CN118679197A - Polymer particles, polymer particle compositions, and optical films - Google Patents
Polymer particles, polymer particle compositions, and optical films Download PDFInfo
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- CN118679197A CN118679197A CN202280091025.XA CN202280091025A CN118679197A CN 118679197 A CN118679197 A CN 118679197A CN 202280091025 A CN202280091025 A CN 202280091025A CN 118679197 A CN118679197 A CN 118679197A
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- 239000002245 particle Substances 0.000 title claims abstract description 473
- 229920000642 polymer Polymers 0.000 title claims abstract description 336
- 239000000203 mixture Substances 0.000 title claims abstract description 73
- 239000012788 optical film Substances 0.000 title claims description 10
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- 238000000576 coating method Methods 0.000 claims abstract description 94
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 35
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- 239000010408 film Substances 0.000 claims description 86
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 39
- 125000005842 heteroatom Chemical group 0.000 claims description 24
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 21
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- 239000004094 surface-active agent Substances 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 238000009826 distribution Methods 0.000 claims description 18
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 15
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 11
- 125000001424 substituent group Chemical group 0.000 claims description 11
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Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention provides: polymer particles which can be uniformly dispersed in a dispersion medium such as an organic solvent or a binder resin and which can be maintained in a uniformly dispersed state even in a coating film obtained from a polymer particle composition produced by dispersing in an organic solvent. The polymer particles of the present invention are characterized by comprising an acrylic polymer containing 55 to 98 mass% of an acrylic monomer unit represented by a predetermined structural formula, and thus being uniformly dispersed in a dispersion medium such as an organic solvent or a binder resin.
Description
Technical Field
The present invention relates to polymer particles, polymer particle compositions, and optical films.
Background
Polymer particles produced by suspension polymerization and seed polymerization are used in a wide variety of fields as matting agents for paints, additives for improving the physical properties of resins, light diffusion agents, and the like.
When the polymer particles obtained by the suspension polymerization method or the seed polymerization method are used by including them in a coating material or the like, the polymer particles generally form irregularities on the surface of the coating film, and impart a matting effect to the surface of the coating film or impart light diffusibility to the coating film.
Patent document 1 discloses a silicone resin composition containing polymer particles and an addition reaction curable silicone resin, wherein the polymer particles contain crosslinked polymer particles of a polymerizable composition containing at least one ester compound selected from the group consisting of (meth) acrylic acid esters having an alkyl group or cycloalkyl group having 4 or more carbon atoms and vinyl carboxylates, a styrene compound, and a crosslinking agent, and patent document 1 describes that a silicone resin layer is formed on the surface of the polymer particles.
Patent document 2 discloses an organic particle obtained by polymerizing a monomer composition, wherein the organic particle has a coefficient of variation of particle diameter of 20% or less and a hydrophobicity index of 35 to 65.
Patent document 3 discloses (meth) acrylic microparticles obtained by polymerizing a monomer composition containing 50 to 90% by weight of a monofunctional (meth) acrylic monomer (a) having a linear or branched alkyl group having 8 to 18 carbon atoms and 10 to 50% by weight of a monomer (B) having 2 or more (meth) acryloyl groups, wherein the 10% compression strength of the (meth) acrylic microparticles in a micro compression tester is 1 to 5MPa.
Patent document 4 discloses a resin particle containing a polymer containing a structural unit represented by a predetermined structural formula.
Prior art literature
Patent literature
Patent document 1: WO2018/180739
Patent document 2: japanese patent application laid-open No. 2012-57177
Patent document 3: japanese patent laid-open No. 2018-24786
Patent document 4: japanese patent laid-open No. 2020-15857
Disclosure of Invention
Problems to be solved by the invention
In the silicone resin composition containing polymer particles of patent document 1, although a silicone resin layer is formed on the surface of crosslinked polymer particles in order to improve dispersibility in an organic solvent, the silicone resin layer may be unevenly formed due to the surface state of the polymer particles, and as a result, there is a concern that the dispersibility of the polymer particles in the organic solvent may become uneven.
In addition, the polymer particles contained in the silicone resin composition containing polymer particles contain (meth) acrylate units having cycloalkyl groups of 4 or more carbon atoms, but since the (meth) acrylate monomers having cycloalkyl groups of 4 or more carbon atoms have high hydrophobicity, the absorbability into seed particles is reduced during seed polymerization, absorption residues occur, and small particles are produced. Since the small particles and the polymer particles obtained by absorbing the seed particles are different in composition, the dispersibility in an organic solvent is different from that of the polymer particles, and as a result, there is a problem that the dispersibility of the whole particles in an organic solvent becomes uneven.
In the organic particles of patent document 2, when the organic solvent is volatilized from the organic particle-containing composition produced by mixing the organic particle-containing composition with a solvent or the like, aggregation occurs due to interaction of the organic particles even without adding an additive such as a flocculant or the like, but it is difficult to adjust the aggregation degree, and the particle diameter of the 2-order particles obtained by aggregating the organic particles tends to fluctuate. Therefore, there is a problem that uneven coating of the composition containing the organic particles occurs or particles easily fall off from the surface of a coating film formed of the composition containing the organic particles.
Since the (meth) acrylic fine particles of patent document 3 contain a monofunctional (meth) acrylic monomer (a) unit having a linear or branched alkyl group having 8 to 18 carbon atoms, the monofunctional (meth) acrylic monomer has high hydrophobicity, and therefore, similar to the polymer particles of patent document 1, particles are generated during seed polymerization, and there is a problem that the particles are derived from the particles and the dispersibility of the particles in an organic solvent becomes uneven as a whole.
The resin particles of patent document 4 contain a specific monomer having a dioxolane skeleton, but since dioxolane is highly hydrolyzable, the dioxolane opens as a side reaction in the production of the resin particles, and therefore, the following problems arise: since desired hydrophobicity cannot be imparted to the resin particles and hydrolysis of dioxolane ring becomes uneven, hydrophobicity of the resin particles becomes uneven, dispersibility of the resin particles in an organic solvent becomes uneven, and coating unevenness also occurs.
The present invention provides: polymer particles which can be uniformly dispersed in a dispersion medium such as an organic solvent or a binder resin, can maintain a uniform dispersion state in a coating film formed from a polymer particle composition produced by dispersing in the dispersion medium, and can reduce the falling-off from the coating film. The present invention provides: polymer particle compositions and optical films using polymer particles.
Solution for solving the problem
[ Polymer particles ]
The polymer particles of the present invention contain an acrylic polymer containing 55 to 98 mass% of an acrylic monomer unit represented by formula (1).
In the formula (1), R 1～R3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 4 is a monovalent substituent having 5 to 8 carbon atoms and having a hetero ring and a hetero atom number ratio (hetero atom number N/constituent atom number N) in the hetero ring of more than 0 and less than 0.4. ]
Since the polymer particles contain the acrylic monomer unit represented by the formula (1), the polymer particles have excellent affinity with a dispersion medium such as an organic solvent and a binder resin, and can be given appropriate interactions with each other. Therefore, the dispersion medium can be uniformly dispersed in a dispersion medium such as an organic solvent or a binder resin, and the dispersion stability in the dispersion medium is excellent.
The polymer particles have excellent affinity with the dispersion medium due to the acrylic monomer unit represented by formula (1), and have moderate interactions between the polymer particles. Therefore, when a coating film is formed from a polymer particle composition obtained by dispersing polymer particles in a dispersion medium, the coating film is formed while maintaining a state in which the polymer particles are uniformly dispersed with each other even when the viscosity of the polymer particle composition in the process of forming the coating film from the polymer particle composition increases. Thus, polymer particles are uniformly dispersed in the obtained coating film. Furthermore, the polymer particles are reliably held in the coating film by the binder resin, and the falling-off of the polymer particles from the surface of the coating film is reduced.
In the case where polymer particles are aggregated with each other in the process of forming a coating film from the polymer particle composition, as described above, since the affinity with the dispersion medium is excellent and the interaction between the polymer particles is moderate strength, the polymer particles are not excessively aggregated with each other, but can be aggregated with a moderate size, while forming aggregated particles having a uniform size, whereby the aggregated particles of a uniform size are uniformly dispersed in the coating film.
