WO2015159556A1 - 樹脂組成物、電子写真用トナーおよびホットメルト組成物 - Google Patents
樹脂組成物、電子写真用トナーおよびホットメルト組成物 Download PDFInfo
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- WO2015159556A1 WO2015159556A1 PCT/JP2015/002129 JP2015002129W WO2015159556A1 WO 2015159556 A1 WO2015159556 A1 WO 2015159556A1 JP 2015002129 W JP2015002129 W JP 2015002129W WO 2015159556 A1 WO2015159556 A1 WO 2015159556A1
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- polyethylene wax
- toner
- resin composition
- molecular weight
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08775—Natural macromolecular compounds or derivatives thereof
- G03G9/08782—Waxes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0853—Vinylacetate
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08706—Polymers of alkenyl-aromatic compounds
- G03G9/08708—Copolymers of styrene
- G03G9/08711—Copolymers of styrene with esters of acrylic or methacrylic acid
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08755—Polyesters
Definitions
- the present invention relates to a resin composition, an electrophotographic toner, and a hot melt composition.
- Polyethylene wax is a composition having a wide range of application fields, such as being used in a hot melt composition for an electrophotographic toner and a hot melt adhesive.
- Polyethylene wax is used in combination with various resins.
- polyethylene wax can be used for toner for image formation by using it together with a binder resin for toner.
- it can be used as a hot melt composition for a hot melt adhesive by blending a resin for imparting desired properties to polyethylene wax.
- the offset phenomenon refers to fixing the toner by bringing a heating member such as a heating roller into contact with the toner transferred to the paper from the image developed on the photosensitive member or directly attached to the paper on which the photosensitive layer is formed. This is a phenomenon in which a part of the toner adheres to the surface of the heating body and is transferred to the subsequent image portion.
- a nonpolar wax such as a low molecular weight polyethylene wax or a low molecular weight polypropylene wax is added to the toner, it is considered that the toner is given release properties from the heating body, so that the occurrence of an offset phenomenon is reduced.
- the above toner can be easily fixed by a relatively low temperature (around 130 ° C.) heating body (low temperature fixability), and the toner has been stored. It has been found that there is room for further improvement in the toner blocking (increase in particle size) due to the occurrence of stickiness in some cases (storability). As for the latter, it has been found that if wax blocking occurs during heat curing, the particle size of the toner increases and the handling properties may decrease.
- An object of the present invention is to provide a toner that can be easily fixed by a relatively low-temperature heating body, has good offset resistance, and has a small increase in particle diameter even when the toner is stored for a long period of time. It is to provide a useful resin composition.
- this invention relates to the following resin compositions.
- the weight average molecular weight (Mw) measured by GPC is in the range of 400-1500.
- the molecular weight distribution (Mw / Mn) measured by GPC is in the range of 1.2 to 2.5.
- the penetration measured at 25 ° C. is 5 dmm or less in accordance with JIS K 2207.
- the melting point (Tm) measured by differential scanning calorimetry (DSC) is in the range of 50 to 110 ° C.
- (V) The ratio of the heat of fusion ( ⁇ H ⁇ 50 ) derived from a peak of 50 ° C. or less to the total heat of fusion ( ⁇ H all ) derived from all the peaks measured by differential scanning calorimetry (DSC) is 1.0%. It is in the range of ⁇ 5.0%.
- the present invention also relates to the following toner.
- An electrophotographic toner comprising the resin composition according to any one of [1] to [6] and a colorant.
- a hot melt composition comprising 100 parts by mass of the resin composition according to any one of [1] to [5] and 5 to 300 parts by mass of a tackifier.
- fixing can be performed by a relatively low-temperature heating body, the offset resistance is good, and further useful for providing a toner with little increase in particle diameter even when the toner is stored for a long period of time.
- a resin composition can be provided.
- the resin composition according to an embodiment of the present invention includes at least one resin selected from the group consisting of polyethylene wax (A) satisfying the following (i) to (iv), a thermoplastic resin, and a thermosetting resin: (B) and the mass ratio of (A) to (B) ((A) / (B)) is 0.1 / 99.9 to 50/50.
- the weight average molecular weight (Mw) measured by GPC is in the range of 400-1500.
- the molecular weight distribution (Mw / Mn) measured by GPC is in the range of 1.2 to 2.5.
- the penetration measured at 25 ° C. is 5 dmm or less in accordance with JIS K 2207.
- the melting point (Tm) measured by differential scanning calorimetry (DSC) is in the range of 50 to 110 ° C.
- the mass ratio [(A) / (B)] of the polyethylene wax (A) and the resin (B) is 0.1 / 99.9 to 50/50, preferably 1 / 99 to 50/50, more preferably 2/98 to 30/70, and still more preferably 8/92 to 25/75.
- the mass ratio is 0.1 / 99.9 to 50/50, the resin composition of the present invention can easily achieve both handling properties and a reduction effect of the deformation start temperature at the time of temperature rise.
- the mass ratio [(A) / (B)] of the polyethylene wax (A) and the resin (B) is preferably 0.1 / 99.9 to 30/70. It is.
- the more preferred lower limit of the polyethylene wax (A) is such that the mass ratio [(A) / (B)] of the polyethylene wax (A) and the resin (B) is 0.5 / 99.5, more preferably 1.0. /99.0, particularly preferably 1.5 / 98.5, most preferably 2.0 / 98.0.
- the more preferable upper limit value of the polyethylene wax (A) is that the mass ratio [(A) / (B)] of the polyethylene wax (A) and the resin (B) is 25/75, more preferably 15/85, particularly preferably. 10/90, most preferably 6/94.
- the mass ratio [(A) / (B)] is less than 0.1 / 99.9, the toner may have insufficient offset resistance and storage stability.
- the mass ratio [(A) / (B)] exceeds 30/70, the fixing property and particularly the fixing stability with time after printing become insufficient, that is, the character part is easily peeled off from the paper surface, and information is stored. May not be used.
- the mass ratio [(A) / (B)] of the polyethylene wax (A) and the resin (B) is preferably 1/99 to 50/50. is there.
- the mass ratio is more preferably 15/85 to 45/55 in order to easily reduce the melt viscosity while maintaining good adhesiveness.
- the polyethylene wax (A) of the present invention has (i) a weight average molecular weight (Mw) measured by GPC of 400 to 1500, preferably 400 to 1300, more preferably 400 to 1000, and particularly preferably 500 to 1000. is there.
- Mw weight average molecular weight measured by GPC
- the component having too high molecular weight is small, so that the miscibility with the resin (B) and other resins is improved.
- there are comparatively few components whose molecular weight is too small extreme stickiness does not generate
- the weight average molecular weight (Mw) of the polyethylene wax (A) can be measured by GPC. GPC measurement can be performed under the following conditions.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) described later can be obtained based on the following conversion method by creating a calibration curve using commercially available monodisperse standard polystyrene (PS).
- the coefficient of the Mark-Houwink viscosity equation can be used for calculation of general-purpose calibration.
- the values described in the literature J. Polym. Sci., Part A-2, 8, 1803 (1970), Makromol. Chem., 177, 213 (1976)) are used for the Mark-Houwink coefficients of PS and PE, respectively. be able to.
- the polyethylene wax (A) of the present invention has (ii) molecular weight distribution (Mw / Mn) measured by GPC in the range of 1.2 to 2.5, preferably 1.3 to 2.5.
- Mw / Mn molecular weight distribution measured by GPC in the range of 1.2 to 2.5, preferably 1.3 to 2.5.
- the polyethylene wax (A) of the present invention has a penetration of 5 dmm or less, preferably 4 dmm or less, measured at 25 ° C. according to (iii) JIS K 2207.
- the resin composition when polyethylene wax (A) having a penetration of 5 dmm or less measured at 25 ° C. is used for the resin composition, the resin composition has high hardness. Natural binding between the compositions is easily prevented.
- the polyethylene wax (A) of the present invention has (iv) a melting point (Tm) measured by differential scanning calorimetry (DSC) in the range of 50 to 110 ° C., preferably 60 to 110 ° C., more preferably 65 to 110 ° C. It is particularly preferably in the range of 65 to 100 ° C.
- Tm melting point measured by differential scanning calorimetry
- the melting point (Tm) of polyethylene wax (A) can be measured by DSC-20 (manufactured by Seiko Denshi Kogyo Co., Ltd.) according to DSC (differential scanning calorimetry). About 10 mg of the sample is heated from ⁇ 20 ° C. to 200 ° C. at 10 ° C./min, and the temperature of the endothermic peak of the obtained curve can be obtained as the melting point. Before the temperature rise measurement, the sample (polyethylene wax (A)) is once heated to about 200 ° C., held for 5 minutes, and then cooled to room temperature ( ⁇ 20 ° C.) at 20 ° C./min. It is preferable to unify the thermal history of the sample (polyethylene wax (A)). When there are a plurality of endothermic peaks in the obtained curve, the peak temperature at which the endothermic amount at the endothermic peak is the largest is taken as the melting point (Tm).
- the polyethylene wax (A) of the present invention has (v) the heat of fusion derived from the peak of 50 ° C. or less with respect to the total heat of fusion ( ⁇ H all ) derived from all the peaks obtained from the results of differential scanning calorimetry (DSC).
- the ratio of ( ⁇ H ⁇ 50 ) is usually 1.0 to 20.0%, preferably 1.0 to 10.0%, more preferably 1.0 to 5.0%.
- the amount of heat of fusion can be calculated as the amount of heat of fusion ( ⁇ H) (J / g) divided by the endothermic peak obtained by DSC and the baseline of the entire endothermic peak.
- the polyethylene wax (A) of the present invention preferably has (vi) two or more melting peaks measured by DSC.
- DSC melting peak measured by DSC
- the difference in peak temperature between adjacent melting peaks is preferably 5 ° C. or more and 30 ° C. or less.
- B (hereinafter also referred to as B value) is a component in the polyethylene wax (A), which is a component having a molecular weight in terms of polyethylene of 5000 or more when measured by gel permeation chromatography.
- the content ratio (% by mass) of K is the melt viscosity (mPa ⁇ s) at 140 ° C. of the polyethylene wax (A) measured with a Brookfield (B type) viscometer.
- polyethylene wax (A) satisfying the above formula (I) has few extremely high molecular weight components, when such polyethylene wax (A) is used in a resin composition, resin (B) and other resins The deterioration of miscibility is suppressed.
- the polyethylene wax (A) according to the present invention preferably has an intrinsic viscosity [ ⁇ ] measured in decalin at 135 ° C. in the range of 0.01 to 0.10 dl / g.
- the polyethylene wax (A) according to the present invention more preferably has an intrinsic viscosity [ ⁇ ] of 0.02 dl / g or more, more preferably 0.03 dl / g or more.
