JP7049915B2 - Bound resin composition for toner - Google Patents

Description

The present invention relates to a binder resin composition for toner, a toner for developing an electrostatic charge image containing the binder resin composition, and the like.

In the field of electrophotographic, with the development of electrophotographic systems, there is a demand for the development of toner for static charge image development that supports high image quality and high-speed printing.
For example, Patent Document 1 describes a binder resin composition for toner containing a polyester resin containing a compound (X) satisfying the following conditions (i) to (iii) as a constituent unit.
(I) The number of functional groups (f) capable of reacting with an acid or alcohol is 1.0 (mmol / g) or more.
(Ii) It contains a long-chain alkyl group (r) having a branch and having 30 or more carbon atoms.
(Iii) The amount of heat absorbed during melting is 100 (J / g) or less.
It is stated that this provides a toner and a binder resin composition for toner having good fixing performance, non-offset property, image stability, and durability.

Patent Document 2 comprises (a) an aromatic dicarboxylic acid or a lower alkyl ester thereof, (b) a specific aromatic diol, and (c) a polyester polymer containing an ester bond-forming group of Mw 50,000 or less, and (a). Is a polymer consisting of 60 mol% or more of the total acid component in the polyester and (c) 50 wt% or less of the total condensed polyester, with a Tg of 40 to 70 ° C and a softening temperature of 85 to 120 ° C. A polyester resin for toner is described. It is described that this provides a polyester resin for toner having good blocking resistance, melt fluidity, low temperature fixing property and offset resistance.

Patent Document 3 contains a polyester-based resin and a polypropylene-based wax (W-1), and formula (1): endothermic amount ratio ΔH _{CW / W} = ΔH _CW / ΔH _W (1) (ΔH _CW : the above-mentioned conclusion. Endothermic amount of melt endothermic peak per 1 g of polypropylene-based wax (W-1) when measured as a resin-coated composition, ΔH _W : Polypropylene-based wax when measured alone as polypropylene-based wax (W-1) (W-1) A binder resin composition for static charge image developing toner, wherein the endothermic amount ratio ΔH _{CW / W} represented by (the amount of heat absorption of the melt endothermic peak per 1 g) is 0.10 or more and 0.80 or less. .. It is described that the binder resin composition can provide a binder resin composition for static charge image developing toner and the like, which can obtain a toner having excellent fixability to a PP film.

Japanese Unexamined Patent Publication No. 2009-14820 Japanese Unexamined Patent Publication No. 7-114208 International release WO2016 / 186129

On the other hand, due to the diversification of print media, electronic photo printing on print media other than paper has begun to be required. One of the main media is polypropylene film (hereinafter also referred to as "PP film"), which is used for PET bottle labels and various packages. On the other hand, paper and polypropylene have significantly different characteristics as print media, such as the polarity of the material and the state of the surface. Therefore, for example, the conventionally developed toners described in Patent Documents 1 and 2 have a problem that they do not fix on the PP film.
Further, since the toner disclosed in Patent Document 3 contains polypropylene wax dispersed in a very fine size in the binder resin, further improvement is desired from the viewpoint of stability and manufacturability.
Generally, toner is required to have storage stability so that toner particles do not aggregate even when stored for a long period of time.
Further, there has been a demand for a binder resin composition capable of obtaining a toner having excellent chargeability while exhibiting high fixability to the above-mentioned PP film.
The present invention relates to a binder resin composition capable of obtaining a toner excellent in fixability, storage stability, and chargeability on a polypropylene film, a toner for static charge image development containing the binder resin composition, and the like.

The present invention relates to the following [1] to [2].
[1] A binder resin composition for a toner containing an amorphous polyester resin A.
The amorphous polyester-based resin A has a constituent portion derived from a polyester resin, a constituent moiety derived from an addition polymerization-based resin, and a constituent moiety derived from a modified polypropylene-based polymer A having a carboxylic acid group or an anhydrous carboxylic acid group. Then, the constituent portion derived from the polyester resin and the constituent portion derived from the addition polymerization-based resin are connected via a covalent bond, and the constituent portion derived from the polyester resin and the constituent portion derived from the modified polypropylene-based polymer A are formed. Concatenate via co-join and
The polymer A is a polypropylene-based polymer modified with a carboxylic acid compound having an unsaturated bond or an anhydride thereof, and is a binder resin composition for toner.
[2] A toner for developing an electrostatic charge image, which comprises the binder resin composition according to [1].

According to the present invention, there is provided a binder resin composition capable of obtaining a toner excellent in fixability, storage stability, and chargeability on a polypropylene film, a toner for static charge image development containing the binder resin composition, and the like. be able to.
Further, according to the present invention, in addition to the above-mentioned effects, excellent productivity is exhibited by using the binder resin composition of the present invention in the method for producing a toner for static charge image development by a melt-kneading method.

[Bundling resin composition]
The binder resin composition for toner according to one embodiment of the present invention (hereinafter, also simply referred to as “binding resin composition”) contains an amorphous polyester resin A.
The amorphous polyester resin A has a constituent portion derived from the polyester resin, a constituent moiety derived from the addition polymerization based resin, and a constituent moiety derived from the modified polypropylene polymer A having a carboxylic acid group or an anhydrous carboxylic acid group.
Then, the constituent portion derived from the polyester resin and the constituent portion derived from the addition polymerization resin are linked via a covalent bond, and the constituent moiety derived from the polyester resin and the constituent moiety derived from the modified polypropylene polymer A are connected via a covalent bond. And connect.
Further, the polymer A is a polypropylene-based polymer modified with a carboxylic acid compound having an unsaturated bond or an anhydride thereof.

It is not clear why the binder resin composition according to one embodiment can obtain a static charge image developing toner (hereinafter, also simply referred to as “toner”) having excellent fixability, storage stability, and chargeability on a PP film. However, it can be considered as follows.
The binder resin composition according to one embodiment contains a polyester resin-derived constituent moiety and a polyester-based resin A having a constituent moiety derived from a modified polypropylene-based polymer A having a carboxylic acid group or an anhydrous carboxylic acid group. .. The constituent site derived from the polyester resin and the constituent moiety derived from the polymer A are linked via a covalent bond and have a complex structure at the molecular level. Then, the constituent parts derived from the polymer A of the polyester resin A are oriented toward the PP film due to the fixing heat when printing on the PP film by the electrophotographic method, and the intermolecular interaction between the PP film and the polyester resin is performed. It is considered that the fixability to the PP film can be achieved by the expression of.

The reasons for the improvement in storage stability and chargeability are considered as follows.
By using the polyester resin A, the constituent parts derived from the polyester resin and the constituent parts derived from the polymer A are linked via a covalent bond and are composited at the molecular level, whereby they are bound to the polymer A. It is considered that the storage stability was improved by making the resin uniform and obtaining thermal stability.
Further, it is considered that the chargeability is improved by having the portion derived from the addition polymerization resin.