In addition, the polymer particles may form aggregated particles of a proper size while properly incorporating the binder resin between the polymer particles. Therefore, the aggregated particles are reliably held in the binder resin in the coating film, and the dropping of the aggregated particles from the surface of the coating film is reduced.
In the formula (1), R 1～R3 is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R 1～R3 is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and thus, in combination with the interaction of the heterocyclic ring derived from the substituent R 4, a proper interaction can be imparted to the polymer particles.
In the formula (1), when R 1～R3 is an alkyl group having 1 to 3 carbon atoms, the alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
In formula (1), R 1 and R 2 are preferably hydrogen atoms, since appropriate interactions can be imparted to the polymer particles by also matching the interactions between the polymer particles derived from the heterocyclic ring of the substituent R 4.
R 3 is also coordinated with interactions between polymer particles derived from heterocyclic ring of substituent R 4, and can impart moderate interactions between polymer particles, and therefore, is preferably a hydrogen atom, methyl group or ethyl group, and is preferably a hydrogen atom or methyl group.
R 4 is a monovalent substituent having 5 to 8 carbon atoms and having a heterocyclic ring. The substituent R 4 has a heterocyclic ring and has a carbon number of 5 to 8 as a whole, and thus the polymer particles containing a predetermined amount of the acrylic monomer unit represented by the formula (1) have a proper interaction between the polymer particles. Therefore, the polymer particles have excellent dispersibility and dispersion stability in a dispersion medium such as an organic solvent or a binder resin, and can maintain excellent dispersibility in a coating film.
R 4 has a carbon number of 5 or more, preferably 6 or more. R 4 has a carbon number of 8 or less, preferably 7 or less. When the carbon number of R 4 is in the above range, the affinity between the polymer particles and the dispersion medium is excellent, and a proper interaction can be imparted to the polymer particles. Therefore, the polymer particles have excellent dispersibility and dispersion stability in a dispersion medium such as an organic solvent or a binder resin, and can maintain excellent dispersibility in a coating film.
R 4 has a heterocycle. R 4 has a heterocycle, so that the affinity between the polymer particles and the dispersion medium is excellent, and a moderate interaction can be imparted to the polymer particles. Therefore, the polymer particles have excellent dispersibility and dispersion stability to a dispersion medium such as an organic solvent, a binder resin, or the like.
The heterocyclic ring means a ring structure in which atoms constituting the ring include carbon atoms and atoms (hetero atoms) other than carbon atoms. The hetero atom of the heterocyclic ring in R 4 is preferably an oxygen atom. If the hetero atom is an oxygen atom, the polymer particles have excellent affinity with the dispersion medium, and a proper interaction can be imparted to the polymer particles. Therefore, the polymer particles have excellent dispersibility and dispersion stability in a dispersion medium, and excellent dispersibility can be maintained in a coating film as well.
In R 4, the heteroatom ratio (heteroatom N/constituent atom N) in the heterocycle is more than 0 and less than 0.4, preferably more than 0 and 0.35 or less, more preferably more than 0 and 0.25 or less. If the heteroatom ratio of the heterocycle is within the above range, the affinity between the polymer particles and the dispersion medium is excellent, and appropriate interaction can be imparted to the polymer particles. Therefore, the polymer particles have excellent dispersibility and dispersion stability in a dispersion medium, and excellent dispersibility can be maintained in a coating film as well. The number of constituent atoms n of a heterocycle is the number of atoms directly constituting the heterocycle, and does not include atoms constituting an atomic group (including a hydrogen atom) bonded to the heterocycle as a substituent.
As the substituent R 4, monovalent substituents represented by the following formula (2) and formula (3) are preferable.
[ In formula (2), R 5 represents an alkylene group having 1 to 3 carbon atoms, R 7 and R 8 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 6 and R 9 each independently represent an oxygen atom, and the other represents a hydrocarbon group having 2 valences obtained by removing (abstracting) 2 hydrogen atoms bonded to the same carbon atom at the end of an aliphatic saturated hydrocarbon having 1 to 4 carbon atoms. *1 is an atomic bond and is a single bond. ]
R 5 represents an alkylene group having 1 to 3 carbon atoms. In the present invention, the alkylene group is a 2-valent atomic group obtained by removing (abstracting) 2 hydrogen atoms bonded to 2 different carbon atoms in an aliphatic saturated hydrocarbon, and includes both linear and branched atomic groups. Examples of the alkylene group having 1 to 3 carbon atoms include methylene group (-CH 2 -), ethylene group, propylene group [ -CH (CH 3)-CH2 - ], trimethylene group [ -CH 2-CH2-CH2 - ], and the like, and the polymer particles have excellent affinity with the dispersion medium and can impart moderate interactions between the polymer particles, so that methylene group is preferable.
R 7 and R 8 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and the polymer particles have excellent affinity with the dispersion medium and can impart a proper interaction with each other, so that a hydrogen atom is preferable. When R 7 and R 8 are an alkyl group having 1 to 3 carbon atoms, the alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
R 6 and R 9 are each independently an oxygen atom, and the other is a 2-valent hydrocarbon group in which 2 hydrogen atoms bonded to the same carbon atom at the terminal of an aliphatic saturated hydrocarbon having 1 to 4 carbon atoms are removed (taken off), and preferably, either one is an oxygen atom and the other is a methylene group. By using either one of R 6 and R 9 as an oxygen atom and the other as the above-mentioned 2-valent hydrocarbon group, the affinity between the polymer particles and the dispersion medium is excellent, and a proper interaction can be imparted to the polymer particles. Further, the heterocyclic ring is prevented from opening by hydrolysis, and the interaction between the polymer particles in the whole polymer particles is uniformed, so that the polymer particles are uniformly dispersed in the dispersion medium and the coating film.
The 2-valent hydrocarbon group produced by removing (abstracting) 2 hydrogen atoms bonded to the same carbon atom at the terminal end of the aliphatic saturated hydrocarbon having 1 to 4 carbon atoms is not particularly limited, and examples thereof include methylene groups (-CH 2-)、＝CH-CH3 [ formula (10) ], =c (CH 3)2 [ formula (11) ], =ch-CH 2-CH3 [ formula (12) ], =ch-CH 2-CH2-CH3 [ formula (13) ], =ch-CH 2(CH3)-CH2 [ formula (13) ], and the like, and preferably methylene groups.
[ In formula (3), R 10 represents an alkylene group having 1 to 3 carbon atoms, R 11～R13 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 14 and R 15 each independently represents an oxygen atom or a methylene group, and at least one represents an oxygen atom. *12 denotes an atomic bond and is a single bond. ]
R 10 represents an alkylene group having 1 to 3 carbon atoms. Examples of the alkylene group having 1 to 3 carbon atoms include methylene group (-CH 2 -), ethylene group, propylene group [ -CH (CH 3)-CH2 - ], trimethylene group [ -CH 2-CH2-CH2 - ], and the like, and the polymer particles have excellent affinity with the dispersion medium and can impart moderate interactions between the polymer particles, so that methylene group is preferable.
R 11～R13 is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R 11 is preferably methyl or ethyl, and more preferably ethyl, because the polymer particles have excellent affinity with the dispersion medium and can impart moderate interactions between the polymer particles. R 12 and R 13 are preferably hydrogen atoms because of the reduced volume and the efficient interaction between polymer particles due to the oxygen atoms of the heterocycle. When R 11～R13 is an alkyl group having 1 to 3 carbon atoms, the alkyl group is not particularly limited, and examples thereof include methyl, ethyl, n-propyl, isopropyl and the like.
R 14 and R 15 are each independently an oxygen atom or a methylene group. Preferably, R 14 and R 15 are both oxygen atoms. Since R 14 and R 15 are each independently an oxygen atom or a methylene group, the polymer particles have excellent affinity with the dispersion medium, and a moderate interaction can be imparted to the polymer particles.
Therefore, as the acrylic monomer represented by the formula (1), acrylic monomers represented by the following formulas (4) and (5) are preferable, and acrylic monomers represented by the following formulas (6), (7) and (8) are more preferable. In the formulas (4) and (5), R 1～R13 is the same as described above, and therefore, the description thereof is omitted.
