Resin composition
阅读说明：本技术 树脂组合物 (Resin composition ) 是由 小西翔太 安东博幸 于 2019-07-23 设计创作，主要内容包括：本申请提供一种树脂组合物,所述树脂组合物含有热塑性树脂(A),其中,仅以上述树脂组合物作为原料并且通过注射成型而得到的厚度为3mm的平板满足全部下述式1～式3：(式1)x<8、(式2)y<12、(式3)y<12x~(-0.75)[式中,x为在钢丝棉擦伤试验前按照JIS K 7136测定的上述平板的初始雾度(％),y为在钢丝棉擦伤试验后按照JIS K 7136测定的上述平板的雾度(％)相对于上述初始雾度(％)的变化量。上述钢丝棉擦伤试验是将#0000的钢丝棉以14kPa的压力按压在上述平板表面上并沿与钢丝棉的纤维方向垂直的方向以15cm/秒的速度往复摩擦11次的试验]。(The present application provides a resin composition containing a thermoplastic resin (a), wherein a flat plate having a thickness of 3mm obtained by injection molding using only the above resin composition as a raw material satisfies all of the following formulae 1 to 3: (formula 1) x<8. (formula 2) y<12. (formula 3) y<12x ‑0.75 [ wherein x is the initial haze (%) of the flat plate measured in accordance with JIS K7136 before the steel wool galling test, and y is the initial haze (%) of the flat plate measured in accordance with JIS K7136 after the steel wool galling testAmount of change in haze (%) from the above initial haze (%). The steel wool scratch test was conducted by pressing #0000 steel wool against the surface of the plate at a pressure of 14kPa and rubbing the steel wool back and forth 11 times at a speed of 15 cm/sec in a direction perpendicular to the fiber direction of the steel wool]。)
1. A resin composition comprising a thermoplastic resin (A) wherein,
a flat plate having a thickness of 3mm obtained by injection molding using only the resin composition as a raw material satisfies all of the following formulae 1 to 3:
(formula 1) x <8
(formula 2) y <12
(formula 3) y<12x-0.75
[ wherein x is the initial haze (%) of the flat sheet measured according to JIS K7136 before the steel wool scratch test,
y is the amount of change in haze (%) of the flat sheet relative to the initial haze (%) after the steel wool scratch test, measured in accordance with JIS K7136,
the steel wool scratch test is a test in which steel wool of #0000 is pressed against the surface of the flat plate with a pressure of 14kPa and rubbed reciprocally at a speed of 15 cm/sec in a direction perpendicular to a fiber direction of the steel wool 11 times ].
2. The resin composition according to claim 1, wherein the resin composition comprises a thermoplastic resin (A) and silica composite oxide particles (B).
3. The resin composition according to claim 2, wherein the content of the silica composite oxide particles (B) in the resin composition is 0.001 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin (A).
4. The resin composition according to claim 2 or 3, wherein when the silica composite oxide particles (B) and the thermoplastic resin (A) are each irradiated with light having a wavelength of 589nm at 25 ℃, the difference in refractive index between the silica composite oxide particles (B) and the thermoplastic resin (A) is 0.03 or less.
5. The resin composition according to any one of claims 2 to 4, wherein the silica composite oxide is a silica-titania composite oxide, a silica-zirconia composite oxide, or a silica-alumina composite oxide.
6. The resin composition according to any one of claims 1 to 5, wherein the thermoplastic resin (A) is a methacrylic resin.
7. The resin composition according to any one of claims 2 to 6, wherein,
the thermoplastic resin (A) is a methacrylic resin containing 85 to 100 mass% of a monomer unit derived from methyl methacrylate,
the silica composite oxide is a silica-titania composite oxide containing 0.01 to 10 mol% of titanium atoms based on 100 mol% of all atoms of the silica composite oxide, and
the content of the silica-titania composite oxide in the resin composition is 0.01 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the methacrylic resin.
8. The resin composition according to any one of claims 2 to 6, wherein,
the thermoplastic resin (A) is a methacrylic resin containing 85 to 100 mass% of a monomer unit derived from methyl methacrylate,
the silica composite oxide is a silica-zirconia composite oxide containing 0.01 to 10 mol% of zirconium atoms based on 100 mol% of all atoms of the silica composite oxide, and
the content of the silica-zirconia composite oxide in the resin composition is 0.01 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the methacrylic resin.
9. The resin composition according to any one of claims 2 to 8, wherein the silica composite oxide particles (B) in the resin composition do not include an image in which a circle having a diameter of 10nm is completely contained in at least one of 10 images obtained by imaging the silica composite oxide particles (B) in a field of view of 310nm x 310nm using TEM-EDX.
10. The resin composition according to any one of claims 2 to 7 and claim 9,
a part or all of the silica composite oxide particles (B) in the resin composition are silica-titania composite oxides, and
the silica-titania composite oxide in the resin composition has an absorption intensity of 0.5 or more in an XAFS spectrum of a K absorption edge of Ti,
here, the absorption intensity is an absorption intensity at an incident X-ray energy of 4967.5eV when normalized with an absorption intensity at an incident X-ray energy of 5128.0eV being 1.0.
11. A resin composition comprising a thermoplastic resin (A) and silica composite oxide particles (B),
the content of the silica composite oxide particles (B) in the resin composition is 0.001 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin (A), and
the difference in refractive index between the silica composite oxide particles (B) and the thermoplastic resin (A) at a wavelength of 589nm, measured at 25 ℃, is 0.03 or less.
12. A molded article comprising the resin composition according to any one of claims 1 to 11.
13. A laminate, the laminate comprising:
a layer comprising the resin composition according to any one of claims 1 to 10, and
a layer containing a thermoplastic resin (C),
wherein the content of the first and second substances,
a flat plate having a thickness of 3mm obtained by injection molding using only the thermoplastic resin (C) as a raw material satisfies the following formula 1':
(formula 1') x.ltoreq.2, and
the flat plate does not satisfy at least any one of the following formulas 2 to 3,
(formula 2) y <12
(formula 3) y<12x-0.75
[ wherein x is the initial haze (%) of the flat sheet measured according to JIS K7136 before the steel wool scratch test,
y is the amount of change in haze (%) of the flat sheet relative to the initial haze (%) after the steel wool scratch test, measured in accordance with JIS K7136,
the steel wool scratch test is a test in which steel wool of #0000 is pressed against the surface of the flat plate with a pressure of 14kPa and rubbed reciprocally at a speed of 15 cm/sec in a direction perpendicular to a fiber direction of the steel wool 11 times ].
14. A laminate, the laminate comprising:
a layer comprising the resin composition of claim 11, and
a layer containing a thermoplastic resin (C),
wherein the content of the first and second substances,
a flat plate having a thickness of 3mm obtained by injection molding using only the thermoplastic resin (C) as a raw material satisfies the following formula 1':
(formula 1') x.ltoreq.2
[ wherein x is the initial haze (%) of the flat sheet measured according to JIS K7136 before the steel wool scratch test ], and
the content of the silica composite oxide particles (B) in the layer containing the thermoplastic resin (C) is less than 0.001 parts by mass with respect to 100 parts by mass of the thermoplastic resin (C).
Technical Field
The present disclosure relates to a resin composition.
Background
Thermoplastic resins can have excellent transparency, mechanical properties, and molding processability, and thus are used for various purposes.
The thermoplastic resin is mixed with other components according to the use and used as a thermoplastic resin composition. For example, patent document 1 discloses a transparent thermoplastic resin composition obtained by mixing a transparent thermoplastic resin with silica flakes containing titanium dioxide particles dispersed therein.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2006-342211
Disclosure of Invention
Problems to be solved by the invention
The thermoplastic resin composition is required to have both transparency and scratch resistance depending on the application, for example, when used for vehicle members such as vehicle headlamps. However, the thermoplastic resin composition described in patent document 1 is not sufficient from the viewpoint of having both transparency and scratch resistance.
Accordingly, an object of the present disclosure is to provide a resin composition having excellent transparency and scratch resistance.
Means for solving the problems
The present disclosure includes the following means.
