JP5291649B2 - Resin particles - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide resin particles excellent in low-temperature fixability and blocking resistance. <P>SOLUTION: There are provided resin particles (I) including a crystalline resin (A) and an amorphous resin (B). The crystalline resin (A) has a maximum peak temperature (TaA) of heat of fusion of 40-100&deg;C and a ratio of a softening point to TaA (softening point/TaA) of 0.8-1.55, and the amorphous resin (B) has a maximum peak temperature (TaB) of heat of fusion of 35-100&deg;C. The resin particles (I) satisfy the following conditions [1] and [2]: [1] G'(TaI+20)=1&times;10<SP>2</SP>to 5&times;10<SP>5</SP>[Pa] and [2] G"(TaI+20)=1&times;10<SP>2</SP>to 5&times;10<SP>5</SP>[Pa], wherein G' is the storage modulus (Pa), and G" is the loss modulus (Pa), and TaI is the maximum peak temperature (&deg;C) of heat of fusion of the resin particles (I). <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to resin particles.

A technique for fixing resin particles with lower energy than before has been desired. Therefore, there is a strong demand for resin particles that can be fixed at a lower temperature.
As a means for lowering the fixing temperature of the resin particles, a technique for lowering the glass transition point of the resin is generally performed. However, if the glass transition point is too low, particle aggregation (blocking) tends to occur, and the preservability of the resin particles on the fixing surface is deteriorated, so 50 ° C. is practically the lower limit. When a resin is used as a binder, this glass transition point is a design point of the resin, and it has not been possible to obtain resin particles that can be fixed at a lower temperature than before by the method of lowering the glass transition point.
As a means for achieving both blocking prevention and low-temperature fixability, a method using a crystalline resin as a resin has been known for a long time. However, there has been a problem that fixing deterioration occurs due to insufficient elasticity at the time of melting.
Further, as means for achieving both blocking prevention and low-temperature fixability, resin particles having a shell using a melt suspension method or the like have been proposed (for example, see Patent Document 1). However, the above techniques are still insufficient to obtain good blocking resistance while maintaining low temperature fixing.

JP 2007-70621 A

  The object of the present invention is to solve the above-mentioned problems of the prior art. That is, an object of the present invention is to provide resin particles having excellent low-temperature fixability and blocking resistance.

The above-mentioned subject is achieved by the following present invention.
The present invention is a resin particle (I) containing a crystalline resin (A) and an amorphous resin (B), wherein the maximum peak temperature (TaA) of heat of fusion of the crystalline resin (A) is 40-100. ° C, the ratio of softening temperature to TaA (softening temperature / TaA) is 0.8 to 1.55, and the maximum peak temperature (TaB) of the heat of fusion of the amorphous resin (B) is 35 to 100 ° C. The crystalline resin (A) is a resin selected from a polyester resin, a polyurethane resin, and a composite resin thereof, and the crystalline resin (A) includes a crystalline part (b) and an amorphous part (c). The resin particles are characterized in that the proportion of (b) in (A) in the case of a block resin is 50% by weight or more, and the resin particles (I) satisfy the following conditions.
[Condition 1] G ′ (TaI + 20) = 1 × 10 ^{2 to} 5 × 10 ⁵ [Pa]
[Condition 2] G ″ (TaI + 20) = 1 × 10 ^{2 to} 5 × 10 ⁵ [Pa]
[G ′: storage elastic modulus (Pa), G ″: loss elastic modulus (Pa), TaI: resin particle
Maximum peak temperature of melting heat of child (I) (° C.)]

  According to the present invention, resin particles excellent in both low-temperature fixability and blocking resistance can be provided. Also, the charging characteristics are good.

Hereinafter, the resin particles (I) of the present invention will be described in detail.
The resin particles (I) contain a crystalline resin (A) and an amorphous resin (B).
In the present invention, “crystallinity” means that the ratio (softening temperature / Ta) between the softening temperature and the maximum peak temperature (Ta) of the heat of fusion is 0.8 to 1.55, and differential scanning calorimetry (DSC) In FIG. 4, it indicates that the endothermic amount does not change stepwise but has a clear endothermic peak. “Non-crystalline” means that the ratio (softening temperature / Ta) between the softening temperature and the maximum peak heat of fusion (softening temperature / Ta) is greater than 1.55.
Even if the resin is a block body of a crystalline resin and an amorphous resin, the differential scanning calorimetry (DSC) has a clear endothermic peak, and the softening temperature and the maximum peak temperature (Ta) of the heat of fusion When the ratio is 0.8 to 1.55, this is also a crystalline resin.

