JP7097201B2 - Composites, methods for producing composites, thermoplastic resin compositions and molded products - Google Patents

Description

The present invention relates to a composite, a method for producing the composite, a thermoplastic resin composition, and a molded product.

Surface-treated silica particles may be used as a filler for the resin. For example, Patent Document 1 discloses a silica particle material having a specific functional group, and a filler-containing composition containing the silica particle material and a resin material and / or a resin material precursor. Patent Document 2 discloses an additive composition containing a sorbitol acetal compound and a silica component having specific physical characteristics.

Japanese Patent Application Laid-Open No. 2015-038036 Special Table 2009-507982 Gazette

An object of the present invention is to provide a silica particle-containing additive useful for crystalline thermoplastic resins.

As a result of diligent studies by the present inventors, when a composite in which a silica particle material having a specific structure is attached to the surface of a nucleating agent is applied to a thermoplastic resin composition, a molded product having high transparency can be obtained. And completed the present invention.
According to the present invention, the following complexes and the like are provided.
1. 1. With a nucleating agent,
The silica particles include a functional group represented by the following formula (1) and a silica particle material in which a functional group represented by the following formula (2) is bonded.
A complex in which the silica particle material is attached to the surface of the nucleating agent.
-OSI (X ¹ ) (X ² ) (X ³ ) ... (1)
-OSI (Y ¹ ) (Y ² ) (Y ³ ) ... (2)
(In the formula (1), X ¹ is a phenyl group, a vinyl group, an epoxy group, a methacrylic group, an amino group, a ureido group, a mercapto group, an isocyanate group or an acrylic group. X ² and X ³ are independent of each other. , -OSi (R) ₃ or -OSi (Y ⁴ ) (Y ⁵ ) (Y ⁶ ).
In equation (2), Y ¹ is R. Y ² and Y ³ are independently R or -OSi (Y ⁴ ) (Y ⁵ ) (Y ⁶ ).
Y ⁴ is R. Y ⁵ and Y ⁶ are independently R or -OSi (R) ₃ . R is an alkyl group having 1 to 3 carbon atoms independently. When a plurality of Y ^4s exist, the plurality of Y ^4s may be the same or different. When a plurality of Y ^5s exist, the plurality of Y ^5s may be the same or different. When there are a plurality of Y ^6s , the plurality of Y ^6s may be the same or different.
Any of X ² , X ³ , Y ² , Y ³ , Y ⁵ and Y ⁶ via -O- with any of adjacent X ² , X ³ , Y ² , Y ³ , Y ⁵ and Y ⁶ . May be combined. )
2. 2. 2. The complex according to 1, wherein the content of the silica particle material is 1 to 100 parts by mass with respect to 100 parts by mass of the nucleating agent.
A thermoplastic resin composition comprising the composite according to 3.1 or 2 and a crystalline thermoplastic resin.
4. 3. The thermoplastic resin composition according to 3, wherein the content of the composite is 0.01 to 400 parts by mass with respect to 100 parts by mass of the crystalline thermoplastic resin.
5. 3. The thermoplastic resin composition according to 3 or 4, wherein the crystalline thermoplastic resin is polypropylene.
A molded product produced by using the thermoplastic resin composition according to any one of 6.3 to 5.
7. 1 or 2 including a step of surface-treating silica particles with a silane coupling agent and organosilazane in a liquid medium containing water to produce a silica particle material, and a step of mixing the silica particle material and a nucleating agent. The method for producing a complex according to.

According to the present invention, it is possible to provide a silica particle-containing additive useful for a crystalline thermoplastic resin.

[Complex]
The composite according to one aspect of the present invention contains a nucleating agent and a silica particle material in which a functional group represented by the formula (1) and a functional group represented by the formula (2) are bonded to the silica particles. It has a structure in which the silica particle material is attached to the surface of the nucleating agent.
The functional groups represented by the formulas (1) and (2) will be described later.

By "adhering" the silica particle material to the surface of the nucleating agent, it means that at least a part of the surface of the nucleating agent is covered with the silica particle material. As will be described later, by stirring and mixing the nucleating agent and the silica particle material, a composite in which the silica particle material is attached to the surface of the nucleating agent can be obtained.

Since the complex of the present invention has a structure in which a specific silica particle material is attached to the surface of the nucleating agent, the dispersibility of the complex (nucleating agent) in the thermoplastic resin composition can be greatly improved, and the nucleation can be achieved. The effect of adding the agent can be increased. This makes it possible to manufacture a highly transparent molded product.
Hereinafter, each component will be described. In this specification, "x to y" represents a numerical range of "x or more and y or less".

