohexane, triglycidyl cyanurate, triglycidyl isocyanurate, etc. Examples of glycidyl imide compounds may include N-glycidylphthalimide, N-glycidyl-4-methylphthalimide, N-glycidyl-4,5-dimethylphthalimide, N-glycidyl-3-methylphthalimide, N-glycidyl-3,6-dimethylphthalimide, N-glycidyl-4-ethoxyphthalimide, N-glycidyl-4-chlorophthalimide, N-glycidyl-4,5-dichlorophthalimide, and N-glycidyl-3,4,5,6-tetrabromophthalimide. Amines, N-glycidyl-4-n-butyl-5-bromophthalimide, N-glycidylsuccinimide, N-glycidylhexahydrophthalimide, N-glycidyl-1,2,3,6-tetrahydrophthalimide, N-glycidylmaleimide, N-glycidyl-α,β-dimethylsuccinimide, N-glycidyl-α-ethylsuccinimide, N-glycidyl-α-propylsuccinimide, N-glycidylbenzamide, N-glycidyl-p-methylbenzamide, N-glycidylnaphthamide, N-glycidylstearamide, etc. Among these, N-glycidylphthalimide is desirable.

[0044] Examples of alicyclic epoxides may include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene diester, N-methyl-4,5-epoxycyclohexane-1,2-dicarboxylic acid imide, N-ethyl-4,5-epoxycyclohexane-1,2-dicarboxylic acid imide, N-phenyl-4,5-epoxycyclohexane-1,2-dicarboxylic acid imide, N-naphthyl-4,5-epoxycyclohexane-1,2-dicarboxylic acid imide, N-tolyl-3-methyl-4,5-epoxycyclohexane-1,2-dicarboxylic acid imide, etc.

[0045] Other epoxy compounds that can be used include epoxidized fatty acid glycerides such as epoxidized soybean oil, epoxidized linseed oil, and epoxidized whale oil, as well as phenolic epoxy resins and cresol-type phenolic epoxy resins.

[0046] The isocyanate crosslinking agent used in this embodiment is not particularly limited, as long as the isocyanate crosslinking agent includes an isocyanate group as a functional group in the compound. Known polyisocyanate crosslinking agents can be used. Specifically, commonly used water-dispersible polyisocyanate crosslinking agents can be used. Water-dispersible polyisocyanate crosslinking agents are obtained by introducing hydrophilic groups into the polyisocyanate polymer. If the water-dispersible polyisocyanate crosslinking agent is added to water and stirred, the water-dispersible polyisocyanate crosslinking agent can be dispersed in water as particulate matter.

[0047] Examples of polyisocyanates constituting water-dispersible polyisocyanates include: aliphatic isocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, etc.; aromatic polyisocyanates such as toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, tetramethylxylene diisocyanate, 1,5-naphthalene diisocyanate, 1,4-naphthalene diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether isocyanate, (m- or p-)phenyl diisocyanate. Polyisocyanates, such as 4,4'-biphenyl diisocyanate, 3,3'-biphenyl diisocyanate, bis(4-isocyanatophenyl)sulfone, and isopropylidene bis(4-phenylisocyanate); and alicyclic diisocyanate compounds such as hydrogenated xylene diisocyanate, isophorone diisocyanate, 4,4'-methylene bis(cyclohexyl)isocyanate, methylcyclohexane-2,4-(or -2,6-)diisocyanate, 1,3-(or 1,4-)bis(isocyanatomethyl)cyclohexane, 1,4-cyclohexane diisocyanate, 1,3-cyclopentane diisocyanate, and 1,2-cyclohexane diisocyanate. Polyisocyanate compounds having isocyanurate structures, carbamate structures, biuret structures, urethane structures, diurea structures, trimer structures, etc., can also be used as such polyisocyanate compounds. So-called capped isocyanates, obtained by blocking isocyanate groups with active hydrogen groups, can also be used.

[0048] It is desirable that the matrix resin is formed from one of these polymers or a mixture of these polymers.

[0049] [Elastomer Materials]

[0050] It is known that adding elastomer materials to resins improves impact strength. Elastomers are copolymers composed of a combination of hard segments that act as crosslinking points and soft segments that exhibit rubber-like elasticity, and thermoplastic elastomers possessing properties of both plastics and rubber are desirable.

[0051] Examples of elastomer materials include polyurethane elastomers, ester elastomers, amide elastomers, acrylic elastomers, olefin elastomers, and styrene elastomers. It is desirable for the elastomer to be an acrylic elastomer or an ester elastomer.

[0052] Examples of polyurethane elastomers include elastomers in which the hard segment is a polyurethane comprising urethane groups and the soft segment is a polyester comprising ester bonds or a polyether comprising ether bonds. The urethane groups and ester bonds are polar.

[0053] Examples of ester-based elastomers include elastomers in which the hard segment is a polyester comprising ester bonds and the soft segment is a polyester comprising ester bonds or a polyether comprising ether bonds, etc. Ester bonds are polar.

[0054] Examples of amide-based elastomers include elastomers in which the hard segment is a polyamide comprising amide groups and the soft segment is a polyester comprising ester bonds or a polyether comprising ether bonds, etc. The amide groups and ester bonds are polar.

[0055] Examples of acrylic elastomers include elastomers in which the hard segments are polymethyl methacrylate (a polymer of methyl methacrylate) and include ester bonds, and the soft segments are copolymers of butyl acrylate, 2-ethylhexyl acrylate, etc., including ester bonds. Examples of acrylic elastomers also include elastomers in which the hard segments are polyolefins (such as polyethylene) and the soft segments are polymethyl methacrylate (a polymer of methyl methacrylate) and include ester bonds. The ester bonds are polar.

[0056] Examples of olefin-based elastomers include elastomers in which the hard segment is a polyolefin (such as polypropylene, polyethylene, etc.) and the soft segment is an ethylene propylene rubber, ethylene propylene diene rubber, etc.

[0057] Examples of styrene-based elastomers include elastomers in which the hard segment is polystyrene and the soft segment is butadiene, isoprene, ethylene, etc.

[0058] If the matrix resin is a polar polymer, then the elastomer material is expected to include polar groups in terms of affinity with the matrix resin. For example, polar groups included in the elastomer material are urethane groups, amide groups, ester bonds, etc. In particular, it is desirable for the elastomer material to include ester bonds in one or both of the hard and soft segments.

[0059] Elastomer materials include polar groups such as ester bonds, which endow them with heat resistance and allow them to be melt- and compounded with polar polymers, especially those with high heat resistance. Elastomer materials containing ester bonds contribute to relatively high mechanical properties, particularly improved impact strength. However, if the affinity for the matrix resin is too high, depending on the number or type of polar groups, the elastomer material may be completely compatible with the matrix resin and unable to form a phase-separated structure. In this case, the flexural modulus is significantly reduced.

[0060] Elastomer materials have a glass transition point (glass transition temperature) below room temperature, thus enabling them to function as elastomers at room temperature. It is desirable for the glass transition point of elastomer materials to be below 0°C. More ideally, the glass transition point of elastomer materials should be -20°C or lower.