The maximum peak temperature (Ta) of the heat of fusion and the softening temperature in the present invention are values measured as follows.
<Maximum peak temperature of melting heat (Ta)>
Using a differential scanning calorimeter {DSC, for example, DSC210, manufactured by Seiko Denshi Kogyo Co., Ltd.], the measurement sample is cooled from room temperature (25 ° C) to 0 ° C at a rate of 0.5 ° C / min, and the temperature rising rate is 20 ° C. Measure the endothermic change by raising the temperature at a minute / minute, draw a graph of "endothermic amount" and "temperature", and set the temperature corresponding to the maximum peak of endothermic amount as the maximum peak temperature of melting heat (Ta) And
As a sample for measuring Ta, a sample previously stored at (Ta′-7) ° C. for 6 hours is used. Here, (Ta ′) is a temperature drop of the sample from room temperature (25 ° C.) to 10 ° C. at a rate of 0.5 ° C./min, and DSC measurement is performed by the above method. A certain endothermic peak temperature is assumed. When there are a plurality of peaks, the peak temperature with the largest endothermic amount is defined as (Ta ′).
Moreover, the sample which does not have an endothermic peak by the said method considers the glass transition point (Tg) measured by the method mentioned later as (Ta) and (Ta ').

<Softening temperature>
The temperature at which the loss elastic modulus G "= 10 ^6.5 (Pa) is set as the softening temperature. G" is obtained from a dynamic viscoelasticity measuring device (dynamic viscoelasticity measuring device RDS-2 manufactured by Rheometric Scientific) under a frequency of 1 Hz. It is obtained by measuring.
After setting the measurement sample on the jig of the measurement apparatus, the temperature was raised to (Ta + 30) ° C. [Ta is the maximum peak temperature of the heat of fusion of the object to be measured] and brought into close contact with the jig, and from (Ta + 30) ° C. 30) Decrease in temperature at a rate of 0.5 ° C./min to 30 ° C., allow to stand at (Ta-30) ° C. for 1 hour, then increase to (Ta-10) ° C. at a rate of 0.5 ° C./min. Further, the sample is allowed to stand at (Ta-10) ° C. for 1 hour to sufficiently advance crystallization, and then measurement is performed using this. The measurement temperature range is 0 ° C. to 200 ° C., and the softening temperature can be determined by measuring the melt viscoelasticity of the resin between these temperatures.

The resin particles (I) of the present invention are resin particles containing one or more crystalline resins (A) and non-crystalline resins (B), respectively, and a total of two or more types of resins. Therefore, it is preferable that the crystalline resin (A) and the amorphous resin (B) in the resin particles (I) are not completely compatible. Therefore, it is preferable to have an endothermic peak derived from the crystalline resin (A) in the measurement of the endothermic amount by DSC of the resin particles (I). At this time, the endothermic amount P derived from the crystalline resin is P ≧ Q × [( I)% of crystalline resin (A) in resin] × 0.5 / 100
Is preferred. More preferably,
P ≧ Q × [% of crystalline resin (A) in resin in (I)] × 0.65 / 100,
More preferably,
P ≧ Q × [% of crystalline resin (A) in resin in (I)] × 0.8 / 100
It is.
P: endothermic amount derived from the crystalline resin (A) of the resin particles (I), Q: endothermic amount of the crystalline resin (A) alone In the above and below, “%” means “% by weight” unless otherwise specified. To do.

  The crystalline resin (A) used in the resin particles (I) of the present invention may be used alone or in combination of two or more. However, two or more crystalline resins used in combination may be melt-mixed or an organic solvent. When the mixed resin is dissolved and mixed by (u) or the like, and the mixed resin is taken out again by cooling or solvent removal, the mixed resin also preferably has crystallinity. Moreover, it is preferable that the maximum temperature of the melting | fusing point difference of each crystalline resin is 10 degrees C or less, More preferably, it is 7 degrees C or less, More preferably, it is 5 degrees C or less.

  The amorphous resin (B) used in the resin particles (I) of the present invention may be used alone or in combination of two or more. However, two or more of the amorphous resins used in combination may be melt-mixed or When the mixed resin is dissolved and mixed with an organic solvent (u) or the like and the mixed resin is taken out again by cooling or solvent removal, the mixed resin is preferably compatible and has only one glass transition point.