- the intrinsic viscosity [ ⁇ ] is more preferably 0.09 dl / g or less, further preferably 0.08 dl / g or less, particularly preferably 0.07 dl / g or less.
- the polyethylene wax (A) having an intrinsic viscosity [ ⁇ ] of 0.10 dl / g or less tends to increase the miscibility with the resin (B) and other resins.
- the polyethylene wax (A) having an intrinsic viscosity [ ⁇ ] of 0.01 dl / g or more has good miscibility with the resin (B) and other resins, and has relatively few components that cause extreme stickiness. Therefore, the handling property of the resin composition is improved.
- the polyethylene wax (A) of the present invention contains a structural unit derived from ethylene.
- the polyethylene wax (A) of the present invention is preferably an ethylene homopolymer.
- the polyethylene wax (A) of the present invention contains a small amount of structural units derived from ⁇ -olefins having 3 to 10 carbon atoms other than ethylene, for example, 0.1 mol% of all structural units of the polyethylene wax (A). It may be included in an amount less than.
- Specific examples of the ⁇ -olefin having 3 or more carbon atoms include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene.
- the absence of a structural unit derived from an ⁇ -olefin having 3 to 10 carbon atoms is also one of preferred embodiments from the viewpoint of storage stability of the toner when blended in the toner.
- the polyethylene wax (A) of the present invention includes olefin polymerizable monomers other than ethylene, such as vinyl acetate; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; methyl acrylate, ethyl acrylate, isobutyl acrylate, acrylic acid unsaturated carboxylic esters such as n-butyl, 2-ethylhexyl acrylate, methyl methacrylate, glycidyl methacrylate, dimethyl maleate; structural units derived from olefin polymerizable monomers such as styrene, all of polyethylene wax (A) Although it may be contained in the structural unit in an amount of 0.1 mol% or less, it is preferably not contained from the viewpoint of the hardness of the polyethylene wax (A).
- the polyethylene wax (A) according to the present invention may be obtained by directly polymerizing ethylene or the like, or may be obtained by thermally decomposing a high molecular weight ethylene copolymer.
- the polyethylene wax (A) may be purified by a method such as solvent fractionation that is fractionated based on a difference in solubility in a solvent, or distillation. Further, it may be obtained from one kind of ethylene polymer, or may be obtained by mixing two or more kinds of ethylene polymers.
- the polyethylene wax (A) according to the present invention is obtained by directly polymerizing ethylene or the like, various known production methods, for example, ethylene and, if necessary, an ⁇ -olefin having 3 to 10 carbon atoms, a Ziegler / Natta catalyst or
- the polyethylene wax (A) can be produced by a production method in which polymerization is performed using a metallocene catalyst or the like.
- the polymerization of the polyethylene wax (A) is carried out by a suspension polymerization method in which the monomer to be polymerized and the polymerized polyethylene wax (A) are polymerized in the state of being present as particles in an inert hydrocarbon medium such as hexane,
- a gas phase polymerization method in which polymerization is performed without using a solvent
- a solution polymerization method in which a monomer to be polymerized and a polymerized polyethylene wax (A) coexist with an inert hydrocarbon medium or are melted alone are possible.
- solution polymerization is preferable in terms of both economy and quality.
- the polymerization reaction may be performed by either a batch method or a continuous method.
- the polymerization can be carried out in two or more stages having different reaction conditions.
- Examples of the inert hydrocarbon medium used in the suspension polymerization method and the solution polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane And alicyclic hydrocarbons such as methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane.
- An inert hydrocarbon medium may be used individually by 1 type, and 2 or more types may be mixed and used for it.
- a so-called bulk polymerization method in which liquefied ⁇ -olefin itself that can be supplied to the polymerization is used as a solvent can also be used.
- a metallocene catalyst is preferable.
- the metallocene catalyst include (a) a metallocene compound of a transition metal selected from Group 4 of the periodic table, (b) (b-1) an organoaluminum oxy compound, and (b-2) a metallocene compound (a).
- a catalyst comprising a compound that reacts to form an ion pair hereinafter sometimes abbreviated as “ionized ionic compound”
- b-3 at least one compound selected from organoaluminum compounds is suitable.
- transition metal metallocene compounds (a) selected from Group 4 of the periodic table include metallocene compounds described in JP-A No. 08-239414 and International Publication No. WO2007 / 114102. Among them, bis (n -Butylcyclopentadienyl) zirconium dichloride and bis (n-butylcyclopentadienyl) zirconium dimethyl are particularly preferably used. *
- organoaluminum oxy compound (b-1) a conventionally known aluminoxane can be used as it is. Examples thereof include organoaluminum oxy compounds described in Japanese Patent Application Laid-Open No. 08-239414 and International Publication WO2007 / 114102.
- organoaluminum oxy compound (b-1) methylaluminoxane which is easily available for commercial products and modified methylaluminoxane (MMAO) prepared using trimethylaluminum and triisobutylaluminum are preferable.
- MMAO modified methylaluminoxane
- Examples of the ionized ionic compound (b-2) include ionized ionic compounds described in JP-A-08-239414 and International Publication No. WO2007 / 114102. Since the ionized ionic compound (b-2) is easily available as a commercial product and greatly contributes to the improvement of the polymerization activity, triphenylcarbenium tetrakis (pentafluorophenyl) borate and N, N-dimethyl are used. Anilinium tetrakis (pentafluorophenyl) borate is preferred.
- organoaluminum compound (b-3) examples include organoaluminum compounds described in International Publication WO2007 / 114102 Pamphlet.
- organoaluminum compound (b-3) trimethylaluminum, triethylaluminum and triisobutylaluminum that are easily available for commercial products are preferable. Of these, triisobutylaluminum that is easy to handle is particularly preferred.
- the content of each component can be set as follows.
- the metallocene compound (a) can be used in an amount of 10 ⁇ 9 to 10 ⁇ 1 mol, preferably 10 ⁇ 8 to 10 ⁇ 2 mol, per liter of reaction volume.
- a catalyst containing a metallocene compound (a) and an organoaluminum oxy compound (b-1) is used as a component of an olefin polymerization catalyst, the compound (b-1) is contained in the compound (b-1).
- the molar ratio [Al / M] of aluminum atoms (Al) in the metal to all transition metal atoms (M) in the metallocene compound (a) is 0.01 to 5000, preferably 0.05 to 2000 Can be used.
- the compound (b-2) is composed of the compound (b-2) and the metallocene.
- the compound (a) can be used in such an amount that the molar ratio [(b-2) / M] to all transition metal atoms (M) in the compound (a) is 1 to 10, preferably 1 to 5.
- a catalyst containing a metallocene compound (a) and an organoaluminum compound (b-3) is used as a component of the olefin polymerization catalyst, the compound (b-3) and all of the metallocene compound (a)
- the molar ratio [(b-3) / M] with the transition metal atom (M) is usually 0.01 to 50000, preferably 0.05 to 10,000.
- the polymerization temperature is usually in the range of 10 to 200 ° C. From the viewpoint of producing the polyethylene wax (A) having a content of units derived from ⁇ -olefin in the preferred range described above, the polymerization temperature is It is preferably in the range of 60 to 180 ° C, more preferably in the range of 75 to 170 ° C.
- the polymerization pressure can be normal pressure to 7.8 MPa-G (G is a gauge pressure), preferably normal pressure to 4.9 MPa-G (G is a gauge pressure).
- a molecular weight regulator such as hydrogen can be added.
- the produced polymer is usually obtained as a polymerization solution containing the polymer, so that polyethylene wax (A) can be obtained by treatment by a conventional method.
- the polymer obtained by the above method is degassed under vacuum at a temperature equal to or higher than the melting point, such as methanol, acetone, etc. once dissolved in a solvent such as toluene, xylene, hexane, heptane, etc. Further purification may be performed by a method in which a polar solvent is added and filtered to remove the low molecular weight part, or a method in which the entire amount is dissolved in the solvent and then precipitated at a specific temperature to remove the high molecular weight or low molecular weight part.
- the weight average molecular weight Mw and intrinsic viscosity [ ⁇ ] of the polyethylene wax (A) according to the present invention tend to decrease when the polymerization temperature at the time of polymerization is increased or the hydrogen concentration is increased, and can be controlled within the above range. Or it can adjust with the usage-amount of the organoaluminum oxy compound and / or ionized ionic compound used as a cocatalyst. Further, it can be adjusted by purification after polymerization.
- Mw / Mn of the polyethylene wax (A) according to the present invention can be controlled by catalyst type, polymerization temperature and the like.
- a Ziegler-Natta catalyst or a metallocene catalyst is used for the polymerization of polyethylene wax, but a metallocene catalyst is preferably used in order to obtain a suitable range of Mw / Mn.
- the penetration of polyethylene wax (A) can be controlled within the above range depending on the catalyst type and polymerization temperature. It can also be adjusted by purification after polymerization.
- the melting point of the polyethylene wax (A) can be controlled within the above range depending on the catalyst type and the polymerization temperature. It can also be adjusted by purification after polymerization.
- the number of endothermic peaks in the DSC measurement of polyethylene wax (A) can be controlled by the catalyst type, polymerization temperature, and the like. It can also be obtained by mixing two or more kinds of polyethylene waxes.
- the ratio of the heat of fusion ( ⁇ H ⁇ 50 ) derived from the peak of 50 ° C. or less to the total heat of heat ( ⁇ H all ) of the polyethylene wax (A) can be controlled within the above range by controlling the catalyst species and the polymerization temperature. It can also be adjusted by purification after polymerization.
- a weather resistance stabilizer In the polyethylene wax (A) according to the present invention, a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an anti-slip agent, an antiblocking agent, an antifogging agent, a nucleating agent, as long as the object of the present invention is not impaired.
- Additives such as lubricants, pigments, dyes, plasticizers, anti-aging agents, hydrochloric acid absorbents, antioxidants, copper damage inhibitors and fillers may be blended as necessary.
- the polyethylene wax (A) according to the present invention is represented by additives for paints, polishes, polyolefins and engineering plastics, in addition to being used as a hot melt composition for toner additives or hot melt adhesives. Fluidity improvers, resin strength improvers, resin compatibilizers, resin lubricants, resin hardness / melting point modifiers, resin molding release agents, urethane release agents for various thermoplastic resins or thermosetting resins Molding agents, rubber processing aids, rubber antioxidants, paper quality improvers, various additives such as anti-wear and leveling agents for printing inks, thermal transfer ink additives, textile processing aids, electricity Insulating agent, natural wax compounding agent, polyolefin film antifogging agent, pigment dispersant (dispersant for pigment masterbatch), molding processing aid, antioxidant for rubber, paper coating , Emulsion components, floor polish additives, textile finishes, PVC lubricants, heat resistant PVC lubricants, asphalt additives, foamed polystyrene
- the resin (B) contained in the resin composition of the present invention is at least one selected from the group consisting of thermoplastic resins and thermosetting resins.