[1] A resin composition comprising a thermoplastic resin (A) wherein,
a flat plate having a thickness of 3mm obtained by injection molding using only the above resin composition as a raw material satisfies all of the following formulas 1 to 3:
(formula 1) x <8
(formula 2) y <12
(formula 3) y<12x-0.75
Wherein x is the initial haze (%) of the plate measured in accordance with JIS K7136 before the steel wool scratch test,
y is the amount of change in haze (%) of the flat plate relative to the initial haze (%) after the steel wool scratch test, measured in accordance with JIS K7136,
the steel wool scratch test was a test in which #0000 steel wool was pressed against the surface of the plate at a pressure of 14kPa and rubbed reciprocally at a speed of 15 cm/sec in a direction perpendicular to the fiber direction of the steel wool 11 times ].
[2] The resin composition according to [1], wherein the resin composition comprises a thermoplastic resin (A) and silica composite oxide particles (B).
[3] The resin composition according to item [2], wherein the content of the silica composite oxide particles (B) in the resin composition is 0.001 to 5 parts by mass relative to 100 parts by mass of the thermoplastic resin (A).
[4] The resin composition according to [2] or [3], wherein when the silica composite oxide particles (B) and the thermoplastic resin (A) are irradiated with light having a wavelength of 589nm at 25 ℃, respectively, the difference in refractive index between the silica composite oxide particles (B) and the thermoplastic resin (A) is 0.03 or less.
[5] The resin composition according to any one of the above [2] to [4], wherein the silica composite oxide is a silica-titania composite oxide, a silica-zirconia composite oxide or a silica-alumina composite oxide.
[6] The resin composition according to any one of the above [2] to [5], wherein the thermoplastic resin (A) is a methacrylic resin.
[7] The resin composition according to any one of the above [2] to [6], wherein,
the thermoplastic resin (A) is a methacrylic resin containing 85 to 100% by mass of a monomer unit derived from methyl methacrylate,
the silica composite oxide is a silica-titania composite oxide containing 0.01 to 10 mol% of titanium atoms based on 100 mol% of all atoms of the silica composite oxide, and
the content of the silica-titania composite oxide in the resin composition is 0.01 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the methacrylic resin.
[8] The resin composition according to any one of the above [2] to [6], wherein,
the thermoplastic resin (A) is a methacrylic resin containing 85 to 100% by mass of a monomer unit derived from methyl methacrylate,
the silica composite oxide is a silica-zirconia composite oxide containing 0.01 to 10 mol% of zirconium atoms based on 100 mol% of all atoms of the silica composite oxide, and
the content of the silica-zirconia composite oxide in the resin composition is 0.01 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the methacrylic resin.
[9] The resin composition according to any one of the above [2] to [8], wherein the silica composite oxide particles (B) in the resin composition do not include an image in which a circle having a diameter of 10nm is completely contained in at least one of 10 images obtained by imaging the silica composite oxide particles (B) in a field of view of 310nm × 310nm using TEM-EDX.
[10] The resin composition according to any one of the above [2] to [7] and [9], wherein,
a part or all of the silica composite oxide particles (B) in the resin composition are silica-titania composite oxides, and
the silica-titania composite oxide in the resin composition has an absorption intensity of 0.5 or more in an XAFS spectrum of a K absorption edge of Ti,
here, the absorption intensity is an absorption intensity at an incident X-ray energy of 4967.5eV when normalized with an absorption intensity at an incident X-ray energy of 5128.0eV being 1.0.
[11] A resin composition comprising a thermoplastic resin (A) and silica composite oxide particles (B),
the content of the silica composite oxide particles (B) in the resin composition is 0.001 to 5 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A), and
the difference in refractive index between the silica composite oxide particles (B) and the thermoplastic resin (A) at a wavelength of 589nm, measured at 25 ℃, is 0.03 or less.
[12] A molded article comprising the resin composition according to any one of the above [1] to [11 ].
[13] A laminate, the laminate comprising:
a layer containing the resin composition according to any one of the above [1] to [10], and
a layer containing a thermoplastic resin (C),
wherein the content of the first and second substances,
a flat plate having a thickness of 3mm obtained by injection molding using only the above thermoplastic resin (C) as a raw material satisfies the following formula 1':
(formula 1') x.ltoreq.2, and
the flat plate does not satisfy at least any one of the following formulas 2 to 3,
(formula 2) y <12
(formula 3) y<12x-0.75
Wherein x is the initial haze (%) of the plate measured in accordance with JIS K7136 before the steel wool scratch test,
y is the amount of change in haze (%) of the flat plate relative to the initial haze (%) after the steel wool scratch test, measured in accordance with JIS K7136,
the steel wool scratch test was a test in which #0000 steel wool was pressed against the surface of the plate at a pressure of 14kPa and rubbed reciprocally at a speed of 15 cm/sec in a direction perpendicular to the fiber direction of the steel wool 11 times ].
[14] A laminate, the laminate comprising:
a layer containing the resin composition according to [11] above, and
a layer containing a thermoplastic resin (C),
wherein the content of the first and second substances,
a flat plate having a thickness of 3mm obtained by injection molding using only the above thermoplastic resin (C) as a raw material satisfies the following formula 1':
(formula 1') x.ltoreq.2
Wherein x is the initial haze (%) of the above plate measured according to JIS K7136 before the steel wool scratch test, and
the content of the silica composite oxide particles (B) in the layer containing the thermoplastic resin (C) is less than 0.001 parts by mass with respect to 100 parts by mass of the thermoplastic resin (C).
Effects of the invention
According to the present disclosure, a resin composition having excellent transparency and scratch resistance can be provided.
Drawings
FIG. 1 is a diagram for explaining JIS K7136.
Detailed Description
Hereinafter, the invention of the present disclosure will be described in detail.
The resin composition of the present disclosure contains a thermoplastic resin (a).
Examples of the thermoplastic resin (a) include: (meth) acrylic resins, polycarbonate resins, polyetherimide resins, polyester resins and the like, polystyrene resins, polyethersulfone resins, fluorine-containing resins, ABS (acrylonitrile-butadiene-styrene) resins, AS (acrylonitrile-styrene) resins, polyvinyl chloride, and polyolefin resins. The thermoplastic resin to be used may be appropriately selected depending on the desired characteristics. The thermoplastic resin may be one kind or a mixture of two or more kinds. From the viewpoint of transparency and scratch resistance, a (meth) acrylic resin is preferable, and a methacrylic resin is more preferable. One kind of these resins may be used, or two or more kinds thereof may be used.
In the present specification, the term "(meth) acrylic resin" includes acrylic resins and methacrylic resins.
The methacrylic resin described above is a polymer having a monomer unit derived from a monomer having a methacryloyl group.
Examples of the methacrylic resin include: a methacrylic homopolymer containing only monomer units derived from an alkyl methacrylate having an alkyl group with 1 to 4 carbon atoms; a methacrylic copolymer having 85% by mass or more and less than 100% by mass of a monomer unit derived from an alkyl methacrylate having an alkyl group with 1 to 4 carbon atoms and more than 0% by mass and 15% by mass or less of a monomer unit derived from another vinyl monomer copolymerizable with a monomer unit derived from an alkyl methacrylate having an alkyl group with 1 to 4 carbon atoms.
The "alkyl methacrylate having an alkyl group with 1 to 4 carbon atoms" is represented by CH2＝CH(CH3) COOR (R is an alkyl group having 1 to 4 carbon atoms). The vinyl monomer copolymerizable with an alkyl methacrylate having an alkyl group with 1 to 4 carbon atoms is a monomer copolymerizable with an alkyl methacrylate having an alkyl group with 1 to 4 carbon atoms and having a vinyl group.
Examples of the alkyl methacrylate having an alkyl group of 1 to 4 carbon atoms include: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, sec-butyl methacrylate and isobutyl methacrylate. The alkyl methacrylate having an alkyl group with 1 to 4 carbon atoms is preferably methyl methacrylate. The alkyl methacrylate may be used alone or in combination of two or more.