The weight ratio (A) / (B) of the crystalline resin (A) and the amorphous resin (B) is preferably 0.05 or more and less than 4, more preferably 0.07 or more and 3.5 or less, and still more preferably 0.08 or more and 3 or less. When the weight ratio (A) / (B) is 0.05 or more, the loss elastic modulus G ″ (TaI + 20) of a resin particle (I) described later tends to be 5 × 10 ⁵ [Pa] or less, and therefore the low temperature side When the weight ratio (A) / (B) is less than 4, the storage elastic modulus G ′ (TaI + 20) described later is 1 ×. 10 ² [Pa] or more, and therefore, the fixing temperature is not easily deteriorated due to insufficient elasticity, and the fixing temperature range is widened.

The total content of the crystalline resin (A) and the amorphous resin (B) in the resin particles (I) is preferably 50% or more, more preferably 60% or more, and further preferably 70% or more. If it is 50% or more, the loss elastic modulus G ″ (TaI + 20) described later tends to be 5 × 10 ⁵ [Pa] or less, the viscosity becomes fixable on the low temperature side, and the fixability at low temperature is good. .

  The resin particles (I) of the present invention preferably have a maximum heat of fusion (TaI) in the range of 40 to 100 ° C., more preferably 43 to 80 ° C., particularly preferably from the viewpoint of heat-resistant storage stability. Is 45-70 degreeC.

In the viscoelastic characteristics of the resin particles (I), the storage elastic modulus G ′ at (TaI + 20) ° C. [TaI is the maximum peak temperature of heat of fusion of (I)] is 1 × 10 ^{2 to} 5 × 10 ⁵ [Pa]. The range is [Condition 1], preferably 2 × 10 ^{2 to} 3 × 10 ⁵ [Pa].
When G ′ at (TaI + 20) ° C. is less than 1 × 10 ² Pa, fixing deterioration is likely to occur due to insufficient elasticity, and the fixing temperature region becomes narrow. On the other hand, if it exceeds 5 × 10 ⁵ [Pa], it becomes difficult for the viscosity to be fixed on the low temperature side, and the fixing property at low temperature is deteriorated.
In the present invention, the dynamic viscoelasticity measurement values (storage elastic modulus G ′, loss elastic modulus G ″) are measured under a frequency of 1 Hz using a dynamic viscoelasticity measuring device RDS-2 manufactured by Rheometric Scientific.
After setting the measurement sample on the jig of the measurement apparatus, the temperature was raised to (Ta + 30) ° C. [Ta is the maximum peak temperature of the heat of fusion of the object to be measured] and brought into close contact with the jig, and from (Ta + 30) ° C. 30) Decrease in temperature at a rate of 0.5 ° C./min to 30 ° C., allow to stand at (Ta-30) ° C. for 1 hour, then increase to (Ta-10) ° C. at a rate of 0.5 ° C./min. Further, the sample is allowed to stand at (Ta-10) ° C. for 1 hour to sufficiently advance crystallization, and then measurement is performed using this. The measurement temperature range is 30 ° C. to 200 ° C., and by measuring the melt viscoelasticity of the resin between these temperatures, it can be obtained as temperature-G ′ and temperature-G ″ curves.
The resin particles (I) satisfying [Condition 1] can be obtained by adjusting the ratio of the crystalline component in the resin constituting the resin particles (I), adjusting the resin molecular weight, or the like. For example, when the use ratio of the crystalline resin (A) is increased, or when the crystalline resin (A) to be used is a block resin of a crystalline part (b) and an amorphous part (c), the crystalline part ( Increasing the ratio of b) or the ratio of the crystalline component decreases the value of G ′ (TaI + 20). Examples of the crystalline component include polyols having a linear structure, polycarboxylic acids, polyisocyanates, and the like. Also, the value of G ′ (TaI + 20) is decreased by decreasing the resin molecular weight.