(Nucleating agent)
The nucleating agent is an additive that is directly involved in the crystallization process of the crystalline thermoplastic resin. The addition of the nucleating agent promotes the crystallization of polymer chains from the molten state of the resin and increases the crystallization rate of the material as a whole, resulting in improved productivity during molding, improved mechanical properties, and It is expected that the transparency of the molded product will be improved by refining the crystal structure.

Examples of the nucleating agent include an organic nucleating agent and an inorganic nucleating agent.
Examples of the organic nucleating agent include a dispersed nucleating agent and a dissolving type nucleating agent.

Examples of the dispersed type nucleating agent include a phosphate ester metal salt-based nucleating agent, a carboxylic acid metal salt-based nucleating agent, and a rosin metal salt-based nucleating agent.

Examples of the phosphoric acid ester metal salt-based nucleating agent include phosphoric acid-2,2'-methylenebis (4,6-di-tert-butylphenyl) sodium and aluminum hydroxybis [2,2'-methylenebis (4,). 6-di-tert-butylphenyl) phosphate], phosphoric acid-2,2'-methylenebis (4,6-di-tert-butylphenyl) lithium and the like can be mentioned.
Phosphoric acid ester metal salt-based nucleating agents are commercially available, for example, as "ADEKA STAB NA-11" and "ADEKA STAB NA-21" manufactured by ADEKA Corporation.

Examples of the carboxylic acid metal salt-based nucleating agent include benzoic acid metal salt-based nucleating agents, and specific examples thereof include sodium benzoate, lithium benzoate, and di-p-tert-butyl hydroxyaluminum benzoate (AL). -PTBBA) and the like.
The carboxylic acid metal salt-based nucleating agent is commercially available, for example, as "AL-PTBBA" manufactured by Japan Chemtech Co., Ltd.

Examples of the rosin metal salt-based nucleating agent include magnesium dehydroabietic acid, calcium dehydroabietic acid, and alkali metal salts of dehydroabietic acid.
The rosin metal salt-based nucleating agent is commercially available, for example, as "Pine Crystal KM-1500", "Pine Crystal KM-1300", "Pine Crystal KR-50M" manufactured by Arakawa Chemical Industry Co., Ltd.

Examples of the dissolution-type nucleating agent include a sorbitol-based nucleating agent, a nonitol-based nucleating agent, a xylitol-based nucleating agent, an amide-based nucleating agent, and the like.

Examples of the sorbitol-based nucleating agent include dibenzylidene sorbitol and the like, for example, 1,3: 2,4-bis-O- (benzylidene) sorbitol, 1,3: 2,4-bis-O- (4-). Examples thereof include methylbenzylidene) sorbitol and bis (3,4-dimethylbenzylidene) sorbitol.
The sorbitol-based nucleating agent is commercially available, for example, as "Gelol D" and "Gelall MD" manufactured by Shin Nihon Rika Co., Ltd.

Examples of the nonitol-based nucleating agent include (1,2,3-trideoxy-4,6: 5,7-bis-[(4-propylphenyl) methylene] -nonitol.
The nonitol-based nucleating agent is commercially available, for example, as "Milllad NX8000" manufactured by Milliken & Company.

Examples of the xylitol-based nucleating agent include bis-1,3: 2,4- (5', 6', 7', 8'-tetrahydro-2-naphthaldehydebenzylidene) 1-allylxylitol and bis-1,3. : 2,4- (3', 4'-dimethylbenzylidene) 1-propylxylitol and the like can be mentioned.

Examples of the amide-based nucleating agent include (N, N', N "-tris [2-methylcyclohexane-1-yl] -propane-1,2,3-triylcarboxamide).
The amide-based nucleating agent is commercially available, for example, as "Irgacreal XT386" manufactured by BASF.

Examples of the inorganic nucleating agent include silicate compounds such as talc and silica, and metal oxides such as magnesium oxide.

(Silica particle material)
The silica particle material used in one aspect of the present invention has a structure in which a functional group represented by the formula (1) and a functional group represented by the formula (2) are bonded to the silica particles.
-OSI (X ¹ ) (X ² ) (X ³ ) ... (1)
-OSI (Y ¹ ) (Y ² ) (Y ³ ) ... (2)
(In the formula (1), X ¹ is a phenyl group, a vinyl group, an epoxy group, a methacrylic group, an amino group, a ureido group, a mercapto group, an isocyanate group or an acrylic group. X ² and X ³ are independent of each other. , -OSi (R) ₃ or -OSi (Y ⁴ ) (Y ⁵ ) (Y ⁶ ).
In equation (2), Y ¹ is R. Y ² and Y ³ are independently R or -OSi (Y ⁴ ) (Y ⁵ ) (Y ⁶ ).
Y ⁴ is R. Y ⁵ and Y ⁶ are independently R or -OSi (R) ₃ . R is an alkyl group having 1 to 3 carbon atoms independently. When a plurality of Y ^4s exist, the plurality of Y ^4s may be the same or different. When a plurality of Y ^5s exist, the plurality of Y ^5s may be the same or different. When there are a plurality of Y ^6s , the plurality of Y ^6s may be the same or different.
Any of X ² , X ³ , Y ² , Y ³ , Y ⁵ and Y ⁶ via -O- with any of adjacent X ² , X ³ , Y ² , Y ³ , Y ⁵ and Y ⁶ . May be combined. )