Examples of the vinyl monomer copolymerizable with the alkyl methacrylate having an alkyl group of 1 to 4 carbon atoms include: methacrylates such as cyclohexyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, and glycerol monomethacrylate (excluding alkyl methacrylates having an alkyl group having 1 to 4 carbon atoms); acrylic esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and glycerol monoacrylate; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride, or anhydrides thereof; nitrogen-containing monomers such as acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, diacetone acrylamide, and dimethylaminoethyl methacrylate; epoxy group-containing monomers such as allyl glycidyl ether, glycidyl acrylate, and glycidyl methacrylate; styrene monomers such as styrene and alpha-methylstyrene.
Examples of the method for producing the methacrylic resin include a method of polymerizing an alkyl methacrylate having an alkyl group with 1 to 4 carbon atoms and, if necessary, a vinyl monomer copolymerizable with the alkyl methacrylate having an alkyl group with 1 to 4 carbon atoms by a method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization.
(polycarbonate resin)
In the present specification, "polycarbonate resin" refers to a polycarbonate resin containing a structural unit derived from a dihydroxy compound. As the polycarbonate resin that can be used as the thermoplastic resin in the present disclosure, for example, there can be mentioned: a polycarbonate resin obtained by reacting a dihydroxy compound such as a dihydric phenol or isosorbide with a carbonylating agent by an interfacial polycondensation method, a melt transesterification method or the like; a polycarbonate resin obtained by polymerizing a carbonate prepolymer by a solid-phase transesterification method or the like; and a polycarbonate resin obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method.
Examples of the dihydric phenol include: hydroquinone, resorcinol, 4' -dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, bis { (4-hydroxy-3, 5-dimethyl) phenyl } methane, 1-bis (4-hydroxyphenyl) ethane, 1-bis (4-hydroxyphenyl) -1-phenylethane, 2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), 2-bis { (4-hydroxy-3-methyl) phenyl } propane, 2-bis { (4-hydroxy-3, 5-dimethyl) phenyl } propane, 2-bis { (4-hydroxy-3, 5-dibromo) phenyl } propane, 2-bis { (3-isopropyl-4-hydroxy) phenyl } propane, bis { (4-hydroxy) phenyl } propane, 2, 2-bis { (4-hydroxy-3-phenyl) phenyl } propane, 2-bis (4-hydroxyphenyl) butane, 2-bis (4-hydroxyphenyl) -3-methylbutane, 2-bis (4-hydroxyphenyl) -3, 3-dimethylbutane, 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, 2-bis (4-hydroxyphenyl) pentane, 2-bis (4-hydroxyphenyl) -4-methylpentane, 1-bis (4-hydroxyphenyl) cyclohexane, 1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane, 9-bis (4-hydroxyphenyl) fluorene, 9-bis { (4-hydroxy-3-methyl) phenyl } fluorene, α '-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α' -bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α ' -bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1, 3-bis (4-hydroxyphenyl) -5, 7-dimethyladamantane, 4' -dihydroxydiphenylsulfone, 4' -dihydroxydiphenylsulfoxide, 4' -dihydroxydiphenylsulfide, 4' -dihydroxybenzophenone, 4' -dihydroxydiphenylether, and 4,4' -dihydroxydiphenylether. These dihydric phenols may be used alone or in combination of two or more.
Of these dihydric phenols, preferred are bisphenol A, 2-bis { (4-hydroxy-3-methyl) phenyl } propane, 2-bis (4-hydroxyphenyl) butane, 2-bis (4-hydroxyphenyl) -3-methylbutane, 2-bis (4-hydroxyphenyl) -3, 3-dimethylbutane, 2-bis (4-hydroxyphenyl) -4-methylpentane, 1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane and α, α' -bis (4-hydroxyphenyl) -m-diisopropylbenzene. Particularly, bisphenol A is preferably used alone or in combination with at least one selected from the group consisting of 1, 1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane, 2-bis { (4-hydroxy-3-methyl) phenyl } propane and α, α' -bis (4-hydroxyphenyl) -m-diisopropylbenzene.
Examples of the carbonylating agent include: carbonyl halides (phosgene, etc.), carbonic acid esters (diphenyl carbonate, etc.), and haloformates (dihaloformates of dihydric phenols, etc.). These carbonylating agents may be used alone, or two or more thereof may be used in combination.
In one embodiment, the resin composition of the present disclosure contains silica composite oxide particles (B).
The silica composite oxide is a material in which a part of silicon (Si) element in silica is replaced with another element, that is, a material in which silicon and another element form an oxide having a uniform structure. The structure of the silica composite oxide can be performed by X-ray absorption fine structure (XAFS) spectroscopy.
The other element is not particularly limited as long as it is an element other than silicon and oxygen and is an oxide which can form a uniform structure together with silicon. Examples of the other elements include elements from group 2 to group 14, and preferably include: titanium, zirconium, aluminum, zinc, chromium, manganese, magnesium, cerium, boron, iron, indium, and tin. In a more preferred embodiment, the other element is titanium, zirconium, or aluminum, and titanium is more preferred.
That is, in one embodiment, the silica composite oxide may be a silica-titania composite oxide, a silica-zirconia composite oxide, or a silica-alumina composite oxide, preferably a silica-titania composite oxide or a silica-zirconia composite oxide, and more preferably a silica-titania composite oxide.
The silica composite oxide particles contain the silica composite oxide. The silica composite oxide particles are preferably substantially composed of a silica composite oxide, but may contain, for example, an aggregate of a substance containing the above-mentioned other element (hereinafter also simply referred to as "aggregate") other than the silica composite oxide. As described above, the other element may be an element other than silicon and oxygen, but the "aggregate of substances containing other elements" means an aggregate containing at least an element other than silicon and oxygen, and does not exclude silicon and oxygen. That is, in other words, the silica composite oxide particles contain the silica composite oxide, and may further contain an aggregate containing at least an element other than silicon and oxygen.
When the silica composite oxide particles (B) contain the aggregate, in at least one of 10 images obtained by imaging the silica composite oxide particles (B) in a field of view of 310nm × 310nm using TEM-EDX (transmission electron microscope-energy dispersive X-ray spectroscopy), an image of the aggregate completely containing a circle having a diameter of 10nm does not exist in the imaged image of the aggregate. That is, in the at least one image, the images of the aggregates captured are all images that do not completely contain a circle having a diameter of 10 nm. TEM-EDX of the silica composite oxide particles (B) may be measured directly or by recovering insoluble components when the resin composition is immersed in a solvent such as chloroform, in which the thermoplastic resin (a) is soluble. The diameter of a circle that can be included in an image of an aggregate in the resin composition obtained by TEM-EDX is less than 10nm, and a molded body having higher transparency can be obtained.
In one embodiment, the content of the other element contained in the silica composite oxide particles (B) is preferably 0.01 to 10 mol%, more preferably 0.1 to 5 mol%, still more preferably 1 to 5 mol%, for example 1.5 to 3 mol%, based on all atoms of the silica composite oxide. The content of other elements contained in the silica composite oxide can be measured by an ICP-AES method, an SEM-EDX method, a TEM-EDX method, or the like.
The silica composite oxide particles (B) may have a shape such as a nearly spherical shape, a rectangular parallelepiped shape, or a pulverized shape having a plurality of corners. The shape of the silica composite oxide particles is preferably approximately spherical, and more preferably true spherical.
The average primary particle diameter of the silica composite oxide particles (B) used in the present disclosure is 0.1 μm or more and 2 μm or less, more preferably 0.2 μm or more and 1.5 μm or less, and still more preferably 0.3 μm or more and 1.0 μm or less. The average primary particle diameter can be measured, for example, by a laser diffraction particle size distribution measuring apparatus. When the average primary particle diameter of the silica composite oxide particles is within the above range, a molded article excellent in both scratch resistance and transparency can be provided. Here, the primary particles are particles constituting the smallest unit of the silica composite oxide particles.