[0061] The elastomer material is melted and compounded with a matrix resin, which is a thermoplastic resin, in a molten state, and is finely dispersed into the matrix resin as elastomer particles, thereby improving impact strength. Therefore, it is desirable that the melting point of the elastomer material is lower than the heating temperature (molding temperature) of the resin composition, allowing the elastomer material to melt and compound with the matrix resin. The heating temperature of the resin composition is the melting temperature of the matrix resin, which is a thermoplastic polymer. The heating temperature of the resin composition is higher than the glass transition point of the matrix resin. If the matrix resin is a crystalline polymer, it is desirable that the heating temperature of the resin composition is higher than the melting point of the matrix resin. Therefore, it is desirable that the melting point of the elastomer material is lower than the melting point of the matrix resin. Although the melting point of the elastomer material can be higher than the melting point of the matrix resin, this may lead to thermal degradation, such as a decrease in the molecular weight of the matrix resin due to melting the elastomer material by heating the matrix resin. If the matrix resin is a crystalline polymer, the melting point of the elastomer material can be higher than the glass transition point of the matrix resin. If the matrix resin is a non-crystalline polymer, the melting point of the matrix resin is not limited, therefore it is desirable that the melting point of the elastomer material is lower than the glass transition point of the matrix resin.

[0062] It is desirable that the glass transition point of the matrix resin is above 50°C to ensure strength when using the matrix resin. Considering processability, it is also desirable that the glass transition point of the matrix resin is below 200°C. Considering heat resistance, it is desirable that the melting point of the matrix resin is above 100°C, and even more so that it is above 200°C. Considering processability, it is desirable that the melting point of the matrix resin is below 300°C. Similarly, it is desirable that the melting point of the elastomer material is above 50°C to ensure strength when using the elastomer material. It is desirable that the melting point of the elastomer material is below 300°C, and even more so that it is desirable that it is below 200°C, considering processability.

[0063] Elastomer materials possess rubber-like elasticity, i.e., flexibility, which helps improve the impact strength of the matrix resin. When an impact is applied to the molded article according to this embodiment, the matrix resin orients around the elastomer particles and forms cracks, thereby more effectively mitigating the impact. Therefore, it is desirable for a large number of elastomer particles to be finely dispersed. Thus, the particle diameter of the elastomer particles is preferably 10 μm or less. More preferably, the particle diameter of the elastomer particles is 5 μm or less. The particle diameter of the elastomer particles is preferably 0.1 μm or more, allowing the elastomer particles to function mechanically and efficiently. More preferably, the particle diameter of the elastomer particles is 0.5 μm or more. Typically, the elastomer particles are particles formed by dispersing and mixing through melting and kneading, and the particle diameter of such elastomer particles may be referred to as the "dispersed particle diameter" or "dispersed particle size".

[0064] [Particle packing]

[0065] It is known that adding filler particles to a resin improves mechanical properties such as flexural modulus. Therefore, in this embodiment, filler particles can be added to further improve flexural modulus and impact strength. Examples of filler particle shapes include many shapes such as spheres (e.g., true spheres, oblate spheroids, etc.), polyhedra, amorphous shapes, plate-like shapes, scaly shapes, needle-like shapes, fibrous shapes, etc., and any of these shapes can be used. For example, the length of needle-like or fibrous fillers is less than 100 μm. It is desirable for the length of needle-like or fibrous fillers to be less than 30 μm. More desirable is a length of needle-like or fibrous fillers to be less than 10 μm.

[0066] There are no particular limitations on filler particles with inorganic materials as the main component. Examples of filler particles include the following: mica, glass fiber, glass spheres, zinc oxide, titanium dioxide, calcium carbonate, clay, talc, silica, wollastonite, zeolite, diatomaceous earth, silica sand, fly ash, pumice powder, slate powder, alumina, white corundum, aluminum sulfate, carbon fiber, carbon nanotubes, metal fibers, barium sulfate, calcium sulfate, molybdenum disulfide, shirasu balloons, and fly ash balloons. Surface treatment of the filler may be performed if necessary.

[0067] All filler particles may include an inorganic material matrix as the main component, and a surface layer of organic or inorganic material covering the matrix. For example, the thickness of the surface layer is less than 100 nm. Ideally, the thickness of the surface layer should be less than 10 nm. In filler particles with inorganic material as the main component, the volume occupied by the inorganic material is greater than the volume occupied by the organic material. Ideally, the volume occupied by the inorganic material should be 90% or more by volume.

[0068] When an impact is applied to the molded article, the matrix resin orients around the elastomer particles and forms cracks, thereby more effectively mitigating the impact. At this point, to prevent a decrease in impact strength due to material defects in the filler particles, it is desirable for the filler particles to have a small particle diameter. If the filler particles are coarse particles with a large diameter, they act as stress concentration points. Therefore, impact strength may decrease, and cracks may develop. On the other hand, to adequately break down and disperse the particles during the manufacturing process of the resin composition, it is desirable to avoid dispersion failure caused by particle aggregation due to small particle diameters. If the filler particles are fine particles with a small diameter, it may be difficult to disperse them due to particle aggregation during the manufacturing process of the resin composition. This may lead to material defects due to particle aggregation and a decrease in impact strength, and cracks may develop.

[0069] Therefore, for example, the particle diameter of the filler particles to be independently dispersed is 10 μm or less. The particle diameter of the filler particles is preferably 5 μm or less. The particle diameter of the filler particles is preferably 2 μm or less. If the particle diameter of the filler particles is 10 μm or less, the reduction in impact strength due to the addition of filler particles can be effectively prevented. If the particle diameter is 0.2 μm or more, the filler particles can be finely dispersed in the matrix resin, and the reduction in impact strength can be prevented. Therefore, the particle diameter of the filler particles is preferably 0.2 μm or more and 10 μm or less. The particle diameter of the filler particles is more preferably 0.2 μm or more and 5 μm or less. The particle diameter of the filler particles is even more preferably 0.2 μm or more and 2 μm or less. The resin composition may contain filler particles with a particle diameter greater than 10 μm. It is desirable that the particle diameter of the filler particles with a particle diameter greater than 10 μm is 100 μm or less. It is even more desirable that the particle diameter of the filler particles with a particle diameter greater than 10 μm is 50 μm or less. Even more desirable is that filler particles with a diameter greater than 10 μm have a diameter of less than 30 μm.

[0070] Examples of methods for measuring particle diameter include the following: A cross-sectional sample of the molded product is prepared by pretreatment such as section polishing, microtomy, or ion milling, using a resin composition according to this embodiment. Ion milling is suitable because it achieves high smoothness in the cross-section and prevents particle shedding. If the temperature of the resin composition rises due to processing, it can be cooled by cryogenic treatment or similar methods. Then, an SEM image of the cross-section is obtained by observation using a scanning electron microscope (SEM) under the following conditions. It is desirable to use an appropriate magnification based on the particle diameter of the filler particles. For example, if the particle diameter is less than 5 μm, observation at 10,000x magnification is desirable, and if the particle diameter is greater than 5 μm, observation at 1,000x magnification is desirable. The obtained SEM image is binarized and image analyzed under the following conditions, and the median diameter of the filler particles within a selectable range of the molded body cross-section is determined as the particle diameter of the filler particles. For example, the selectable range of the shaped body cross-section can be a quadrilateral region where the lengths of two adjacent sides are length L and length M. For example, lengths L and M are 5 μm or more. Lengths L and M of 10 μm or more are desirable. For example, lengths L and M are less than 500 μm, or for example, lengths L and M are less than 100 μm. Lengths L and M can be the same or different from each other. The ratio of length L to length M can be from 0.5 to 2. Binarization and image analysis of the SEM images were performed using ImageJ, an image processing software from the National Institutes of Health (available at https: / / imagej.nih.gov / ij / ).