When the functional group represented by the formula (1) and the functional group represented by the formula (2) are "bonded" to the silica particles, the hydroxyl group existing on the surface of the silica particles is represented by the formula (1). It means that it was substituted with a group and a functional group represented by the formula (2).
Hereinafter, the functional group represented by the formula (1) may be referred to as a "first functional group", and the functional group represented by the formula (2) may be referred to as a "second functional group".

One of the functions of the nucleating agent, the effect of improving the transparency by refining the crystal structure, is due to the action of increasing the crystal starting point in the crystallization process of the crystalline thermoplastic resin, and this action is due to the action of the nucleating agent. Affected by the dispersibility of.
When the silica particles and the nucleating agent are stirred and mixed at high speed in the gas phase, the miniaturization of the nucleating agent due to the impact force and the adhesion of the silica particles to the surface of the nucleating agent proceed in parallel. As a result, a composite in which the surface of the finely divided nucleating agent is coated with silica particles is obtained.

In one aspect of the present invention, by adopting a composite in which a silica particle material having a specific functional group is attached to a nucleating agent, the affinity for the crystalline thermoplastic resin is dramatically enhanced. As a result, reaggregation between the complexes is suppressed, and it becomes possible to significantly improve the dispersibility of the complex, that is, the nucleating agent, with respect to the crystalline thermoplastic resin.

Any of X ² , X ³ , Y ² , Y ³ , Y ⁵ , and Y ⁶ with any of the adjacent functional groups X ² , X ³ , Y ² , Y ³ , Y ⁵ , and Y ^6- . It may be bonded via O-.
For example, any of the ^first functional groups X2, X3 ^{, Y5} , and ^Y6 is the ^first functional group X2, X3 ^{, Y5} , and adjacent to this first functional group. It may be coupled to any of ^Y6 via —O—.
Similarly, one of the second functional groups Y ² , Y ³ , Y ⁵ and Y ⁶ is the second functional group Y ² , Y ³ , Y ⁵ adjacent to the second functional group. And any of ^Y6 may be coupled via —O—.
Furthermore, any of the first functional groups X ² , X ³ , Y ⁵ and Y ⁶ is the second functional group Y ² , Y ³ , Y ⁵ adjacent to the first functional group. And any of ^Y6 may be coupled via —O—.

The silica particle material used in one aspect of the present invention preferably has one or more characteristics selected from the group consisting of the following (a) to (e).
(A) Can be redispersed in methyl ethyl ketone.
(A) Silica particle material and methyl ethyl ketone are mixed in a ratio of silica particle material: methyl ethyl ketone = 1: 1 to 1: 4 (mass ratio) and stirred to prepare a dispersed sample, and the particle size distribution of the dispersed sample is adjusted. When measured with a distribution measuring device, no peak is seen at a position having a particle diameter of 100 nm or more.
(C) A silica particle material and a methyl ethyl ketone are mixed at a ratio of silica particle material: methyl ethyl ketone = 1: 1 to 1: 4 (mass ratio) and stirred to prepare a dispersed sample, and the dispersion sample has an oscillation frequency of 39 kHz. When the particle size distribution was measured by a particle size distribution measuring device after being irradiated with an ultrasonic wave having an output of 500 W for 10 minutes, no peak was observed at a position having a particle size of 100 nm or more.
(D) The electric conductivity of the extracted water obtained by immersing the silica particle material at 121 ° C. for 24 hours is 50 μS / cm or less.
(E) The average particle size is 3 to 200 nm, preferably 5 to 50 nm.

The more -OSiR ₃ contained in the first functional group and the second functional group, the more R (alkyl groups having 1 to 3 carbon atoms) on the surface of the silica particle material, and the more R, the more the silica particle material aggregates. It becomes difficult.
Since the silica particle material used in one embodiment of the present invention has a certain amount or more of R, it is difficult to aggregate. (A) to (C) indicate that the silica particle material is difficult to aggregate, and that even if the silica particle material is slightly aggregated, it can be dispersed again by ultrasonic treatment.
Further, since the silica particle material is hard to aggregate, it can be easily washed with water, which makes it possible to apply it as a material for electronic parts. (D) indicates this, and when it is used as a material for electronic parts, it is preferable to wash it with water until it has the electrical conductivity shown in (d).
Similarly, (e) is also a feature derived from the fact that the silica particle material is difficult to aggregate, and this property makes it possible to use a material having a small particle size.