- Thermoplastic resins include olefin resin, styrene resin, thermoplastic polyester resin, polyamide, polycarbonate, polyacetal, polyphenylene oxide, polyimide, polyvinyl alcohol, polyvinyl acetate, acrylic resin, rosin resin, alkyd resin, coumarone resin, ketone Examples thereof include resins, cellulosic resins, chlorinated polyolefins, and mixed resins thereof.
- thermosetting resin examples include polyurethane, epoxy resin, thermosetting unsaturated polyester resin, urea resin, melamine resin and phenol resin, and mixed resins thereof.
- Resin (B) may be composed of one of these thermoplastic resins and thermosetting resins, or may be a combination of two or more.
- thermoplastic resin or thermosetting resin may contain fibers and organic fillers as long as the object of the present invention is not impaired.
- thermoplastic resins or thermosetting resins are well known, and are described in publications such as “Practical Plastics Dictionary” (edited by the Practical Plastics Dictionary Editorial Board, published by the Industrial Research Council, Inc.).
- Resin (B) is preferably a thermoplastic resin. Since mixing of the polyethylene wax (A) and the resin (B) can be performed at a high temperature (for example, 100 ° C. or higher), the resin (B) being mixed can be obtained by using the resin (B) as a thermoplastic resin. Can be prevented, and the dispersion of the polyethylene wax (A) in the resin (B) can be easily made uniform.
- Resin (B) may be obtained by graft copolymerization of a polar monomer as required.
- polar monomers include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, unsaturated carboxylic acids and their anhydrides and derivatives, and vinyl ester compounds. .
- the resin (B) when the resin composition of the present invention is used for toner corresponds to a binder resin for toner.
- the binder resin for toner various known binder resins can be used as the resin (B).
- styrene polymer ketone resin, maleic resin, aliphatic polyester resin, aromatic polyester resin, polyester resin such as aliphatic / aromatic polyester resin, coumarone resin, phenol resin, epoxy resin
- amorphous resins such as terpene resin, polyvinyl butyral, polybutyl methacrylate, polyvinyl chloride, polyethylene (however, Mw is higher than 1500), polypropylene, polybutadiene, and ethylene / vinyl acetate copolymer.
- binder resins for toner can be used alone or in combination of two or more.
- at least one resin selected from the group consisting of polyester resins and styrenic polymers has an appropriate softening point of around 100 ° C. and exhibits good fixability. Styrene polymers are particularly preferred.
- styrenic polymer examples include a homopolymer or a copolymer composed of only a styrenic monomer, or a copolymer of a styrenic monomer and another vinyl monomer.
- styrene monomer examples include styrene, p-chlorostyrene, vinyl naphthalene and the like.
- Examples of the other vinyl monomers include ethylenically unsaturated monoolefins such as ethylene, propylene, 1-butene and isobutene; vinyl halides such as vinyl chloride, vinyl bromide and vinyl fluoride; acetic acid Vinyl esters such as vinyl, vinyl propionate, vinyl benzoate and vinyl butyrate; ⁇ -methylene aliphatic monocarboxylic acids such as acrylic acid and methacrylic acid; methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid ⁇ -methylene aliphatic monocarboxylic acids such as isobutyl, n-octyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl ⁇ -chloroacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate Esters of acrylonitrile, methacryl
- esters of ⁇ -methylene aliphatic monocarboxylic acid are preferred.
- a method for synthesizing a styrene polymer it can be produced by a known polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method and an emulsion polymerization method.
- the resin (B) when the resin composition of the present invention is used for a hot melt composition may be a polymer usually used for a hot melt adhesive, and examples thereof are as follows. Can do.
- EVA Ethylene-vinyl acetate copolymer
- Modified EVA polymers such as saponified EVA and graft-modified EVA
- Ethylene / (meth) acrylate copolymers such as ethylene / (meth) ethyl acrylate (EEA) (however, Mw is higher than 1500)
- An ionomer resin obtained by partially neutralizing an ethylene / (meth) acrylic acid copolymer Specific examples include those marketed by Mitsui DuPont Polychemicals under the trade name: High Milan.
- Ethylene / propylene copolymer or ethylene / propylene / (meth) acrylic acid terpolymer (however, Mw is higher than 1500) 7)
- Polyamide Reaction product of dibasic acid and diamine, for example, reaction product of dimer acid, which is a dimer of fatty acids such as soybean oil, tung oil, tall oil and the like, and alkyl diamine such as ethylenediamine and diethylenetriamine And nylons such as nylon 12. Specific examples thereof include Daiamide (Daicel Chemical Industries), Platilon (Toa Gosei Chemical Industry), Amilan (Toray), and the like.
- Polyester examples include ester resins 200 and 300 (Toyobo), Vita 1200, 300 (Goodyear).
- Propylene-based polymer atactic polypropylene, propylene / ⁇ -olefin copolymer having 4 or more carbon atoms and the like.
- Copolymer comprising vinyl aromatic compound and conjugated diene compound, and hydrogenated product thereof: specifically, styrene / butadiene random copolymer, styrene / isoprene random copolymer, butadiene / polystyrene block copolymer , Polystyrene / polyisoprene block copolymer, polystyrene / polyisoprene / polystyrene triblock copolymer, polystyrene / polybutadiene / polystyrene triblock copolymer, poly ( ⁇ -methylstyrene) / polybutadiene / poly ( ⁇ -methylstyrene) Examples include triblock copolymers and hydrogenated products thereof.
- the resin (B) is preferably 2) an ethylene-vinyl acetate copolymer (EVA), 6) an ethylene / propylene copolymer, 6) an ethylene / propylene / (meth) acrylic acid terpolymer, and 9) a propylene-based polymer. From the viewpoint of compatibility with polyethylene wax (A), 2) ethylene-vinyl acetate copolymer (EVA) is particularly preferred.
- EVA ethylene-vinyl acetate copolymer
- resins (B) can be obtained as commercial products.
- examples of the resin (B) include Califlex TR-1101, TR-1107, TR-4113 (manufactured by Shell Chemical Co., Ltd.), Kraton G-6500, G-6521, G-1650, G-1652, G-1657 ( Shell Chemical Co., Ltd.), sorbulene, hydrogenated sorbulene (manufactured by Philips), and the like.
- Resin (B) may be used individually by 1 type, or may be used in combination of 2 or more type.
- the resin composition of the present invention contains the polyethylene wax (A) and the resin (B).
- the resin composition of the present invention is within a range that does not impair the object of the present invention, and other thermoplastic resins, weather resistance stabilizers, heat stabilizers, antistatic agents, anti-slip agents, antiblocking agents, Further includes additives such as fogging agent, nucleating agent, lubricant, pigment, organic filler, inorganic filler, fiber, filler, dye, plasticizer, anti-aging agent, hydrochloric acid absorbent, antioxidant, copper damage inhibitor You may go out.
- fibers examples include glass fiber, carbon fiber, natural fiber (wood flour, wood fiber, bamboo, cotton, cellulose, nanocellulosic fiber, etc.) or agricultural fiber (straw, hemp, flax, kenaf, kapok, jute) Ramie, sisal, henecken, corn fiber or coir, or nut shell or rice husk).
- organic fillers include lignin, starch, and products containing the same.
- the type of glass fiber is not particularly limited, but roving glass, chopped strand glass, milled glass, and the like can be used. These may be used alone or in combination of two or more.
- the shape and type of the carbon fiber are not particularly limited, and the shape may be a chopped strand, a roving strand, a milled fiber, or the like, and the type may be either pitch-based or polyacrylonitrile-based. In addition to those obtained by spinning or molding these raw material compositions and then carbonizing them, it is also possible to use carbon fibers obtained basically without passing through a spinning step as in the vapor phase growth method.
- Fillers include calcium carbonate, silica, kaolin, clay, titanium oxide, barium sulfate, zinc oxide, amorphous fillers such as aluminum hydroxide, alumina, magnesium hydroxide, plate shapes such as talc, mica, or glass flakes. Fillers, wollastonite, potassium titanate, basic magnesium sulfate, sepiolite, zonotlite, acicular fillers such as aluminum borate, metal powder, metal flakes, fillers such as carbon black and carbon fine particles, and the like are used. Other glass beads, glass powder, etc. are used. These fillers may be used alone or in combination, or those whose surfaces are subjected to carbon coating or silane coupling treatment may be used alone or in combination.
- the resin composition of the present invention can be produced by dry blending or melt blending using any of various methods.
- polyethylene wax (A), resin (B) and other optional components can be added simultaneously or in any order in a tumbler, V-type blender, Nauter mixer, Banbury mixer, kneading roll, A blending method using a twin or twin screw extruder is appropriately used.
- the polyethylene wax (A), the resin (B), and other optional components are once dispersed or dissolved in an arbitrary solvent, and then dried by an appropriate method such as natural drying or heat forced drying, You may blend.
- An electrophotographic toner according to an embodiment of the present invention includes the resin composition and a colorant.
- the toner of the present invention further contains a charge control agent, a release agent, a pigment dispersant and the like as necessary.
- Examples of the colorant contained in the toner of the present invention include known black pigments such as carbon black, acetylene black, lamp black, and magnetite; known inorganic pigments such as yellow lead, yellow iron oxide, titanium oxide, and zinc white; Yellow G, Quinoline Yellow Lake, Permanent Yellow NCG, Molybdenum Orange, Vulcan Orange, Indanthrene, Brilliant Orange GK, Bengala, Brilliant Carmine 6B, Fritherin Lake, Methyl Violet Lake, Fast Violet B, Cobalt Blue, Alkaline Blue Lake, Phthalocyanine Blue And known organic pigments such as First Sky Blue, Pigment Green B, Malachite Green Lake and the like.
- the content of the colorant is usually 5 to 250 parts by mass with respect to 100 parts by mass of the resin composition.
- the toner of the present invention includes, for example, polyvinyl chloride, polyvinyl acetate, polyolefin, polyester, polyvinyl butyral, polyurethane, polyamide, rosin, modified rosin, and terpene as long as the effects of the present invention are not impaired as required.
- Resin phenol resin, aliphatic hydrocarbon resin, aromatic petroleum resin, paraffin wax, polyolefin wax (excluding the polyethylene wax (A) of the present invention), ceramic wax, rice wax, sugar wax, urushi wax, bean paste, carnauba wax
- a part of conventionally known release agents such as natural waxes such as candelilla wax and montan wax, fatty acid amide wax, vinyl chloride resin, styrene-butadiene resin, chroman-indene resin and melamine resin may be used.