[0071] [condition]

[0072] {Device Name}

[0073] Schottky field emission scanning electron microscope JSM-F100 (manufactured by JEOL Ltd.)

[0074] {Accelerating Voltage}

[0075] 3kV

[0076] {Magnification}

[0077] 10,000 times or 1,000 times

[0078] {Measurement Range}

[0079] 12.8μm × 9.6μm (10000x) or 128μm × 96μm (1000x)

[0080] {Number of reviews}

[0081] 10 regions / samples

[0082] {Binarization and Image Analysis}

[0083] ImageJ

[0084] {Binarization Method}

[0085] MaxEntropy (appropriately adjusts the threshold so that filler particles can be distinguished by binarization. If the filler particles cannot be binarized by image processing software, an image in which only the filler particles are visually filled by using drawing software or similar tools is prepared).

[0086] {Methods for calculating particle diameter}

[0087] Median diameter (50% of particle diameter)

[0088] Ideally, the matrix should be surface-treated with surface-treatment agents such as coupling agents or fatty acids in the filler particles. For surface-treated filler particles, commercially available products that have undergone prior surface treatment can be used, or the surface treatment step can be provided independently during the manufacture of the resin composition. The amount of surface-treatment agent can be calculated from the specific surface area of ​​the filler particles to be treated and the minimum coverage area of ​​the surface-treatment agent. When filler particles with small particle diameters are used, the specific surface area of ​​the filler particles is large, therefore, the amount of surface-treatment agent inevitably increases. Therefore, the amount of surface-treatment agent to be added varies, and typically about 0.5 wt% to 5 wt% of surface-treatment agent is added to the filler particles. As a treatment method, known methods can be used, such as dry treatment methods (e.g., monolithic blending) or wet treatment methods using aqueous solutions of surface-treatment agents. The surface layer formed by surface treatment constitutes part of the filler particles.

[0089] Examples of surface treatment agents include silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-trimethoxysilylpropylsuccinic anhydride, etc. Alternatively, titanate or aluminate coupling agents can be used. Examples of fatty acids include lauric acid, stearic acid, oleic acid, etc. Among these, silane coupling agents are desirable. One of these surface treatment agents can be used, or two or more of these surface treatment agents can be used in combination.

[0090] [Composition ratio of ingredients]

[0091] When an elastomer material is added to a matrix resin, the matrix resin forms a phase-separated structure. For example, the matrix resin content is 30% by mass or more relative to the total amount of the resin composition. The matrix resin content is desirablely 40% by mass or more. More desirablely, it is 50% by mass or more. For example, the matrix resin content is 90% by mass or less relative to the total amount of the resin composition. The matrix resin content is desirablely 80% by mass or less. More desirablely, it is 70% by mass or less. The composition ratio in the resin composition can be obtained by performing thermogravimetric analysis (TGA).

[0092] Depending on the desired mechanical and physical properties, the composition ratio of the elastomer material and filler particles can be appropriately adjusted without deviating from the desired composition ratio range of the matrix resin. A higher amount of elastomer material can increase impact strength. A higher amount of filler particles can increase the elastic modulus. For example, the elastomer material content is 1% by mass or more relative to the total composition. The elastomer material content is preferably 5% by mass or more. The elastomer material content is preferably 10% by mass or more. For example, the elastomer material content is 50% by mass or less. The elastomer material content is preferably 40% by mass or less. The elastomer material content is preferably 30% by mass or less. For example, the filler particle content is 1% by mass or more relative to the total composition. The filler particle content is preferably 5% by mass or more. The filler particle content is preferably 10% by mass or more. For example, the filler particle content is 50% by mass or less relative to the total composition. The filler particle content is preferably 40% by mass or less. The content of filler particles is more preferably below 30% by mass.

[0093] [Other ingredients]

[0094] In this embodiment, various additives may be incorporated as needed. While there are no particular limitations on the types of additives, examples include flame retardants, conductive materials, waxes, various lubricants, mold release agents, antistatic agents, crosslinking agents, decomposition inhibitors, antioxidants, colorants, etc. One or more of the above-mentioned additives may be used in combination.

[0095] Many resins and elastomers exhibit poor compatibility, and in many cases, simple blending systems lead to interfacial separation and fail to adequately improve impact resistance. Therefore, in many cases, compatibilizing agents are added to compatibility between the resin and the elastomer, thereby improving impact strength. However, the addition of compatibilizing agents to compatibility between the matrix resin and the thermoplastic elastomer results in resin compositions in compatibility systems lacking phase separation structures. Furthermore, the flexural modulus of resin compositions obtained by adding elastomers and compatibilizing agents is significantly reduced. This disclosure offers high effectiveness because the matrix resin and elastomer possess phase separation structures. Therefore, it is desirable to use compatibilizing agents within the range where the matrix resin and thermoplastic elastomer can possess phase separation structures.

[0096] The resin composition according to this embodiment may contain at least one of the following materials that are different from the inorganic material that is the main component of the filler particles: a metallic material including a transition metal element, a compound material including a transition metal element, a metallic material including a typical metal element, and a compound material including a typical metal element.

[0097] Examples of transition metals include titanium (Ti), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zirconium (Zr), niobium (Nb), molybdenum (Mo), hafnium (Hf), tantalum (Ta), tungsten (W), palladium (Pd), platinum (Pt), silver (Ag), and gold (Au). Examples of typical metallic elements include sodium (Na), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), zinc (Zn), aluminum (Al), gallium (Ga), germanium (Ge), indium (In), tin (Sn), and antimony (Sb). Although silicon (Si) and arsenic (As) can be classified as half-metals along with germanium (Ge) and antimony (Sb), they are considered non-metallic elements here. Each metallic material is either an elemental metal or an alloy; for example, metallic compounds (which are compounds containing metallic elements) are oxides, nitrides, carbides, inorganic acid salts, or organic acid salts of metallic elements. Although compounds are classified into inorganic compounds and organic compounds, organic compounds (i.e., organometallic compounds) are compounds that combine carbon and metal elements.

[0098] The aforementioned materials comprising transition metal elements or typical metal elements can be particles with a particle diameter of 0.1 μm or more when dispersed in a matrix resin, or particles with a particle diameter of less than 0.1 μm. The aforementioned materials comprising transition metal elements or typical metal elements can be particles smaller than elastomer particles, or particles dispersed within elastomer particles. Alternatively, the aforementioned materials comprising transition metal elements or typical metal elements can be dissolved in the matrix resin or elastomer particles.

[0099] It is desirable that the content of the aforementioned materials, including transition metal elements or typical metal elements, is less than the content of the matrix resin, the inorganic materials (as the main component of the filler particles), and the elastomer materials (as the main component of the elastomer particles).

[0100] If the content of a particular metal element differs between the matrix resin and the elastomer material, a distribution image (mapping image) of that metal element is obtained, thereby making it easy to distinguish the matrix resin and the elastomer material in the observed image. For example, when a polar polymer is polymerized, aluminum (Al), germanium (Ge), antimony (Sb), or titanium (Ti) can be included in the compound as a polymerization catalyst and can be dissolved or dispersed in the matrix resin. Alternatively, materials including transition metal elements or typical metal elements can be included in the compound as pigments for coloring the resin composition and can be dispersed in the matrix resin. Alternatively, for example, filler particles can include filler particles with calcium carbonate as the main component and filler particles with titanium oxide as the main component, and the two types of filler particles can be dispersed independently.