Definitions of various terms in the present specification are shown below.
Whether the resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is the ratio of the softening point of the resin to the maximum endothermic temperature derived from the polyester constituent part (softening point (° C.) / maximum endothermic temperature (° C.)) in the measurement method described in Examples described later. ). The crystalline resin is a resin having a crystallinity index of 0.65 or more and less than 1.4, preferably 0.7 or more, more preferably 0.9 or more, and preferably 1.2 or less. The amorphous resin is a resin having a crystallinity index of 1.4 or more or less than 0.65. The crystallinity index can be appropriately adjusted depending on the type and ratio of the raw material monomers, and the production conditions such as reaction temperature, reaction time, and cooling rate. The peak derived from the polyester resin constituent site can be attributed by a conventional method, but usually appears on the lower temperature side than the endothermic peak derived from the constituent site derived from the modified polypropyrene polymer A. When it is unclear which peak should belong to, the polyester resin alone and the modified polypropylene polymer A alone are measured under the above conditions using a differential scanning calorimeter, and the temperature is closer to each endothermic peak. The endothermic peak belongs to the endothermic peak derived from each constituent part.
The "carboxylic acid compound" is a concept including not only the carboxylic acid but also an anhydride that decomposes during the reaction to generate an acid, and an alkyl ester of the carboxylic acid (for example, the alkyl group has 1 to 3 carbon atoms). Is.
When the carboxylic acid compound is an alkyl ester of a carboxylic acid, the carbon number of the alkyl group which is an alcohol residue of the ester is not included in the carbon number of the carboxylic acid compound.
The "binding resin" means a resin component contained in the toner including the polyester resin A.

<Polyester resin A>
The polyester-based resin A has, for example, a constituent portion derived from the polyester resin, a constituent portion derived from the addition polymerization-based resin, and a constituent portion derived from the polymer A, and is derived from the constituent portion derived from the polyester resin and the constituent portion derived from the addition polymerization-based resin. A polyester-based resin in which the constituent parts are connected via a covalent bond and the constituent parts derived from the polyester resin and the constituent parts derived from the modified polypropylene-based polymer A are connected via a covalent bond, substantially the characteristics thereof. Contains a polyester resin modified to the extent that it does not impair. Examples of the modified polyester resin include a urethane-modified polyester resin in which a constituent portion derived from the polyester resin is modified by a urethane bond, and an epoxy-modified polyester resin in which a constituent portion derived from the polyester resin is modified by an epoxy bond. Be done.
The constituent part derived from the polyester resin and the constituent portion derived from the addition polymerization resin are connected via a covalent bond. Then, the constituent portion derived from the polyester resin and the constituent portion derived from the modified polypropylene-based polymer A are linked via a covalent bond.
Linking via a covalent bond means that the components are linked via a covalent bond.
Examples of linking constituent sites via covalent bonds include, for example, ester bonds, ether bonds, amide bonds, urethane bonds, and bonds having these bonds and linking groups.
Examples of the linking group include a divalent or higher hydrocarbon group having 1 or more and 6 or less carbon atoms. Examples of the linking group include a methylene group, an ethylene group, a propylene group, a phenyl group and the like.
Above all, it is preferable that they are linked via an ester bond, and it is more preferable that they are directly linked by an ester bond.

（式中、ＯＲ及びＲＯはオキシアルキレン基であり、Ｒはエチレン又はプロピレン基であり、ｘ及びｙはアルキレンオキサイドの平均付加モル数を示し、それぞれ正の数であり、ｘとｙの和の値は、1以上、好ましくは1.5以上であり、16以下、好ましくは8以下、より好ましくは4以下である）で表されるビスフェノールＡのアルキレンオキサイド付加物を含むことが好ましい。
式(I)で表されるビスフェノールＡのアルキレンオキサイド付加物としては、2,2-ビス(4-ヒドロキシフェニル)プロパンのポリオキシプロピレン付加物、2,2-ビス(4-ヒドロキシフェニル)プロパンのポリオキシエチレン付加物等が挙げられる。これらの1種又は2種以上を用いてもよい。
式(I)で表されるビスフェノールＡのアルキレンオキサイド付加物の含有量は、アルコール成分中、好ましくは70モル％以上、より好ましくは80モル％以上、更に好ましくは90モル％以上、更に好ましくは95モル％以上であり、そして、100モル％以下であり、更に好ましくは100モル％である。 [Constituent parts derived from polyester resin]
Hereinafter, the constituent parts derived from the polyester resin will be described.
The “polyester resin-derived constituent portion” means a constituent portion of a resin in which a part of the polyester resin binds to another molecular group.
The polyester resin is, for example, a polycondensate of an alcohol component and a carboxylic acid component.
As the alcohol component, the formula (I): is used from the viewpoint of improving the storage stability.

(In the formula, OR and RO are oxyalkylene groups, R is ethylene or propylene group, x and y indicate the average number of adducts of alkylene oxide, which are positive numbers, respectively, and are the sum of x and y. The value is 1 or more, preferably 1.5 or more, and preferably 16 or less, preferably 8 or less, more preferably 4 or less), and preferably contains an alkylene oxide adduct of bisphenol A.
Examples of the alkylene oxide adduct of bisphenol A represented by the formula (I) include a polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (4-hydroxyphenyl) propane. Examples include polyoxyethylene adducts. One or more of these may be used.
The content of the alkylene oxide adduct of bisphenol A represented by the formula (I) is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 90 mol% or more in the alcohol component. It is 95 mol% or more and 100 mol% or less, more preferably 100 mol%.

Other alcohol components include, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4. -Examples include aliphatic diols such as butenediol, 1,3-butanediol and neopentyl glycol, and trihydric or higher alcohols such as glycerin.
The content of the other alcohol component is preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less.

Examples of the carboxylic acid component include aromatic dicarboxylic acid compounds, aliphatic dicarboxylic acid compounds, and carboxylic acid compounds having a valence of 3 or more.
Among these, the carboxylic acid component preferably contains an aromatic dicarboxylic acid compound from the viewpoint of further improving the chargeability.
Examples of the aromatic dicarboxylic acid compound include phthalic acid, isophthalic acid, and terephthalic acid. Among these, at least one selected from terephthalic acid and isophthalic acid is more preferable, and terephthalic acid is further preferable, from the viewpoint of further improving the chargeability.
The content of the aromatic dicarboxylic acid compound is preferably 20 mol% or more, more preferably 40 mol% or more, still more preferably 60 mol% or more, still more preferably 60 mol% or more, from the viewpoint of further improving the chargeability in the carboxylic acid component. It is 80 mol% or more, 100 mol% or less, and preferably 100 mol%.

Examples of the aliphatic dicarboxylic acid compound include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. Examples thereof include aliphatic dicarboxylic acids such as succinic acid and adipic acid which may be substituted with.
The succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms is preferably a succinic acid substituted with an alkyl group or an alkenyl group having 6 to 14 carbon atoms. More preferably, it is a succinic acid substituted with an alkyl group or an alkenyl group having 8 or more and 12 or less carbon atoms. Specific examples thereof include octyl succinic acid and dodecenyl succinic acid (tetrapropenyl succinic acid).
Of these, fumaric acid is preferred.
The content of the aliphatic dicarboxylic acid compound is preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 65 mol% or more, and more preferably 65 mol% or more in the carboxylic acid component from the viewpoint of further improving the storage stability. , 100 mol% or less, and preferably 100 mol%.

Examples of the trivalent or higher carboxylic acid compound include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, and pyromellitic acid. A merit acid or an acid anhydride thereof (hereinafter, also referred to as "trimellitic acid compound") is preferable.
The content of the trivalent or higher carboxylic acid compound is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 12 mol% or more, and preferably 50 mol% or less in the carboxylic acid component. , More preferably 40 mol% or less, still more preferably 30 mol% or less.
A monohydric alcohol may be appropriately contained in the alcohol component, and a monovalent carboxylic acid compound may be appropriately contained in the carboxylic acid component.

The ratio of the carboxy group of the carboxylic acid component to the hydroxyl group of the alcohol component [COOH group / OH group] is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, more preferably 1.2 or less. ..
The equivalent ratio of COOH groups to OH groups in the raw materials of the polyester resin (alcohol component and carboxylic acid component) is excessive in COOH groups from the viewpoint of increasing the softening point of the obtained polyester resin (the above ratio [COOH group / OH group]]. Is more than 1.0). Further, from the viewpoint of lowering the softening point of the obtained polyester resin, it is preferable that the OH group is excessive (the above ratio [COOH group / OH group] is less than 1.0).