When the silica composite oxide particles (B) are in a true spherical shape, the average particle diameter (diameter) of the silica composite oxide particles is preferably 0.1 μm or more and 2 μm or less, more preferably 0.2 μm or more and 1.5 μm or less, and still more preferably 0.3 μm or more and 1.0 μm or less. When the silica composite oxide particles are not true spheres, the average major axis of the silica composite oxide particles is preferably 0.1 μm or more and 2 μm or less, and more preferably greater than 0.2 μm and 1.5 μm or less. Here, the "major axis" refers to the length of the longest portion among the linear distances of the particles. The average major axis and the average particle diameter can be measured by reading from an observation image of the particles obtained by a scanning electron microscope. When the average major axis or average particle diameter of the silica composite oxide particles is within the above range, a molded article excellent in both scratch resistance and transparency can be provided. Here, in the present specification, the average particle diameter refers to the median particle diameter (d 50).
The silica composite oxide particles (B) have a refractive index of preferably 1.47 or more and 1.60 or less, more preferably 1.48 or more and 1.52 or less, and still more preferably 1.49 or more and 1.51 or less. When the refractive index of the silica composite oxide particles is within the above range, a molded article of the resin composition having high transparency can be obtained. Here, in the present specification, the refractive index refers to the refractive index of light having a wavelength of 589nm measured at 25 ℃.
When the thermoplastic resin (A) is irradiated with light having a wavelength of 589nm at 25 ℃, the difference between the refractive index of the thermoplastic resin (A) and the refractive index of the silica composite oxide particles (B) is preferably 0.03 or less, more preferably 0.02 or less, and still more preferably 0.01 or less. It is particularly preferable that the refractive indices of both be the same. When the difference between the refractive indices is 0.03 or less, a molded article of the resin composition having high transparency can be obtained. By further reducing the difference in refractive index between the two, a molded article having higher transparency can be obtained.
The refractive index of the thermoplastic resin (a) can be measured by using a critical angle method, a V-block method, an immersion method, or the like. The refractive index of the silica composite oxide particles (B) can be measured by an immersion method or the like.
The silica composite oxide particles (B) can be obtained by a known method such as a flame fusion method, a flame hydrolysis method, or a sol-gel method.
As the silica composite oxide particles (B), for example, silica-titania SiTi0449 (average particle diameter: 0.4 μm, refractive index: 1.49), silica-titania SiTi0448 (average particle diameter: 0.4 μm, refractive index: 1.48), silica-titania SiTi0450 (average particle diameter: 0.4 μm, refractive index: 1.50), silica-titania SiTi0451 (average particle diameter: 0.4 μm, refractive index: 1.51), silica-titania SiTi0452 (average particle diameter: 0.4 μm, refractive index: 1.52), silica-titania SiTi0349 (average particle diameter: 0.3 μm, refractive index: 1.49), silica-titania SiTi0849 (average particle diameter: 0.8 μm, refractive index: 1.49), silica-zirconia SiZr0452 (average particle diameter: 0.4 μm, refractive index: 1.52), and the like.
When the resin composition of the present disclosure contains the thermoplastic resin (a) and the silica composite oxide particles (B), the content of the silica composite oxide particles (B) contained in the resin composition is preferably 0.001 parts by mass or more and 5 parts by mass or less, more preferably 0.01 parts by mass or more and 5 parts by mass or less, and further preferably 0.01 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass of the thermoplastic resin (a). The content of the silica composite oxide particles (B) in the resin composition can be measured by the ICP-AES method. The supply concentration of the silica composite oxide particles (B) when the thermoplastic resin (a) and the silica composite oxide particles (B) are melt-kneaded may be set as the content. The values of both are approximately the same, but from the viewpoint of accuracy, it is preferable to measure them by the ICP-AES method. When the content of the silica composite oxide particles (B) is 0.001 parts by mass or more, a molded article of the resin composition having high scratch resistance can be obtained. When the content of the silica composite oxide particles (B) is 5 parts by mass or less, a molded article of a resin composition having high transparency can be obtained.
The resin composition of the present disclosure preferably: a flat plate having a thickness of 3mm obtained by injection molding using only the resin composition of the present disclosure as a raw material satisfies all of the following formulae 1 to 3.
(formula 1) x <8
(formula 2) y <12
(formula 3) y<12x-0.75
Wherein x is the initial haze (%) of the plate measured in accordance with JIS K7136 before the steel wool scratch test,
y is the amount of change in haze (%) of the flat plate relative to the initial haze (%) after the steel wool scratch test, measured in accordance with JIS K7136.
The steel wool scratch test was a test in which #0000 steel wool was pressed against the surface of the plate at a pressure of 14kPa and rubbed reciprocally at a speed of 15 cm/sec 11 times in a direction perpendicular to the fiber direction of the steel wool. ]
x is preferably x <5, more preferably x < 2.
y is preferably y <10, more preferably y < 6.
The relationship between x and y is preferably y<10x-0.75More preferably y<6x-0.75。
By satisfying the above formulae (1) to (3), a molded article having higher transparency and scratch resistance can be obtained.
The haze measurement method according to JIS K7136 is as follows.
(preamble)
This standard is a japanese industrial standard which was produced without changing the technical contents and the format of the specification table, and which was published in 1999 as ISO14782, Plastics-Determination of haze for transparent materials, release 1 st edition.
1. Scope of application
This standard specifies the method for determining the haze of a transparent and substantially colorless plastic as a specific optical property associated with wide-angle scattering of light. This test method can be applied to a material having a haze value of 40% or less as measured by this method.
2. Definition of
The haze (haze) is a percentage of transmitted light which is deviated from the incident light by 0.044 radian (2.5 °) or more by forward scattering in the transmitted light passing through the test piece.
3. Device for measuring the position of a moving object
3-1. the device is composed of a stable light source, a connection optical system, an integrating sphere having an opening, and a photometer composed of a light receiver, a signal processing device, and a display device or a recorder (see FIG. 1).
3-2. the combined characteristics of the light source used and the photometer after passing through the filters must provide a photopic standard luminous efficacy V (λ) (defined by IEC 60050-845) equal to the color matching function y (λ) based on ISO/CIE10527 and an output equivalent to the combination of CIE standard light D65 specified in ISO/CIE 10526. The output of the photometer must be proportional to the accuracy of the incident beam to within 1% of the error, within the range of the beam used. It is desirable that the spectral and photometric characteristics of the light source and photometer remain constant during the measurement.
3-3. the light source is combined with an optical system to obtain a parallel light beam. The maximum angle between any ray contained in the beam and the optical axis cannot exceed 0.05 radians (3 °). The light beam must be clear at any opening of the integrating sphere.
3-4. the device needs to be designed to read a constant value without a beam.
3-5. to collect the transmitted beam, an integrating sphere is used. The diameter of the integrating sphere may be any value as long as the area of all the openings does not exceed 3.0% of the inner surface area of the integrating sphere. The diameter of the integrating sphere is desirably 150mm or more to enable measurement of a large sample.
3-6. the integrating sphere has an inlet opening, an outlet opening, a compensation opening, and a light receiving opening (refer to fig. 1). The centers of the inlet and outlet openings are on the same great circle of the ball, and the central angle of the circular arc on the great circle corresponding to the centers of the openings is 3.14 radian +/-0.03 radian (180 +/-2 ℃). The diameter of the outlet opening is angled relative to the center of the inlet opening by 0.140 radians + -0.002 radians (8 + -0.1 deg.). The outlet opening and the compensation opening are of the same size. The inlet opening, the compensation opening and the light receiving opening cannot be located on the same large circle of the integrating sphere. The compensating opening is disposed at a position within 1.57 radians (90 °) of the central angle of the inlet opening.
3-7. in the case where no specimen is placed at the inlet opening, the cross section of the light beam at the outlet opening must be approximately circular and clear, and a ring portion must remain around the outlet opening in a concentric circle with the outlet opening. The annulus is angled relative to the center of the inlet opening by 0.023 radians ± 0.002 radians (1.3 ° ± 0.1 °).