[0101] <Method for manufacturing resin composition>

[0102] The method for manufacturing the resin composition according to this embodiment includes the steps of melting and mixing a matrix resin, an elastomer material, and other raw materials constituting the resin composition. The elastomer material is melted and mixed with the matrix resin in a molten state, and the elastomer material is dispersed and mixed into the matrix resin, thereby improving the impact strength of the resin composition. The particle diameter of the elastomer particles formed by dispersion and mixing may be referred to as the "dispersion particle diameter" or "dispersion particle size". Examples of mixing equipment include twin-screw extruders, twin-roll extruders, etc. Specifically, examples of mixing equipment include TEM extruders (manufactured by ShibauraMachine Co., Ltd.), TEX twin-screw mixers (manufactured by The Japan Steel Works, Ltd.), PCM mixers (manufactured by Ikegai Iron Works Co., Ltd.), KNEADEX (manufactured by Nippon Coke & Engineering Co., Ltd.), etc.

[0103] To manufacture the injection-molded article according to this embodiment, it is desirable to use granules of two types of resin compositions that differ in the average particle diameter of the elastomer particles dispersed in the matrix resin. The average particle diameter of the elastomer particles in the granules of resin composition A may be larger than that in the granules of resin composition B. For example, the difference between the average particle diameter of the elastomer particles in the granules of resin composition A and the average particle diameter of the elastomer particles in the granules of resin composition B is 0.8 μm or more. It is desirable that the difference between the average particle diameter of the elastomer particles in the granules of resin composition A and the average particle diameter of the elastomer particles in the granules of resin composition B is 1.0 μm or more. More preferably, the difference between the average particle diameter of the elastomer particles in the granules of resin composition A and the average particle diameter of the elastomer particles in the granules of resin composition B is 1.5 μm or more. For example, the average particle diameter of the elastomer particles in the granules of resin composition A is more than twice the average particle diameter of the elastomer particles in the granules of resin composition B. It is desirable that the average particle diameter of the elastomer particles in the granules of resin composition A is at least three times that of the average particle diameter of the elastomer particles in the granules of resin composition B. For example, the average particle diameter of the elastomer particles in the granules of resin composition A is less than 30 times that of the average particle diameter of the elastomer particles in the granules of resin composition B. It is desirable that the average particle diameter of the elastomer particles in the granules of resin composition A is less than 20 times that of the average particle diameter of the elastomer particles in the granules of resin composition B. The average particle diameter of the elastomer particles in the granules of resin composition A may be less than 10 times that of the average particle diameter of the elastomer particles in the granules of resin composition B. Specifically, for example, it is desirable to use granules of resin composition A in which the average particle diameter of the elastomer particles is 1.5 μm or more, and preferably 2.0 μm or more, and granules of resin composition B in which the average particle diameter of the elastomer particles is less than 1.5 μm, and preferably 1.0 μm or less.

[0104] In the melt-blending step, the shear force applied to the molten and blended product is typically reduced by keeping the discharge rate constant and decreasing the screw speed. Elastomer materials usually exist in aggregate form. Therefore, the reduced shear force applied to the molten and blended product allows the elastomer particles to be dispersed in the matrix resin at a larger particle size. Furthermore, the size of the dispersed particles can be altered by adding thickeners, dispersants, or controlling the concentration or surface tension of the elastomer material.

[0105] Resin composition A is a resin composition compounded under melt mixing condition α. ​​As melt mixing condition α, the mixing conditions are adjusted, for example, by reducing the screw speed, so that the average particle diameter of the elastomer particles is 1.5 μm or more, preferably 2.0 μm or more. Similarly, resin composition B is a resin composition compounded under melt mixing condition β. As melt mixing condition β, the mixing conditions are adjusted, for example, by increasing the screw speed, so that the average particle diameter of the elastomer particles is less than 1.5 μm, preferably less than 1.0 μm.

[0106] <Injection Molding Methods>

[0107] The molded article according to this embodiment is formed by molding the resin composition according to this embodiment. Injection molding in a metal mold is used as the molding method. The resin composition obtained by injection molding may be referred to as an "injection-molded article". Typically, the injection molding apparatus is a screw-type injection molding apparatus. In this embodiment, a screw-type injection molding apparatus is also desirable.

[0108] In order to mold the injection-molded article according to this embodiment, it is desirable to use granules of resin composition A and granules of resin composition B by blending granules. Ideally, resin composition A is 50 parts by weight or more and 200 parts by weight relative to 100 parts by weight of resin composition B. More preferably, resin composition A is 50 parts by weight or more and 100 parts by weight or less.

[0109] If a blended resin composition is fed into an injection molding machine and molded, and when the molten and compounded product is extruded in the injection molding machine, the elastomer particles with high flowability and large particle diameter flow first and form a portion close to the metal mold. Typically, at the outermost surface of the blended resin composition in contact with the metal mold, the matrix resin, which has a higher melting point or glass transition point than the elastomer material, solidifies first, thereby forming a third portion 3 with a low elastomer-to-matrix resin ratio. This third portion 3 is referred to as the "surface layer". A core layer is formed inside the surface layer (on the side away from the metal mold). In this embodiment, the core layer may include a first portion 1 and a second portion 2. It is assumed that the elastomer particles with large particle diameter remain near the metal mold and form the second portion 2. Furthermore, the elastomer particles with small particle diameter that subsequently flow form the first portion 1. By melting and compounding in the injection molding machine, the elastomer particles in the granules of resin composition A are separated and / or combined, or the elastomer particles in the granules of resin composition B are separated and / or combined. The elastomer particles in the granules of resin composition A and the elastomer particles in the granules of resin composition B are also merged. Therefore, the particle diameter of the elastomer particles in the injection molded article is related to the particle diameter of the elastomer particles in the granules, but is not necessarily the same as the particle diameter of the elastomer particles in the granules.

[0110] <Evaluation>

[0111] This paper describes a method for measuring the particle diameter of elastomer particles. The particle diameter of the elastomer can be measured in a molded body, or in strips or granules after melting and mixing. Furthermore, the molded body, strips, or granules can be treated with processes such as resin embedding. Transverse cross-sectional samples are prepared by pretreatment such as section polishing, slicing, or ion milling. Then, SEM images of the cross-section are obtained by observation using a scanning electron microscope (SEM) at an accelerating voltage of 3 kV. It is desirable to use an appropriate observation magnification based on the particle diameter of the elastomer. For example, if the particle diameter is less than 5 μm, it is desirable to observe at 10,000x magnification; if the particle diameter is greater than 5 μm, it is desirable to observe at 1,000x magnification. For example, the obtained SEM images are binarized and image analyzed using ImageJ, and the particle diameter is calculated using a particle calculation method based on median diameter. Similarly, the particle diameter is calculated from 10 SEM images, and the average particle diameter is determined as the average particle diameter of the elastomer particles. ImageJ, an image processing software from the National Institutes of Health (available at https: / / imagej.nih.gov / ij / ), was used to binarize and analyze the SEM images.

[0112] The method for observing a molded body is described. Examples of methods for generating a cross-section of the molded body to be observed include the following: A transverse cross-sectional sample of the molded body is prepared by using a fracture surface obtained from a Charpy impact test and performing processes such as cross-section polishing, slicing, or ion milling. Then, an SEM image of the cross-section is obtained by observation using a scanning electron microscope (SEM) at an accelerating voltage of 3 kV. Observation is expected at a magnification of approximately 5000x.