[Constituents derived from addition polymerization resin]
Hereinafter, the constituent parts derived from the addition polymerization resin will be described.
The “component derived from the addition polymerization resin” means a component of the resin in which a part of the addition polymerization resin binds to another molecular group.
The addition polymerization-based resin is preferably an addition polymer of a raw material monomer containing a styrene-based compound, and more preferably a raw material containing a styrene-based compound and a vinyl-based monomer having an aliphatic hydrocarbon group having 3 or more and 22 or less carbon atoms. It is an addition polymer of a monomer.

Examples of the styrene-based compound include substituted or unsubstituted styrene. Examples of the substituent include an alkyl group having 1 or more and 5 or less carbon atoms, a halogen atom, an alkoxy group having 1 or more and 5 or less carbon atoms, a sulfonic acid group or a salt thereof and the like.
Examples of the styrene-based compound include styrenes such as styrene, methylstyrene, α-methylstyrene, β-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrenesulfonic acid or salts thereof. Can be mentioned. Among these, styrene is preferable.

The content of the styrene-based compound, preferably styrene, is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass, from the viewpoint of improving the chargeability in the raw material monomer of the vinyl-based resin segment. And more, preferably 95% by mass or less, more preferably 93% by mass or less, still more preferably 90% by mass or less.

From the viewpoint of improving the storage stability of the toner, the number of carbon atoms of the hydrocarbon group of the vinyl-based monomer having an aliphatic hydrocarbon group is preferably 3 or more, more preferably 4 or more, still more preferably 6 or more, and It is preferably 22 or less, more preferably 20 or less, and even more preferably 18 or less.

Examples of the aliphatic hydrocarbon group include an alkyl group, an alkynyl group and an alkenyl group. Among these, an alkyl group or an alkenyl group is preferable, and an alkyl group is preferable. The aliphatic hydrocarbon group may be either branched or linear.
The vinyl-based monomer having an aliphatic hydrocarbon group is preferably a (meth) acrylic acid alkyl ester. In the case of alkyl esters of (meth) acrylic acid, the hydrocarbon group is the alcohol-side residue of the ester.
Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and (iso or tertiary) butyl (iso or tertiary) butyl ( Examples thereof include (meth) acrylate, 2-ethylhexyl (meth) acrylate, (iso) octyl (meth) acrylate, (iso) decyl (meth) acrylate, and (iso) stearyl (meth) acrylate. One or more of these may be used. Here, "(iso or tertiary)" and "(iso)" mean that these prefixes include both when they are present and when they are not, and these prefixes are present. If not, it indicates that it is normal. Further, "(meth) acrylate" is at least one selected from acrylate and methacrylate.

The amount of the vinyl-based monomer having an aliphatic hydrocarbon group having 3 or more and 22 or less carbon atoms is preferably 5% by mass or more, more preferably 5% by mass or more, in the raw material monomer of the vinyl-based resin segment from the viewpoint of improving the storage stability of the toner. It is 10% by mass or more, more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 35% by mass or less, still more preferably 25% by mass or less.

Examples of other raw material monomers include ethylenically unsaturated monoolefins such as ethylene and propylene; conjugated dienes such as butadiene; halovinyls such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; (meth). ) (Meta) acrylic acid aminoalkyl esters such as dimethylaminoethyl acrylate; vinyl ethers such as methyl vinyl ether; vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinylpyrrolidone.

Among the raw material monomers of the addition polymerization resin, the total amount of the styrene compound and the vinyl monomer having an aliphatic hydrocarbon group having 3 or more and 22 or less carbon atoms is preferable from the viewpoint of improving the storage stability and chargeability of the toner. It is 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and 100% by mass or less, preferably 100% by mass.

In the polyester resin A, in order to connect the constituent portion derived from the polyester resin and the constituent portion derived from the addition polymerization resin, both the constituent portion derived from the polyester resin and the constituent portion derived from the addition polymerization resin are bonded via a covalent bond. It has a structural unit derived from a reactive monomer.
The “structural unit derived from a bireactive monomer” means a unit in which the functional group and the vinyl moiety of the bireactive monomer have reacted.
Examples of the bireactive monomer include vinyl-based monomers having at least one functional group selected from a hydroxyl group, a carboxy group, an epoxy group, a primary amino group and a secondary amino group in the molecule. Among these, from the viewpoint of reactivity, a vinyl-based monomer having a hydroxyl group or a carboxy group is preferable, and a vinyl-based monomer having a carboxy group is more preferable.
Examples of the bireactive monomer include acrylic acid, methacrylic acid, fumaric acid, maleic acid and the like. Among these, acrylic acid or methacrylic acid is preferable, and acrylic acid is more preferable, from the viewpoint of reactivity of both the polycondensation reaction and the addition polymerization reaction.
The amount of the structural unit derived from the bireactive monomer is preferably 1 mol part or more, more preferably 5 mol parts or more, still more preferably 8 parts with respect to 100 mol parts of the alcohol component of the polyester resin segment of the composite resin (A). It is more than a molar portion, and is preferably 30 mol parts or less, more preferably 25 mol parts or less, still more preferably 20 mol parts or less.

The amount of the constituent parts derived from the polyester resin is preferably 40% by mass or more, more preferably 50% by mass or more, and further, from the viewpoint of improving the fixability of the toner to the polypropylene film and the storage stability. It is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 75% by mass or more, and preferably 95% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less. be.
The amount of the constituent parts derived from the addition polymerization resin is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, further preferably 10% by mass or more in the polyester resin A from the viewpoint of improving the chargeability. It is preferably 15% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, still more preferably 30% by mass or less.
The amount of the structural unit derived from the bireactive monomer is preferably 0.1% by mass or more, more preferably 0.5 in the polyester resin A from the viewpoint of improving the fixability, storage stability, and chargeability of the toner on the polypropylene film. It is by mass or more, more preferably 0.8% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less.
In the polyester resin A, the total amount of the constituent parts derived from the polyester resin, the constituent parts derived from the addition polymerization resin, and the constituent units derived from the bireactive monomer is the fixing property, storage stability, and charge of the toner on the polypropylene film. From the viewpoint of improving the properties, it is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 93% by mass or more, still more preferably 95% by mass or more, and 100% by mass or less. It is preferably 99% by mass or less.

In the polyester resin A, the mass ratio of the constituent portion derived from the polyester resin and the constituent portion derived from the addition polymerization resin (the constituent portion derived from the polyester resin / the constituent portion derived from the addition polymerization resin) is preferably 55/45 or more. , More preferably 60/40 or more, still more preferably 65/35 or more, still more preferably 70/30 or more, and preferably 99/1 or less, more preferably 97/3 or less, more preferably 93/7. Below, it is more preferably 90/10 or less, still more preferably 85/15 or less.

The above amount is calculated based on the ratio of the amounts of the raw material monomer, the bireactive monomer, and the polymerization initiator of the constituent parts derived from the polyester resin and the constituent parts derived from the addition polymerization resin, and the weight in the constituent parts derived from the polyester resin and the like. The amount of dehydration due to condensation is excluded. When a polymerization initiator is used, the mass of the polymerization initiator is calculated by including it in the constituent parts derived from the addition polymerization resin.

[Polymer A]
The polyester-based resin A has a constituent portion derived from the modified polypropylene-based polymer A having a carboxylic acid group or an anhydrous carboxylic acid group from the viewpoint of obtaining a toner having excellent fixing property, storage stability, and chargeability on a PP film. Have.
The polymer A is a polypropylene-based polymer modified with a carboxylic acid compound having an unsaturated bond or an anhydride thereof (hereinafter, from the viewpoint of obtaining a toner having excellent fixing property, storage stability, and chargeability on a PP film). Also referred to as "acid-modified polypropylene-based polymer").