The content of the acrylic monomer unit represented by the formula (1) in the acrylic polymer contained in the polymer particles is 55 mass% or more, preferably 61 mass% or more, and more preferably 65 mass% or more. The content of the acrylic monomer unit represented by the formula (1) in the polymer particles is 98 mass% or less, preferably 90 mass% or less, more preferably 85 mass% or less, and still more preferably 80 mass% or less. If the content of the acrylic monomer unit is within the above range, the affinity between the polymer particles and the dispersion medium is excellent, and a proper interaction can be imparted between the polymer particles. Therefore, the polymer particles can be uniformly dispersed in a dispersion medium such as an organic solvent or a binder resin, and the dispersion stability in the dispersion medium is also excellent. Further, in a coating film formed of a polymer particle composition obtained by dispersing polymer particles in a dispersion medium, the polymer particles are also reliably held by a binder resin, and the falling-off of the polymer particles from the surface of the coating film can be reduced. In addition, in the process of forming a coating film from the polymer particle composition, even in the case where polymer particles are aggregated with each other, the polymer particles are not excessively aggregated with each other, but can be aggregated with a moderate size while forming aggregated particles having a uniform size. Thus, the aggregated particles of uniform size are uniformly dispersed in the coating film, and the falling-off of the aggregated particles from the surface of the coating film can also be reduced.
The acrylic polymer contained in the polymer particles preferably contains a polyfunctional monomer unit, and is crosslinked by the polyfunctional monomer unit. If the acrylic polymer contains a polyfunctional monomer unit, the fluctuation of the interactions among the polymer particles due to the absorption of the dispersion medium by the polymer particles can be reduced, and the uniformity and dispersion stability of the dispersion state of the polymer particles in the dispersion medium can be improved. Further, by absorbing the dispersion medium by the polymer particles, it is possible to reduce the unevenness of the viscosity of the polymer particle composition due to the occurrence of partial fluctuation in the viscosity of the polymer particle composition obtained by dispersing the polymer particles in the dispersion medium, and to reduce the occurrence of uneven coating of the polymer particle composition.
The polyfunctional monomer is a monomer having a plurality of polymerizable functional groups (e.g., vinyl groups, epoxy groups, isocyanate groups, etc.). The polyfunctional monomer preferably has a plurality of vinyl groups as functional groups. Examples of the polyfunctional monomer include acrylic polyfunctional monomers such as 1, 10-decanediol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, pentadecaethylene glycol di (meth) acrylate, one hundred fifty ethylene glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1, 3-butanediol di (meth) acrylate, allyl (meth) acrylate, and aromatic divinyl compounds such as divinylbenzene, divinyl naphthalene, and derivatives thereof. In the present invention, (meth) acrylate means acrylate or methacrylate. The polyfunctional monomer may be used alone or in combination of two or more.
The content of the polyfunctional monomer unit in the acrylic polymer is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more. The content of the polyfunctional monomer unit in the acrylic polymer is preferably 45% by mass or less, more preferably 40% by mass or less, more preferably 35% by mass or less, and more preferably 30% by mass or less. If the content of the polyfunctional monomer unit is 5 mass% or more, the fluctuation of the interaction between the polymer particles due to absorption of the dispersion medium by the polymer particles can be reduced, and the uniformity and dispersion stability of the dispersion state of the polymer particles in the dispersion medium can be improved. Further, absorption of the dispersion medium by the polymer particles can be reduced, and unevenness in the viscosity of the polymer particle composition due to partial fluctuation in the viscosity of the polymer particle composition obtained by dispersing the polymer particles in the dispersion medium can be reduced, whereby occurrence of coating unevenness of the polymer particle composition can be reduced. If the content of the polyfunctional monomer unit is 45 mass% or less, the affinity between the polymer particles and the dispersion medium is excellent, and a proper interaction can be imparted to the polymer particles. Therefore, uniformity and dispersion stability of the dispersion state of the polymer particles in the dispersion medium can be improved, and a state in which the polymer particles are uniformly dispersed in a coating film formed of a polymer particle composition obtained by dispersing the polymer particles in the dispersion medium can be formed.
The gel fraction of the polymer particles is preferably 90 mass% or more, more preferably 91 mass% or more, and still more preferably 95 mass% or more. If the gel fraction of the polymer particles is 90 mass% or more, the solvent resistance of the polymer particles can be improved. For example, in the case of preparing a polymer particle composition by dispersing polymer particles in a dispersion medium, the swelling of the polymer particles by absorption of the dispersion medium can be reduced, and the dispersibility and dispersion stability of the polymer particles in the dispersion medium can be improved. Further, even in a coating film formed of a polymer particle composition produced by dispersing polymer particles in a dispersion medium, a more uniform dispersion state can be maintained, and also the falling-off of polymer particles from the coating film can be more effectively reduced.
The gel fraction of the polymer particles is a value measured as follows. First, 1.0g of polymer particles and 0.03g of zeolite as samples were precisely weighed and put into a 200mL eggplant-shaped bottle, 100mL of toluene was further added thereto, and then a condenser tube was attached to the eggplant-shaped bottle, and the eggplant-shaped bottle was immersed in an oil bath maintained at 130℃and refluxed for 24 hours.
After the reflux, the content (solution) in the above-mentioned eggplant-shaped bottle was filtered by a glass fiber filter "GB-140" manufactured by ADVANTEC companySum GA-200"A Buchner funnel type filter 3G (glass particle size: 20 to 30 μm, capacity: 30 mL) manufactured by TOP Co., ltd.) was weighed and filtered, and the solid content was recovered in the Buchner funnel type filter 3G. Then, the solid content recovered in the Buchner funnel-type filter 3G was dried in a vacuum oven at 130℃for 1 hour together with the Buchner funnel-type filter 3G, and then dried under a gauge pressure of 0.06MPa for 2 hours, toluene was removed, and cooled to room temperature.
After cooling, the total mass of the buchner funnel filter 3G, the glass fiber filter, and the solid content was measured in a state where the solid content was contained in the buchner funnel filter 3G. Then, the mass of the buchner funnel filter 3G and the glass fiber filter and the mass of the zeolite were subtracted from the total mass measured to determine the mass (G) of the dry powder.
Then, using the mass (g) of the dry powder and the mass (g) of the sample put into the eggplant-shaped bottle, the gel fraction was calculated according to the following calculation formula.
Gel fraction (mass%) = [ mass of dry powder (g)/mass of sample (g) ]×100
The acrylic polymer contained in the polymer particles preferably contains a styrene-based monomer unit. The acrylic polymer contains a styrene monomer unit, so that the affinity between the polymer particles and the dispersion medium is excellent, and a proper interaction between the polymer particles can be imparted. Therefore, the polymer particles can be uniformly dispersed in a dispersion medium such as an organic solvent or a binder resin, and the dispersion stability in the dispersion medium is also excellent. Further, the polymer particles can be uniformly dispersed in the coating film formed from the polymer particle composition obtained by dispersing the polymer particles in the dispersion medium, and the falling-off of the polymer particles from the surface of the coating film can be reduced. In addition, in the process of forming a coating film from the polymer particle composition, even in the case where polymer particles are aggregated with each other, the polymer particles are not excessively aggregated with each other, but aggregated particles having a uniform size can be formed while being aggregated with a proper size. Thus, the aggregated particles of a uniform size can be uniformly dispersed in the coating film, and the falling-off of the aggregated particles from the surface of the coating film can be reduced.
The styrene monomer is not particularly limited, and examples thereof include styrene, α -methylstyrene, vinyltoluene, chlorostyrene, ethylstyrene, isopropylstyrene, dimethylstyrene, bromostyrene, and the like. The styrene monomer may be used alone or in combination of two or more.
The acrylic polymer may not contain a styrene monomer unit. When the acrylic polymer contains a styrene monomer unit, the content of the styrene monomer unit in the acrylic polymer is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less. If the content of the styrene-based monomer unit is 40 mass% or less, in the case where the polymer particles are aggregated with each other in the process of forming a coating film from the polymer particle composition, it is possible to reduce the case where the polymer particles are excessively aggregated with each other, and the polymer particles are aggregated with a proper size to form aggregated particles having a uniform size. Therefore, the aggregated particles of a uniform size can be uniformly dispersed in the coating film, and the falling-off of the aggregated particles from the surface of the coating film can be reduced.