[0113] Examples of methods for measuring the ratio of elastomer to matrix resin in a molded article include the following methods. For the molded article according to this embodiment, a transverse cross-sectional sample of the molded article is prepared by pretreatment such as section polishing, slicing, or ion milling. Then, at 10... 2 μm 2 Above and 130 2 μm 2 Within the following area range, for example, 25 μm square (25 2 μm 2Within the range of ), analysis was performed in the cross-section using a Spotlight 400 Fourier transform infrared spectrophotometer (manufactured by PerkinElmer, Inc.). The desired analysis objects were multiple area ranges linearly arranged along the cross-section in a direction perpendicular to surface 4 (the depth direction of the molded body). For example, in Figure 1 In the data, the area ranges 21, 22, 11, and 12 are linearly arranged. It is desirable to use the analysis results of these multiple area ranges to obtain statistical values, such as averages, maximum values, etc. Individual matrix resins and individual elastomer materials were also measured. All data were normalized using the peak values ​​of the measurements. The normalized 1160 cm⁻¹ was used. -1 The value is calculated based on the following premises: the elastomer to matrix resin ratio is 0% when the matrix resin is measured, and the elastomer material ratio is 100% when the elastomer material is measured.

[0114] Examples of methods for measuring the impact strength of molded specimens include the following: A strip-shaped specimen is molded according to JIS K7111. A notch is made in the specimen using a notching machine; the notched specimen is then broken from the back side using a Charpy impact testing machine according to JIS K7111-1 with an energy of 1 J. The energy required for failure is calculated from the angle of the pendulum raised to 150° after the specimen breaks, and this energy is determined as the Charpy impact value.

[0115] The desired Charpy impact value of the molded part is 3 kJ / m 2 The above. A Charpy impact value of 6 kJ / m is more desirable for the molded part. 2 That's all. If the Charpy impact value of the molded part is less than 3 kJ / m 2 Cracks may develop during drop tests or similar tests.

[0116] Examples of methods for measuring the flexural modulus of molded specimens include the following: Following JIS K7171, a three-point bending fixture is installed in a universal testing machine, and the molded strip specimen is measured under conditions where the distance between the supports is 64 mm and the indenter descends at a rate of 2 mm / min. The flexural modulus is then calculated from the stress gradient within a specified strain range (0.05% to 0.25%).

[0117] It is desirable for the flexural modulus of the molded body to be 1500 MPa or higher. More preferably, it is desirable for the flexural modulus to be 1700 MPa or higher. This is because if the flexural modulus is within this range, the deformation caused by the assumed external force is in the elastic deformation region, and the shape will not deform. On the other hand, if the flexural modulus is less than 1200 MPa, the assumed external force will cause plastic deformation.

[0118] <Device>

[0119] Figure 3 The device 100 shown includes injection-molded bodies 10 according to this embodiment as components 10a and 10b. Examples of devices 100 include office equipment (e.g., printers, copiers, etc.), medical devices (e.g., computed tomography (CT) equipment), video equipment (e.g., projectors, monitors, etc.). In addition to components 10a and 10b made of injection-molded bodies according to this embodiment, each of these different devices also includes at least one of electrical components 13, optical components 12, and metal components 11. Electrical components 13, optical components 12, and metal components 11 perform the functions of device 100. Metal components 11 can also be used as a housing to ensure the mechanical strength of device 100.

[0120] Components 10a and 10b, formed by the injection-molded body 10 according to this embodiment, can be used as components to ensure the mechanical strength of the device 100 or to provide mechanical protection for the device 100. Component 10a, formed by the injection-molded body 10 according to this embodiment, can be an external body of the device 100, such as an external cover. The external body can be fixed to a metal housing (metal component 11). Component 10b, formed by the injection-molded body 10 according to this embodiment, can be an internal body of the device 100, such as a mechanical component. The internal body can be fixed to a metal housing (metal component 11).

[0121] (Example)

[0122] The materials used in this implementation are shown below.

[0123] (A) Matrix resin

[0124] [Table 1]

[0125]

[0126] (B) Elastomer materials

[0127] [Table 2]

[0128]

[0129] (C) Filler particles

[0130] The average particle diameter [μm] of the filler shown in Table 3 is the catalog value of the product.

[0131] [Table 3]

[0132]

[0133] (D) Additives

[0134] (D-1) Compatibility reagent: "AX8700", manufactured by Tokyo Zairyo Co., Ltd.

[0135] <<Preparation of Granules of Resin Compositions 1A to 8A and 1B to 8B>>

[0136] <Preparation of Granules of Resin Compositions 1A and 1B>

[0137] The matrix resins shown in Table 4 were pre-dried to a moisture content of 100 ppm. This is to prevent hydrolysis during the mixing process, and the conditions (such as temperature and time) vary depending on the resin type. The moisture content was measured using a polymer moisture meter “AQUATRAC-V (product name), manufactured by ITS Japan Inc.”.

[0138] Then, the ingredients were added such that the mass percentage of each ingredient in the final resin composition was as shown in Table 4, and a blended product of the raw materials was prepared. The blended product was melted and kneaded using a twin-screw extruder, “PCM30 (product name) manufactured by Ikegai Corp.,” at a barrel temperature of 260°C and a screw speed of 50 rpm to prepare strips, which were then cut by a granulator to obtain granules of resin composition 1A.

[0139] In addition to changing the screw speed to 250 rpm, granules of resin composition 1B were obtained in a similar manner.

[0140] <Preparation of granules from resin compositions 2A to 8A and 2B to 8B>

[0141] Except for changing the mass percentage of each component to achieve the blending amounts shown in Table 4, the granules of resin compositions 2A to 8A and 2B to 8B are manufactured in a manner similar to that used for manufacturing the granules of resin composition 1A and resin composition 1B.

[0142] Measurement of Particle Diameter in Elastomers

[0143] The obtained granules were resin-embedded, and the particle diameter of the elastomers in the matrix resin was confirmed. The cross-sections to be observed were polished sequentially using polishing paper with particle sizes #400 to #2500, followed by grinding with diamond slurry with a particle diameter of 0.5 μm, thus preparing the cross-sections to be observed. Observations were performed at 10,000x magnification using a scanning electron microscope (JSM-F100, manufactured by JEOL Ltd.) under an accelerating voltage of 3 kV. The obtained SEM images were binarized and analyzed using ImageJ, and the particle diameter was calculated using a particle size distribution method based on median diameter. Similarly, the particle diameters in 10 SEM images were calculated, and the average particle diameter was determined as the particle diameter of the elastomers in the resin composition, as shown in Table 4. Table 4 also describes the difference between the average particle diameter of the elastomer particles in resin compositions 1A to 6A and the average particle diameter of the elastomer particles in resin compositions 1B to 6B. These differences are calculated from the average particle diameter of the elastomer particles in resin compositions 1A to 6A and the average particle diameter of the elastomer particles in resin compositions 1B to 6B. The ratio of the average particle diameter of the elastomer particles in resin compositions 1A to 6A to the average particle diameter of the elastomer particles in resin compositions 1B to 6B can also be calculated from the average particle diameter of the elastomer particles, and therefore will not be described.

[0144] Compatibilizing agent D-1, which is compatible with both the matrix resin and the elastomer and comprises multiple chemical structures, was added to resin compositions 7A and 7B. The addition of the compatibilizing agent improved the compatibility of the elastomer with the matrix resin, thereby preventing the observation of elastomer particles. Elastomer B-5, comprising functional groups highly compatible with the matrix resin, was added to resin compositions 8A and 8B. This elastomer was sufficiently compatible with the matrix resin, thereby preventing the observation of elastomer particles.