Examples of the polypropylene-based polymer before modification include polypropylene, a copolymer of propylene and other olefins.
Polypropylene is produced, for example, by a method obtained by polymerizing general propylene, a method obtained by thermally decomposing polypropylene used in a container for general molding, or a method for producing polypropylene used in a container for general molding. Examples thereof include polypropylene obtained by a method for separating and purifying low molecular weight polypropylene.
Examples of the copolymer of propylene and other olefins include copolymers obtained by polymerizing propylene with other olefins having an unsaturated bond copolymerizable with propylene. The copolymer may be either a random copolymer or a block copolymer.
Examples of other olefins include ethylene and olefins having 4 or more and 10 or less carbon atoms. Examples of other olefins include ethylene, butene, pentene, hexene, and 2-ethylhexene.

Examples of the acid-modified polypropylene-based polymer include a carboxylic acid compound having an unsaturated bond or a polypropylene-based polymer terminal-modified with an anhydride thereof (hereinafter, also simply referred to as “terminal-modified polypropylene-based polymer”) and unsaturated. Examples thereof include a polypropylene-based polymer in which a carboxylic acid compound having a bond or an anhydride thereof is randomly graft-modified (hereinafter, also simply referred to as “random graft-modified polypropylene-based polymer”).
Among these, a carboxylic acid compound having an unsaturated bond or a polypropylene-based polymer end-modified with an anhydride thereof is preferable. The terminal-modified polypropylene-based polymer is preferably a polypropylene-based polymer modified with a carboxylic acid compound having an unsaturated bond only at one end or an anhydride thereof (hereinafter, also referred to as "one-terminal modified polypropylene-based polymer"). It is said).
Examples of the carboxylic acid compound having an unsaturated bond or an anhydride thereof include maleic anhydride, fumaric acid, and itaconic acid. Of these, maleic anhydride is preferred.
Examples of the polypropylene-based polymer terminal-modified with an unsaturated bond-bearing carboxylic acid compound or its anhydride include a carboxylic acid compound having an unsaturated bond at the terminal-terminal unsaturated bond or an unsaturated bond thereof. It is obtained by reacting an object with an Ene. The one-terminal modified polypropylene-based polymer can be obtained, for example, by subjecting a polypropylene-based polymer having an unsaturated bond at one end to an Ene reaction with a carboxylic acid compound having an unsaturated bond or an anhydride thereof. The polypropylene-based polymer having an unsaturated bond at one end can be obtained by a known method, and can be produced, for example, by using a vanadium-based catalyst, a titanium-based catalyst, a zirconium-based catalyst, or the like.

Examples of the polymer A include terminal maleic anhydride-modified polypropylene and a copolymer of terminal maleic anhydride-modified propylene and other olefins.
Among these, terminal maleic anhydride-modified polypropylene is preferable, and one-terminal maleic anhydride-modified polypropylene is more preferable, from the viewpoint of improving fixability, storage stability, and chargeability on the PP film. By introducing the maleic anhydride moiety into the polypropylene-based polymer, the constituent moieties derived from the two polyester-based resins can be linked via an ester bond. In particular, by using a single-ended maleic anhydride-modified polypropylene-based polymer, a polyester-based resin having a structure in which two polyester-based resin-derived constituent portions are connected by the maleic anhydride-based moiety at the terminal of the polypropylene-based polymer can be obtained. it is conceivable that. Therefore, it is considered that the fixability to the polypropylene film can be further improved, and the storage stability and chargeability of the toner can be further improved by using the one-terminal maleic anhydride-modified polypropylene-based polymer.

Commercially available products of the terminal-modified polypropylene-based polymer include, for example, one-ended maleic anhydride-modified polypropylene "X-10065" (Mn = 1,000), one-ended maleic anhydride-modified polypropylene "X-10088" (Mn = 2,500), and the like. One-ended maleic anhydride-modified polypropylene "X-10082" (Mn = 8,000), one-ended maleic anhydride-modified propylene / hexene copolymer "X-10087" (Mn = 800), one-ended maleic anhydride-modified propylene / hexene Examples thereof include the copolymer "X-10053" (Mn = 2,000) and the one-ended maleic anhydride-modified propylene / hexene copolymer "X-10052" (Mn = 4,000) (all manufactured by BAKER HUGHES).

The random graft-modified polypropylene-based polymer is preferably a polypropylene-based polymer in which maleic anhydride is randomly grafted and modified (hereinafter, also referred to as “random-grafted maleic anhydride-modified polypropylene-based polymer”).
Random Graft Maleic anhydride-modified polypropylene-based polymer is preferably modified by grafting one or more maleic anhydride in one molecule. Whether it is modified with maleic anhydride can be determined by general spectral measurement. When modified with maleic anhydride, the double bond of maleic anhydride changes to a single bond, which can be specified by measuring the spectral change.
The random graft-modified polypropylene-based polymer is obtained, for example, by generating a radical in the polypropylene-based polymer molecule and reacting it with a carboxylic acid compound having an unsaturated bond or an anhydride thereof.

Commercially available products of the random graft modified polypropylene polymer include, for example, the random graft maleic anhydride-modified polypropylene polymer "M-100", "M-300", and "M-310" of the "TOYO-TAC" series. , "PMA H1000A", "PMA H1100A", "PMA H3000A", "PMA-T", "PMA-F2", "PMA-L" (all manufactured by Toyobo Co., Ltd.), "1001" in the "Yumex" series. , "1010", "100TS", "110TS" (above, manufactured by Sanyo Kasei Kogyo Co., Ltd.), "003", "006" (above, manufactured by Axonobel Co., Ltd.) of the "Kayabrit" series.

The melting point of the polymer A is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, still more preferably 40 ° C. or higher, still more preferably 60 ° C. or higher, still more preferably 60 ° C. or higher, from the viewpoint of further improving the fixability to the PP film. 70 ° C. or higher, more preferably 80 ° C. or higher, and preferably 170 ° C. or lower, more preferably 150 ° C. or lower, still more preferably 140 ° C. or lower, still more preferably 120 ° C. or lower, still more preferably 100 ° C. or lower. ..

The acid value of the polymer A is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, still more preferably 100 mgKOH / g or less, still more preferably 80 mgKOH / g, from the viewpoint of further improving the fixability to the PP film. It is preferably 0.1 mgKOH / g or more, more preferably 1 mgKOH / g or more, still more preferably 5 mgKOH / g or more, still more preferably 10 mgKOH / g or more.

The hydroxyl value of the polymer A is preferably 70 mgKOH / g or less, more preferably 30 mgKOH / g or less, still more preferably 10 mgKOH / g or less, and 0 mgKOH / g, from the viewpoint of further improving the fixability to the PP film. It is g or more, preferably 0 mgKOH / g.
The method for measuring the melting point, acid value, and hydroxyl value is as described in Examples.

The number average molecular weight of the polymer A is preferably 300 or more, more preferably 500 or more, still more preferably 700 or more, still more preferably 1,000 or more, and preferably 1,000 or more, from the viewpoint of further improving the fixability to the PP film. Is 50,000 or less, more preferably 15,000 or less, still more preferably 8,000 or less, still more preferably 4,000 or less, still more preferably 3,000 or less.
The number average molecular weight is measured by gel permeation chromatography using polystyrene as a standard sample.