3-8, installing a light shielding plate on the integrating sphere to ensure that the light receiver does not directly detect the light passing through the sample. The light receiver forms a central angle of 1.57 radians ± 0.26 radians (90 ° ± 15 °) with the inlet opening on the integrating sphere. The optical traps placed at the exit opening and the compensation opening must be optical traps that completely absorb light in the absence of the sample or the device must be designed such that no optical traps are needed at the exit opening and the compensation opening.
3-9. Y of the tristimulus values of the inner surface of the integrating sphere, the light-shielding plate and the reference white plate (which are usually supplied by the apparatus manufacturer) determined according to ISO772-210Must be above 90% and its variation must be within ± 3%. In the case where it is difficult to directly measure the reflectance of the inner surface of the integrating sphere, a surface separately produced from the same material and under the same conditions as the inner surface may be measured.
3-10. the test piece holder holds the test piece at right angles to the light beam with an accuracy within ± 2 °, and mounts the test piece as close to the integrating sphere as possible, so that all transmitted light including diffused light can be captured. In addition, the holder can hold the test piece having flexibility flat. For a thin and flexible film, its end portion may be sandwiched between double-layered ring-shaped holders or attached to the end portion of the holder using a double-sided adhesive tape. The latter method is also used for thick test pieces that cannot be mounted on a double-layered ring-shaped stent. The test piece may be mounted on the sample stage by using a vacuum pump or a vacuum adsorption plate.
4. Test piece
4-1. cutting out a test piece from a film, a sheet or a molded article obtained by injection molding or compression molding.
4-2. the test piece was free from defects, dust, grease, adhesive from protective material, scratches, debris, etc., and free from voids, foreign materials visible to the naked eye.
4-3. the test piece has a size sufficient to cover the inlet opening of the integrating sphere and the compensation opening. It may be a circular plate having a diameter of 50mm or a square plate having one side of 50 mm.
4-4. in the case where no particular regulation is made, 3 test pieces were prepared for each sample of the test material.
5. Condition regulation
5-1. before the test, the test piece was conditioned according to ISO291 at a temperature of (23. + -.2). degree.C. and a relative humidity of (50. + -.10)% for 40 hours or more, if necessary.
5-2. the test apparatus was set in an atmosphere maintained at a temperature of (23. + -. 2 ℃ C.) and a relative humidity of (50. + -. 10)% as required.
6. Step (ii) of
6-1. the test unit is left for a sufficient time before testing to allow it to reach thermal equilibrium.
And 6-2, mounting the test piece on the test piece bracket.
6-3. read 4 values (τ 1, τ 2, τ 3, and τ 4) from the metrology instrument as shown in the table below.
6-4. the thickness of the test piece was measured at 3 positions, precisely to 0.02mm in the case of a piece and to 1 μm in the case of a film.
6-5, the above steps were performed sequentially for 3 test pieces.
7. Computing
Haze (%) was calculated according to the following formula.
Haze ═ [ (τ 4/τ 2) - τ 3(τ 2/τ 1) ] × 100
Here, τ 1: beam of incident light
τ 2: all light beams after passing through the test piece
τ 3: light beam diffused in the device
τ 4: light beam diffused in device and test piece
Remarking: in order to accurately determine the total light transmittance using a single beam device, it is necessary (as specified in ISO 13468-1) to place a test strip at the compensation opening instead of an optical trap. This is to counteract the change in efficiency of the integrating sphere. Alternatively, the measurement value can be determined by correcting the measurement value using a standard test piece corrected by a two-beam apparatus. However, since there is little difference in the obtained haze value, it is practically sufficient to use τ 1 obtained by placing a light trap at the compensation opening instead of the test piece.
The injection molding machine and conditions used for molding the above-described "flat plate having a thickness of 3mm obtained by injection molding using only the resin composition of the present disclosure as a raw material" are not particularly limited. For example, injection molding can be performed using EC130 SXIII-4A manufactured by Toshiba mechanical Co. For example, the molding conditions may be as follows.
Screw temperature: the 5 heaters from the raw material inlet to the outlet were set at 60 ℃, 230 ℃, 240 ℃, 250 ℃ and 250 ℃ from the raw material inlet, respectively.
Injection speed: 90 mm/s
Maximum injection pressure: 200MPa
Maintaining the pressure: 80MPa
Temperature of the die: 60 deg.C
And (3) cooling timing: 45 seconds
In one embodiment, the resin composition of the present disclosure is a resin composition containing a thermoplastic resin (a) and silica composite oxide particles (B), wherein the content of the silica composite oxide particles (B) in the resin composition is 0.001 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin (a), and the difference in refractive index between the silica composite oxide particles (B) and the thermoplastic resin (a) at a wavelength of 589nm, measured at 25 ℃, is 0.03 or less. The resin composition can give a molded article excellent in both scratch resistance and transparency.
The resin composition of the present disclosure may contain, if necessary, an ultraviolet absorber, an antioxidant, a mold release agent, an antistatic agent, a flame retardant, and the like. Examples of the ultraviolet absorber include: benzophenone-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, malonate-based ultraviolet absorbers, oxanilide-based ultraviolet absorbers, and the like; as the antioxidant, there may be mentioned: phenolic antioxidants, sulfur-containing antioxidants, phosphorus-containing antioxidants, and the like; examples of the release agent include: higher fatty acid esters, higher fatty alcohols, higher fatty acids, higher fatty acid amides, higher fatty acid metal salts, fatty acid derivatives, and the like; examples of the antistatic agent include: conductive inorganic particles, tertiary amines, quaternary ammonium salts, cationic acrylate derivatives, cationic vinyl ether derivatives, and the like; as the flame retardant, there may be mentioned: cyclic nitrogen compounds, phosphorus-containing flame retardants, silicon-containing flame retardants, cage-type silsesquioxanes or partially cracked structures thereof, silica-based flame retardants, and the like.
The resin composition of the present disclosure is formed into a predetermined shape. Accordingly, the present disclosure includes a molded article obtained by molding the resin composition of the present disclosure.
As a method for producing the molded article of the present disclosure, for example, a method for molding the resin composition of the present disclosure using a molding machine can be cited. Specifically, an injection molding method using an injection molding machine as a molding machine and injecting a resin composition into a mold of the molding machine to mold the resin composition is preferable because a molded body having a complicated shape can be obtained.
The temperature of the cylinder during injection molding is preferably 230 ℃ or higher, and usually 290 ℃ or lower.
The thickness of the molded article of the present disclosure is preferably 0.5mm or more and 8mm or less, more preferably 1mm or more and 6mm or less, and further preferably 1mm or more and 3mm or less. When the thickness of the molded article is within the above range, a molded article having excellent transparency can be obtained, and the molded article can be suitably used as a vehicle lamp cover, for example.
In addition, the resin composition of the present disclosure can constitute a layer of a laminate. Accordingly, the present disclosure includes laminates comprising a layer comprising the resin composition of the present disclosure.
In one embodiment, the laminate includes a layer containing the resin composition of the present disclosure and a layer containing the thermoplastic resin (C). The laminate of the present disclosure has an excellent balance between scratch resistance and transparency, as compared with a layer containing the resin composition of the present disclosure alone and a layer containing the thermoplastic resin (C) alone.
The thermoplastic resin (C) may be the same as the thermoplastic resin (a), and examples thereof include: (meth) acrylic resins, polycarbonate resins, polyetherimide resins, polyester resins and the like, polystyrene resins, polyethersulfone resins, fluorine-containing resins, ABS (acrylonitrile-butadiene-styrene) resins, AS (acrylonitrile-styrene) resins, polyvinyl chloride, polyolefin resins and the like. The thermoplastic resin may be one kind or a mixture of two or more kinds. The thermoplastic resin (C) is preferably the same resin as the thermoplastic resin (a) used in the layer containing the resin composition of the present disclosure.