The average particle size is 1 mm. 100 particles with a particle size of 1 nm to 1 μm in a ^square region are indiscriminately selected visually using photographs taken with an electronic microscope (“SU-70” manufactured by Hitachi High-Technologies Co., Ltd.). Then, a simple average (arithmetic average) of the particle sizes of the 100 particles is obtained and measured. The major axis is used as the particle size.

The number of X1 and R contained in the ^first functional group and the number of R contained in the second functional group depend on the abundance ^ratio of R and X1 and the particle size and application of the silica particle material. It may be set appropriately.

The silica particle material used in one embodiment of the present invention preferably has a ratio of abundance of the first functional group to the second functional group of 1:12 to 1:60. Within this range, since X ¹ and R are present on the surface of the silica particle material in a well-balanced manner, the affinity for the crystalline thermoplastic resin and the effect of suppressing aggregation are excellent.

The silica particle material used in one embodiment of the present invention preferably has 0.5 to 2.5 X1s ^per unit surface area (nm ² ) of the silica particle material. Within this range, a sufficient number of first functional groups are bonded to the surface of the silica particle material, and a sufficient number of Rs derived from the first functional group and the second functional group are also present. The affinity for the thermoplastic resin and the effect of suppressing the aggregation of the silica particle material are fully exhibited. The number of X1s ^per unit surface area (nm ² ) is measured by the method described in Examples.

The silica particle material used in one embodiment of the present invention preferably has 1 to 10 Rs per unit surface area (nm ² ) of the silica particle material. Within this range, the balance between the number of ^X1s and the number of Rs present on the surface of the silica particle material is good, and both the affinity for the crystalline thermoplastic resin and the aggregation suppressing effect of the silica particle material are balanced. It is well demonstrated.

The silica particle material used in one aspect of the present invention is preferably one in which all the hydroxyl groups existing on the surface of the silica particles are replaced with the first functional group and the second functional group. If the sum of the first functional group and the second functional group was 2.0 or more per unit surface area (nm ² ) of the silica particle material, it was present on the surface of the silica particles in the silica particle material. It can be said that almost all of the hydroxyl groups are substituted with the first functional group and the second functional group.

The content of the silica particle material is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the nucleating agent.
When the content of the silica particle material is 1 part by mass or more with respect to 100 parts by mass of the nucleating agent, the effect of improving the performance of the nucleating agent is sufficiently exhibited. If it is 100 parts by mass or less, it is excellent in economy.
The content of the silica particle material is preferably 1 to 30 parts by mass, and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the nucleating agent.

(Manufacturing method of silica particle material)
The silica particle material used in one aspect of the present invention is a step of surface-treating silica particles with a silane coupling agent (first silane coupling agent) and organosilazane in a liquid medium containing water (surface treatment step). It can be manufactured by a manufacturing method including.
The silane coupling agent includes a phenyl group, a vinyl group, an epoxy group, a methacrylic group, an amino group, a ureido group, a mercapto group, an isocyanate group, or an acrylic group (that is, ^a group corresponding to X1) and three alkoxy groups. A compound bonded to a silicon atom can be used.

By surface-treating with a silane coupling agent, the hydroxyl groups present on the surface of the silica particles are replaced with functional groups derived from the silane coupling agent. The functional group derived from the silane coupling agent is represented by, for example, the following formula (10).
-OSI (X ¹ ) (X ⁴ ) (X ⁵ ) ... (10)
(In formula (10), X ¹ is the same as X ¹ in formula (1). X ⁴ and X ⁵ are each independently an alkoxy group.)

Next, by surface-treating with organosilazane, the functional groups X4 and ^X5 represented by the formula (10) are derived from organosilazane ^- OSi (Y ¹ ) (Y ² ) (Y ³ ) ( It is substituted with a functional group represented by the formula (2): a second functional group).

Of the hydroxyl groups present on the surface of the silica particles, the remaining hydroxyl groups that are not substituted with the functional group derived from the silane coupling agent are substituted with the second functional group. Therefore, the first functional group and the second functional group are bonded to the surface of the silica particle material used in one aspect of the present invention.

The molar ratio of the silane coupling agent to the organosilazane is preferably silane coupling agent: organosilazane = 1: 2 to 1:10. In this case, the abundance ratio of the first functional group and the second functional group in the obtained silica particle material is theoretically 1:12 to 1:60.

As a surface treatment method, a method of simultaneously surface-treating with a silane coupling agent and organosilazane; a method of surface-treating with a silane coupling agent and then surface-treating with organosilazane; a method of surface-treating with organosilazane, and then silane. Examples thereof include a method of surface-treating with a coupling agent and then surface-treating with organosilazane, and any of them may be used.
In either method, the amount of organosilazane may be adjusted so that all the hydroxyl groups present on the surface of the silica particles are not replaced by the second functional group.