In the polyester resin A, the amount of the constituent parts derived from the polymer A is preferably 3% by mass from the viewpoint of improving the fixability to the polypropylene film, the storage stability, and the chargeability, and from the viewpoint of increasing the productivity of the toner. % Or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, and from the viewpoint of fixability to the PP film, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25. By mass or less, more preferably 15 parts by mass or less.
In the above amount, the amount of the polyester-based resin A is the total amount of the polymer A, the raw material monomer of the constituent part derived from the polyester resin and the constituent part derived from the addition polymerization-based resin, the bireactive monomer, and the polymerization initiator. It is the amount excluding the amount of dehydration due to polycondensation in the constituent parts derived from the polyester resin.

[Manufacturing method of binder resin composition containing polyester resin A]
The binder resin composition contains the polyester resin A.
The polyester resin A is, for example,
(A) In the presence of a modified polypropylene-based polymer A having a carboxylic acid group or an anhydrous carboxylic acid group, a raw material monomer containing an alcohol component and a carboxylic acid component is polycondensed, and a raw material monomer for an addition polymerization-based resin and both. A method comprising addition polymerization with a reactive monomer, or (b) a modified polypropylene-based weight having a carboxylic acid group or an anhydrous carboxylic acid group in a resin containing a constituent moiety derived from a polyester resin and a constituent moiety derived from an addition polymerization based resin. Obtained by a method comprising reacting coalesced A.
Examples of the reaction (b) include dehydration condensation and transesterification reaction. The reaction conditions are preferably conditions in which the carboxylic acid group or anhydrous carboxylic acid group of the polymer A is dehydrated and condensed or ester-exchanged with the alcohol component, the carboxylic acid component and the like.

Polycondensation of the alcohol component and the carboxylic acid component should be performed, for example, in an inert gas atmosphere at a temperature of about 180 ° C. or higher and 250 ° C. or lower in the presence of an esterification catalyst, a polymerization inhibitor, etc., if necessary. Can be done. Examples of the esterification catalyst include tin compounds such as dibutyltin oxide and tin (II) 2-ethylhexanoate, and titanium compounds such as titanium diisopropyrate bistriethanol aminated. Examples of the esterification co-catalyst that can be used together with the esterification catalyst include gallic acid and the like. The amount of the esterification catalyst used is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, and preferably 1 part by mass or less, based on 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. More preferably, it is 0.8 parts by mass or less. The amount of the esterification co-catalyst used is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and preferably 0.5 part by mass or less with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. , More preferably 0.1 parts by mass or less.

In addition polymerization, a raw material monomer and a bireactive monomer of a constituent part derived from an addition polymerization resin are addition-polymerized.
The temperature of the addition polymerization is preferably 110 ° C. or higher, more preferably 130 ° C. or higher, and preferably 220 ° C. or lower, more preferably 200 ° C. or lower. Further, it is preferable to accelerate the reaction by reducing the pressure of the reaction system in the latter half of the polymerization.
Examples of the polymerization initiator for the addition polymerization include peroxides such as di-tert-butyl peroxide, persulfates such as sodium persulfate, and 2,2'-azobis (2,4-dimethylvaleronitrile). A known polymerization initiator such as an azo compound can be used.
The amount of the polymerization initiator used is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and further preferably 5 parts by mass or more with respect to 100 parts by mass of the raw material monomer of the structural unit derived from the addition polymerization system resin. , And more preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less.
The temperature at which the polymer A is reacted is preferably 180 ° C. or higher, more preferably 190 ° C. or higher, further preferably 200 ° C. or higher, and preferably 250 ° C. or lower, more preferably 240 ° C. or lower, still more preferably 235 ° C. It is below ° C.

[Physical characteristics of polyester resin A]
The softening point of the polyester resin A is preferably 80 ° C. or higher, more preferably 85 ° C. or higher from the viewpoint of further improving the storage stability, and preferably 170 ° C. or lower from the viewpoint of further improving the low temperature fixability. , More preferably 150 ° C. or lower, still more preferably 120 ° C. or lower.

The glass transition temperature of the polyester resin A is preferably 40 ° C. or higher, more preferably 50 ° C. or higher from the viewpoint of further improving the storage stability, and preferably 80 ° C. from the viewpoint of further improving the low temperature fixability. Below, it is more preferably 70 ° C. or lower, further preferably 60 ° C. or lower, still more preferably 58 ° C. or lower.

According to the binder resin composition according to one embodiment, a toner having excellent fixability to a PP film can be obtained. Therefore, it is used as a binder resin composition for a toner for polypropylene film printing.

[toner]
The toner contains the above-mentioned binder resin composition. According to the binder resin composition, a toner having excellent fixability to a polypropylene film can be obtained, so that a toner for printing a polypropylene film is provided. That is, it is used as an electrostatic charge developing toner for polypropylene film printing.

The toner preferably contains two or more types of polyester-based resins having different softening points of 15 ° C. or higher, from the viewpoint of further improving low-temperature fixability and hot offset resistance, and at least one of them is the above-mentioned polyester-based resin A. Is more preferable. When either one is the polyester resin A, the polyester resin A having a low softening point is preferably the polyester resin A from the viewpoint of further improving the fixability of the PP film.

The softening point of the polyester resin H having a higher softening point (hereinafter, also simply referred to as “resin H”) is preferably 110 ° C. or higher, more preferably 130 ° C. or higher, from the viewpoint of further improving the hot offset resistance. Yes, and from the viewpoint of further improving the low temperature fixability, the temperature is preferably 170 ° C. or lower, more preferably 150 ° C. or lower.

The softening point of the polyester resin L having a lower softening point (hereinafter, also simply referred to as “resin L”) is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, from the viewpoint of further improving hot offset resistance. Yes, and from the viewpoint of further improving the low temperature fixability, the temperature is preferably 120 ° C. or lower, more preferably 110 ° C. or lower.

The difference between the softening points of the resin H and the resin L is preferably 15 ° C. or higher, more preferably 20 ° C. or higher from the viewpoint of further improving the low temperature fixability, and is preferable from the viewpoint of further improving the low temperature fixability. Is 60 ° C. or lower, more preferably 50 ° C. or lower.

The softening point of the polyester resin can be adjusted by the degree of cross-linking or the like. From this point of view, the resin H contains a carboxylic acid compound having a valence of 3 or more as a carboxylic acid component. The content of the trivalent or higher carboxylic acid compound in the carboxylic acid component is preferably 10 mol% or more, more preferably 15 mol% or more, and preferably 35 mol from the viewpoint of further improving low temperature fixability. % Or less, more preferably 30 mol% or less.

On the other hand, the resin L preferably contains a carboxylic acid compound having a valence of 3 or more from the viewpoint of further improving the hot offset resistance, and the content of the trimellitic acid compound in the carboxylic acid component is low-temperature fixing. From the viewpoint of further improving the property, it is preferably 10 mol% or less, more preferably 8 mol% or less, still more preferably 5 mol% or less, still more preferably 3 mol% or less, and 0 mol%.

The mass ratio of the resin H to the resin L (resin H / resin L) is preferably 20/80 or more, more preferably 30/70 or more, still more preferably 40/60 or more, from the viewpoint of further improving the hot offset resistance. And, from the viewpoint of further improving the low temperature fixability, it is preferably 90/10 or less, more preferably 80/20 or less, and further preferably 70/30 or less.

The content of the polyester resin A is preferably 20% by mass or more, more preferably 30% or more in the binder resin from the viewpoint of further improving the fixability to the PP film, the storage stability, the printing durability, and the offset resistance. By mass or more, more preferably 40% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less.

Addition of, for example, a colorant, a mold release agent, a charge control agent, a magnetic powder, a fluidity improver, a conductivity adjusting agent, a reinforcing filler such as a fibrous substance, an antioxidant, a cleaning property improving agent, etc. to the toner. The agent may be contained, and it is preferable that a colorant, a mold release agent and a charge control agent are contained.