The acrylic polymer contained in the polymer particles may contain other monomer units within a range that does not impair the physical properties of the polymer particles. Examples of such monomers include acrylic acid esters and methacrylic acid esters. The acrylic acid ester is not particularly limited, and examples thereof include alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, and isobutyl acrylate. Examples of the methacrylate include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate.
The content of the monomer unit contained in the polymer particles means a value measured as follows. Samples of the polymer particles were precisely weighed between about 0.1 and 0.5mg. A test piece was coated with a ferromagnetic metal body having a Curie point of 590 ℃ (trade name "Pyrofoil" manufactured by Japanese analytical industries Co., ltd.) to prepare a test piece.
The test body was produced by crimping a ferromagnetic metal body to a sample. The test piece was heated in a Curie point pyrolyzer (Curie Point Pyrolyser) apparatus (trade name "JPS-700" manufactured by Japanese analytical industries Co., ltd.) to decompose the sample. The monomer component produced by the decomposition was measured by gas chromatography (Agilent Technologies, inc. Trade name "GC7820", detector=fid), and the peak area of the monomer to be measured was determined. A standard curve showing the relationship between the amount of monomer and the peak area is prepared in advance for the monomer to be measured. The amount of monomer contained in the sample was calculated from the measured peak area based on the standard curve.
(Measurement conditions)
Heating = 590-5 seconds
Oven temperature = 300 °c
Pin temperature = 300 °c
Column = Agilent Technologies "DB-5"
(GC oven temperature conditions)
Initial temperature=50 ℃ (hold 0.5 min)
Stage 1 ramp rate = 10 ℃/min (up to 200 ℃, hold 0 min)
Stage 2 heating rate = 20 ℃/min (up to 320 ℃)
Final temperature = 320 ℃ (hold 0.5 min)
Carrier gas = He
He flow = 1.275 mL/min
Injection port pressure = 100kPa
Column inlet pressure = 100kPa
Injection port temperature=300℃
Detector temperature = 300 °c
Split ratio=1/50
The amount of the surfactant contained in 1g of the polymer particles is preferably 45. Mu.g/g or less, more preferably 40. Mu.g/g or less, still more preferably 35. Mu.g/g or less, still more preferably 30. Mu.g/g or less, still more preferably 25. Mu.g/g or less. When the amount of the surfactant is 45. Mu.g/g or less, moderate interaction between the polymer particles can be imparted, and the dispersibility and dispersion stability of the polymer particles in the dispersion medium are excellent. Further, the polymer particles can be uniformly dispersed in the coating film formed from the polymer particle composition obtained by dispersing the polymer particles in the dispersion medium, and the falling-off of the polymer particles from the surface of the coating film can be reduced. In addition, even when the polymer particles are aggregated with each other during the formation of the coating film, the polymer particles are not excessively aggregated with each other, but aggregated particles having a uniform size can be formed while being aggregated with a proper size. Thus, the aggregated particles of a uniform size can be uniformly dispersed in the coating film, and the falling-off of the aggregated particles from the surface of the coating film can be reduced.
The amount of surfactant in the polymer particles was determined as follows. About 0.10g of polymer particles as a sample was precisely weighed into a centrifuge tube, and 5mL of methanol as an extraction solution was poured into the tube with a quantitative pipette, so that the polymer particles and the extraction solution were thoroughly mixed. After ultrasonic extraction for 15 minutes, centrifugation was performed at 3500rpm for 15 minutes, and the supernatant thus obtained was used as a test solution. The surfactant concentration in the test solution was measured. Then, from the measured surfactant concentration (μg/mL), the mass of the polymer particles used as the sample [ sample mass (g) ] and the amount of the extract (extract amount (mL)), the surfactant content (μg/g) in the polymer particles was calculated according to the following calculation formula. The amount of the extract was 5mL.
Surfactant content (μg/g)
= [ Surfactant concentration in test solution (μg/mL) ×extract amount (mL) ]/sample mass (g)
The arithmetic mean particle diameter in the particle size distribution based on the number of polymer particles is preferably 0.5 μm or more, more preferably 1 μm or more, still more preferably 1.5 μm or more. The arithmetic mean particle diameter in the particle size distribution based on the number of polymer particles is preferably 10 μm or less, more preferably 8 μm or less, still more preferably 6 μm or less, still more preferably 4 μm or less. If the arithmetic mean particle diameter in the particle size distribution based on the number of polymer particles is 0.5 μm or more, the polymer particles are preferably used for optical applications such as light diffusion agents, since they exhibit excellent optical properties such as light diffusion. If the arithmetic mean particle diameter in the particle size distribution based on the number of polymer particles is 10 μm or less, the thickness of the coating film covering the surface of the polymer particles protruding from the surface of the coating film can be made uniform. Therefore, homogenization of the coating film can be achieved, and the falling-off of the polymer particles from the surface of the coating film can be reduced.
The content of small particles having a particle diameter of 50% or less of the arithmetic mean particle diameter in the number-based particle size distribution in the polymer particles is preferably 6% or less, more preferably 5% or less. If the content of the small particles is 6% or less, the interaction between the polymer particles in the whole polymer particles can be made more uniform in the whole. Therefore, the homogenization of the dispersion and the dispersion stability of the polymer particles in the dispersion medium can be improved. Further, the polymer particles can be more uniformly dispersed in the coating film formed from the polymer particle composition, and the falling-off from the surface of the coating film can be further reduced.
The coefficient of variation (CV value) of the particle diameter of the particle size distribution of the polymer particles based on the number basis is preferably 15% or less, more preferably 14% or less. If the coefficient of variation of the polymer particles is 15% or less, the interaction between the polymer particles in the whole polymer particles can be made more uniform in the whole. Therefore, the homogenization of the dispersion and the dispersion stability of the polymer particles in the dispersion medium can be improved. Further, the polymer particles can be more uniformly dispersed in the coating film formed from the polymer particle composition, and the falling-off from the surface of the coating film can be further reduced.
The arithmetic mean particle diameter and the coefficient of variation (CV value) of the particle diameter in the particle size distribution based on the number of polymer particles were measured in the following manner.
The arithmetic mean particle diameter in the particle size distribution based on the number of polymer particles was measured by Coulter Multisizer TM e (measuring apparatus manufactured by Beckman Coulter Co., ltd.). The measurement was performed using a pore size corrected according to Multisizer 4 user manual issued by Beckman Coulter Co.
The pore size used in the measurement is appropriately selected according to the size of the polymer particles to be measured. Current (Kong Dianliu) and Gain are suitably set according to the size of the aperture selected.
As a sample for measurement, 0.1g of polymer particles was dispersed in 10mL of a 0.1 mass% nonionic surfactant aqueous solution using a contact mixer (Yamato Scientific Co., ltd. Trade name "TOUCHMIXER MT-31") and an ultrasonic cleaner (trade name "ULTRASONIC CLEANERVS-150" manufactured by Kyowa Co., ltd.) to form a dispersion, and the dispersion was used. In the measurement, the bubbles were slowly stirred in advance to such an extent that they did not enter the beaker, and the measurement was ended at the time of measuring 10 ten thousand polymer particles. The particle size of the polymer particles is the sphere equivalent diameter. That is, the particle diameter of the polymer particles is the diameter of a sphere having the same volume as the polymer particles. The arithmetic (number) average particle diameter of the polymer particles is an arithmetic average in the particle size distribution based on the number of 10 ten thousand particles. The content of particles (small particles) having a particle diameter of 50% or less of the arithmetic (number) average particle diameter of the polymer particles is the number ratio (%) of small particles calculated based on the particle size distribution based on the number of 10 ten thousand particles.
The coefficient of variation (CV value) of the particle diameter of the polymer particles is calculated according to the following formula.
Coefficient of variation (CV value) of particle diameter of polymer particles
=100× (Standard deviation of particle size in particle size distribution based on number of polymer particles)
(Arithmetic mean particle diameter in particle size distribution based on number of polymer particles)
The dispersion coefficient of the polymer particles is preferably less than 0.20, more preferably 0.15 or less. If the dispersion coefficient of the polymer particles is less than 0.20, the homogenization of the dispersion and the dispersion stability of the polymer particles in the dispersion medium can be improved. Further, the polymer particles can be more uniformly dispersed in the coating film formed from the polymer particle composition, and the falling-off from the surface of the coating film can be further reduced.