It is preferable that X ⁴ and X ⁵ of the functional groups represented by the formula (10) are all substituted with the second functional group.

A portion of organosilazane may be replaced with a second silane coupling agent. As the second silane coupling agent, a compound having three alkoxy groups and one alkyl group can be used. In this case, X ⁴ and X ⁵ contained in the functional group represented by the formula (10) are replaced with the functional group derived from the second silane coupling agent. The functional group derived from the second silane coupling agent is represented by, for example, the following formula (11).
-OSI (Y ¹ ) (X ⁶ ) (X ⁷ ) ... (11)
(In formula (11), Y ¹ is the same (R) as Y ¹ in the second functional group. X ⁶ and X ⁷ are independently alkoxy groups or hydroxyl groups, respectively.)

X ⁶ and X ⁷ contained in the functional group represented by the formula (11) are replaced with a second functional group derived from organosilazane, or are other functional groups represented by the formula (11). Will be replaced. In this case, the amount of R present on the surface of the silica particle material can be further increased.
When a part of organosilazane is replaced with a second silane coupling agent, it is usually surface-treated with the second silane coupling agent and then surface-treated with organosilazane again. This is because X ⁶ and X ⁷ contained in the functional group represented by the formula (11) are finally replaced with a second functional group derived from organosilazane.

When a part of organosilazane is replaced with a second silane coupling agent, X ⁴ and X ⁵ contained in the first functional group are replaced with a second functional group derived from organosilazane, or a second. It is substituted with the functional group represented by the formula (11) derived from the silane coupling agent of. When X ⁴ and X ⁵ are substituted with the functional group represented by the formula (11), X ⁶ and X ⁷ contained in the functional group represented by the formula (11) are substituted with the second functional group. Or, it is replaced by another functional group represented by the formula (11). When X ⁶ and X ⁷ contained in the functional group represented by the formula (11) are substituted with another functional group represented by the formula (11), they are contained in the functional group represented by the formula (11). X ⁶ and X ⁷ are substituted with a second functional group. Therefore, the second silane coupling agent is set when the surface is treated only with the first silane coupling agent and organosilazane (when the organosilazane is not replaced with the second silane coupling agent). A maximum of 5a / 3mol can be replaced with respect to the amount (a) mol of silane. The amount of organosilazane required in this case is 8a / 3mol.

The alkoxy group contained in the first silane coupling agent and the second silane coupling agent is not particularly limited, but those having a small number of carbon atoms are preferable, and those having 1 to 12 carbon atoms are preferable. Considering the hydrolyzability of the alkoxy group, a methoxy group, an ethoxy group, a propoxy group or a butoxy group is preferable.

Specific examples of the first silane coupling agent include phenyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropyl. Trimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N- Examples thereof include phenyl-3-aminopropyltrimethoxysilane.

The organosilazane may be any as long as it can replace the hydroxyl group existing on the surface of the silica particles and the alkoxy group derived from the silane coupling agent with the above-mentioned second functional group, but it is preferable to use one having a small molecular weight. .. Specific examples thereof include tetramethyldisilazane, hexamethyldisilazane, and pentamethyldisilazane.

Examples of the second silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, and hexyltriethoxysilane.

In the surface treatment step, a polymerization inhibitor may be added in order to suppress the polymerization of the first silane coupling agent and the polymerization of the second silane coupling agent. As the polymerization inhibitor, general ones such as 3,5-dibutyl-4-hydroxytoluene (BHT) and p-methoxyphenol (methoquinone) can be used.

In the method for producing a silica particle material described above, a solidification step may be provided after the surface treatment step. The solidification step is a step of precipitating the surface-treated silica particle material with mineral acid, washing and drying the precipitate with water to obtain a solid material of the silica particle material.

Examples of the mineral acid include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and the like, and hydrochloric acid is preferable. Mineral acid may be used as it is, but it is preferably used as an aqueous solution of mineral acid. The concentration of mineral acid in the aqueous solution of mineral acid is preferably 0.1% by mass or more, more preferably 0.5% by mass or more. The amount of the mineral acid aqueous solution can be increased to about 6 to 12 times based on the mass of the silica particle material to be washed.

Then, the silica particle material washed and suspended is collected by filtration and washed with water. It is desirable that the water used does not contain ions such as alkali metals (for example, 1 ppm or less on a mass basis). For example, ion-exchanged water, distilled water, pure water, and the like.
The silica particle material can be dried by a conventional method. For example, it may be heated or left under reduced pressure (vacuum).
By removing water, the silica particle material can be mixed or dispersed in the mixed material.