Further, in the viscoelastic properties of the resin particles (I), the loss elastic modulus G ″ at (TaI + 20) ° C. [TaI is the maximum peak temperature of the melting heat of (I)] is 1 × 10 ^{2 to} 5 × 10 ⁵ [Pa ] [Condition 2], preferably 5 × 10 ^{2 to} 3 × 10 ⁵ [Pa].
When G ″ at (TaI + 20) ° C. exceeds 5 × 10 ⁵ Pa, cold offset is likely to occur during low-temperature fixing when toner particles are used, and the low-temperature fixing property deteriorates. Also, less than 1 × 10 ² [Pa]. If this is the case, hot offset occurs even at low temperature fixing, and the fixing temperature region becomes narrow.
The resin particles (I) satisfying [Condition 2] can be obtained by adjusting the ratio of the crystalline component in the resin constituting the resin particles (I). For example, when the ratio of the crystalline resin (A) is increased, or when the crystalline resin (A) to be used is a block resin of a crystalline part (b) and an amorphous part (c), the crystalline part (b ) And the ratio of the crystalline component decrease the value of G ″ (TaI + 20). Examples of the crystalline component include polyols having a linear structure, polycarboxylic acids, and polyisocyanates.

Further, the ratio [G ″ (TaI + 30) / G ″ (TaI + 70)] of the loss elastic modulus G ″ at (TaI + 30) ° C. and the loss elastic modulus G ″ at (TaI + 70) ° C. of the resin particle (I) is 0.05. It is preferably ˜50, more preferably 0.1 to 40, and particularly preferably 0.5 to 30 [TaI is the maximum peak temperature of the heat of fusion of (I)].
When [G ″ (TaI + 30) / G ″ (TaI + 70)] of the resin particle (I) is 0.05 to 50, the elasticity of the resin particle (I) is maintained, and the low temperature side and the high temperature side of the fixing temperature region are maintained. Equivalent fixability can be obtained.
The resin particles (I) satisfying the above G ″ ratio can be obtained by adjusting the ratio of the crystalline component in the resin constituting the resin particles (I) and the molecular weight of the crystalline part (b). For example, when the ratio of the crystalline part (b) or the ratio of the crystalline component is increased, the value of [G ″ (TaI + 30) / G ″ (TaI + 70)] decreases. When the molecular weight is increased, the value of [G ″ (TaI + 30) / G ″ (TaI + 70)] decreases. Examples of the crystalline component include polyols and polyisocyanates having a linear structure.

The resin particles (I) of the present invention contain a crystalline resin (A).
Even if the resin is a block body of a crystalline resin and an amorphous resin, it has a clear endothermic peak in differential scanning calorimetry (DSC), and (softening temperature / maximum peak temperature of heat of fusion) is 0. When there is .8 to 1.55, this is also a crystalline resin.

  From the viewpoint of heat-resistant storage stability, the crystalline resin (A) needs to have a maximum peak heat temperature (TaA) in the range of 40 to 100 ° C, preferably 45 to 85 ° C, more preferably 50 to 50 ° C. 70 ° C.

  The ratio (softening temperature / TaA) between the softening temperature of the crystalline resin (A) and the maximum peak temperature (TaA) of heat of fusion is 0.8 to 1.55, preferably 0.85 to 1.2, More preferably, it is 0.9-1.15. If it is outside the range of 0.8 to 1.55, it is difficult to achieve both heat-resistant storage stability and low-temperature fixability.

In the viscoelastic characteristics of the crystalline resin (A), the storage elastic modulus G ′ at (TaA + 20) ° C. [TaA is the maximum peak temperature of heat of fusion of (A)] is in the range of 50 to 1 × 10 ⁶ [Pa]. Condition 3] is preferable, and 1 × 10 ^{2 to} 5 × 10 ⁵ [Pa] is more preferable.
When G ′ at (TaA + 20) ° C. is 50 Pa or more, fixing deterioration due to insufficient elasticity hardly occurs, and the fixing temperature range is widened.
The crystalline resin (A) satisfying [Condition 3] can be obtained by adjusting the ratio of the crystalline component in the composition constituting (A). For example, when the ratio of the crystalline part (b) or the ratio of the crystalline component is increased, the value of G ′ (TaA + 20) decreases. Examples of the crystalline component include polyols having a linear structure, polyisocyanates, and the like.

The melting start temperature (X) of the crystalline resin (A) is preferably within the temperature range of (TaA ± 30) ° C., more preferably within the temperature range of (TaA ± 20) ° C., particularly preferably (TaA Within the temperature range of ± 15) ° C. [TaA is the maximum peak temperature of the heat of fusion of (A)].
Specifically, (X) is preferably 30 to 100 ° C, more preferably 40 to 80 ° C.
The melting start temperature (X) is a value measured as follows.
<Melting start temperature>
Using a descending flow tester {for example, CFT-500D, manufactured by Shimadzu Corporation), a load of 1.96 MPa was applied by a plunger while heating a measurement sample of 1 g at a heating rate of 6 ° C./min. After extruding from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of “plunger descent amount (flow value)” and “temperature”, and after a slight increase of the piston due to thermal expansion of the sample, the piston again Is read from the graph, and this value is taken as the melting start temperature.