In one embodiment, the laminate of the present disclosure is a laminate comprising a layer comprising the resin composition of the present disclosure and a layer comprising a thermoplastic resin (C), wherein,
a flat plate having a thickness of 3mm obtained by injection molding using only the above thermoplastic resin (C) as a raw material satisfies the following formula 1':
(formula 1') x is less than or equal to 2,
wherein the flat plate does not satisfy at least any one of the following formulas 2 to 3,
(formula 2) y <12
(formula 3) y<12x-0.75
Wherein x is the initial haze (%) of the plate measured in accordance with JIS K7136 before the steel wool scratch test,
y is the amount of change in haze (%) of the flat plate relative to the initial haze (%) after the steel wool scratch test, measured in accordance with JIS K7136.
The steel wool scratch test was a test in which #0000 steel wool was pressed against the surface of the plate at a pressure of 14kPa and rubbed reciprocally at a speed of 15 cm/sec in a direction perpendicular to the fiber direction of the steel wool 11 times ].
In one embodiment, a laminate of the present disclosure is a laminate comprising a layer containing the above-described resin composition of the present disclosure and a layer containing a thermoplastic resin (C), wherein only a flat plate having a thickness of 3mm obtained by injection molding using the above-described thermoplastic resin (C) as a raw material satisfies the following formula 1':
(formula 1') x.ltoreq.2
Wherein x is the initial haze (%) of the above plate measured according to JIS K7136 before the steel wool scratch test, and
the content of the silica composite oxide particles (B) in the layer containing the thermoplastic resin (C) is less than 0.001 parts by mass per 100 parts by mass of the thermoplastic resin (C).
In the laminate, the thickness of the layer containing the resin composition of the present disclosure is preferably 0.1mm or more and 8mm or less, more preferably 0.5mm or more and 6mm or less, and further preferably 0.8mm or more and 3mm or less.
In the laminate, the thickness of the layer containing the thermoplastic resin (C) is preferably 0.5mm or more and 8mm or less, more preferably 1mm or more and 6mm or less, and further preferably 1mm or more and 3mm or less.
The molded article and the laminate of the present disclosure have high transparency and scratch resistance, and are therefore suitable for use as, for example, a vehicle lamp cover. Accordingly, the present disclosure includes a lamp housing, particularly a vehicle lamp housing, including the molded body or the laminated body of the present disclosure.
Examples of the lamp housing for a vehicle include: head lamps (head lamps), tail lamps (tail lamps), stop lamps (stop lamps), winker lamps (fog lamps), vehicle width indicator lamps, covers for reversing lamps and the like. The molded article and the laminate of the present disclosure can be suitably used as a head lamp cover, which is a cover of a head lamp (head lamp) that is frequently rubbed with gravel or the like and requires more excellent scratch resistance.
The molded body and the laminate of the present disclosure can suppress surface damage other than scratches, for example, damage caused by collision of particles such as gravel.
Examples
The resin composition of the present disclosure will be described below with reference to examples, but the present disclosure is not particularly limited to these examples.
(transparency)
The initial haze (unit:%) of the obtained molded article or laminate was measured in accordance with JIS K7136 before the steel wool scratch test. The smaller the initial haze, the more excellent the transparency, and particularly when the initial haze is less than 8%, the transparency can be said to be excellent.
(scratch resistance)
The surface of the obtained molded article or laminate was subjected to a scratch test using steel wool. Specifically, the surface of the molded body or the surface of the laminate was pressed with steel wool #0000 under a load of 14kPa, and rubbed reciprocally 11 times at a speed of 15 cm/sec in a direction perpendicular to the fiber direction of the steel wool. The haze of the molded article or the laminate before and after the friction test was measured according to JIS K7136, and the change in haze (Δ haze (unit:%)) before and after the test was calculated. In the case of the laminate, unless otherwise specified, the surface comprising the thermoplastic resin composition containing the thermoplastic resin composition and the silica composite oxide is rubbed. In particular, when the Δ haze is less than 12%, the scratch resistance is excellent.
12x when initial haze is x%-0.75Defined as delta haze threshold (unit:%). Particularly, when the Δ haze is less than the threshold Δ haze, it can be said that the balance between the transparency and the scratch resistance is excellent.
(inorganic particles used)
silica-Titania SiTi0449 (average particle diameter: 0.4 μm, refractive index: 1.49)
silica-Titania SiTi0448 (average particle diameter: 0.4 μm, refractive index: 1.48)
silica-Titania SiTi0450 (average particle diameter: 0.4 μm, refractive index: 1.50)
silica-Titania SiTi0451 (average particle diameter: 0.4 μm, refractive index: 1.51)
silica-Titania SiTi0452 (average particle diameter: 0.4 μm, refractive index: 1.52)
silica-Titania SiTi0349 (average particle diameter: 0.3 μm, refractive index: 1.49)
silica-Titania SiTi0849 (average particle diameter: 0.8 μm, refractive index: 1.49)
Silica-zirconia SiZr0452 (average particle diameter: 0.4 μm, refractive index: 1.52)
Glass Filler CF0093-P5(T4) (average particle diameter: 0.5 μm, refractive index: 1.495) manufactured by Frit corporation of Japan
Sodium aluminosilicate Silton (registered trademark) AMT-08L (average particle diameter: 0.9 μm, refractive index: 1.50) manufactured by Shuizui chemical industries, Ltd
Sansil (registered trademark) SS-04 (average particle diameter: 0.4 μm, refractive index: 1.46, manufactured by Deshan corporation)
Admafine (registered trademark) manufactured by Admatox corporation, silica Admafine S0-C2 (average particle diameter: 0.5 μm, refractive index 1.46)
Titanium oxide MT-01 (average particle diameter: 10nm), manufactured by TAYCA K.K.
< production of methacrylic resin A >
A mixture of 97.5 parts by mass of methyl methacrylate and 2.5 parts by mass of methyl acrylate, 0.016 part by mass of 1, 1-di (t-butylperoxy) cyclohexane and 0.16 part by mass of n-octyl mercaptan were continuously fed into a polymerization reactor equipped with a stirrer, and polymerization was carried out at 175 ℃ for an average residence time of 43 minutes. Subsequently, the reaction solution (partial polymer) discharged from the polymerization reactor was preheated and then supplied to a devolatilizing extruder, and unreacted monomer components were recovered by vaporization to obtain a methacrylic resin a in the form of pellets. The resulting methacrylic resin A had a methyl methacrylate-derived monomer unit content of 97.5% by mass, a methyl acrylate-derived monomer unit content of 2.5% by mass, and an MFR of 2g/10 min. The refractive index was 1.49.
[ example 1]
< melt kneading >
To 100 parts by mass of methacrylic resin A, 0.06 part by mass of SiTi0449 was added and mixed, and then melt-kneaded under the following kneading conditions using a twin-screw extruder (type: TEX30SS-30AW-2V) manufactured by Japan Steel, extruded in strand form, water-cooled, and cut with a strand cutter, to obtain a methacrylic resin composition in pellet form.
(mixing Condition)
Extruder temperature: the 8 heaters from the raw material inlet to the outlet were set at 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ and 250 ℃ from the raw material inlet, respectively.
Rotating speed: 200rpm
Input speed of raw materials: 12 kg/hour
< injection Molding >
The obtained granular methacrylic resin composition was molded into a flat plate shape of 150mm × 90mm × 3.0mm in thickness under the following molding conditions using an injection molding machine (EC 130SXII-4A manufactured by toshiba mechanical corporation), to obtain a molded article.
(Molding conditions)
Screw temperature: the 5 heaters from the raw material inlet to the outlet were set at 60 ℃, 230 ℃, 240 ℃, 250 ℃ and 250 ℃ from the raw material inlet, respectively.
Injection speed: 90 mm/s
Maximum injection pressure: 200MPa
Maintaining the pressure: 80MPa
Temperature of the die: 60 deg.C
And (3) cooling timing: 45 seconds
The obtained molded article was left to stand in an oven at 80 ℃ for 16 hours and then slowly cooled to 40 ℃ over 4 hours, and the transparency and scratch resistance were evaluated. The results are shown in table 2.
[ examples 2 to 18]
A molded article was obtained in the same manner as in example 1, except that 0.06 part by mass of SiTi0449 was added, and the inorganic particles and the addition amount were changed as described in table 1 below. The evaluation results of transparency and scratch resistance are shown in table 2 below.