<Colorant>
As the colorant, all of the dyes and pigments used as colorants for toner can be used, such as carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, and Rhodamine-B base. Solvent Red 49, Solvent Red 146, Solvent Blue 35, quinacridone, carmine 6B, disazoero and the like can be used, and the toner may be either black toner or color toner.

The content of the colorant is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and preferably 40 parts by mass with respect to 100 parts by mass of the binder resin from the viewpoint of improving the image density of the toner. Parts or less, more preferably 20 parts by mass or less, more preferably 10 parts by mass or less.

<Release agent>
Examples of the mold release agent include polypropylene wax, polyethylene wax, polypropylene-polyethylene copolymer wax; fatty acid hydrocarbon waxes such as microcrystallin wax, paraffin wax, Fishertropsh wax, and sazole wax, or oxides thereof; Carna. Ester waxes such as Uva wax, Montan wax or their deoxidized waxes and fatty acid ester waxes; fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts, etc., which may be used alone or in admixture of two or more. Can be used.

The melting point of the release agent is preferably 60 ° C. or higher, more preferably 70 ° C. or higher from the viewpoint of further improving the hot offset resistance of the toner, and preferably 160 ° C. from the viewpoint of further improving the low temperature fixability. ° C. or lower, more preferably 140 ° C. or lower, still more preferably 120 ° C. or lower, still more preferably 110 ° C. or lower.

The content of the release agent is preferably 0.5 parts by mass or more, more preferably 1.0 part by mass or more, and further, with respect to 100 parts by mass of the binder resin, from the viewpoint of further improving the low temperature fixability and offset resistance of the toner. It is preferably 1.5 parts by mass or more, preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and further preferably 7 parts by mass or less.

<Charge control agent>
The charge control agent may be either a positive charge control agent or a negative charge control agent.
Positive charge control agents include niglosin dyes such as "niglocin base EX", "oil black BS", "oil black SO", "bontron N-01", "bontron N-04", and "bontron N-07". , "Bontron N-09", "Bontron N-11" (all manufactured by Orient Chemical Industries Co., Ltd.), etc .; Triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salt compounds, for example, " Bontron P-51 "(manufactured by Orient Chemical Industries Co., Ltd.), cetyltrimethylammonium bromide," COPY CHARGE PX VP435 "(manufactured by Clariant), etc .; Polyamine resin, for example," AFP-B "(manufactured by Orient Chemical Industries Co., Ltd.), etc. Imidazole derivatives such as "PLZ-2001" and "PLZ-8001" (manufactured by Shikoku Kasei Kogyo Co., Ltd.); styrene-acrylic resins such as "FCA-701PT" (manufactured by Fujikura Kasei Co., Ltd.). Be done.

Examples of the negative charge control agent include metal-containing azo dyes such as "Varifast Black 3804", "Bontron S-31", "Bontron S-32", "Bontron S-34", and "Bontron S-36". (Above, manufactured by Orient Chemical Industry Co., Ltd.), "Eisenspiron Black TRH", "T-77" (above, manufactured by Hodoya Chemical Industry Co., Ltd.), etc .; Metal compounds of benzylic acid compounds, for example, "LR-" 147 ”,“ LR-297 ”(above, manufactured by Nippon Carlit Co., Ltd.), etc .; Metal compounds of salicylic acid compounds, for example,“ Bontron E-81 ”,“ Bontron E-84 ”,“ Bontron E-88 ”,“ Bontron E-304 "(above, manufactured by Orient Chemical Industry Co., Ltd.)," TN-105 "(manufactured by Hodoya Chemical Industry Co., Ltd.), etc .; Copper phthalocyanine dye; Quadruple ammonium salt, for example," COPY CHARGE NX VP434 "(Clarian) Manufactured by), nitroimidazole derivatives, etc .; organic metal compounds and the like can be mentioned.

The content of the charge control agent is preferably 0.01 part by mass or more, more preferably 0.2 part by mass or more, and preferably 10 parts by mass with respect to 100 parts by mass of the binder resin from the viewpoint of charge stability of the toner. Parts or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less.

[Toner manufacturing method]
The toner may be a toner obtained by any known method such as a melt-kneading method, an emulsification phase inversion method, a polymerization method, and a coagulation fusion method, but from the viewpoint of productivity and dispersibility of the colorant, the toner may be obtained. Crushed toner by the melt-kneading method is preferable. In the case of pulverized toner by the melt-kneading method, for example, raw materials such as a binder resin, a colorant, a mold release agent, and a charge control agent are uniformly mixed with a mixer such as a Henshell mixer, and then a closed kneader, 1 shaft or 2 It can be manufactured by melt-kneading with a shaft extruder, an open roll type kneader, etc., cooling, crushing, and classifying.

The volume median particle size (D ₅₀ ) of the toner particles is preferably 3 μm or more, more preferably 4 μm or more, and preferably 15 μm or less, more preferably 10 μm or less.
In the present specification, the volume median particle size (D ₅₀ ) means a particle size in which the cumulative volume frequency calculated by the volume fraction is 50% calculated from the smaller particle size.

It is preferable to use an external additive as the toner in order to improve the storage stability. Examples of the external additive include inorganic fine particles such as silica, alumina, titania, zirconia, tin oxide, and zinc oxide, and organic fine particles such as resin particles such as melamine-based resin fine particles and polytetrafluoroethylene resin fine particles. These may be used alone or in combination of two or more.
Examples of silica include hydrophobic silica that has been hydrophobized.
Examples of the hydrophobizing agent for hydrophobizing the surface of silica fine particles include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), and methyltriethoxysilane. Can be mentioned. One or more of these may be used.
Among these, silica is preferable, and hydrophobic silica which has been hydrophobized is more preferable from the viewpoint of toner transferability.
The average particle size of the external additive is preferably 10 nm or more, more preferably 15 nm or more, and preferably 250 nm or less, more preferably 200 nm or less, and further, from the viewpoint of the chargeability, fluidity, and transferability of the toner. It is preferably 150 nm or less, more preferably 90 nm or less.

From the viewpoint of the chargeability, fluidity, and transferability of the toner, the content of the external additive is preferably 0.05 part by mass or more, more preferably 0.1 mass by mass, based on 100 parts by mass of the toner before being treated with the external additive. More than parts, more preferably 0.3 parts by mass or more, and preferably 5 parts by mass or less, more preferably 3 parts by mass or less.

The toner can be used as a one-component developer toner or as a two-component developer by mixing with a carrier.

[Printing on PP film]
Printing on PP film using toner is performed using a normal electrophotographic system.
Examples of the PP film include an untreated biaxially stretched PP film, a corona-treated PP film, a chemically treated PP film, a plasma-treated PP film, and a stretched film of a composite resin of PP and other resins or additives. From the viewpoint of cost, untreated biaxially stretched PP film and corona-treated PP film are preferable.
As the fixing temperature of the binder resin, it is preferable to set the fixing temperature at a temperature equal to or higher than the melting point of the polymer A from the viewpoint of effectively generating an interaction between the polymer A and the PP film.

In the electrophotographic method, the fixing temperature is preferably 180 ° C. or lower, more preferably 160 ° C. or lower, still more preferably 140 ° C. or lower from the viewpoint of heat resistance of the PP film, and preferably from the viewpoint of fixability. It is 70 ° C. or higher, more preferably 80 ° C. or higher, and even more preferably 90 ° C. or higher.

Each property was measured by the following method.