(Manufacturing method of complex)
The complex according to one aspect of the present invention can be produced by mixing the above-mentioned nucleating agent and silica particle material. The mixing method is not particularly limited, but for example, it is carried out by a powder mixer equipped with a chopper (for example, manufactured by Dalton Corporation).
By mixing the nucleating agent and the silica particle material, a complex in which at least a part of the surface of the nucleating agent is coated with the silica particle material can be obtained.

For example, 70% by mass or more, 80% by mass or more, 90% by mass or more, 98% by mass or more, 99% by mass or more, 99.9% by mass or more or 100% by mass of the composite according to one aspect of the present invention. The above-mentioned nucleating agent and silica particle material may be used.
The complex according to one aspect of the present invention may essentially consist of the nucleating agent and silica particle material described above. In this case, unavoidable impurities may be contained.

[Thermoplastic resin composition]
The thermoplastic resin composition according to one aspect of the present invention contains the above-mentioned composite and a crystalline thermoplastic resin.
Examples of the crystalline thermoplastic resin include polypropylene resin (PP), polyethylene resin (PE), polyamide resin (PA), polyacetal resin (POM), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polytrimethylene. Examples thereof include fluororesins such as terephthalate (PTT), lactic acid resin (PLA), polyphenylene sulfide (PPS), polyether ether ketone (PEEK) and PTFE, and liquid crystal polymers (LCP), and polypropylene is preferable. The polypropylene is not particularly limited, and polypropylene of various commercially available copolymer species, catalyst species and the like can be used.

Polypropylene preferably has a melt flow rate (MFR) of 0.1 to 200 g / 10 minutes at 230 ° C. and a load of 2.16 kg from the viewpoint of obtaining a resin composition that is lightweight and has excellent moldability. Further, from the viewpoint of obtaining a molded product having excellent rigidity and impact resistance, it is more preferable that the melt flow rate at 230 ° C. and a load of 2.16 kg is 0.1 to 50 g / 10 minutes. The melt flow rate is measured by a method according to ASTM standard D1238.

The shape of the crystalline thermoplastic resin is not particularly limited, and may be in the form of pellets, powder, slurry, or the like.

The content of the composite in the thermoplastic resin composition is preferably 0.01 to 400 parts by mass, more preferably 0.1 to 100 parts by mass, and more preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the crystalline thermoplastic resin. It is preferably 0.1 to 10 parts by mass.
When the content of the complex is 0.01 or more, the effect of adding the complex is sufficiently exhibited.

If necessary, additives such as known heat stabilizers, light stabilizers, processability improvers, and colorants may be added to the thermoplastic resin composition.

The thermoplastic resin composition according to one aspect of the present invention, for example, 70% by mass or more, 80% by mass or more, 90% by mass or more, 98% by mass or more, 99% by mass or more, 99.9% by mass or more or 100% by mass. % May be the above-mentioned composite and crystalline thermoplastic resin.
The thermoplastic resin composition according to one aspect of the present invention may essentially consist of the above-mentioned composite and crystalline thermoplastic resin. In this case, unavoidable impurities may be contained.

The thermoplastic resin composition according to one aspect of the present invention can be produced by melt-mixing the above-mentioned composite and the crystalline thermoplastic resin. The melting and mixing method is not particularly limited, and it can be carried out using a mixer, a roll, a kneader or the like.

[Molded product]
A molded product can be produced using the thermoplastic resin composition according to one aspect of the present invention. The shape of the molded product is not particularly limited. The molding method is not particularly limited, and known methods such as extrusion molding, pressing, casting, and calendar roll can be used.

The fields of use of the obtained molded body are not particularly limited, and for example, as automobile parts, exterior parts such as bumpers, cowl tops and weather strips, instrument panels, meter clusters, door trims, luggage boards, HVAC units and other interior parts. , Engine parts such as air cleaner elements, etc., and home appliance parts include refrigerators and freezers, rice cookers, microwave ovens, washing machines, personal computers, air conditioners, outdoor units for air conditioners, hot water washing toilet seats, TV receivers, etc. Examples include housings and various parts, as well as OA equipment parts such as housings for printer compound machines and various parts such as bearings, acoustic parts such as speaker housings, speaker frames, and vibration plates, and electrical equipment parts such as clamp covers. , Bathroom counters, building materials such as kitchen panels, medical materials utilizing biocompatibility, etc. can be used for various purposes.

Example 1
[Manufacturing of complex]
1. 1. Preparation of silica particle material The silica particle material was produced by the following method.
(1) Surface treatment process (preparation process: preparation of dispersion)
Add 60 parts by mass of isopropanol to 100 parts by mass of colloidal silica ("Snowtex OS" manufactured by Nissan Chemical Industry Co., Ltd., average particle size 10 nm, slurry in which silica particles are dispersed in water, solid content concentration 20% by mass), and room temperature (about). Mixing at 25 ° C.) gave a dispersion in which silica particles were dispersed in a liquid medium.