- the amount is 0.1 to 40 parts by mass with respect to 100 parts by mass of the resin composition.
- the monomer constituting the polyolefin wax includes, for example, ethylene, propylene, 1-butene, 1-pentene and all other olefin monomers.
- the polyolefin wax obtained from these monomers may be a homopolymer type obtained from a single monomer, or may be a copolymer type obtained from two or more monomers.
- the polyolefin wax may be either an unmodified polyolefin wax or a modified polyolefin wax in which a modified component is blocked or grafted with respect to an olefin component.
- modifying component in the modified polyolefin wax examples include aromatic monomers such as styrene, methylstyrene, p-ethylstyrene, and pn-butylstyrene, and monocarboxylic acids such as methyl (meth) acrylate and ethyl (meth) acrylate.
- Ester monomers maleic acid, fumaric acid, itaconic acid, crotonic acid, nadic acid, dicarboxylic acids such as methylhexahydrophthalic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, allyl succinic anhydride, glutaconic anhydride, nadic anhydride
- dicarboxylic acids such as methylhexahydrophthalic acid
- maleic anhydride, itaconic anhydride, citraconic anhydride allyl succinic anhydride, glutaconic anhydride, nadic anhydride
- anhydrides such as acids.
- charge control agent known charge control agents including nigrosine, quaternary ammonium salts and metal-containing azo dyes can be appropriately selected and used, and the amount used is usually used with respect to 100 parts by mass of the resin composition. 0.1 to 10 parts by mass.
- the toner of the present invention can be produced by employing any conventionally known method, for example, contact dispersion, melt dispersion, solution dispersion and the like.
- the toner of the present invention is produced by melt dispersion
- the polyethylene wax (A), the resin (B) used as a toner binder resin, a colorant, a charge control agent, a release agent, and the like are used in a ball mill, a Henschel mixer.
- a mixer such as a hot roll kneader
- knead in a heated and melted state using a heat kneader such as a hot roll kneader, uniaxial or biaxial kneader, and then finely pulverized using a fine pulverizer such as a hammer mill after cooling
- the particles are classified by an air classifier, and usually particles having a diameter in the range of 8 to 20 ⁇ m are collected to obtain a toner.
- the heating and melting conditions in the case of kneading with the biaxial heat kneader differ depending on physical properties such as the melting point of the resin (B) used as the binder resin for toner.
- the resin temperature of the biaxial kneader discharge part is preferably less than 190 ° C. and the residence time is less than 180 seconds.
- the cooling method is preferably a rapid cooling using a steel belt cooler or the like.
- a master batch is prepared in which the polyethylene wax (A) is kneaded with the resin (B) using the polyethylene wax (A) as a binder resin for toner under the condition that the content of the polyethylene wax (A) is high.
- this is further kneaded with other components such as a binder resin for toner and a colorant. This method is effective when the resin (B) used as the binder resin for toner and the polyethylene wax (A) are a combination that is relatively difficult to mix.
- the polyethylene wax (A) is 5 to 900 parts by weight, preferably 5 to 300 parts by weight, more preferably 100 parts by weight of the resin (B) used as the binder resin for toner. 5 to 100 parts by mass, particularly preferably 5 to 50 parts by mass.
- the toner of the present invention includes a resin particle dispersion in which resin particles are dispersed in a dispersant, a colorant dispersion in which colorant particles are dispersed in a dispersant, and a polyethylene wax (A) a mixing step of mixing a release agent particle dispersion liquid in which particles are dispersed, an aggregating step of forming aggregated particles corresponding to the toner particle diameter, and a fusion step of fusing the aggregated particles by heating It can also be manufactured by a method including:
- the toner of the present invention can also be produced by a method including a step of polymerizing a composition comprising a polymerizable monomer, a colorant, polyethylene wax (A), a charge control agent and the like.
- the storage stability is improved and the toner quality is less likely to vary.
- the number of molecules having a large molecular weight is small, the penetration property of the toner into the printing medium is improved, so that it is considered that the fixing property and development durability of printing are improved.
- the weight average molecular weight (Mw) of the polyethylene wax (A) is 400 or more, the number of molecules having a molecular weight that is too small is reduced. Therefore, blocking due to stickiness of the polyethylene wax (A), polyethylene wax (A), and toner The polyethylene wax (A) is hardly detached from the resin composition containing the resin (B) used as the binder resin. Therefore, it is considered that the storage stability of the toner itself is improved and the stability of the toner after printing is improved.
- the ratio of the heat of fusion ( ⁇ H ⁇ 50 ) derived from the peak of 50 ° C. or less to the total heat of fusion ( ⁇ H all ) is usually 1.0 to 20.0%, preferably 1.0 to 10 0.0%, more preferably 1.0 to 5.0%.
- a resin composition having a polyethylene wax (A) having a ratio of ⁇ H ⁇ 50 in the above range is used for the toner, the low-temperature fixability of the toner can be enhanced.
- the ratio of the heat of fusion ( ⁇ H -50 ) derived from the peak of 50 ° C. or less to the total heat of fusion ( ⁇ H all ) not more than the above upper limit value, natural deformation or natural binding between the resin compositions is difficult. Therefore, it is considered that it is easy to achieve both low-temperature fixability and storage stability of the toner.
- the miscibility with the resin (B) used as a binder resin for toner and other resins is considered to be sufficient, and the toner composition tends to be uniform, so that the toner particles melt and adhere to the paper. After that, it becomes easy to harden again, and it is considered that the offset resistance is likely to increase. Further, when the composition is uniform, it is considered that the storage stability is likely to be improved and the toner quality is less likely to vary.
- the resin composition contains blocking due to stickiness of the polyethylene wax (A) and the resin (B) used as the binder resin for the toner and the polyethylene wax (A).
- the polyethylene wax (A) is hardly detached from the product. Therefore, it is considered that the storage stability of the toner itself is improved and the stability of the toner after printing is sufficient.
- the polyethylene wax (A) according to the present invention does not have a polar group, it is difficult to absorb moisture, has a low surface tension, and is appropriately dispersed in the binder resin, thereby improving the storage stability due to less blocking. In addition, it is considered that offset resistance is also improved. Further, it is considered that development durability is improved by appropriate dispersion.
- the use of the toner of the present invention is not particularly limited. It can also be used as a five-component developer, a magnetic one-component developer containing no magnetic carrier in a toner, or a one-component developer not using a carrier or magnetic powder, or a microtoning developer Can also be used.
- the toner of the present invention has two components or one. When used as a five-component developer, any conventionally known carrier can be used as the carrier.
- Examples of the carrier that can be used include magnetic powder such as iron powder, ferrite powder, and nickel powder, glass beads, and the like, or those whose surfaces are treated with resin or the like.
- Examples of the resin for coating the carrier surface include styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, acrylic acid ester copolymer, methacrylic acid ester copolymer, fluorine-containing resin, silicon-containing resin, and polyamide.
- Examples thereof include a resin, an ionomer resin, a polyphenylene sulfide resin, and a mixture thereof.
- the hot melt composition according to an embodiment of the present invention includes the resin composition and a tackifier (C).
- a tackifier (C) can be mix
- the tackifier (C) include aliphatic hydrogenated tackifiers, rosins, modified rosins or esterified products thereof, aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, aliphatic Ingredients and aromatic copolymerized petroleum resins, low molecular weight styrene resins, isoprene resins, alkylphenol resins, terpene resins, coumarone / indene resins and the like are included.
- the tackifier (C) may be used alone or in combination of two or more.
- the tackifier (C) can be appropriately selected according to the resin (B) contained in the resin composition.
- the resin (B) contained in the resin composition.
- EVA ethylene-vinyl acetate copolymer
- the content of the tackifier (C) is preferably 5 to 300 parts by mass with respect to 100 parts by mass of the resin composition, so as to make it easy to develop an adhesive force while maintaining an appropriate melt viscosity. Therefore, the amount is more preferably 50 to 200 parts by mass.
- the hot melt composition of the present invention may further contain an unmodified polyolefin such as, for example, a sazol wax (H-1: manufactured by Sazol Co., Ltd.) blended in a normal hot melt adhesive.
- an unmodified polyolefin such as, for example, a sazol wax (H-1: manufactured by Sazol Co., Ltd.) blended in a normal hot melt adhesive.
- the hot melt composition of the present invention if necessary, within a range that does not impair the purpose of the present invention, such as various compounding agents such as a softening agent, a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an anti-slip agent, Add additives such as anti-blocking agents, anti-fogging agents, nucleating agents, lubricants, pigments, fillers, dyes, plasticizers, anti-aging agents, hydrochloric acid absorbents, antioxidants, copper damage inhibitors as necessary. be able to.
- various compounding agents such as a softening agent, a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an anti-slip agent
- Add additives such as anti-blocking agents, anti-fogging agents, nucleating agents, lubricants, pigments, fillers, dyes, plasticizers, anti-aging agents, hydrochloric acid absorbents, antioxidants, copper damage inhibitors as necessary. be able to.
- the hot melt composition of the present invention can be obtained by supplying each of the above components to a mixer such as a Brabender, heating and melt-mixing; and molding it into a desired shape, for example, a granular shape, a flake shape, a rod shape, etc. it can.
- a mixer such as a Brabender, heating and melt-mixing
- a desired shape for example, a granular shape, a flake shape, a rod shape, etc. it can.
- the hot melt composition of the present invention is, for example, heated and melted and applied to an article to be coated such as cloth, kraft paper, aluminum foil, and polyester film by a usual method to form a hot melt adhesive layer. Can be used.
- the hot melt composition of the present invention contains a low-melting polyethylene wax (A), and therefore can be melted even at a low temperature.
- the weight average molecular weight (Mw) of the polyethylene wax (A) is 1500 or less, the number of molecules having a large molecular weight is decreased, so that the miscibility with the resin (B) and the tackifier is considered to be sufficient. Therefore, since the composition of the hot melt composition tends to be uniform, it is considered that the heat resistant adhesiveness and the solidification speed are improved.
- the weight average molecular weight (Mw) of the polyethylene wax (A) is 400 or more, the number of molecules having a molecular weight that is too small decreases, so that blocking due to stickiness of the polyethylene wax (A) and polyethylene wax from a hot melt composition are possible. Inhibition of detachment and crystallization of (A) hardly occurs. Therefore, it is considered that the heat resistant adhesiveness and the solidification speed are improved.
- the hot melt composition has low-temperature adhesiveness. Can do. Further, due to the effect of other requirements, the toner of the present invention is considered to have good heat-resistant adhesiveness while having low-temperature adhesiveness.