The dispersion behavior shift of the polymer particles is preferably below 0.02, more preferably below 0.015. If the dispersion behavior shift of the polymer particles is less than 0.02, the homogenization of the dispersion and the dispersion stability of the polymer particles in the dispersion medium can be improved. Further, the polymer particles can be more uniformly dispersed in the coating film formed from the polymer particle composition, and the falling-off from the surface of the coating film can be further reduced.
The dispersion coefficient and dispersion behavior shift of the polymer particles were measured in the following manner.
[ Method for producing Dispersion ]
To a 10mL sample tube, 0.10g of polymer particles and 5.00g of butyl acetate as a dispersion medium were added, and the mixture was stirred with an ultrasonic cleaner (trade name "ULTRASONIC CLEANERVS-150" manufactured by VELVO-CLEAR, inc.) for 1 minute to disperse the polymer particles in butyl acetate, thereby obtaining a dispersion. To this dispersion, 0.50g of an acrylic resin (trade name "ACRYDIC (registered trademark)" A-817-Ba "manufactured by DIC Co., ltd.) was further added, and the resultant was stirred with the ultrasonic cleaner for about 10 minutes to prepare a dispersion in which polymer particles were dispersed in butyl acetate and the acrylic resin.
[ Measurement method ]
The viscosity value of the dispersion was measured by a viscometer (NIHON RUFUTO CO., LTD. Micro-sample viscometer m-VROC) according to the following method. The viscometer was left to stand in the measurement environment for 30 minutes or longer before the measurement of the viscosity value.
The prepared dispersion was allowed to stand for 5 hours in a room temperature atmosphere (laboratory temperature: 23℃to 27 ℃) by the above-mentioned viscometer, and then the dispersion was stirred for 5 minutes by an ultrasonic cleaner (redispersion), and the viscosity (mPas) of the dispersion was measured.
Then, the viscosity value V (mpa·s/K) per unit temperature (K) was obtained from the measured value of viscosity (mpa·s) and the measured temperature (K) according to the following calculation formula. The measurement of the viscosity value was repeated 10 times, and the average value of the viscosity value, the maximum value of the viscosity value, and the minimum value of the viscosity value were calculated.
Viscosity number V (mPa-s/K) =measurement value (mPa-s)/measurement temperature (K)
[ Method for calculating dispersion behavior Displacement ]
The displacement of the viscosity value, that is, the dispersion behavior displacement was calculated from the following calculation formula using the maximum value, the minimum value, and the average value of the viscosity values in 10 measurements.
Calculation of dispersion behavior Displacement
Dispersion behavior shift= (VMAX-VMIN)/VAVE
VMAX: maximum value of viscosity number (mPa.s/K) in 10 measurements
VMIN: minimum value of viscosity number (mPa.s/K) in 10 determinations
VAVE: average value of viscosity values (mPa.s/K) in 10 determinations
[ Method for calculating dispersion coefficient ]
A dispersion was prepared in the same manner as in the case of measuring the dispersion behavior shift. The prepared dispersion was allowed to stand at room temperature (laboratory temperature: 23 ℃ C. To 27 ℃ C.) for 4 hours, 5 hours or 6 hours by the above-mentioned viscometer, and then, after stirring the dispersion with an ultrasonic cleaner for 5 minutes (redispersion), the viscosity value V (mPas/K) of the dispersion after standing for 4 hours, 5 hours or 6 hours was measured in the same manner as in the dispersion behavior shift measurement. The dispersion coefficient was calculated based on the following equation.
Calculation of the dispersion coefficient
Dispersion coefficient = | V6hr AVE-V4 hr-AVE/V5 hr-AVE
V4hr AVE: average value of viscosity values in 10 measurements of the dispersion after 4 hours of standing
V5hr AVE: average value of viscosity values in 10 measurements of dispersion after 5 hours of standing
V6hr AVE: average value of viscosity values in 10 measurements of dispersion after 6 hours of standing
[ Method for producing Polymer particles ]
Next, a method for producing the polymer particles will be described. The method for producing the polymer particles is not particularly limited, and the polymer particles can be produced by polymerizing a raw material monomer containing an acrylic monomer represented by the formula (1) as needed in the presence of a polymerization initiator according to a general-purpose protocol.
The polymerization method is not particularly limited, and a general polymerization method such as suspension polymerization, seed polymerization, bulk polymerization, and solution polymerization can be used, and seed polymerization is preferable. Emulsion polymerization is a polymerization method in which a raw material monomer is dispersed in an aqueous medium described later and polymerized in the presence of a polymerization initiator and an emulsifier, and is included in suspension polymerization.
The seed polymerization is as follows: when polymerization of a raw material monomer including an acrylic monomer represented by formula (1) is initiated, seed particles formed of a polymer of a separately prepared vinyl monomer are put in to perform polymerization.
In detail, seed polymerization is as follows: polymer particles made of a polymer of a vinyl monomer are used as seed particles, and the seed particles are allowed to absorb a raw material monomer containing an acrylic monomer represented by formula (1) in an aqueous medium, and the raw material monomer is polymerized in the seed particles. In this method, by growing seed particles, polymer particles having a larger particle diameter than the original seed particles can be obtained. The following describes a general method of seed polymerization, but the polymerization method is not limited to this method.
The weight average molecular weight of the polymer constituting the seed particles used in the seed polymerization is preferably 40000 or less, more preferably 35000 or less. The weight average molecular weight of the polymer constituting the seed particles used in the seed polymerization is preferably 6000 or more, more preferably 8000 or more. In a swollen state in which the raw material monomer is absorbed in the seed particles, the polymer constituting the seed particles is dispersed in the raw material monomer. If the weight average molecular weight of the polymer constituting the seed particles is 6000 or more, the viscosity of the raw material monomer is moderately increased in the swollen state, and the raw material monomers can be inhibited from coalescing with each other. If the weight average molecular weight of the polymer constituting the seed particles is 40000 or less, the absorbability of the raw material monomer improves, the fluctuation in particle diameter of the polymer particles becomes small, the interaction between the polymer particles in the whole polymer particles becomes uniform, and the dispersibility and dispersion stability in the dispersion medium of the polymer particles improve.
In the present invention, the weight average molecular weight of the polymer means a value measured in accordance with the following procedure. In detail, the measurement was performed in accordance with the following procedure.
The weight average molecular weight of the polymer can be measured by GPC (gel permeation chromatography). The weight average molecular weight of the polymer means a weight average molecular weight in terms of polystyrene. Specifically, 0.003g of polymer particles as a sample was dissolved in 10mL of Tetrahydrofuran (THF) at room temperature for 24 hours or more, and then the mixture was filtered through a non-aqueous 0.45 μm chromatographic disk, and the weight average molecular weight of the whole polymer particles was determined from a standard curve of a standard polystyrene prepared in advance using the obtained mixture as a measurement solution. The measurement conditions of the chromatograph are set as follows.
Device: high-speed GPC apparatus
Trade name: HLC-8320GPC EcoSEC-WorkStation (internal RI detector) manufactured by Tosoh Co., ltd
Analysis conditions
Column: TSKgel SuperHZM-Hx2 root (4.6 mmI.Dx15 cmL x 2 root)
Protective column: TSKguardcolumn SuperHZ-Hx1 root (4.6 mmID. Times.2 cmL)
Flow rate: sample side 0.175 mL/min, reference side 0.175 mL/min
A detector: built-in RI detector
Concentration: 0.3g/L
Injection amount: 50 mu L
Column temperature: 40 DEG C
System temperature: 40 DEG C
Eluent: THF (tetrahydrofuran)
In seed polymerization, first, a mixed solution containing a raw material monomer including an acrylic monomer represented by formula (1) and an aqueous medium is mixed with seed particles. The mixed solution may contain a surfactant as needed.
The mixed solution can be prepared by a known method. For example, a raw material monomer containing an acrylic monomer represented by formula (1) and a surfactant as required are added to an aqueous medium and mixed by a micro-emulsifying machine such as a homogenizer, an ultrasonic processor, a Nanomizer (registered trademark), etc., to prepare a mixed solution. As the aqueous medium, water or a mixture of water and an organic solvent [ for example, a lower alcohol (alcohol having 5 or less carbon atoms) ] may be used, but water is preferable.