[Measuring method]
[Melting point of polymer A (Mp)]
A sample that was heated to 200 ° C using a differential scanning calorimeter "DSC210" (manufactured by Seiko Instruments Inc.) and cooled to 0 ° C at a temperature lowering rate of 10 ° C / min was cooled at a heating rate of 10 ° C / min. The temperature rises. The melting point is the maximum peak temperature of the heat of fusion.

[Acid value of binder resin, polyester resin A, and polymer A]
Measure based on the method of JIS K 0070: 1992. However, only the measurement solvent is changed from the mixed solvent of ethanol and ether specified in JIS K 0070: 1992 to the mixed solvent of chloroform and dimethylformamide (hereinafter also referred to as "DMF") (chloroform: DMF = 7: 3 (volume ratio)). change.

[Softening point, maximum peak temperature and glass transition temperature of binder resin, polyester resin A, and polymer A]
(1) Softening point Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), a 1 g sample is heated at a heating rate of 6 ° C / min, and a load of 1.96 MPa is applied by a plunger to a diameter of 1 mm. , Extrude from a 1 mm long nozzle. The amount of plunger drop of the flow tester is plotted against the temperature, and the temperature at which half of the sample flows out is used as the softening point.
(2) Maximum peak temperature of endothermic of polyester resin-derived components Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), the temperature drops from room temperature (20 ° C) to 10 ° C / The sample cooled to 0 ° C. in 1 minute is held as it is for 1 minute, and then the measurement is performed while raising the temperature to 180 ° C. at a heating rate of 10 ° C./min. Among the observed endothermic peaks derived from the polyester resin-derived constituent parts, the temperature of the peak appearing on the highest temperature side is defined as the maximum endothermic temperature.
The peak of the constituent portion derived from the polyester resin can be assigned by a conventional method, but usually appears on the lower temperature side than the endothermic peak derived from the constituent moiety derived from the modified polypropyrene polymer A. When it is unclear which peak should be attributed, the polyester resin alone and the modified polypropylene polymer A alone are measured under the above conditions using a differential scanning calorimeter, and the temperature is closer to each endothermic peak. The endothermic peak belongs to the endothermic peak derived from each constituent part.
(3) Glass transition temperature Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.01 to 0.02 g of the sample in an aluminum pan, raise the temperature to 200 ° C, and then raise the temperature to 200 ° C. Cool from temperature to 0 ° C at a temperature drop rate of 10 ° C / min. Next, the measurement is performed while raising the temperature to 150 ° C at a heating rate of 10 ° C / min.
The temperature at the intersection of the extension of the baseline below the maximum endothermic temperature and the tangent line indicating the maximum slope from the rising portion of the peak to the peak of the peak is defined as the glass transition temperature.

[Volume medium particle size of toner particles (D ₅₀ )]
The volume median particle size (D ₅₀ ) of the toner particles is measured by the following method.
Measuring machine: Coulter Multisizer II (manufactured by Beckman Coulter)
Aperture diameter: 50 μm
Analysis software: Coulter Multisizer AccuComp version 1.19 (manufactured by Beckman Coulter)
Electrolyte: Isoton II (manufactured by Beckman Coulter)
Dispersion: Emulgen "109P" (manufactured by Kao Co., Ltd., polyoxyethylene lauryl ether, HLB: 13.6) 5% by mass electrolyte Dispersion condition: Add 10 mg of the measurement sample to 5 mL of the dispersion and use an ultrasonic disperser for 1 minute. Disperse, then add 25 mL of electrolyte and further disperse with an ultrasonic disperser for 1 minute.
Measurement conditions: Add 100 mL of electrolytic solution and dispersion to a beaker, measure 30,000 particles at a concentration that can measure the particle size of 30,000 particles in 20 seconds, and measure the volume medium particle size (from the particle size distribution). D ₅₀ ) is calculated.

[Manufacturing of resin]
Production Example A1 (Production of Resin A-1)
Place the polyester resin raw material monomer (P) shown in Table 1 in a 10-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser equipped with a dehydration tube, and a nitrogen introduction tube to create a nitrogen atmosphere. A mixed solution of the raw material monomer (V) of the addition polymerization resin, acrylic acid and the polymerization initiator was added dropwise over 60 minutes while stirring at 160 ° C. After maintaining 160 ° C for 1 hour, the temperature was raised to 200 ° C and addition polymerization was carried out. After that, an esterification catalyst and a co-catalyst were added, polycondensation was carried out at 235 ° C., the pressure was reduced to 60 torr, and dehydration condensation was carried out for 1 hour. After that, the mixture was cooled to an atmospheric pressure of 160 ° C., polymer A was added, the reaction was carried out at 220 ° C. for another hour, and then the condensation reaction was carried out under the conditions of 220 ° C. and 60 torr to reach the softening point shown in Table 1. The reaction was carried out to obtain resin A-1.

Production Examples A2 to A10 and A51 to A52 (Production of resins A-2 to A-10 and A-51 to A-52)
Resins A-2 to A-10 and A-51 to A-52 were obtained in the same manner as in Production Example A1 except that the raw materials were changed to the types and amounts shown in Table 1.

Production Example A11 (Production of Resin A-11)
Four 10-liter flasks equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser equipped with a dehydration tube, and a nitrogen introduction tube using the raw material monomer (P) of a polyester resin other than trimellitic acid anhydride shown in Table 1. The mixture was placed in a flask and a mixed solution of the raw material monomer (V) of the addition polymerization resin, acrylic acid and the polymerization initiator was added dropwise over 60 minutes while stirring at 160 ° C. in a nitrogen atmosphere. After maintaining 160 ° C for 1 hour, the temperature was raised to 200 ° C and addition polymerization was carried out. After that, an esterification catalyst and a co-catalyst were added, polycondensation was carried out at 235 ° C., the pressure was reduced to 60 torr, and dehydration condensation was carried out for 1 hour. After that, the mixture was cooled to an atmospheric pressure of 160 ° C., polymer A and trimellitic acid anhydride were added, and then the reaction was carried out at 220 ° C. for 1 hour, and then the condensation reaction was carried out under the conditions of 220 ° C. and 60 torr. The reaction was carried out until the softening point shown in 1 was reached to obtain resin A-11.

Manufacturing Example P (Manufacturing of resin P)
Place the polyester resin raw material monomer, esterification catalyst, and co-catalyst in a 10-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser equipped with a dehydration tube, and a nitrogen introduction tube, and place them in a nitrogen atmosphere. After polycondensation was carried out at 235 ° C. in a mantle heater to confirm that the raw material monomers were uniformly melted, the pressure was reduced to 60 torr and dehydration condensation was carried out for 1 hour. Then, a condensation reaction was carried out under the condition of 220 ° C. and 60 torr, and the reaction was carried out until the softening point reached the softening point shown in Table 1 to obtain a resin P.

[Manufacturing of toner]
Examples 1 to 11 and Comparative Examples 1 to 2 (manufacturing of toners 1 to 11, 51 to 52)
100 parts by mass of the binder resin shown in Table 2, 1 part by mass of the negative charge control agent "Bontron E-81" (manufactured by Orient Chemical Industries Co., Ltd.), and the colorant "Pigment blue 15: 3" (Dainichi Seisakusho). After thoroughly mixing 5 parts by mass of (manufactured by Kogyo Co., Ltd.) and 2 parts by mass of the mold release agent "HNP-9" (manufactured by Nippon Seiwa Co., Ltd., paraffin wax, melting point: 80 ° C) with a Henshell mixer, the total length of the kneaded part. Using a co-rotating twin-screw extruder with a screw diameter of 1560 mm, a screw diameter of 42 mm, and a barrel inner diameter of 43 mm, the mixture was melt-kneaded at a roll rotation speed of 200 r / min and a heating temperature of 100 ° C. in the roll. The supply rate of the mixture was 20 kg / h and the average residence time was about 18 seconds. The obtained melt-kneaded product was cooled and roughly pulverized, then pulverized by a jet mill and classified to obtain toner particles having a volume medium particle size (D ₅₀ ) of 8 μm.