- the ratio of the heat of fusion ( ⁇ H ⁇ 50 ) derived from the peak of 50 ° C. or less to the total heat of fusion ( ⁇ H all ) is usually 1.0 to 20.0%, preferably 1.0 to 10 0.0%, more preferably 1.0 to 5.0%.
- a resin composition having a polyethylene wax (A) having a ratio of ⁇ H ⁇ 50 in the above range is used in the hot melt composition, the solidification rate can be increased.
- the ratio of the heat of fusion ( ⁇ H -50 ) derived from the peak of 50 ° C. or less to the total heat of fusion ( ⁇ H all ) not more than the above upper limit value, natural deformation or natural binding between the resin compositions is difficult. Therefore, it is considered that the heat resistant adhesiveness is improved.
- B value the content of the component having a molecular weight of 5000 or more
- K melt viscosity
- ⁇ Method of measuring physical properties of polyethylene wax (A)> Measuring method of weight average molecular weight Mw, molecular weight distribution (Mw / Mn) and B value The number average molecular weight Mn and the weight average molecular weight Mw of the polyethylene wax (A) were determined from GPC measurement. The measurement was performed under the following conditions. The number average molecular weight Mn and the weight average molecular weight Mw were determined based on the following conversion method by creating a calibration curve using a commercially available monodisperse standard polystyrene.
- Apparatus Gel permeation chromatograph Alliance GPC2000 (manufactured by Waters) Solvent: o-dichlorobenzene Column: TSKgel GMH6-HT ⁇ 2, TSKgel GMH6-HTL column ⁇ 2 (both manufactured by Tosoh Corporation) Flow rate: 1.0 ml / min Sample: 0.15 mg / mL o-dichlorobenzene solution Temperature: 140 ° C Molecular weight conversion: PE conversion / General calibration method
- Mw / Mn The molecular weight distribution (Mw / Mn) was determined by dividing Mw by Mn from the GPC measurement results described above.
- the B value was obtained by mass percent of the component having a molecular weight of 5000 or more from the GPC measurement results described above.
- the melting point of polyethylene wax (A) is DSC-20 (manufactured by Seiko Denshi Kogyo Co., Ltd.) according to differential scanning calorimetry (DSC). ). About 10 mg of a sample (polyethylene wax (A)) was sealed in an aluminum pan, the temperature was raised from ⁇ 20 ° C. to 200 ° C. at 10 ° C./min, and the endothermic peak of the obtained curve was obtained as the melting point. Before the temperature rise measurement, the sample was once heated to about 200 ° C., held for 5 minutes, and then lowered to ⁇ 20 ° C.
- Tm melting point
- the total heat of fusion ( ⁇ H all ) was calculated by determining the area divided by the endothermic peak obtained by DSC and the baseline of the entire endothermic peak.
- the ratio of the heat of fusion ( ⁇ H ⁇ 50 ) derived from the peak at 50 ° C. or less to the total heat of fusion ( ⁇ H all ) was calculated by the same procedure for the heat of fusion ( ⁇ H ⁇ 50 ) derived from the peak at 50 ° C. or less. It was obtained by dividing by the total heat of fusion ( ⁇ H all ).
- the number of DSC melting peaks was determined by measuring the number of endothermic peaks obtained by DSC.
- ⁇ Evaluation method of hot melt adhesive composition (1) Melt viscosity (normal operating temperature) The melt viscosity at 180 ° C. was measured with a Brookfield viscometer. 10g of sample was charged into the device heated to 180 ° C and melted for 10 minutes before starting measurement. A rotor No. 31 was used, and the viscosity (mPa ⁇ s) after 20 minutes was read at 5 revolutions per minute.
- Adhesive test adherend A general-purpose cardboard (K ′′ liner) was used as the adherend.
- the test piece prepared by the method for preparing the adhesive test piece was cut into a size of 25 mm ⁇ 100 mm, used as a T-type peeled base material, suspended in a load of 300 g / 25 mm, and the base material in an oven set at 65 ° C. The time during which the adhesive did not withstand the weight and failed to bond (the weight dropped) was evaluated as the peel adhesion failure time.
- the hot melt adhesive composition was charged into a 100 ml test tube (diameter 2.5 cm) and heated with a heater set at 180 ° C. After standing for 10 minutes, the dissolved contents were finely stirred for 1 minute with a thin spatula. Thereafter, a thermometer was inserted into the composition, and the internal temperature was raised to 170 ° C. Thereafter, the test tube was quickly taken out and allowed to cool, and the internal temperature at the moment when the bottom of the test tube became cloudy was read. During cooling, the test tube was fixed at a position 1 cm from the bottom of the 500 ml beaker to prevent local cooling by airflow.
- ethylene is supplied from another supply port of the polymerization vessel at a rate of 5.5 kg / hr and hydrogen at a rate of 480 NL / hr, and the residence time is 50 minutes at a polymerization temperature of 150 ° C. and a total pressure of 3.0 to 3.2 MPaG.
- Continuous solution polymerization was carried out under the following conditions.
- the oligomer solution produced in the polymerization vessel was continuously discharged and sent to a flash tank to evaporate unreacted ethylene and n-hexane. This was thin-film distilled at 210 ° C. under reduced pressure (43 Pa) at a treatment rate of 6 g per minute. The above operation was repeated until the required amount was obtained to obtain polyethylene wax (A-1).
- the physical property measurement results are shown in Table 1.
- Example 1 For 100 parts by weight of binder resin C-1, 6 parts by weight of carbon black (MA100; manufactured by Mitsubishi Kasei), 5 parts by weight of polyethylene wax (A-1) obtained in Synthesis Example 1, and a charge control agent (T-77) ; Hodogaya Chemical Co., Ltd.) 0.5 parts by mass was added, mixed with a Henschel mixer, and then mixed with a twin-screw kneader (PCM-30 type, manufactured by Ikekai Machinery). The kneading was performed for 30 seconds. Then, the toner was obtained by cooling, pulverizing and classifying. Table 2 shows the evaluation results of the obtained toner.
- binder resin C-1 6 parts by weight of carbon black (MA100; manufactured by Mitsubishi Kasei), 5 parts by weight of polyethylene wax (A-1) obtained in Synthesis Example 1, and a charge control agent (T-77) ; Hodogaya Chemical Co., Ltd.) 0.5 parts by mass was added, mixed with a Henschel mixer
- Example 1 A toner was obtained in the same manner as in Example 1 except that the polyethylene wax (A-2) obtained in Synthesis Example 2 was used in place of the polyethylene wax (A-1) used in Example 1. Table 2 shows the evaluation results of the obtained toner.
- Example 2 Except for using polyethylene wax (A-1) used in Example 1, trade name: High Wax 200P (Mitsui Chemicals, ethylene: 100.0 mol%, physical properties are shown in Table 1) A toner was obtained in the same manner as in Example 1. Table 2 shows the evaluation results of the obtained toner.
- Example 3 In place of the polyethylene wax (A-1) used in Example 1, trade name: High Wax 220P (manufactured by Mitsui Chemicals, ethylene / propylene copolymer, propylene-derived structural unit: 5.1 mol%, physical properties are A toner was obtained in the same manner as in Example 1 except that (shown in Table 1) was used. Table 2 shows the evaluation results of the obtained toner.
- Example 2 40 parts by mass of an ethylene-vinyl acetate copolymer (Evaflex (registered trademark) EV220, manufactured by Mitsui DuPont Polychemical Co., Ltd.) as the resin (B), and an aromatic hydrocarbon resin (FTR (registered trademark) 6125 as a tackifier, 40 parts by mass of Mitsui Chemicals, Inc.) and 20 parts by mass of the polyethylene wax (A-1) obtained in Synthesis Example 1 were blended and kneaded at 180 ° C. for 15 minutes using an autoclave to obtain a hot melt composition. .
- the evaluation results of the obtained hot melt adhesive composition are shown in Table 3.
- Example 4 A hot melt composition was obtained in the same manner as in Example 2 except that the polyethylene wax (A-2) obtained in Synthesis Example 2 was used instead of the polyethylene wax (A-1) used in Example 2. .
- the evaluation results of the obtained hot melt adhesive composition are shown in Table 3.
- Example 5 Example except that the trade name: High Wax 200P (Mitsui Chemicals, ethylene: 100.0 mol%, physical properties are shown in Table 1) was used instead of the polyethylene wax (A-1) used in Example 2. In the same manner as in No. 2, a hot melt composition was obtained. The evaluation results of the obtained hot melt adhesive composition are shown in Table 3.