The amount of the surfactant used in the seed polymerization is preferably 1.5 parts by mass or less per 100 parts by mass of the raw material monomer including the acrylic monomer represented by formula (1). If the amount of the surfactant is 1.5 parts by mass or less, the outflow of the raw material monomer absorbed into the seed particles out of the seed particles and the side reaction of polymerization outside the seed particles can be reduced, and the fluctuation in the particle diameter of the obtained polymer particles can be reduced. By reducing the fluctuation in the particle diameter of the polymer particles, the interactions between the polymer particles can be made uniform throughout the polymer particles. Therefore, the dispersibility and dispersion stability of the polymer particles in the dispersion medium can be improved, and a state in which the polymer particles are uniformly dispersed in the coating film obtained from the polymer particle composition can be formed.
After the mixed liquid is mixed with the seed particles, the raw material monomer containing the acrylic monomer represented by formula (1) is absorbed by the seed particles. The absorption is usually carried out by stirring the mixture at room temperature (20 to 50 ℃) for 1 to 12 hours.
Since the acrylic monomer represented by the formula (1) is slightly soluble in water, it is excellent in the absorbability of the seed particles, and can reduce polymerization as a side reaction in an aqueous medium, promote polymerization in the seed particles, and produce polymer particles having small fluctuation in particle diameter. The polymer particles having small fluctuation in particle diameter can uniformize the interaction between the polymer particles, and the dispersion in the dispersion medium and the dispersion stability are excellent. Further, the polymer particles can be uniformly dispersed in the coating film formed from the polymer particle composition, and the falling-off of the polymer particles from the surface of the coating film can be reduced.
The seed particles swell by absorbing the raw material monomer containing the acrylic monomer represented by formula (1). The mixing ratio of the raw material monomer containing the acrylic monomer represented by formula (1) to the seed particles is preferably in the range of 9 to 110 parts by mass relative to 1 part by mass of the seed particles. If the amount of the raw material monomer is 9 parts by mass or more, the production efficiency of the polymer particles improves. If the amount of the raw material monomer is 110 parts by mass or less, polymerization of the raw material monomer outside the seed particles as a side reaction can be reduced, and fluctuation in particle diameter of the polymer particles can be reduced.
Then, the raw material monomer absorbed into the seed particles is polymerized, whereby polymer particles can be obtained. The step of absorbing the raw material monomer into the seed particles and polymerizing the same is repeated a plurality of times, whereby polymer particles can be produced.
The raw material monomer may be added with a polymerization initiator as needed. The polymerization initiator is not particularly limited, and examples thereof include organic peroxides such as benzoyl peroxide, lauroyl peroxide, benzoyl peroxide ortho-chloro, benzoyl peroxide ortho-methoxy, 3, 5-trimethylhexanoyl peroxide, t-butylperoxy-2-ethylhexanoate, and di-t-butylperoxide; 2,2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), 2 '-azobis (2, 3-dimethylbutyronitrile) 2,2' -azobis (2-methylbutanenitrile), 2 '-azobis (2, 3-trimethylbutyronitrile), 2' -azobis (2-isopropylbutyronitrile) azo compounds such as 1,1 '-azobis (cyclohexane-1-carbonitrile), 2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile), (2-carbamoylazo) isobutyronitrile, 4 '-azobis (4-cyanovaleric acid), and dimethyl-2, 2' -azobisisobutyrate. The polymerization initiator is preferably used in the range of 0.1 to 1.0 parts by mass relative to 100 parts by mass of the raw material monomer.
The polymerization temperature of the seed polymerization can be appropriately selected depending on the kind of the raw material monomer and the kind of the polymerization initiator to be used if necessary. The polymerization temperature of seed polymerization is particularly preferably 25 to 110℃and more preferably 50 to 100 ℃. The polymerization time of seed polymerization is preferably 1 to 12 hours.
In seed polymerization, a polymer dispersion stabilizer may be added to the polymerization reaction system in order to improve the dispersion stability of the polymer particles. Examples of the polymer dispersion stabilizer include polyvinyl alcohol, polycarboxylic acid, celluloses (hydroxyethyl cellulose, carboxymethyl cellulose, etc.), polyvinyl pyrrolidone, etc., and polyvinyl alcohol and polyvinyl pyrrolidone are preferable. The amount of the polymer dispersion stabilizer to be added is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the raw material monomer.
In the polymerization reaction, in order to reduce polymerization of the raw material monomer in the aqueous medium outside the seed particles, a water-soluble polymerization inhibitor such as nitrite, sulfite, hydroquinone, ascorbic acid, water-soluble vitamin B, citric acid, polyphenol, and the like may be added to the aqueous medium.
The polymerization method for polymerizing the vinyl monomer to obtain seed particles is not particularly limited, and for example, dispersion polymerization, emulsion polymerization, soap-free emulsion polymerization (emulsion polymerization not using a surfactant as an emulsifier), seed polymerization, suspension polymerization, and the like can be used.
The reaction solution containing the polymer particles obtained by the polymerization according to the above-mentioned requirements is supplied to a general-purpose filter, and the polymer particles contained in the reaction solution are separated from the aqueous medium. The separated polymer particles are washed with a washing liquid and then dried in a general manner to substantially completely remove the washing liquid, and classified (preferably, air-classified) as needed, whereby the polymer particles can be obtained.
The cleaning liquid may be, for example: water; lower alcohols (alcohols having 5 or less carbon atoms) such as methanol and ethanol; mixtures of water and lower alcohols, and the like.
[ Use of Polymer particles ]
The polymer particles can be suitably used as a coating for an optical member such as an antiglare film, a light diffusion film, or the like, and can be particularly suitably used as a coating for an antiglare member. The polymer particles can also be used as a matting agent for paint, an additive for improving the physical properties of resin, and the like.
[ Polymer particle composition ]
The polymer particle composition can be produced by dispersing the polymer particles in a dispersion medium. The polymer particle composition is applied to a substrate and dried, whereby a coating film containing polymer particles can be produced on the substrate. Examples of the substrate include films and other molded articles.
Since the polymer particles contain an acrylic polymer containing a predetermined amount of the acrylic monomer unit represented by formula (1) and are excellent in dispersibility and dispersion stability in a dispersion medium, the polymer particles are stably and uniformly dispersed in the polymer particle composition, and the polymer particle composition can be easily coated on a substrate without causing coating unevenness.
Further, in the coating film formed by drying the polymer particle composition, the polymer particles are maintained in a uniformly dispersed state, and a coating film having uniform physical properties can be obtained. Further, the polymer particles are firmly held in the coating film, and therefore, the falling-off of the polymer particles from the surface of the coating film is also reduced.
In addition, even when the polymer particles are aggregated with each other to form aggregated particles during formation of the coating film, the polymer particles are not excessively aggregated to form aggregated particles having a proper size and a uniform size, the coating film has uniform physical properties, and the falling-off of the aggregated particles from the surface of the coating film is reduced.
The dispersion medium is not particularly limited, and examples thereof include a binder resin and an organic solvent.
The binder resin may be appropriately selected according to the application of the coating film, and the like. Examples of the binder resin include (meth) acrylic resins; (meth) acrylic-urethane resin; a urethane resin; polyvinyl chloride resin; polyvinylidene chloride-based resins; melamine resin; a styrene resin; alkyd resin; a phenol resin; an epoxy resin; a polyester resin; silicone resins such as alkyl polysiloxane resins; modified silicone resins such as (meth) acrylic-silicone resins, silicone-alkyd resins, silicone-polyurethane resins, and silicone-polyester resins; and fluororesins such as polyvinylidene fluoride and fluoroolefin vinyl ether polymers. (meth) acrylic acid means acrylic acid or methacrylic acid.
The binder resin may be a curable resin capable of forming a crosslinked structure by a crosslinking reaction. The curable resins are classified into ionizing radiation curable resins such as ultraviolet curable resins and electron beam curable resins, thermosetting resins, hot air curable resins, and the like, depending on the kind of curing. The curable resin further comprises: the curable resin of the binder component is produced by curing. The curable resin further comprises: a composition comprising a monomer prior to curing.