[0145] [Table 4]

[0146]

[0147] <<Examples 1 to 8 and Comparative Examples 1 to 4>>

[0148] The granules of resin compositions A and B shown in Table 5 were blended at the ratios in Table 5 and pre-dried to a moisture content of 100 ppm. The moisture content was measured using a method similar to that used for measuring the moisture content of the matrix resin. Then, the granules of resin compositions A and B were injection molded using an injection molding machine “SE-180D (product name) manufactured by Sumitomo Heavy Industries, Ltd.” at a barrel temperature of 280°C and a metal mold temperature of 30°C, thereby forming strip specimens of type B1 (length 80 mm × width 10 mm × thickness) as defined in JISK7152-1.

[0149] <Charlie Impact Value>

[0150] According to JIS K7111, a notch (shape A) was machined on a preformed strip specimen using a notching machine "No. 189-PN (product name) manufactured by Yasuda Seiki Seisakusho, Ltd.", and the central portion of the specimen was cut open (notch cut) to a depth of 2 mm, a notch tip radius of 0.25 mm, and a 45° angle. According to JIS K7111-1, a Charpy impact testing machine "No. 258 (product name) manufactured by Yasuda Seiki Seisakusho, Ltd." was used to break the specimen from the back of the notch with an energy of 1 J. The energy required for breakage was calculated from the angle of the pendulum raised to 150° after the specimen broke. The average of the measurements from five specimens was then determined as the Charpy impact value.

[0151] The results of each Charpy impact test measurement were evaluated using the following metrics. Table 5 shows the evaluation results. A higher Charpy impact strength corresponds to a higher evaluation.

[0152] A: Charpy impact strength is 6 kJ / m 2 above.

[0153] B: Charpy impact strength is 3 kJ / m 2 Above and less than 6 kJ / m 2 .

[0154] C: Charpy impact strength is 1.53 kJ / m 2 Above and less than 3 kJ / m 2 .

[0155] D: Charpy impact strength less than 1.5 kJ / m 2 .

[0156] <Flexural Modulus>

[0157] According to JIS K7171, a three-point bending fixture was installed in a universal testing machine "5581 (product name) manufactured by Instron," and measurements were taken on a formed strip specimen under conditions of a distance of 64 mm between the supports and a descent rate of 2 mm / min for the indenter. The flexural modulus was then calculated from the stress gradient within a specified strain range (0.05% to 0.25%). The average of the measurements from five specimens was determined as the flexural modulus.

[0158] The flexural modulus was evaluated using the following criteria. Table 5 shows the results. A higher flexural modulus indicates a better evaluation.

[0159] A: The flexural modulus is above 1700 MPa.

[0160] B: Flexural modulus is above 1500 MPa and less than 1700 MPa.

[0161] C: Flexural modulus is above 1200 MPa and less than 1500 MPa.

[0162] D: Flexural modulus less than 1200 MPa.

[0163] <Ratio of elastomer to matrix resin>

[0164] A cross-section of the central portion of the molded strip specimen was obtained, and the ratio of elastomer in the matrix was calculated. The measured cross-section was prepared by polishing sequentially with polishing paper of grit sizes #400 to #2500, followed by grinding with diamond slurry with a particle diameter of 0.5 μm. Analysis was performed continuously in a vertical direction from the outermost surface side within a 25 μm square area using a Spotlight 400 Fourier transform infrared spectrophotometer (manufactured by PerkinElmer, Inc.). Individual matrix resins and individual elastomers were also measured. All data were normalized to the peak values ​​of the measurements. The normalized 1160 cm⁻¹ values ​​were used. -1The elastomer to matrix resin ratio was calculated based on the following assumptions: the matrix resin alone had a 0% elastomer ratio, and the elastomer material alone had a 100% elastomer ratio. The maximum elastomer to matrix resin ratio in the region 50 μm to 500 μm inward from the surface of the molded body was determined as the elastomer ratio in the second part. Similarly, the regions 500 μm inward from each other's two opposing surfaces were measured, and the average elastomer to matrix resin ratio in this region was determined as the elastomer ratio in the first part. Table 5 shows the elastomer ratio in the second part / the elastomer ratio in the first part. In Example 1, the elastomer ratio in the second part was 33.5%, and the elastomer ratio in the first part was 14.0%. In Example 4, the elastomer ratio in the second part was 29%, and the elastomer ratio in the first part was 12.5%. In Comparative Example 1, the elastomer ratio in the second part was 21.0%, and the elastomer ratio in the first part was 19.0%.

[0165] <Average particle size of elastomer particles in Part 1 and Part 2>

[0166] The central portion of the formed strip specimen was observed in the cross-sectional direction, and the average particle size of the elastomer particles in the first and second portions was measured. The fracture surface of a specimen subjected to a Charpy impact test was used as the observation cross-section. The structure was observed using a scanning electron microscope ("JSM-F100" manufactured by JEOL Ltd.) at 5000x magnification under an accelerating voltage of 3 kV. The SEM image obtained by photographing the second portion was binarized and analyzed using ImageJ, and the average particle diameter of the elastomer was calculated. The threshold was appropriately adjusted based on the shape and contrast of the elastomer. If the shape of the elastomer particles was not circular, the number of elastomer particles and the area of ​​the elastomer were counted and converted, thereby calculating the average particle diameter of the elastomer.

[0167] Similarly, 10 SEM images were processed, and the maximum value of the average particle diameter of the elastomer was determined as the average particle diameter of the elastomer in the second part. Similarly, the first part was photographed, and the average particle diameter of the elastomer was calculated. Table 5 shows the average particle diameters in the second and first parts. Table 5 also describes the difference between the average particle diameter of the elastomer particles in the first part and the average particle diameter of the elastomer particles in the second part. This difference is calculated from the average particle diameter of the elastomer particles in the first and second parts. The ratio of the average particle diameter of the elastomer particles in the second part to the average particle diameter of the elastomer particles in the first part can also be calculated from the average particle diameter of the elastomer particles, and therefore is not described.

[0168] Figure 2A The image shows a cross-sectional SEM image obtained by photographing the second part 2 of the injection-molded body according to Example 1. Figure 2B A cross-sectional SEM image obtained by photographing the first portion 1 of the injection-molded body according to Example 1 is shown. Figure 2A and Figure 2B In each of them, the field of view of the SEM image is 25.6 μm × 19.2 μm, and the width of the scale written at the lower right corner of the SEM image is 1 μm. Figure 2A The following state is shown: observe the region 100 μm to 200 μm inward from the surface in the thickness direction of the injection molded part. Figure 2B The following condition is shown: Observe a region approximately 1 mm inward from the surface in the thickness direction of the injection-molded part. Figure 2A and Figure 2B In each of these, arrow M indicates the matrix resin. Figure 2B In the diagram, arrow E1 indicates an elastomer dispersed obliquely upwards in the form of amoebas, approximately 5 μm in length. Figure 2A In the diagram, arrow E2 indicates an elastomer dispersed in the form of spheres with a diameter of approximately 1 μm, and arrow E3 indicates an elastomer dispersed in the form of spheres with a diameter of less than 0.5 μm. Figure 2B In the diagram, arrow E4 indicates an elastomer dispersed in the form of spheres with a diameter of approximately 0.5 μm, and arrow E5 indicates an elastomer dispersed in the form of spheres with a diameter of approximately 1 μm.