Abstract
Description
[1]下記(i)~(iv)を満たすポリエチレンワックス(A)と、熱可塑性樹脂および熱硬化性樹脂からなる群から選択される少なくとも1種類の樹脂(B)とを含み、(A)と(B)の質量比〔(A)/(B)〕が0.1/99.9~50/50である樹脂組成物。
(i)GPCで測定した重量平均分子量(Mw)が400~1500の範囲にある。
(ii)GPCで測定した分子量分布(Mw/Mn)が1.2~2.5の範囲にある。
(iii)JIS K 2207に従い、25℃にて測定した針入度が5dmm以下である。
(iv)示差走査熱量測定(DSC)で測定した融点(Tm)が50~110℃の範囲にある。
[2]前記ポリエチレンワックス(A)が更に下記(v)を満たす[1]に記載の樹脂組成物。
(v)示差走査熱量測定(DSC)で測定した、すべてのピークに由来する全融解熱量(ΔHall)に対する50℃以下のピークに由来する融解熱量(ΔH-50)の割合が1.0%~5.0%の範囲にある。
[3]前記ポリエチレンワックス(A)が更に下記(vi)を満たす[1]または[2]に記載の樹脂組成物。
(vi) 示差走査熱量測定(DSC)で測定した融解ピークの数が2以上である。
[4]前記ポリエチレンワックス(A)が更に下記(vii)を満たす請求項[1]~[3]のいずれかに記載の樹脂組成物。
(vii)B≦0.15×K
(上記式中、Bは、ゲルパーミエーションクロマトグラフィーで測定したときの、上記ポリエチレンワックス(A)中のポリエチレン換算の分子量が5000以上となる成分の含有割合(質量%)であり、Kは上記ポリエチレンワックス(A)の140℃における溶融粘度(mPa・s)である。)
[5]前記樹脂(B)は熱可塑性樹脂である請求項[1]~[4]のいずれかに記載の樹脂組成物。
[6]前記樹脂(B)がポリエステル樹脂およびスチレン系重合体からなる群から選択される少なくとも1種類の樹脂である[1]~[5]のいずれかに記載の樹脂組成物。
[7][1]~[6]のいずれかに記載の樹脂組成物及び着色剤を含む電子写真用トナー。
[8][1]~[5]のいずれかに記載の樹脂組成物100質量部及び粘着付与剤5~300質量部を含む、ホットメルト組成物。
(i)GPCで測定した重量平均分子量(Mw)が400~1500の範囲にある。
(ii)GPCで測定した分子量分布(Mw/Mn)が1.2~2.5の範囲にある。
(iii)JIS K 2207に従い、25℃にて測定した針入度が5dmm以下である。
(iv)示差走査熱量測定(DSC)で測定した融点(Tm)が50~110℃の範囲にある。
〔重量平均分子量Mw〕
本発明のポリエチレンワックス(A)は、(i)GPCで測定した重量平均分子量(Mw)が400~1500、好ましくは400~1300、更に好ましくは400~1000、特に好ましくは500~1000の範囲にある。重量平均分子量(Mw)が400~1500であるポリエチレンワックス(A)を樹脂組成物に用いると、分子量が大きすぎる成分が少ないため、樹脂(B)やその他の樹脂との混和性がよくなる。また、分子量が小さすぎる成分も比較的少ないため、極端なべたつきが発生せず、樹脂組成物のハンドリング性がよくなる。
装置:ゲル浸透クロマトグラフAlliance GPC2000型(Waters社製)
有機溶媒:o-ジクロロベンゼン
カラム:TSKgel GMH6-HT×2、TSKgel GMH6-HTLカラム×2(何れも東ソー社製)
流速:1.0 ml/分
試料:0.15mg/mL o-ジクロロベンゼン溶液
温度:140℃
分子量換算 :ポリエチレン(PE)換算/汎用較正法
本発明のポリエチレンワックス(A)は、(ii)GPCで測定した分子量分布(Mw/Mn)が1.2~2.5、好ましくは1.3~2.5の範囲にある。Mw/Mnが1.2~2.5であるポリエチレンワックス(A)を樹脂組成物に用いると、極端な低分子量成分による、べたつきおよびブロッキングの発生ならびにそれに伴う樹脂組成物のハンドリング性の悪化や、極端な高分子量成分による、樹脂(B)やその他の樹脂との混和性の悪化が、抑制される。
本発明のポリエチレンワックス(A)は、(iii)JIS K 2207に従い、25℃にて測定した針入度が5dmm以下、好ましくは4dmm以下である。
本発明のポリエチレンワックス(A)は、(iv)示差走査熱量測定(DSC)で測定した融点(Tm)が50~110℃の範囲、好ましくは60~110℃、更に好ましくは65~110℃、特に好ましくは65~100℃、の範囲にある。融点(Tm)が50~110℃であるポリエチレンワックス(A)を樹脂組成物に用いると、樹脂組成物が溶融または変形する温度を低くすることができる。
本発明のポリエチレンワックス(A)は、(v) 示差走査熱量測定(DSC)の結果により得られる、すべてのピークに由来する全融解熱量(ΔHall)に対する50℃以下のピークに由来する融解熱量(ΔH-50)の割合は通常、1.0~20.0%であるが、好ましくは1.0~10.0%、より好ましくは1.0~5.0%である。
本発明のポリエチレンワックス(A)は、(vi)DSCで測定した融解ピークの数が2以上であることが好ましい。DSCで測定した融解ピークが2以上であるポリエチレンワックス(A)を樹脂組成物に用いた場合、低温側のピークにおいて樹脂組成物の溶融または変形が開始されるが、樹脂組成物の自然変形や樹脂組成物同士の自然結着を生じるような大きな溶融または変形は、高温側のピークまで生じにくい。
本発明のポリエチレンワックス(A)は、(vii)その分子量が5000以上となる成分の含有割合と溶融粘度とが、下記式(I)で示される特定の関係を満たすことが好ましい。
B≦0.15×K ・・・式(I)
本発明に係るポリエチレンワックス(A)は、135℃デカリン中で測定した極限粘度〔η〕が0.01~0.10dl/gの範囲にあることが好ましい。本発明に係るポリエチレンワックス(A)は、より好ましくは、極限粘度〔η〕が0.02dl/g以上、さらに好ましくは0.03dl/g以上である。また、より好ましくは極限粘度〔η〕が0.09dl/g以下、さらに好ましくは0.08dl/g以下、特に好ましくは0.07dl/g以下である。
本発明のポリエチレンワックス(A)は、エチレンから誘導される構成単位を含む。
本発明に係るポリエチレンワックス(A)は、エチレンなどを直接重合して得られるものであってもよく、高分子量のエチレン共重合体を熱分解して得られるものであってもよい。またポリエチレンワックス(A)は、溶媒に対する溶解度の差で分別する溶媒分別、または蒸留などの方法で精製されていてもよい。また1種単独のエチレン重合体から得られるものでもよいし、2種以上のエチレン重合体を混合して得られるものであってもよい。
(2)オレフィン重合用触媒の成分としてメタロセン化合物(a)と有機アルミニウムオキシ化合物(b-1)とを含む触媒を用いる場合には、化合物(b-1)は、化合物(b-1)中のアルミニウム原子(Al)とメタロセン化合物(a)中の全遷移金属原子(M)とのモル比〔Al/M〕が、0.01~5000、好ましくは0.05~2000となるような量で用いることができる。
(3)オレフィン重合用触媒の成分としてメタロセン化合物(a)とイオン性化合物(b-2)とを含む触媒を用いる場合には、化合物(b-2)は、化合物(b-2)とメタロセン化合物(a)中の全遷移金属原子(M)とのモル比〔(b-2)/M〕が、1~10、好ましくは1~5となるような量で用いることができる。
(4)オレフィン重合用触媒の成分としてメタロセン化合物(a)と有機アルミニウム化合物(b-3)とを含む触媒を用いる場合には、化合物(b-3)と、メタロセン化合物(a)中の全遷移金属原子(M)とのモル比〔(b-3)/M〕が通常0.01~50000、好ましくは0.05~10000となるような量で用いられる。
本発明の樹脂組成物に含まれる樹脂(B)は、熱可塑性樹脂および熱硬化性樹脂からなる群から選ばれる少なくとも1種である。熱可塑性樹脂としては、オレフィン系樹脂、スチレン系樹脂、熱可塑性ポリエステル樹脂、ポリアミド、ポリカーボネート、ポリアセタール、ポリフェニレンオキシド、ポリイミド、ポリビニルアルコール、ポリ酢酸ビニル、アクリル樹脂、ロジン樹脂、アルキド樹脂、クマロン樹脂、ケトン樹脂、セルロース系樹脂、塩素化ポリオレフィン、およびこれらの混合樹脂等が挙げられる。
後述するように、本発明の樹脂組成物をトナーとして用いる場合、本発明に係る樹脂(B)はトナー用バインダー樹脂に相当する。トナー用バインダー樹脂としては、種々公知のバインダー樹脂を樹脂(B)として使用し得る。具体的には、例えば、スチレン系重合体、ケトン樹脂、マレイン酸樹脂、脂肪族ポリエステル樹脂、芳香族ポリエステル樹脂、脂肪族・芳香族ポリエステル樹脂などのポリエステル樹脂、クマロン樹脂、フェノール樹脂、エポキシ樹脂、テルペン樹脂、ポリビニルブチラール、ポリブチルメタクリレート、ポリ塩化ビニル、ポリエチレン(但し、Mw:1500より高い)、ポリプロピレン、ポリブタジエン、エチレン・酢酸ビニル共重合体等の非晶性樹脂があげられる。
また、後述するように、本発明の樹脂組成物をホットメルト組成物として用いる場合、樹脂(B)は、ホットメルト接着剤に通常使用されるポリマーであってよく、以下のものを例示することができる。
2)エチレン-酢酸ビニル共重合体(EVA)
3)ケン化EVA、グラフト変性EVA等の変性EVAポリマー
4)エチレン・(メタ)エチルアクリレート(EEA)などのエチレン・(メタ)アクリレート共重合体(但し、Mw:1500より高い)
5)エチレン・(メタ)アクリル酸共重合体を部分中和してなるアイオノマー樹脂。具体的には、三井・デュポンポリケミカル社から商品名:ハイミランとして上市されているものなどが挙げられる。
6)エチレン・プロピレン共重合体またはエチレン・プロピレン・(メタ)アクリル酸ターポリマー(但し、Mw:1500より高い)
7)ポリアミド:二塩基酸とジアミンの反応生成物であり、たとえば、大豆油、桐油、トール油等の脂肪酸の2量体であるダイマー酸と、エチレンジアミン、ジエチレントリアミン等のアルキルジアミンとの反応生成物、ならびにナイロン12等のナイロン類等が挙げられる。これらの具体例として、ダイアミド(ダイセル化学工業)、プラチロン(東亜合成化学工業)、アミラン(東レ)等が挙げられる。
8)ポリエステル:例えば、エステルレジン200および300(東洋紡)、Vita1200、300(グッドイヤー社)等が挙げられる。
9)プロピレン系ポリマー:アタクチックポリプロピレン、プロピレン・炭素数4以上のα-オレフィン共重合体等が挙げられる。
10)ビニル芳香族化合物と共役ジエン化合物からなる共重合体、およびその水添物:具体的には、スチレン・ブタジエンランダム共重合体、スチレン・イソプレンランダム共重合体、ブタジエン・ポリスチレンブロック共重合体、ポリスチレン・ポリイソプレンブロック共重合体、ポリスチレン・ポリイソプレン・ポリスチレントリブロック共重合体、ポリスチレン・ポリブタジエン・ポリスチレントリブロック共重合体、ポリ(α-メチルスチレン)・ポリブタジエン・ポリ(α-メチルスチレン)トリブロック共重合体、およびこれらの水添物等が挙げられる。