Examples of the thermosetting resin include thermosetting urethane resins containing an acrylic polyol and an isocyanate prepolymer, phenolic resins, urea melamine resins, epoxy resins, unsaturated polyester resins, silicone resins, and the like.
Examples of the ionizing radiation-curable resin include polyfunctional (meth) acrylate resins such as polyol polyfunctional (meth) acrylates, e.g., trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, and 1,2, 4-cyclohexane tri (meth) acrylate; a polyfunctional urethane acrylate resin synthesized from a diisocyanate, a polyol, a (meth) acrylate having a hydroxyl group, etc., a polyether resin having an acrylate functional group, a polyester resin, an epoxy resin, an alkyd resin, a spiroacetal resin, a polybutadiene resin, a polythiol polyene resin, etc.
In order to adjust the viscosity of the polymer particle composition, an organic solvent may be contained. Examples of the organic solvent include: aromatic solvents such as toluene and xylene; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and propylene glycol monomethyl ether; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; glycol ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, and propylene glycol methyl ether; glycol ether esters such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate (cellosolve acetate), 2-butoxyethyl acetate, and propylene glycol methyl ether acetate; a chlorine-based solvent such as chloroform, methylene chloride, and chloroform; ether solvents such as tetrahydrofuran, diethyl ether, 1, 4-dioxane, and 1, 3-dioxolane; amide solvents such as N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide, and dimethylacetamide. The organic solvents may be used alone or in combination of two or more.
The amount of the polymer particles in the polymer particle composition is preferably 2 parts by mass or more, more preferably 4 parts by mass or more, and still more preferably 6 parts by mass or more, relative to 100 parts by mass of the binder resin. The amount of the polymer particles in the polymer particle composition is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and still more preferably 100 parts by mass or less, relative to 100 parts by mass of the binder resin.
The material of the base material for coating the polymer particle composition is not particularly limited, and examples thereof include: polyester polymers such as polyethylene terephthalate (PET) and polyethylene naphthalate, cellulose polymers such as diacetylcellulose and Triacetylcellulose (TAC), synthetic resins such as polycarbonate polymers, and (meth) acrylic polymers such as polymethyl methacrylate, cement, tile, metal, glass, and the like.
The method of applying the polymer particle composition to the substrate is not particularly limited, and examples thereof include: bar coating, blade coating, spin coating, reverse coating, die coating, spray coating, roll coating, gravure coating, micro gravure coating, lip coating, air knife coating, dip coating, and the like.
The thickness of the coating film formed from the polymer particle composition is not particularly limited, and is appropriately determined according to the particle diameter of the polymer particles, and is preferably 1 to 20. Mu.m, more preferably 2 to 10. Mu.m.
ADVANTAGEOUS EFFECTS OF INVENTION
The polymer particles of the present invention can be uniformly dispersed in a dispersion medium such as an organic solvent or a binder resin. The polymer particles of the present invention can maintain a uniform dispersion state in a coating film obtained from a polymer particle composition prepared by dispersing in an organic solvent.
The polymer particles of the present invention can easily form a coating film in which the shedding of the polymer particles from the surface is reduced.
Detailed Description
The present invention will be described in more detail with reference to the following examples, but is not limited to the examples.
Examples
In examples and comparative examples, the following compounds were used.
[ Acrylic monomer ]
Tetrahydrofurfuryl acrylate [ formula (6), carbon number of THFA, R 4: 5. heteroatom number ratio: 0.2]
Tetrahydrofurfuryl methacrylate [ formula (7), carbon number of THFMA, R 4: 5. heteroatom number ratio: 0.2]
Trimethylolpropane methylal acrylate [ carbon number of formula (8), CTFA, R 4: 7. heteroatom number ratio: 0.33]
Cyclohexyl methacrylate [ CHMA, carbon number of R 4: 6. heteroatom number ratio: 0]
Benzyl methacrylate [ carbon number of BzMA, R 4: 7. heteroatom number ratio: 0]
Phenoxyethyl methacrylate [ FEMA, carbon number of R 4: 8. heteroatom number ratio: 0]
Lauryl methacrylate [ carbon number of LMA, R 4: 12. heteroatom number ratio: 0]
(2-Methyl-2-ethyl-1, 3-dioxolan-4-yl) methacrylate [ carbon number of formula (9), MEOMA, R 4: 7. heteroatom number ratio: 0.4]
Hydroxyethyl methacrylate [ HEMA, carbon number of R 4: 2. heteroatom number ratio: 0]
In table 1, the carbon number and heteroatom number ratio of R 4 are shown in the order below the column of the types of acrylic monomers.
[ Styrene monomer ]
Styrene monomer [ St ]
[ Multifunctional monomer ]
Ethylene glycol dimethacrylate [ EGDMA ]
Trimethylolpropane triacrylate [ TMPTA ]
Divinylbenzene [ DVB ]
Examples 1 to 12, 14 and 15 and comparative examples 1 to 7
[ Production of seed particles ]
Into a 5L reactor equipped with a stirrer and a thermometer, 2900 parts by mass of water as an aqueous medium, 500 parts by mass of ethyl methacrylate, and a predetermined amount of n-octylmercaptan shown in Table 1 as a molecular weight regulator were supplied, and the inside of the reactor was purged with nitrogen while stirring the content, and the temperature of the inside of the reactor was raised to 55 ℃. Further, an aqueous solution prepared by dissolving 3.0 parts by mass of potassium persulfate as a polymerization initiator in 100 parts by mass of water was supplied to the contents of the reactor while maintaining the internal temperature of the reactor at 55 ℃, and then polymerization was carried out for 12 hours.
The reaction solution after polymerization was filtered through a 400-mesh (opening 32 μm) wire gauze to prepare a slurry containing 15 mass% of seed particles of polyethylmethacrylate as a solid content. The seed particles contained in the slurry are spherical particles. The arithmetic mean particle diameter in the number-based particle size distribution in the seed particles was 0.70. Mu.m. The weight average molecular weight Mw of the polyethylmethacrylate constituting the seed particles is shown in Table 1.
[ Production example of Polymer particles ]
A monomer mixture was prepared by dissolving 6 parts by mass of benzoyl peroxide as a polymerization initiator in a raw material monomer containing a predetermined amount of an acrylic monomer, a polyfunctional monomer, and a styrene monomer (St) shown in table 1.
To 1000 parts by mass of ion-exchanged water as an aqueous medium, 10 parts by mass of sodium dodecylbenzenesulfonate (trade name "Neogen (registered trademark) S-20D" manufactured by first industrial pharmaceutical co.) as a surfactant was added as a pure component.
The monomer mixture was mixed with a surfactant solution, placed in a homomixer (model "T.K.HOMOMIXER MARKII 2.5.5" manufactured by PRIMIX Corporation), and treated at 8000rpm for 10 minutes to obtain an emulsion (mixed solution). To this emulsion, a slurry of seed particles was added so that the seed particles became 20 parts by mass, and the mixture was stirred at 30℃for 3 hours to obtain a dispersion.
To the above dispersion, 10 parts by mass of polyvinyl alcohol (trade name "Gohsenol (registered trademark) GM-14L" manufactured by Japanese synthetic chemical Co., ltd.) as a dispersing agent and 2000 parts by mass of an aqueous solution of 0.60 part by mass of sodium nitrite as a polymerization inhibitor were supplied in 1989.4 parts by mass of ion-exchanged water. Then, the dispersion was heated to 75℃while being kept under stirring for 5 hours to carry out polymerization, and then, the dispersion was heated to 100℃and was kept under stirring for 3 hours to carry out polymerization, thereby obtaining a slurry containing polymer particles.
The slurry containing the polymer particles was dehydrated in a press filter, washed with warm water until the amount of surfactant was less than 40. Mu.g/g relative to 1g of the polymer particles, and then vacuum-dried at 70℃for 24 hours, thereby obtaining polymer particles.
The polymer particles thus obtained were subjected to removal of coarse particles having a particle size of 2.5 times or more the arithmetic mean particle size of the particle size distribution based on the number basis from among the polymer particles before classification by an air classifier (Turbo classifie (registered trademark) TC-15, manufactured by NISSHIN ENGINEERING Co., ltd.) and removal of particles having a particle size of less than 0.5 times the arithmetic mean particle size of the particle size distribution based on the number basis from among the polymer particles before classification, to obtain target polymer particles.