[ comparative examples 1 to 14]
A molded article was obtained in the same manner as in example 1, except that 0.06 part by mass of SiTi0449 was added, and the inorganic particles and the addition amount were changed as described in table 1 below. The evaluation results of transparency and scratch resistance are shown in table 2 below.
Comparative example 15
A molded article was obtained in the same manner as in example 1, except that the methacrylic resin a was used as a material for injection molding without adding inorganic particles. The evaluation results of transparency and scratch resistance are shown in table 2 below.
[ Table 1]
Inorganic particles
Addition amount of inorganic particles [ parts by mass ]]
Example 1
SiTi0449
0.06
Example 2
SiTi0449
0.1
Example 3
SiTi0449
0.3
Example 4
SiTi0449
0.5
Example 5
SiTi0448
0.03
Example 6
SiTi0448
0.06
Example 7
SiTi0448
0.1
Example 8
SiTi0448
0.3
Example 9
SiTi0450
0.03
Example 10
SiTi0450
0.06
Example 11
SiTi0450
0.1
Example 12
SiTi0450
0.3
Example 13
SiTi0451
0.03
Example 14
SiTi0451
0.06
Example 15
SiTi0452
0.03
Example 16
SiTi0452
0.06
Example 17
SiZr0452
0.06
Example 18
SiZr0452
0.1
Comparative example 1
CF0093-P5(T4)
0.06
Comparative example 2
CF0093-P5(T4)
0.1
Comparative example 3
CF0093-P5(T4)
0.2
Comparative example 4
AMT-08L
0.1
Comparative example 5
AMT-08L
0.2
Comparative example 6
AMT-08L
0.5
Comparative example 7
SS-04
0.03
Comparative example 8
SS-04
0.06
Comparative example 9
SS-04
0.1
Comparative example 10
SS-04
0.3
Comparative example 11
SS-04
0.5
Comparative example 12
S0-C2
0.03
Comparative example 13
S0-C2
0.06
Comparative example 14
S0-C2
0.1
Comparative example 15
—
—
[ Table 2]
Initial haze [% ]]
Delta haze [%]
Delta haze threshold [% ]]
Example 1
0.53
6.43
19.23
Example 2
0.67
6.08
16.26
Example 3
1.18
6.02
10.58
Example 4
1.80
3.82
7.72
Example 5
0.60
10.10
17.60
Example 6
0.55
7.15
18.79
Example 7
0.90
6.70
12.99
Example 8
2.30
4.10
6.43
Example 9
0.90
9.30
12.99
Example 10
0.70
7.35
15.68
Example 11
0.83
7.33
13.76
Example 12
1.77
3.92
7.83
Example 13
0.60
8.87
17.60
Example 14
1.15
7.83
10.81
Example 15
1.52
6.37
8.78
Example 16
1.87
6.97
7.51
Example 17
3.10
5.10
5.14
Example 18
5.10
3.40
3.54
Comparative example 1
2.00
7.30
7.14
Comparative example 2
3.05
5.38
5.20
Comparative example 3
5.72
4.35
3.25
Comparative example 4
4.10
4.17
4.16
Comparative example 5
7.85
2.88
2.56
Comparative example 6
19.10
2.57
1.31
Comparative example 7
2.27
11.58
6.50
Comparative example 8
3.42
7.65
4.78
Comparative example 9
5.50
8.52
3.34
Comparative example 10
14.92
3.40
1.58
Comparative example 11
23.47
2.08
1.13
Comparative example 12
2.93
7.60
5.35
Comparative example 13
5.32
4.98
3.43
Comparative example 14
8.67
3.12
2.38
Comparative example 15
0.35
19.60
29.37
[ example 19]
< injection Molding >
The granular methacrylic resin composition obtained in example 1 was molded into a flat plate shape of 150mm × 90mm × 1.0mm in thickness under the following molding conditions using an injection molding machine (EC 130SXII-4A manufactured by toshiba mechanical corporation), to obtain a molded article.
(Molding conditions)
Screw temperature: the 5 heaters from the raw material inlet to the outlet were set at 60 ℃, 230 ℃, 240 ℃, 250 ℃ and 250 ℃ from the raw material inlet, respectively.
Injection speed: 90 mm/s
Maximum injection pressure: 200MPa
Maintaining the pressure: 80MPa
Temperature of the die: 60 deg.C
And (3) cooling timing: 45 seconds
< multilayer Molding >
Then, the obtained molded article was stuck to a mold of 150mm × 90mm × 3.0mm in thickness, and the methacrylic resin a was molded into a flat plate shape of 150mm × 90mm × 3.0mm in thickness under the following molding conditions using an injection molding machine (EC 130SXII-4A manufactured by toshiba mechanical corporation), thereby obtaining a laminate including a layer of 1.0mm in thickness containing the methacrylic resin composition and a layer of 2.0mm in thickness containing the methacrylic resin a. Here, the layer having a thickness of 3.0mm, which contained methacrylic resin a alone, had an initial haze of 0.35% and a Δ haze of 19.60%.
(Molding conditions)
Screw temperature: the 5 heaters from the raw material inlet to the outlet were set at 60 ℃, 230 ℃, 240 ℃, 250 ℃ and 250 ℃ from the raw material inlet, respectively.
Injection speed: 90 mm/s
Maximum injection pressure: 200MPa
Maintaining the pressure: 80MPa
Temperature of the die: 60 deg.C
And (3) cooling timing: 45 seconds
The obtained laminate was left to stand in an oven at 80 ℃ for 16 hours and then slowly cooled to 40 ℃ over 4 hours, and the transparency and scratch resistance were evaluated. The results are shown in table 3.
[ example 20]
A laminate was obtained in the same manner as in example 19, except that the pellet-shaped methacrylic resin composition obtained in example 2 was used instead of the pellet-shaped methacrylic resin composition obtained in example 1. The evaluation results of transparency and scratch resistance are shown in table 3 below.
[ example 21]
A laminate was obtained in the same manner as in example 19, except that the pellet-shaped methacrylic resin composition obtained in example 3 was used instead of the pellet-shaped methacrylic resin composition obtained in example 1. The evaluation results of transparency and scratch resistance are shown in table 3 below.
[ example 22]
A laminate was obtained in the same manner as in example 19, except that the pellet-shaped methacrylic resin composition obtained in example 4 was used instead of the pellet-shaped methacrylic resin composition obtained in example 1. The evaluation results of transparency and scratch resistance are shown in table 3 below.
[ example 23]
A laminate was obtained in the same manner as in example 19, except that the pellet-shaped methacrylic resin composition obtained in example 8 was used instead of the pellet-shaped methacrylic resin composition obtained in example 1. The evaluation results of transparency and scratch resistance are shown in table 3 below.
[ example 24]
A laminate was obtained in the same manner as in example 19, except that the pellet-shaped methacrylic resin composition obtained in example 12 was used instead of the pellet-shaped methacrylic resin composition obtained in example 1. The evaluation results of transparency and scratch resistance are shown in table 3 below.
[ Table 3]
Initial haze [% ]]
Delta haze [%]
Delta haze threshold [% ]]
Example 19
0.65
7.63
16.58
Example 20
0.67
7.50
16.26
Example 21
0.90
5.52
12.99
Example 22
1.30
4.57
9.86
Example 23
1.60
5.67
8.44
Example 24
1.30
5.75
9.86
[ example 25]
The molded article having a thickness of 1.0mm obtained in example 19 was allowed to stand in an oven at 80 ℃ for 16 hours, and then slowly cooled to 40 ℃ over 4 hours, and the transparency and scratch resistance were evaluated. The results are shown in table 4.
[ example 26]
The same procedures as in example 25 were repeated except that the molded article having a thickness of 1.0mm obtained in example 20 was used in place of the molded article having a thickness of 1.0mm obtained in example 19, and the transparency and the scratch resistance were evaluated. The results are shown in table 4 below.
[ example 27]
The same procedures as in example 25 were repeated except that the molded article having a thickness of 1.0mm obtained in example 21 was used in place of the molded article having a thickness of 1.0mm obtained in example 19, and the transparency and the scratch resistance were evaluated. The results are shown in table 4 below.