本発明の樹脂組成物は、前記ポリエチレンワックス(A)と、前記樹脂(B)とを含有する。
本発明の樹脂組成物は、本発明の目的を損なわない範囲で、必要に応じて他の熱可塑性樹脂、耐候性安定剤、耐熱安定剤、帯電防止剤、スリップ防止剤、アンチブロッキング剤、防曇剤、核剤、滑剤、顔料、有機充填剤、無機充填剤、繊維、フィラー、染料、可塑剤、老化防止剤、塩酸吸収剤、酸化防止剤、銅害防止剤等の添加剤をさらに含んでいてもよい。繊維の例としては、ガラス繊維、カーボン繊維、天然繊維(木粉、木質繊維、竹、綿花、セルロース、ナノセルロース系繊維等)、又は、農産物繊維(麦わら、麻、亜麻、ケナフ、カポック、ジュート、ラミー、サイザル麻、ヘネッケン、トウモロコシ繊維若しくはコイア、若しくは木の実の殻若しくはもみ殻等)が挙げられる。有機充填剤の例としては、リグニン、スターチ、及びその含有製品等が挙げられる。
本発明の一実施形態に係る電子写真用トナーは、上記樹脂組成物および着色剤を含む。本発明のトナーは、上記樹脂組成物および着色剤の他に、さらに必要に応じて帯電制御剤、離型剤、顔料分散剤等を含む。
本発明のトナーに含まれる着色剤としては、例えばカーボンブラック、アセチレンブラック、ランプブラック、マグネタイト等の公知の黒色顔料;黄鉛、黄色酸化鉄、酸化チタン、亜鉛華等の公知の無機顔料;ハンザイエローG、キノリンイエローレーキ、パーマネントイエローNCG、モリブデンオレンジ、バルカンオレンジ、インダンスレン、ブリリアントオレンジGK、ベンガラ、ブリリアントカーミン6B、フリザリンレーキ、メチルバイオレットレーキ、ファストバイオレットB、コバルトブルー、アルカリブルーレーキ、フタロシアニンブルー、ファーストスカイブルー、ピグメントグリーンB、マラカイトグリーンレーキ等の公知の有機顔料が挙げられる。着色剤の含有量は、通常樹脂組成物100質量部に対して5~250質量部である。
本発明のトナーには、必要に応じて本発明の効果を阻害しない範囲に於いて、例えば、ポリ塩化ビニル、ポリ酢酸ビニル、ポリオレフィン、ポリエステル、ポリビニルブチラール、ポリウレタン、ポリアミド、ロジン、変性ロジン、テルペン樹脂、フェノール樹脂、脂肪族炭化水素樹脂、芳香族石油樹脂、パラフィンワックス、ポリオレフィンワックス(本発明のポリエチレンワックス(A)を除く)、セラミックワックス、ライスワックス、シュガーワックス、ウルシロウ、密鑞、カルナバワックス、キャンデリラワックス、モンタンワックス等の天然ワックス類、脂肪酸アミドワックス、塩ビ樹脂、スチレン-ブタジエン樹脂、クロマン-インデン樹脂、メラミン樹脂等の従来公知の離型剤を一部添加使用してもよい。その量は樹脂組成物100質量部に対して0.1~40質量部である。
本発明のトナーは、前記各成分を、従来公知のいかなる方法、例えば、接触分散、溶融分散、溶液分散等を採用することにより製造することができる。
本発明のトナーが、前記ポリエチレンワックス(A)を含有することにより、低温印刷性、耐オフセット性および保存性がよくなる理由については、明らかではないが、発明者らは以下のように推定している。
ポリエチレンワックス(A)の重量平均分子量(Mw)が1500以下であると、分子量の大きな分子が少なくなるため、トナー用バインダー樹脂として用いる樹脂(B)との混和性が十分になると考えられる。そのため、トナーの組成が均一になり易いので、トナー粒子が溶融して紙に付着した後に、また固まりやすくなり、低温で定着させたときも、耐オフセット性が向上し易いと考えられる。また、組成が均一になると、保存安定性が向上するほか、トナーの品質のバラツキが生じにくいと考えられる。さらには、分子量の大きな分子が少ないと、印刷媒体へのトナーの染み込み性が良好になるため、印刷の定着性及び現像耐久性が向上すると考えられる。一方、ポリエチレンワックス(A)の重量平均分子量(Mw)が400以上であれば、分子量の小さすぎる分子が少なくなるため、ポリエチレンワックス(A)のべたつきによるブロッキングや、ポリエチレンワックス(A)とトナー用バインダー樹脂として用いる樹脂(B)とを含む樹脂組成物からのポリエチレンワックス(A)の脱離が起こりにくい。そのため、トナー自身の保存安定性がよくなるほか、印字された後のトナーの安定性がよくなると考えられる。
本発明のトナーの用途は特に限定されないが、キャリアと混合して二成分または一.五成分現像剤としても用いることができるし、トナー中に磁性粉を含有させた、キャリアを用いない磁性一成分現像剤、もしくはキャリアや磁性粉を使用しない一成分現像剤、あるいはマイクロトーニング現像剤としても用いることができる。本発明のトナーが二成分または一.五成分現像剤として用いられる場合、キャリアとしては、従来公知のキャリアがいずれも使用できる。
本発明の一実施形態に係るホットメルト組成物は、前記樹脂組成物と、粘着付与剤(C)とを含む。
粘着付与剤(C)は、前記樹脂組成物に含まれる樹脂(B)の溶融時の粘度を調整し、ホットタック性や濡れ性を向上させるために配合されうる。粘着付与剤(C)の例には、脂肪族系水添タッキファイヤー、ロジン、変性ロジンまたはこれらのエステル化物、脂肪族系石油樹脂、脂環族系石油樹脂、芳香族系石油樹脂、脂肪族成分と芳香族成分の共重合石油樹脂、低分子量スチレン系樹脂、イソプレン系樹脂、アルキルフェノール樹脂、テルペン樹脂、クマロン・インデン樹脂等が含まれる。粘着付与剤(C)は、1種単独でも2種以上を組み合わせて用いてもよい。
本発明のホットメルト組成物は、例えば通常のホットメルト接着剤に配合されるサゾールワックス(H-1:サゾール社製)などの未変性ポリオレフィンをさらに含んでもよい。それにより、ホットメルト組成物の溶融粘度を低下させ、作業性をさらに向上させうる。
本発明のホットメルト組成物は、上記各成分をブラベンダー等の混合機に供給し、加熱して溶融混合した後;所望の形状、例えば粒状、フレーク状、棒状等に成形して得ることができる。
本発明のホットメルト組成物は、例えば加熱溶融して、布、クラフト紙、アルミ箔、ポリエステルフィルム等の被塗布体に、通常の方法で塗布してホットメルト接着剤層を形成するなどして使用されうる。
本発明のトナーが、前記ポリエチレンワックス(A)を含有することにより、耐熱接着性および固化速度がよくなる理由については、明らかではないが、発明者らは以下のように推定している。
(1)重量平均分子量Mw、分子量分布(Mw/Mn)およびB値の測定方法
ポリエチレンワックス(A)の数平均分子量Mn、および重量平均分子量Mwは、GPC測定から求めた。測定は以下の条件で行った。また、数平均分子量Mn、および重量平均分子量Mwは、市販の単分散標準ポリスチレンを用いて検量線を作成し、下記の換算法に基づいて求めた。
溶剤 : o-ジクロロベンゼン
カラム: TSKgel GMH6-HT×2、TSKgel GMH6-HTLカラム×2(何れも東ソー社製)
流速 : 1.0 ml/分
試料 : 0.15mg/mL o-ジクロロベンゼン溶液
温度 : 140℃
分子量換算 : PE換算/汎用較正法
ポリスチレン(PS)の係数 : KPS=1.38×10-4, aPS=0.70
ポリエチレン(PE)の係数 : KPE=5.06×10-4, aPE=0.70
JIS K 2207に従って、部分的な過熱を避け、泡が入らないように溶融させたポリエチレンワックス(A)の試料を、15~30℃の室温に1~1.5時間放置し固化させた後、恒温槽で25℃に保ち、温度が安定した後に試料表面に規定の針が5秒間で進入する長さを針入度(dmm)とした。
ポリエチレンワックス(A)の融点は、示差走査型熱量測定法(DSC)に従い、DSC-20(セイコー電子工業社製)によって測定した。試料(ポリエチレンワックス(A))約10mgをアルミパンに封じ、-20℃から200℃まで10℃/分で昇温し、得られたカーブの吸熱ピークを融点として求めた。この昇温測定の前に、一旦、試料を200℃程度まで昇温し、5分間保持した後、20℃/分で-20℃まで降温する操作を行い、試料の熱履歴を統一した。得られたカーブの吸熱ピークが複数存在する場合は、吸熱ピークにおける吸熱量が最も大きいピーク温度を融点(Tm)とした。
ブルックフィールド(B型)粘度計を用いて140℃で測定した。
ポリエチレンワックス(A)約20mgをデカリン15mlに溶解し、135℃のオイルバス中で比粘度ηspを測定した。このデカリン溶液にデカリン溶媒を5ml追加して希釈後、同様にして比粘度ηspを測定した。この、デカリン溶媒5mlを追加する希釈操作をさらに2回繰り返し、下記式(Eq-1)に示すように濃度(C)を0に外挿した時のηsp/Cの値を極限粘度[η](単位;dl/g)として求めた。
[η]=lim(ηsp/C) (C→0) ・・・ (Eq-1)
(1)低温定着性
市販の電子写真複写機を改造した複写機にて未定着画像を作成した。その後、この未定着画像を市販の複写機の定着部を改造した熱ローラー定着装置を用いて、熱ローラーの定着速度を190mm/秒とし、130℃の温度で定着させた。得られた定着画像を砂消しゴム(株式会社トンボ鉛筆製)により、1.0kgfの荷重をかけ、6回摩擦させ、この摩擦試験前後の画像濃度をマクベス式反射濃度計により測定した。摩擦後の画像濃度÷摩擦前の画像濃度×100をその温度での変化率とした。130℃での変化率の平均値を定着率として算出した。なお、ここに用いた熱ローラー定着装置はシリコーンオイル供給機構を有しないものであった。また、環境条件は、常温常圧(温度22℃、相対湿度55%)とした。
◎ : 42% ≦ 定着率
○ : 39% ≦ 定着率 < 42%
△ : 35% ≦ 定着率 < 39%
× : 定着率 < 35%
上記複写機にて未定着画像を作成した後、トナー像を転写して上述の熱ローラー定着装置により定着処理を行った。その後、非画像部分にトナー汚れが生ずるか否かを観察した。前記熱ローラー定着装置の熱ローラーの設定温度を150℃より順次降下させた状態で繰り返し、トナーによる汚れの生じた設定温度をもってオフセット発生温度とし、低温側のオフセット発生温度を低温オフセット性とした。また、上記複写機の雰囲気は、温度22℃、相対湿度55%とした。
◎ : オフセット発生温度 < 130℃
○ : 130℃ ≦ オフセット発生温度 < 135℃
△ : 135℃ ≦ オフセット発生温度 < 140℃
× : 140℃ ≦ オフセット発生温度
上記複写機にて未定着画像を作成した後、トナー像を転写して上述の熱ローラー定着装置により定着処理を行った。その後、非画像部分にトナー汚れが生ずるか否かを観察した。前記熱ローラー定着装置の熱ローラーの設定温度を190℃より順次上昇させた状態で繰り返し、トナーによる汚れの生じた設定温度をもってオフセット発生温度とした。また、上記複写機の雰囲気は、温度22℃、相対湿度55%とした。
◎ : 220℃ ≦ オフセット発生温度
○ : 210℃ ≦ オフセット発生温度 < 220℃