To 100 parts by mass of the obtained toner particles, 2.0 parts by mass of the external additive "Aerosil R-972" (hydrophobic silica, manufactured by Nippon Aerosil Co., Ltd., number average particle size: 16 nm) was added, and 3600 r / with a Henshell mixer. By mixing min for 5 minutes, an external additive treatment was performed to obtain toners 1 to 11, 51 to 52.

[Evaluation methods]
[Fixability to PP film]
Toner is mounted on the non-magnetic one-component developer "OKI MICROLINE 5400" (manufactured by Oki Data Corporation), the toner adhesion amount is adjusted to 0.45 ± 0.03 mg / cm ² , and a solid image of 4.1 cm x 13.0 cm is not obtained. Treated Biaxially stretched polypropylene film "Trefan Industrial Type 2500" (manufactured by Toray Co., Ltd., thickness 60 μm) was printed and fixed at a fixing temperature of 130 ° C.
The obtained solid image fixed on the untreated biaxially stretched polypropylene film was traced with a needle to evaluate the peeling of the toner layer on the solid surface. At this time, the mass applied to the needle was changed to 20 g, 50 g, and 100 g.
(Evaluation criteria)
A: No peeling of toner layer is seen under 100 g load B: No peeling of toner layer is seen under 50 g load, but peeling of toner layer is seen under 100 g load C: Peeling of toner layer is seen under 20 g load No, but peeling of the toner layer is seen under a load of 50 g D: The toner layer peels off at a load of 20 g

[Preservation]
Place 5 g of toner in a cylindrical container, leave it at a temperature of 50 ° C and a relative humidity of 50% for 72 hours, sieve it through a 200 mesh (opening: 75 μm) sieve, weigh the amount of toner that has passed through, and store it according to the following evaluation criteria. Gender was evaluated. The heavier the mass of the toner that has passed, the better the storage stability.
(Evaluation criteria)
A: Toner that has passed through the sieve is 90% by mass or more B: Toner that has passed through the sieve is 80% by mass or more and less than 90% by mass C: Toner that has passed through the sieve is 20% by mass or more and less than 80% by mass D: Toner that has passed through the sieve Less than 20% by mass of toner passed through

[Charging]
After leaving the toner in an environment with a temperature of 25 ° C and a relative humidity of 50% for 72 hours, 0.6 g of toner and 19.4 g of silicone ferrite carrier (manufactured by Kanto Denka Kogyo Co., Ltd., average particle size: 90 μm) were added to each toner. Place in a 50 mL polyethylene container, mix at 250 r / min using a ball mill, and measure the amount of toner charge after mixing for 60 seconds and 3600 seconds with a Q / M meter (manufactured by EPPING) by the following method. Measured using.
After the specified mixing time, put the specified amount of toner and carrier mixture into the cell attached to the Q / M meter, and suck only the toner for 90 seconds through a sieve with a mesh opening of 32 μm (stainless steel, twill weave, wire diameter: 0.0035 mm). bottom. The voltage change on the carrier generated at that time was monitored, and the value of [total electricity amount (μC) after 90 seconds / suctioned toner amount (g)] was defined as the charge amount (μC / g).
The ratio of the charge amount after the mixing time of 60 seconds to the charge amount after the mixing time of 3600 seconds (the charge amount after the mixing time of 3600 seconds / the charge amount after the mixing time of 60 seconds) was calculated. The closer the charge amount ratio is to 1, the better the charge stability.
(Evaluation criteria)
A: Charge amount ratio is 0.9 or more B: Charge amount ratio is 0.8 or more and less than 0.9 C: Charge amount ratio is less than 0.8

〔Productivity〕
The pulverization productivity during toner production was evaluated by the following method.
Sift 500 g of coarsely pulverized toner with 16 mesh (hole diameter 1000 μm, line width 588 μm) and 22 mesh (pore diameter 710 μm, line width 450 μm), and collect the toner remaining between 16 mesh and 22 mesh. 20 g of this collected toner was pulverized with a desktop crusher (LAB MILL OML-1: manufactured by Osaka Chemical Co., Ltd.) at 20000 rpm for 10 seconds.
The pulverized toner was sieved with 30 mesh (pore diameter 500 μm, line width 340 μm), the mass of the toner remaining on the 30 mesh was measured, and the pulverization property was calculated by the following formula.
Grindability = [Toner amount on 30 mesh g / 20g] x 100
It can be judged that the smaller the value of pulverizability, the shorter the cycle time at the time of pulverization classification and the better the productivity.
(Evaluation criteria)
A: Grindability index is less than 10 B: Grindability index is 10 or more and less than 15 C: Grindability index is 15 or more

As described above, it can be seen that the toner of the example exhibits excellent fixing property to the PP film as compared with the toner of the comparative example.
Further, it can be seen that the toner of the example exhibits excellent storage stability by containing a specific binder resin.
In addition, it can be seen that the toner of the example exhibits excellent chargeability by containing a specific binder resin composition.
From the results of Examples and Comparative Examples, it can be seen that the toner of Examples is also excellent in productivity.

Claims (8)

A binder resin composition for toner containing an amorphous polyester resin A.
The amorphous polyester-based resin A has a constituent portion derived from a polyester resin, a constituent moiety derived from an addition polymerization-based resin, and a constituent moiety derived from a modified polypropylene-based polymer A having a carboxylic acid group or an anhydrous carboxylic acid group. Then, the constituent part derived from the polyester resin and the constituent portion derived from the addition polymerization system resin are covalently linked, and the constituent portion derived from the polyester resin and the constituent portion derived from the modified polypropylene polymer A are covalently bonded. Connected through
The polymer A is a polypropylene terminal-modified with a carboxylic acid compound having an unsaturated bond or an anhydride thereof.
In the polyester resin A, the amount of the constituent parts derived from the polymer A is 8% by mass or more and 15% by mass or less.
The softening point of the polyester resin A is 80 ° C. or higher and 120 ° C. or lower.
The constituent part derived from the polyester resin is a polycondensate of an alcohol component and a carboxylic acid component, and the content of the aromatic dicarboxylic acid compound in the carboxylic acid component is 60 mol% or more, which is a binder resin for toner. Composition. The constituent part derived from the polyester resin and the constituent portion derived from the addition polymerization resin are connected via an ester bond, and the constituent portion derived from the polyester resin and the constituent portion derived from the modified polypropylene polymer A are formed. The binder resin composition according to claim 1 , which is linked via an ester bond. The binder resin composition according to claim 1 or 2 , wherein the constituent portion derived from the addition polymerization resin is an addition polymer of a raw material monomer containing a styrene compound. The binder resin composition according to any one of claims 1 to 3 , wherein the acid value of the polymer A is 20 mgKOH / g or more and 100 mgKOH / g or less. The binder resin composition according to any one of claims 1 to 4 , wherein the polymer A has a number average molecular weight of 500 or more and 8,000 or less. The binder resin composition according to any one of claims 1 to 5 , wherein the carboxylic acid compound having an unsaturated bond or an anhydride thereof is maleic anhydride. The binder resin composition according to any one of claims 1 to 5 , wherein the mass ratio of the constituent portion derived from the polyester resin to the constituent moiety derived from the addition polymerization resin is 55/45 or more and 99/1 or less. A toner for developing an electrostatic charge image, which comprises the binder resin composition according to any one of claims 1 to 7 .