(First step: Surface treatment with phenyltrimethoxysilane)
To the obtained dispersion, 1.8 parts by mass of phenyltrimethoxysilane (silane coupling agent, "KBM-103" manufactured by Shin-Etsu Chemical Co., Ltd.) was added to 100 parts by mass of colloidal silica, and 72 at 40 ° C. Time mixed. As a result, the hydroxyl groups present on the surface of the silica particles were surface-treated with a silane coupling agent.
The amount of phenyltrimethoxysilane was set so that the amount of hydroxyl groups required in the second step described later remained (1.8 parts by mass with respect to 100 parts by mass of colloidal silica).

(Second step: Surface treatment with hexamethyldisilazane)
Hexamethyldisilazane (“HDMS-1” manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the mixed solution after the first step by 3.7 parts by mass with respect to 100 parts by mass of colloidal silica, and left at 40 ° C. for 72 hours. .. With the progress of the surface treatment, the hydrophobic silica particles could not exist stably in water and isopropanol, and aggregated and precipitated. The molar ratio of phenyltrimethoxysilane to hexamethyldisilazane was 2: 5.

(2) Solidification Step After the second step, 5 parts by mass of 35% hydrochloric acid was added to precipitate the silica particle material, and the precipitate was filtered through a filter paper (“5A” manufactured by Advantech). The filtration residue (solid content) was washed with pure water and then vacuum dried at 100 ° C. to obtain silica particle material 1.

For the obtained silica particle material, the number of X ¹ (group represented by X ¹ in the formula (1)) per unit surface area (nm ² ) was measured. The number of X ¹ present was calculated based on the carbon content of the silica particle material. Specifically, the silica particles after the first step were washed with water, centrifuged, and then dried to obtain a silica particle sample treated with a silane coupling agent. The carbon content of this sample was measured using an organic carbon measuring device, and the X1 ^number was calculated based on the measured value. As a result, the ^number of X1 was about 1.2 / nm ² .

2. 2. Preparation of composite A powder mixer equipped with a chopper (mass ratio) of nucleating agent 1 ("Milllad NX8000" manufactured by Millaken & Company, nonitol-based nucleating agent) and silica particle material 1 at a ratio of 10: 1. (Manufactured by Dalton Corporation) was mixed to obtain complex 1.

[Manufacturing of thermoplastic resin composition]
Composite 1 and crystalline thermoplastic resin (crystalline thermoplastic resin 1, "Prime Polypro J137G" manufactured by Prime Polymer Co., Ltd., homopolypropylene, MFR = 30 g / 10 minutes) using a biaxial continuous extruder 1: A thermoplastic resin composition was prepared by heating, melting and mixing at a ratio of 100 (mass ratio).

[Manufacturing and evaluation of molded products]
The obtained thermoplastic resin composition was injection-molded to prepare a plate (molded body) having a thickness of 1 mm. The haze (turbidity) of the obtained plate was measured with a spectrophotometer "V-650" (manufactured by JASCO Corporation). The results are shown in Table 1.

Comparative Example 1
Comparative silica particles 1 (“Aerosil® R974” manufactured by Nippon Aerosil Co., Ltd., fumed hydrophobic submicron particle size silica, silica particles having only a dimethylsilyl group as a functional group on the surface of the silica particles) instead of the silica particle material 1. ) Was used, and the composite (comparative composite 1), the thermoplastic resin composition, and the molded product were produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2
A thermoplastic resin composition and a molded product were produced and evaluated in the same manner as in Example 1 except that the nucleating agent 1 was used as it was instead of the complex 1. The results are shown in Table 1.

Example 2
Complex (complex 2), thermoplastic, except that nucleating agent 2 (“Gelall MD” manufactured by Shin Nihon Rika Co., Ltd., sorbitol-based nucleating agent) was used as the nucleating agent in the same manner as in Example 1. The resin composition and the molded product were produced and evaluated. The results are shown in Table 2.

Comparative Example 3
A composite (comparative composite 2), a thermoplastic resin composition, and a molded product were produced and evaluated in the same manner as in Example 2, except that the comparative silica particles 1 were used instead of the silica particle material 1. The results are shown in Table 2.

Comparative Example 4
A thermoplastic resin composition and a molded product were produced and evaluated in the same manner as in Example 2 except that the nucleating agent 2 was used as it was instead of the complex 2. The results are shown in Table 2.