△ : 200℃ ≦ オフセット発生温度 < 210℃
× : オフセット発生温度 < 200℃
温度50℃、相対湿度60%の環境条件下に24時間放置したトナー5gを150メッシュのふるいにのせ、パウダーテスター(細川粉体工学研究所)の加減抵抗機の目盛りを3にして、1分間振動を加えた。振動後の150メッシュのふるいの上に残った質量を測定し、残存質量比を求めた。
◎ : 残存質量比 < 45%
○ : 45% ≦ 残存質量比 < 65%
△ : 65% ≦ 残存質量比 < 75%
× : 75% ≦ 残存質量比
(1)溶融粘度(通常使用温度)
180℃における溶融粘度をブルックフィールド型粘度計で測定した。180℃に昇温した装置に試料を10g仕込み、10分間溶融した後に測定を開始。ローターは31番を使用し、1分当たり5回転で、20分後の粘度(mPa・s)を読み取った。
○ : 3,000mPa・s未満
△ : 3,000~4,000mPa・s
× : 4,000mPa・sを超える
(接着試験片作成方法)
ホットメルト接着剤組成物を、ホットメルトオープンタイムテスター(旭化学合成社製)を用いて、塗布温度 180℃、塗布量 0.03g/cm2、塗工速度 7.5m/min、オープンタイム 2秒、プレス荷重 2kgで貼り合わせた。(サイズ:50mm×100mm)
被着体は、汎用のダンボール(K''ライナー)を使用した。
接着試験片作成方法にて作成した試験片を、25mm×100mmサイズに切断し、T型剥離状態の基材とし、300g/25mm荷重を吊して、65℃にセットしたオーブン中において、基材の接着剤が錘に耐えかねて接着破壊(錘が落下)する時間を剥離接着破壊時間として評価した。
○ : 80分以上
× : 80分未満
ホットメルト接着剤組成物を100ml試験管(直径2.5cm)に仕込み180℃にセットしたヒーターで昇温した。10分間静置後、溶解した内容物を細いスパチュラで1分間細目に撹拌した。その後温度計を組成物内部に差し込み、内温170℃まで上昇させた。その後素早く試験管を取り出し、放冷する過程で、試験管底部が白濁する瞬間の内温を読み取った。なお放冷中は500mlビーカー底から1cmの位置に試験管を固定して気流による局部的な冷却を防いだ。
白濁する温度
○ : 118℃以上
× : 118℃以下
[低分子量ビニル樹脂(L-1)の製造例]
[製造例L-1]
混合キシレン100質量部を窒素置換したフラスコに仕込み昇温し、キシレン還流下において、スチレン93質量部、アクリル酸n-ブチル6質量部、メタクリル酸1質量部にt-ブチルパーオキシ-2-エチルヘキサノエート10質量部を混合溶解しておいた混合液を5時間かけて連続添加し、さらに1時間還流を継続した。その後内温 98℃に保ち、更にt-ブチルパーオキシ-2-エチルヘキサノエート0.5質量部を加えて1時間反応を継続し、更にt-ブチルパーオキシ-2-エチルヘキサノエート0.5質量部を加えて2時間反応を継続し、ピーク分子量4600、酸価6.5mgKOH/gを有する低分子量ビニル樹脂L-1の重合液を得た。
[製造例H-1]
スチレン74質量部、アクリル酸n-ブチル23.5質量部、メタクリル酸2.5質量部を窒素置換したフラスコに仕込み、内温120℃に昇温後同温度に保ち、バルク重合を8時間行った。ついで、混合キシレン50質量部を加え、テトラエチレングリコールジアクリレート0.2質量部を加えた後、110℃に昇温した。予め混合溶解しておいた1、1-ビス(t-ブチルパーオキシ)シクロヘキサンの0.35質量部、混合キシレン60質量部を110℃に保ちながら9時間かけて連続添加した後、1時間反応を継続し、1、1-ビス(t-ブチルパーオキシ)シクロヘキサン0.21質量部を加え2時間反応を継続し、更に1、1-ビス(t-ブチルパーオキシ)シクロヘキサン0.52質量部を加え2時間反応を継続して重合を完結し、ピーク分子量300000、酸価16.3mgKOH/gを有する高分子量ビニル樹脂H-1の重合液を得た。
[製造例C-1]
高分子量ビニル樹脂(H-1)50質量部と低分子量ビニル樹脂(L-1)50質量部となるように各重合液を混合した後、これを190℃、1.33kPaのベッセル(容器)中にフラッシュして溶剤等を留去して、第一ピークの分子量4600、第二ピークの分子量300000、酸価11.4mgKOH/gを有するバインダー樹脂C-1を得た。
[合成例1]
充分に窒素置換された容積33Lの攪拌翼付加圧連続重合器の供給口から脱水精製したn-ヘキサンを24L/hr、トリイソブチルアルミニウムを1.0mmol/hr、N,N-ジメチルアニリニウムテトラキス(ペンタフルオロフェニル)ボレートを0.03mmol/hr、ビス(n-ブチルシクロペンタジエニル)ジルコニウムジメチル0.01mmol/hrの速度でそれぞれ供給した。同時に重合器の別の供給口から、エチレンを5.5kg/hr、水素を480NL/hrの速度で供給し、重合温度150℃、全圧3.0~3.2MPaGにて滞留時間を50分の条件下で連続溶液重合を実施した。
蒸留精製を行わなかったこと以外は合成例1と同様に行い、ポリエチレンワックス(A-2)を得た。物性測定結果を表1に示す。
[実施例1]
100質量部のバインダー樹脂C-1に対し、カーボンブラック(MA100;三菱化成製)6質量部、合成例1で得られたポリエチレンワックス(A-1)5質量部、荷電調整剤(T-77;保土ヶ谷化学工業社製)0.5質量部添加し、ヘンシェルミキサーにて混合後、2軸混練機(PCM-30型、池貝機械製)にて 2軸混練機吐出部樹脂温度120℃、滞留時間30秒で混練させた。ついで冷却・粉砕・分級してトナーを得た。得られたトナーの評価結果を表2に示す。
実施例1で用いたポリエチレンワックス(A-1)に替えて、合成例2で得られたポリエチレンワックス(A-2)を用いる以外は、実施例1と同様に行いトナーを得た。得られたトナーの評価結果を表2に示す。
実施例1で用いたポリエチレンワックス(A-1)に替えて、商品名:ハイワックス200P(三井化学社製、エチレン:100.0モル%、物性は表1に示す)を用いる以外は、実施例1と同様に行いトナーを得た。得られたトナーの評価結果を表2に示す。
実施例1で用いたポリエチレンワックス(A-1)に替えて、商品名:ハイワックス220P(三井化学社製、エチレン・プロピレン共重合体、プロピレン由来の構成単位:5.1モル%、物性は表1に示す)を用いる以外は、実施例1と同様に行いトナーを得た。得られたトナーの評価結果を表2に示す。
[実施例2]
樹脂(B)としてエチレン-酢酸ビニル共重合体(エバフレックス(登録商標)EV220、三井デュポンポリケミカル株式会社製)40質量部、粘着付与剤として芳香族炭化水素樹脂(FTR(登録商標)6125、三井化学株式会社製)40質量部、合成例1で得られたポリエチレンワックス(A-1)20質量部を配合し、オートクレーブを使用して180℃で15分混練しホットメルト組成物を得た。得られたホットメルト接着剤組成物の評価結果を表3に示す。
実施例2で用いたポリエチレンワックス(A-1)に替えて、合成例2で得られたポリエチレンワックス(A-2)を用いる以外は、実施例2と同様に行いホットメルト組成物を得た。得られたホットメルト接着剤組成物の評価結果を表3に示す。
実施例2で用いたポリエチレンワックス(A-1)に替えて、商品名:ハイワックス200P(三井化学社製、エチレン:100.0モル%、物性は表1に示す)を用いる以外は実施例2と同様に行いホットメルト組成物を得た。得られたホットメルト接着剤組成物の評価結果を表3に示す。
Claims (8)
- 下記(i)~(iv)を満たすポリエチレンワックス(A)と、
熱可塑性樹脂および熱硬化性樹脂からなる群から選択される少なくとも1種類の樹脂(B)とを含み、
(A)と(B)の質量比〔(A)/(B)〕が0.1/99.9~50/50である、樹脂組成物。
(i)GPCで測定した重量平均分子量(Mw)が400~1500の範囲にある。
(ii)GPCで測定した分子量分布(Mw/Mn)が1.2~2.5の範囲にある。
(iii)JIS K 2207に従い、25℃にて測定した針入度が5dmm以下である。
(iv)示差走査熱量測定(DSC)で測定した融点(Tm)が50~110℃の範囲にある。 - 前記ポリエチレンワックス(A)が更に下記(v)を満たす請求項1に記載の樹脂組成物。
(v)示差走査熱量測定(DSC)で測定した、すべてのピークに由来する全融解熱量(ΔHall)に対する50℃以下のピークに由来する融解熱量(ΔH-50)の割合が1.0%~5.0%の範囲にある。 - 前記ポリエチレンワックス(A)が更に下記 (vi)を満たす請求項1または2に記載の樹脂組成物。
(vi)示差走査熱量測定(DSC)で測定した融解ピークの数が2以上である。 - 前記ポリエチレンワックス(A)が更に下記(vii)を満たす請求項1~3のいずれか1項に記載の樹脂組成物。
(vii)B≦0.15×K
(上記式中、Bは、ゲルパーミエーションクロマトグラフィーで測定したときの、上記ポリエチレンワックス(A)中のポリエチレン換算の分子量が5000以上となる成分の含有割合(質量%)であり、Kは上記ポリエチレンワックス(A)の140℃における溶融粘度(mPa・s)である。) - 前記樹脂(B)は熱可塑性樹脂である請求項1~4のいずれか1項に記載の樹脂組成物。
- 前記樹脂(B)がポリエステル樹脂およびスチレン系重合体からなる群から選択される少なくとも1種類の樹脂である請求項1~5のいずれか1項に記載の樹脂組成物。
- 請求項1~6のいずれか1項に記載の樹脂組成物及び着色剤を含む電子写真用トナー。
- 請求項1~5のいずれか1項に記載の樹脂組成物100質量部及び粘着付与剤5~300質量部を含む、ホットメルト組成物。
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- 2015-04-17 JP JP2016513650A patent/JP6611705B2/ja active Active
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Also Published As
Publication number | Publication date |
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EP3133124A4 (en) | 2018-02-28 |
JP6611705B2 (ja) | 2019-11-27 |
EP3133124A1 (en) | 2017-02-22 |
EP3133124B1 (en) | 2019-04-10 |
US10053562B2 (en) | 2018-08-21 |
JPWO2015159556A1 (ja) | 2017-04-13 |
US20170037227A1 (en) | 2017-02-09 |
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