Example 13
Target polymer particles were obtained in the same manner as in example 1, except that the slurry of seed particles was added to the emulsion and stirred at 30℃for 1.5 hours, and the mixture was classified so that the content of small particles having a particle diameter of 50% or less of the arithmetic average particle diameter was 6.4%.
Example 16
The slurry containing the polymer particles was dehydrated in a press filter, washed with warm water until the amount of the surfactant was 43. Mu.g/g relative to 1g of the polymer particles, and then vacuum-dried at 70℃for 24 hours, whereby target polymer particles were obtained in the same manner as in example 1.
The arithmetic mean particle diameter of the particle size distribution based on the number basis, the coefficient of variation (CV value) of the particle diameter, the content of small particles having a particle diameter of 50% or less of the arithmetic mean particle diameter, the content of surfactant, the dispersion behavior shift, and the dispersion coefficient were measured for the obtained polymer particles in the above-described manner, and the results are shown in table 1.
The content (mass%) of the monomer unit contained in the obtained polymer particles was measured in the above-described manner, and as a result, the content (mass%) was the same as the content (mass%) of the monomer used for producing the polymer particles.
The coating properties and the particle falling-off properties of the obtained polymer particles were measured in the following manner, and the results are shown in table 1.
[ Coatability ]
[ Production of optical film ]
To a 10mL sample tube, 0.20g of polymer particles and 1.00g of butyl acetate as an organic solvent were supplied, and the mixture was stirred with an ultrasonic cleaner (trade name "ULTRASONIC CLEANER VS-150" manufactured by VELVO-CLEAR Co., ltd.) for 1 minute to disperse the polymer particles in butyl acetate, thereby obtaining a dispersion.
To the obtained dispersion, 1.50g of an acrylic resin (trade name "ACRYDIC (registered trademark) A-817-BA" manufactured by DIC Co., ltd.) was supplied as a binder resin, and the mixture was stirred in the ultrasonic cleaner for about 2 minutes.
After the dispersion was allowed to stand for 4 hours, 5.50g of butyl acetate as an organic solvent was supplied to the dispersion, and the mixture was stirred in the ultrasonic cleaner for 1 minute to obtain a polymer particle composition.
The obtained polymer particle composition was coated on a polyethylene terephthalate film (trade name "FUJIX (registered trademark) OHP film for copier" manufactured by fuji film corporation) having a thickness of 100 μm using a 75 μm slit coater. After the coating, the resultant was placed in a dryer maintained at a temperature of 70℃for 1 hour, and the organic solvent in the polymer particle composition was evaporated and removed to obtain an optical film having a coating film formed on a polyethylene terephthalate film. In the coating film, the polymer particles are contained in a state of being dispersed in the acrylic resin.
[ Evaluation of optical Properties (less fluctuation in haze) ]
The optical film was cut into a square shape with a side length of 6cm, and a test piece was produced. The coating film of the test piece was measured for haze at each of the four corners and the center (5 total) by using a measuring device commercially available under the trade name "NDH-4000" manufactured by japan electric color industry co.
The haze difference (%) was calculated from the maximum value, minimum value and arithmetic average value of the measured haze (%) at 5 points according to the following calculation formula, and evaluated based on the following criteria.
Haze difference (%)
100× [ (Maximum haze-minimum haze)/arithmetic mean haze ]
A: the haze difference was less than 0.5%.
B: the haze difference is 0.5% or more and less than 1.0%.
C: the haze difference is 1.0% or more and less than 3.0%.
D: the haze difference was 3.0% or more.
[ Particle falling-off Property ]
An optical film was produced in the same manner as in the measurement of coatability. A20 mm X20 mm flat friction material loaded with 300g was slid 10 times on the surface of the coating film using a vibration type friction tester RT-200 commercially available from Darong scientific finisher, and observed using a digital microscope commercially available under the trade name "VHX" from KEYENCE CORPORATION. The number of polymer particle-removed sites was measured by observing arbitrary measurement sites having a square planar shape with a side length of 1mm on the surface of the coating film, and evaluation was performed based on the following criteria.
A: less than 10.
B: more than 10 and less than 20.
C: more than 20 and less than 30.
D: more than 30.
TABLE 1
(Cross-reference to related applications)
The present application claims priority based on japanese patent application nos. 2022-20484, filed on 14 at 2 months of 2022, and japanese patent application nos. 2022-137108, filed on 30 at 8 months of 2022, the disclosures of which are incorporated herein by reference in their entirety.
Industrial applicability
The present invention can provide particles which can be uniformly dispersed in a dispersion medium such as an organic solvent or a binder resin. The present invention can provide polymer particles capable of maintaining a uniform dispersion state in a coating film obtained from a polymer particle composition produced by dispersing in an organic solvent.
The polymer particles of the present invention can provide a polymer particle composition capable of easily forming a coating film in which the falling-off of the polymer particles from the surface is reduced.
Claims (12)
1. A polymer particle comprising an acrylic polymer containing 55 to 98% by mass of an acrylic monomer unit represented by the formula (1),
In the formula (1), R 1～R3 independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 4 represents a monovalent substituent having 5 to 8 carbon atoms and having a hetero ring and having a hetero atom number ratio calculated as the hetero atom number N/the constituent atom number N of the hetero ring of more than 0 and less than 0.4.
2. The polymer particle according to claim 1, wherein in the formula (1), R 4 is a monovalent substituent having the structure of the following formula (2) or (3),
In the formula (2), R 5 represents an alkylene group having 1 to 3 carbon atoms, R 7 and R 8 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 6 and R 9 each independently represent an oxygen atom, the other represents a 2-valent hydrocarbon group in which 2 hydrogen atoms bonded to the same carbon atom at the end of an aliphatic saturated hydrocarbon having 1 to 4 carbon atoms are removed, 1 represents an atomic bond and is a single bond,
In formula (3), R 10 represents an alkylene group having 1 to 3 carbon atoms, R 11～R13 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 14 and R 15 each independently represents an oxygen atom or a methylene group, and at least one represents an oxygen atom, 12 means an atomic bond and is a single bond.
3. The polymer particles according to claim 1 or claim 2, wherein the polymer particles have a coefficient of variation (CV value) of particle diameter of particle size distribution based on number basis of 15% or less.
4. The polymer particles according to claim 1 or claim 2, wherein the content of small particles is 6% or less, the small particles being small particles having a particle diameter of 50% or less of the arithmetic mean particle diameter in the particle size distribution based on the number of the polymer particles.
5. The polymer particles according to claim 1 or claim 2, wherein the dispersion coefficient is below 0.20.
6. The polymer particles of claim 1 or claim 2, for use in an optical component.
7. The polymer particles according to claim 1 or claim 2, for use in antiglare members.
8. The polymer particles according to claim 1 or claim 2, wherein the gel fraction is 91 mass% or more.
9. The polymer particles according to claim 1 or claim 2, wherein the amount of surfactant contained in 1g of the polymer particles is 40 μg/g or less.
10. A composition of matter comprising a polymer particle, characterized by comprising: a dispersion medium, and the polymer particles according to claim 1 or claim 2 dispersed in the dispersion medium.
11. An optical film, comprising:
A film; and, a step of, in the first embodiment,
A coating film formed on the film and formed from a polymer particle composition comprising a binder resin and the polymer particles of claim 1 or claim 2 dispersed in the binder resin.
12. An optical film according to claim 11, characterized in that it is an antiglare member.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022-020484 | 2022-02-14 | ||
| JP2022-137108 | 2022-08-30 | ||
| JP2022137108A JP2023118042A (en) | 2022-02-14 | 2022-08-30 | Polymer particles, polymer particle composition, and optical film |
| PCT/JP2022/048391 WO2023153109A1 (en) | 2022-02-14 | 2022-12-27 | Polymer particles, polymer particle composition, and optical film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118679197A true CN118679197A (en) | 2024-09-20 |
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ID=92717683
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280091025.XA Pending CN118679197A (en) | 2022-02-14 | 2022-12-27 | Polymer particles, polymer particle compositions, and optical films |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118679197A (en) |
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2022
- 2022-12-27 CN CN202280091025.XA patent/CN118679197A/en active Pending
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