[0169] It is speculated that the elastomer dispersed in an amoeba-like form with a length of 5 μm or more, as shown in Part 2, was obtained by elastomer particles extending in the flow direction when the molten resin flows in the metal mold. In Part 1, no elastomer dispersed in an amoeba-like form with a length of 5 μm or more, as shown in Part 2, was identified.

[0170] [Table 5]

[0171]

[0172] In Examples 1 to 7, the elastomer ratio in the second part / the elastomer ratio in the first part is 1.3 or higher, and the elastomer ratio in the second part is sufficiently high. Therefore, each of these molded articles exhibits excellent flexural modulus and impact strength.

[0173] In Comparative Examples 1 to 4, the elastomer ratio in the second part / the elastomer ratio in the first part was less than 1.3, and the elastomer ratio in the second part was low. In Comparative Example 1, it is presumed that because only resin composition A was used, all elastomer particles had large particle diameters, thus failing to exhibit sufficient impact strength. In Comparative Example 2, it is presumed that because only resin composition B was used, all elastomer particles had small particle diameters, thus failing to exhibit sufficient impact strength. In Comparative Examples 3 and 4, it is presumed that due to the high compatibility between the matrix resin and the elastomer material, no elastomer particles were identified in either the first or second part by observing the SEM images. Therefore, the molded body according to Comparative Example 3 failed to exhibit sufficient flexural modulus and sufficient impact strength, and the molded body according to Comparative Example 4 failed to exhibit sufficient flexural modulus.

[0174] This disclosure is not limited to the above-described embodiments and examples, and can be modified in various ways within the technical concept of this disclosure. The effects described in the embodiments and examples are merely a list of the most suitable effects provided by this disclosure, and the effects of this disclosure are not limited to those described in the embodiments and examples.

[0175] New items may be added to at least one implementation. The disclosure of the specification includes not only the items explicitly described in the specification, but also all items that can be understood from the specification and its accompanying drawings.

[0176] Regarding the specific numerical ranges shown in the specification, the description "e to f" (where e and f are numbers) means above e and / or below f. Regarding the specific numerical ranges shown, if both the range "i to j" and the range "m to n" (where i, j, m, and n are numbers) are described, the sets of lower and upper limits are not limited to the set of i and j or the set of m and n. For example, the lower and upper limits of multiple sets can be considered together. That is, if both the range "i to j" and the range "m to n" are described, consideration can be given in the range "i to n" or in the range "m to j" without causing contradiction. Above e means equal to or greater than e (exceeding e), and values ​​greater than e can be taken without taking e. Below f means equal to or less than f (less than f), and values ​​less than f can be taken without taking f.

[0177] The disclosure in this specification includes supplements to the various concepts described therein. That is, for example, if the specification states "A is B," even if the specification omits the statement "A is not B," it can be assumed that the specification states "A is not B." This is because the statement "A is B" is based on the premise that "A is not B."

[0178] <<Included Structures>>

[0179] The disclosure of this implementation plan includes the following structure.

[0180] (Construction 1)

[0181] An injection-molded article comprising a matrix resin and a thermoplastic elastomer dispersed in the matrix resin, the injection-molded article comprising:

[0182] The first portion of the surface of the injection-molded article is away from the surface of the injection-molded article; and

[0183] The second portion between the first portion and the surface

[0184] In the second part, in 10 2 μm 2 Above and 130 2 μm 2 The ratio of the elastomer to the matrix resin in the following area range is 10 in the first part. 2 μm 2 Above and 130 2 μm 2 The ratio of the elastomer to the matrix resin in the following area ranges is more than 1.3 times.

[0185] (Construction 2)

[0186] According to the injection-molded body described in Construction 1

[0187] In the first part, the elastomer is elastomer particles dispersed in the matrix resin, and

[0188] In the second part, the elastomer is elastomer particles dispersed in the matrix resin.

[0189] (Construction 3)

[0190] According to the injection-molded article of configuration 2, the average particle diameter of the elastomeric particles in the second portion is greater than the average particle diameter of the elastomeric particles in the first portion.

[0191] (Construction 4)

[0192] According to the injection-molded article of configuration 2 or 3, the difference between the average particle diameter of the elastomeric particles in the second part and the average particle diameter of the elastomeric particles in the first part is 0.8 μm or more.

[0193] (Construction 5)

[0194] According to the injection-molded body of configuration 2 or 3, the average particle diameter of the elastomer particles in the first portion is less than 1.0 μm.

[0195] (Construction 6)

[0196] According to the injection-molded body described in configuration 2 or 3, the average particle diameter of the elastomer particles in the second part is greater than 1.0 μm.

[0197] (Construction 7)

[0198] According to the injection-molded article of configuration 2 or 3, the average particle diameter of the elastomeric particles in the second portion is more than twice the average particle diameter of the elastomeric particles in the first portion.

[0199] (Construction 8)

[0200] The injection-molded body according to any one of constructions 1 to 7

[0201] In the second part, in 10 2 μm 2 Above and 130 2 μm 2 The ratio of the elastomer to the matrix resin in the following area ranges is 10% or more, and

[0202] In the first part, in 10 2 μm 2 Above and 130 2 μm 2 The ratio of the elastomer to the matrix resin in the following area ranges is less than 50%.

[0203] (Construction 9)

[0204] The injection-molded body according to any one of constructions 1 to 8

[0205] In the second part, in 10 2 μm 2 Above and 130 2 μm 2 The ratio of the elastomer to the matrix resin in the following area range is 10 in the first part. 2 μm 2 Above and 130 2 μm 2 The ratio of the elastomer to the matrix resin in the following area ranges is more than 1.5 times.

[0206] (Construction 10)

[0207] According to any one of constructions 1 to 9, the injection-molded article, wherein in the first portion at 10 2 μm 2 Above and 130 2 μm 2 The ratio of the elastomer to the matrix resin in the following area range is the average value in the first part.

[0208] (Construction 11)

[0209] According to any one of constructions 1 to 10, the injection-molded article, wherein in the second part in 10 2 μm 2 Above and 130 2 μm 2 The ratio of the elastomer to the matrix resin in the following area range is the maximum value in the second part.

[0210] (Construction 12)

[0211] According to any one of constructions 1 to 11, the injection-molded article is located in a region more than 250 μm inward from the surface, and the second portion is located in a region more than 50 μm and less than 500 μm inward from the surface.

[0212] (Construction 13)

[0213] The injection-molded article according to any one of constructions 1 to 12 further includes a third portion between the second portion and the surface.

[0214] In the third part, in 10 2 μm 2 Above and 130 2 μm 2 The ratio of the elastomer to the matrix resin in the following area range is lower than that in the first portion at 10. 2 μm 2 Above and 130 2 μm 2 The ratio of the elastomer to the matrix resin in the following area range.

[0215] (Construction 14)

[0216] According to the injection-molded body of configuration 13, the third portion is located in a region less than 50 μm inward from the surface.

[0217] (Construction 15)

[0218] The injection-molded article according to any one of constructions 1 to 14, wherein the matrix resin is polyester.

[0219] (Construction 16)

[0220] The injection-molded body according to any one of constructions 1 to 15, wherein the elastomer is an acrylic elastomer.

[0221] (Construction 17)

[0222] According to any one of constructions 1 to 16, the injection-molded article wherein the melting point of the elastomer is lower than the glass transition point or melting point of the matrix resin.

[0223] (Construction 18)

[0224] The injection-molded article according to any one of constructions 1 to 17 further comprises filler particles dispersed in the matrix resin, the filler particles having inorganic material as the main component.