Example 3
A complex (complex 3) was used in the same manner as in Example 1 except that the nucleating agent 3 (“AL-PTBBA” manufactured by Japan Chemtech Co., Ltd., a carboxylic acid metal salt-based nucleating agent) was used. ), The thermoplastic resin composition and the molded product were produced and evaluated. The results are shown in Table 3.

Comparative Example 5
A composite (comparative composite 3), a thermoplastic resin composition, and a molded product were produced and evaluated in the same manner as in Example 3 except that the comparative silica particles 1 were used instead of the silica particle material 1. The results are shown in Table 3.

Comparative Example 6
A thermoplastic resin composition and a molded product were produced and evaluated in the same manner as in Example 3 except that the nucleating agent 3 was used as it was instead of the complex 3. The results are shown in Table 3.

Example 4
A complex (complex 4) was used in the same manner as in Example 1 except that the nucleating agent 4 (“Adecastab NA-11” manufactured by ADEKA Co., Ltd., a phosphate ester metal salt-based nucleating agent) was used. ), The thermoplastic resin composition and the molded product were produced and evaluated. The results are shown in Table 4.

Comparative Example 7
A composite (comparative composite 4), a thermoplastic resin composition, and a molded product were produced and evaluated in the same manner as in Example 4, except that the comparative silica particles 1 were used instead of the silica particle material 1. The results are shown in Table 4.

Comparative Example 8
A thermoplastic resin composition and a molded product were produced and evaluated in the same manner as in Example 4 except that the nucleating agent 4 was used as it was instead of the composite 4. The results are shown in Table 4.

Example 5
A complex (complex 5) was used in the same manner as in Example 1 except that the nucleating agent 5 (“Adecastab NA-21” manufactured by ADEKA Co., Ltd., a phosphoric acid ester metal salt-based nucleating agent) was used. ), The thermoplastic resin composition and the molded product were produced and evaluated. The results are shown in Table 5.

Comparative Example 9
A composite (composite 5), a thermoplastic resin composition, and a molded product were produced and evaluated in the same manner as in Example 5, except that the comparative silica particles 1 were used instead of the silica particle material 1. The results are shown in Table 5.

Comparative Example 10
A thermoplastic resin composition and a molded product were produced and evaluated in the same manner as in Example 5 except that the nucleating agent 5 was used as it was instead of the composite 5. The results are shown in Table 5.

From Tables 1 to 5, it can be seen that the haze of the molded product can be reduced and the transparency can be improved by using the composite of the present invention in which the silica particle material having a specific structure is attached to the nucleating agent.

Claims (7)

One or more nucleating agents selected from the group consisting of organic nucleating agents and magnesium oxide , and
The silica particles include a functional group represented by the following formula (1) and a silica particle material in which a functional group represented by the following formula (2) is bonded.
A complex in which the silica particle material is attached to the surface of the nucleating agent.
-OSI (X ¹ ) (X ² ) (X ³ ) ... (1)
-OSI (Y ¹ ) (Y ² ) (Y ³ ) ... (2)
(In formula (1), X ¹ is a phenyl group. X ² and X ³ are independently -OSI (R) ₃ or -OSi (Y ⁴ ) (Y ⁵ ) (Y ⁶ ). ..
In equation (2), Y ¹ is R. Y ² and Y ³ are independently R or -OSi (Y ⁴ ) (Y ⁵ ) (Y ⁶ ).
Y ⁴ is R. Y ⁵ and Y ⁶ are independently R or -OSi (R) ₃ . R is an alkyl group having 1 to 3 carbon atoms independently. When a plurality of Y ^4s exist, the plurality of Y ^4s may be the same or different. When a plurality of Y ^5s exist, the plurality of Y ^5s may be the same or different. When there are a plurality of Y ^6s , the plurality of Y ^6s may be the same or different.
Any of X ² , X ³ , Y ² , Y ³ , Y ⁵ and Y ⁶ via -O- with any of adjacent X ² , X ³ , Y ² , Y ³ , Y ⁵ and Y ⁶ . May be combined. ) The complex according to claim 1, wherein the content of the silica particle material is 1 to 100 parts by mass with respect to 100 parts by mass of the nucleating agent. A thermoplastic resin composition comprising the composite according to claim 1 or 2 and a crystalline thermoplastic resin. The thermoplastic resin composition according to claim 3, wherein the content of the composite is 0.01 to 400 parts by mass with respect to 100 parts by mass of the crystalline thermoplastic resin. The thermoplastic resin composition according to claim 3 or 4, wherein the crystalline thermoplastic resin is polypropylene. A molded product produced by using the thermoplastic resin composition according to any one of claims 3 to 5. Claim 1 includes a step of surface-treating silica particles with a silane coupling agent and organosilazane in a liquid medium containing water to produce a silica particle material, and a step of mixing the silica particle material and a nucleating agent. Or the method for producing a complex according to 2.