[ example 28]
The same procedures as in example 25 were repeated except that the molded article having a thickness of 1.0mm obtained in example 22 was used in place of the molded article having a thickness of 1.0mm obtained in example 19, and the transparency and the scratch resistance were evaluated. The results are shown in table 4 below.
[ example 29]
The same procedures as in example 25 were repeated except that the molded article having a thickness of 1.0mm obtained in example 23 was used in place of the molded article having a thickness of 1.0mm obtained in example 19, and the transparency and the scratch resistance were evaluated. The results are shown in table 4 below.
[ example 30]
The same procedures as in example 25 were repeated except that the molded article having a thickness of 1.0mm obtained in example 24 was used in place of the molded article having a thickness of 1.0mm obtained in example 19, and the transparency and the scratch resistance were evaluated. The results are shown in table 4 below.
[ Table 4]
Initial haze [% ]]
Delta haze [%]
Delta haze threshold [% ]]
Example 25
0.48
11.10
20.70
Example 26
0.52
8.28
19.69
Example 27
0.88
5.60
13.17
Example 28
1.30
5.58
9.86
Example 29
0.95
6.47
12.47
Example 30
1.30
6.27
9.86
[ examples 31 to 35]
A molded article was obtained in the same manner as in example 1, except that 0.06 part by mass of SiTi0449 was added, and the inorganic particles and the addition amount were changed as described in table 5 below. The evaluation results of transparency and scratch resistance are shown in table 6 below.
[ Table 5]
Inorganic particles
Addition amount of inorganic particles [ parts by mass ]]
Example 31
SiTi0349
0.06
Example 32
SiTi0349
0.1
Example 33
SiTi0749
0.06
Example 34
SiTi0749
0.1
Example 35
SiTi0748
0.3
[ Table 6]
Initial haze [% ]]
Delta haze [%]
Delta haze threshold [% ]]
Example 31
0.68
11.25
15.97
Example 32
0.82
9.95
13.97
Example 33
1.62
3.12
8.37
Example 34
2.38
4.17
6.26
Example 35
6.53
1.57
2.94
< measurement and analysis of X-ray absorption Fine Structure (XAFS) Spectroscopy >
The inorganic particles to be measured were filled in an IR tablet forming machine manufactured by japan spectrographic corporation and provided with an inner cylinder of 7mm Φ, and were subjected to hydraulic pressing with a force of 1 ton, thereby producing pellets of 7mm Φ.
In order to adjust the Ti concentration in the pellet to be measured to a Ti concentration suitable for the measurement, boron nitride may be added. In this case, the inorganic particles to be measured and boron nitride may be pulverized and mixed in a mortar to prepare pellets. Since boron nitride does not contain Ti element, it does not affect XAFS spectrum of K absorption edge of Ti measured by the following method.
The pellets were placed in a test tube and sealed with a stopper having a three-way stopcock. Then, it was heated at 350 ℃ for two hours under vacuum, thereby removing moisture. After the inside of the test tube was depressurized, the test tube was put into a glove box in which the moisture and oxygen concentrations were controlled to be less than 0.1ppm, and the pellets were taken out from the test tube. The pellets were then placed in a tedlar bag a and sealed by heat sealing. Each of the tedlar sampling bags a is then placed into another tedlar sampling bag B and sealed by heat sealing. Then. Each tedlar sampling bag B was placed in an aluminum zipper bag C, sealed by heat-sealing, and each aluminum zipper bag C was placed in another aluminum zipper bag D, and sealed by heat-sealing. The pellets were thus sealed in a double tedlar sampling bag and a double aluminum zipper bag. In this state, the glove box is taken out, put into a sealable container E, depressurized, and transported.
Measurement of XAFS spectrum of K absorption edge of Ti contained in inorganic particles was performed by QuickXAFS method using XAFS measurement apparatus of photonic factory beam line BL-12C of institute of matter structural science, high energy accelerator. The sample was removed from container E immediately before the measurement was performed, and aluminum zipper bags D and C were opened. The tedlar sample bag B was taken out therefrom, and the measurement was performed in the state of the tedlar sample bag B. For monochromatization of X-rays, a monochromator of Si (111) was used, and higher harmonics were cut off using a Ni-plated mirror. Intensity of incident X-rays (I)0) Using the utilization of N2(30 vol%) + He (70 vol%) as a gas in an ion chamber at normal temperature, and transmitted X-ray intensity (I)t) Using the utilization of N2The ion chamber as a gas was measured at room temperature. Measured energy rangeThe interval and the cumulative time at each measurement point are set as follows. The rutile type titanium oxide was used for energy correction, and the peak position at which the first order differential coefficient in the XANES spectrum of the K absorption edge reached the maximum was 4981.6 eV.
Energy range of incident X-rays: 4459.5-6064.5 eV
The number of data points: 3977 points
Scan time: 300 seconds
Accumulation: 1 time of
By the above method, I is measured at each incident X-ray energy (E, X axes)0、ItThe X-ray absorbance (y-axis) was obtained by the following equation, and the X-ray absorbance spectrum was obtained by plotting the X-y axis.
X-ray absorbance μ t ═ ln (I)t/I0)
The XAFS spectrum of the K absorption edge of Ti was obtained from the X-ray absorption spectrum as described below. Specifically, the obtained X-ray absorption spectrum data based on the QuickXAFS method was converted into the EXAFS analysis software format manufactured by science corporation by "Multi File Converter" provided by the research institute of high energy accelerator, and then the XAFS spectrum was analyzed using analysis software (REX 2000 manufactured by science corporation). Energy E of K absorption edge of Ti0The (X-axis) is an energy value (X-axis) at which the first order differential coefficient of Ti in the X-ray absorption spectrum reaches a maximum in a spectrum in the vicinity of the K absorption edge thereof. Background of the spectrum by using the least squares method in the spectrum of the energy region lower than the K absorption edge of Ti described above and applying Victoreen's formula (A lambda3-Bλ4+ C; λ is the wavelength of the incident X-rays, A, B, C is an arbitrary constant) and the background is subtracted from the spectrum. The absorption intensity at 5128.0eV was normalized to 1.0, and the absorption intensity at 4967.5eV was calculated.
The tetradentate Ti element has an absorption at 4967.5 eV. The Ti element of titanium dioxide is hexa-coordinated, so that the absorption strength of 4967.5eV is less than 0.3. On the other hand, since Ti element in the silica-titania composite oxide in which Si element and Ti element are mixed at an atomic level is tetradentate, the absorption intensity of 4967.5eV is 0.5 or more.
The absorption intensities of 4967.5eV obtained from XAFS spectra of SiTi0449, SiTi0448, SiTi0450, SiTi0452 and MT-01 are shown in Table 7.
[ Table 7]
4967.5eV absorption intensity
SiTi0449
0.88
SiTi0448
0.88
SiTi0450
0.85
SiTi0452
0.85
MT-01
0.10
< TEM-EDX measurement >
The inorganic particles were measured using TEM-EDX. The amplification was 50 ten thousand times, and the element distribution of Ti element was analyzed in a field of view of 310 nm. times.310 nm (マッピング). The presence or absence of the Ti element-containing aggregates having a circle with a diameter of 10nm was examined. The results are shown in Table 8.
[ Table 8]
< measurement of SEM-EDX >
For the inorganic particles, the magnification was 2 ten thousand times using SEM-EDX, and the element concentration was measured in a visual field of 6.4. mu. m.times.4.8. mu.m. The results are shown in Table 9.
[ Table 9]
Industrial applicability
The resin composition of the present disclosure can be suitably used in applications requiring transparency and scratch resistance, for example, vehicle exterior materials such as vehicle lamp covers, sun visors, and front grilles, vehicle interior materials such as instrument covers and front panels of vehicle displays, building materials such as windows and sound-proof walls, furniture such as billboards and counter tops, exteriors such as display shelves and carports, and lighting equipment members such as front panels of displays, covers, and globe covers.