[0225] (Construction 19)

[0226] An apparatus comprising:

[0227] A component comprising an injection-molded body according to any one of constructions 1 to 18; and

[0228] At least one of electrical components, metal components, and optical components.

[0229] (Construction 20)

[0230] According to the device described in configuration 19, the component is an external body.

[0231] (Construction 21)

[0232] A method for manufacturing an injection-molded article, comprising:

[0233] A mixture of granules of a first resin composition obtained by dispersing first elastomer particles in a matrix resin and granules of a second resin composition obtained by dispersing second elastomer particles in a matrix resin is injection molded.

[0234] Wherein, the difference between the average particle diameter of the first elastomer particle and the average particle diameter of the second elastomer particle is greater than 0.8 μm.

[0235] (Construction 22)

[0236] According to the method for manufacturing an injection-molded body as described in configuration 21, the average particle diameter of the first elastomer particles is more than twice the average particle diameter of the second elastomer particles.

[0237] (Construction 23)

[0238] According to the method for manufacturing an injection-molded body as described in configuration 21 or 22, the average particle diameter of the first elastomer particles is 1.5 μm or more, and the average particle diameter of the second elastomer particles is less than 1.5 μm.

[0239] (Construction 24)

[0240] The method for manufacturing an injection-molded article according to any one of constructions 21 to 23 further includes manufacturing the first resin composition.

[0241] The first resin composition is manufactured by melting and mixing a matrix resin and an elastomer material, and dispersing the first elastomer particles in the matrix resin.

[0242] This invention is not limited to the above-described embodiments, and various changes and modifications can be made within the spirit and scope of this invention. Therefore, in order to inform the public of the scope of this invention, the following claims are made.

[0243] This application claims priority to Japanese Patent Application No. 2023-177772, filed on October 13, 2023, which is incorporated herein by reference.

[0244] Explanation of reference numerals in the attached figures

[0245] Part 1

[0246] 2 Part Two

[0247] 3 Part Three

[0248] 4 Surface

[0249] 5 sections

[0250] 10 Injection Molded Parts

[0251] 11, 12 Part 1, 10 2 μm 2 Above and 130 2 μm 2 The following area range

[0252] 21, 22 Part Two, 10 2 μm 2 Above and 130 2 μm 2 The following area range

Claims

1. An injection-molded article comprising a matrix resin and a thermoplastic elastomer dispersed in the matrix resin, the injection-molded article comprising: The first portion of the surface of the injection-molded article is away from the surface of the injection-molded article; and The second portion between the first portion and the surface in, In the second part, in 10 2 μm 2 Above and 130 2 μm 2 The ratio of the elastomer to the matrix resin in the following area range is 10 in the first part. 2 μm 2 Above and 130 2 μm 2 The ratio of the elastomer to the matrix resin in the following area ranges is more than 1.3 times.

2. The injection-molded article according to claim 1, in, In the first part, the elastomer is elastomer particles dispersed in the matrix resin, and In the second part, the elastomer is elastomer particles dispersed in the matrix resin.

3. The injection-molded article according to claim 2, wherein, The average particle diameter of the elastomer particles in the second part is greater than the average particle diameter of the elastomer particles in the first part.

4. The injection-molded article according to claim 2 or 3, wherein, The difference between the average particle diameter of the elastomer particles in the second part and the average particle diameter of the elastomer particles in the first part is greater than 0.8 μm.

5. The injection-molded article according to claim 2 or 3, wherein, The average particle diameter of the elastomer particles in the first part is less than 1.0 μm.

6. The injection-molded article according to claim 2 or 3, wherein, The average particle diameter of the elastomer particles in the second part is greater than 1.0 μm.

7. The injection-molded article according to claim 2 or 3, wherein, The average particle diameter of the elastomer particles in the second part is more than twice the average particle diameter of the elastomer particles in the first part.

8. The injection-molded article according to any one of claims 1 to 3, in, In the second part, in 10 2 μm 2 Above and 130 2 μm 2 The ratio of the elastomer to the matrix resin in the following area ranges is 10% or more, and In the first part, in 10 2 μm 2 Above and 130 2 μm 2 The ratio of the elastomer to the matrix resin in the following area ranges is less than 50%.

9. The injection-molded article according to any one of claims 1 to 3, in, In the second part, in 10 2 μm 2 Above and 130 2 μm 2 The ratio of the elastomer to the matrix resin in the following area range is 10 in the first part. 2 μm 2 Above and 130 2 μm 2 The ratio of the elastomer to the matrix resin in the following area ranges is more than 1.5 times.

10. The injection-molded article according to any one of claims 1 to 3, wherein, In the first part, in 10 2 μm 2 Above and 130 2 μm 2 The ratio of the elastomer to the matrix resin in the following area range is the average value in the first part.

11. The injection-molded article according to any one of claims 1 to 3, wherein, In the second part, in 10 2 μm 2 Above and 130 2 μm 2 The ratio of the elastomer to the matrix resin in the following area range is the maximum value in the second part.

12. The injection-molded article according to any one of claims 1 to 3, wherein, The first portion is located in a region more than 250 μm inward from the surface, and the second portion is located in a region more than 50 μm but less than 500 μm inward from the surface.

13. The injection-molded article according to any one of claims 1 to 3, further comprising a third portion between the second portion and the surface. in, In the third part, in 10 2 μm 2 Above and 130 2 μm 2 The ratio of the elastomer to the matrix resin in the following area range is lower than that in the first portion at 10. 2 μm 2 Above and 130 2 μm 2 The ratio of the elastomer to the matrix resin in the following area range.

14. The injection-molded article according to claim 13, wherein, The third part is located in a region less than 50 μm inward from the surface.

15. The injection-molded article according to any one of claims 1 to 3, wherein, The matrix resin is polyester.

16. The injection-molded article according to any one of claims 1 to 3, wherein, The elastomer is an acrylic elastomer.

17. The injection-molded article according to any one of claims 1 to 3, wherein, The melting point of the elastomer is lower than the glass transition point or melting point of the matrix resin.

18. The injection-molded article according to any one of claims 1 to 3 further comprises filler particles dispersed in the matrix resin, said filler particles having inorganic material as a main component.

19. An apparatus comprising: A component made of an injection-molded body according to any one of claims 1 to 3; and At least one of electrical components, metal components, and optical components.

20. The apparatus according to claim 19, wherein, The component is an external body.

21. A method for manufacturing an injection-molded article, comprising: A mixture of granules of a first resin composition obtained by dispersing first elastomer particles in a matrix resin and granules of a second resin composition obtained by dispersing second elastomer particles in a matrix resin is injection molded. Wherein, the difference between the average particle diameter of the first elastomer particle and the average particle diameter of the second elastomer particle is greater than 0.8 μm.

22. The method for manufacturing an injection-molded article according to claim 21, wherein, The average particle diameter of the first elastomer particle is more than twice the average particle diameter of the second elastomer particle.

23. The method for manufacturing an injection-molded article according to claim 21 or 22, wherein, The average particle diameter of the first elastomer particle is greater than 1.5 μm, and the average particle diameter of the second elastomer particle is less than 1.5 μm.

24. The method for manufacturing an injection-molded article according to claim 21 or 22, further comprising manufacturing a first resin composition, in, The first resin composition is manufactured by melting and mixing a matrix resin and an elastomer material and dispersing the first elastomer particles in the matrix resin.

Images