The crystalline resin (A) preferably satisfies the following [Condition 4] with respect to the loss elastic modulus G ″ [Pa] and the melting start temperature (X) [° C.], and satisfies [Condition 4-2]. Is more preferable, and it is particularly preferable to satisfy [Condition 4-3].
[Condition 4] | logG ″ (X) −logG ″ (X + 20) |> 2.0
[Condition 4-2] | logG ″ (X) −logG ″ (X + 20) |> 2.5
[Condition 4-3] | logG ″ (X) −logG ″ (X + 15) |> 2.5
When the melting start temperature (X) of the crystalline resin (A) is within the above range and [Condition 4] is satisfied, the resin has a low viscosity-decreasing rate. The same image quality can be obtained on the high temperature side. Moreover, the process from the start of melting to the fixable viscosity is fast, which is advantageous for obtaining excellent low-temperature fixability. [Condition 4] is an index of the sharp melt property of the resin, which indicates how fast it can be fixed with less heat, and is obtained experimentally.
The crystalline resin (A) satisfying the preferable range of the melting start temperature (X) and [Condition 4] can be obtained by adjusting the ratio of the crystalline component in the composition constituting (A). For example, when the ratio of the crystalline component is increased, the temperature difference between (TaA) and (X) is decreased.

Further, in the viscoelastic property of the crystalline resin (A), the ratio of the loss elastic modulus G ″ at (TaA + 30) ° C. to the loss elastic modulus G ″ at (TaA + 70) ° C. [G ″ (TaA + 30) / G ″ (TaA + 70)] It is preferably 0.05 to 50, more preferably 0.1 to 10 [TaA: maximum peak temperature of heat of fusion of (A)].
By maintaining the ratio of the loss elastic modulus within the above range, the same glossiness can be obtained on the low temperature side and the high temperature side of the fixing temperature region.
The crystalline resin (A) satisfying the above G ″ ratio can be obtained by adjusting the ratio of the crystalline component in the composition constituting (A) and the molecular weight of the crystalline part (b). For example, when the ratio of the crystalline part (b) or the ratio of the crystalline component is increased, the value of [G ″ (TaA + 30) / G ″ (TaA + 70)] decreases. When the molecular weight is increased, the value of [G ″ (TaA + 30) / G ″ (TaA + 70)] decreases. Examples of the crystalline component include polyols having a linear structure, polyisocyanates, and the like.

The crystalline resin (A) has crystallinity regardless of whether it is composed of only the crystalline part (b) or a block resin having the crystalline part (b) and the non-crystalline part (c). However, from the viewpoint of fixability, a block resin composed of (b) and (c) is preferable.
In addition, the block resin is excellent in durability.

Hereinafter, a block resin composed of a crystalline part (b) and an amorphous part (c), which is a preferred resin as the crystalline resin (A), will be described in detail.
In the case of a block resin, the glass transition point (Tg) of (c) is preferably 40 to 250 ° C., more preferably 50 to 240 ° C., particularly preferably 60 to 230 ° C., most preferably from the viewpoint of heat-resistant storage stability. 65 to 180 ° C. The softening temperature of (c) is preferably 100 to 300 ° C, more preferably 110 to 290 ° C, and particularly preferably 120 to 280 ° C.

The glass transition point (Tg) is a value measured by the following method.
<Glass transition point (Tg)>
The glass transition point is a physical property unique to an amorphous resin and is distinguished from the maximum peak temperature of heat of fusion. In the measurement of the maximum peak temperature (Ta) of the heat of fusion, the maximum of the baseline extension line below the maximum peak temperature in the graph of “endothermic heat generation” and “temperature” and the maximum peak rising portion The temperature corresponding to the intersection point with the tangent indicating the maximum inclination to the peak apex is defined as the glass transition point.

The weight average molecular weight (hereinafter referred to as Mw) of the crystalline resin (A) is preferably 5000 to 100,000, more preferably 6000 to 80000, and particularly preferably 8000 to 50000 from the viewpoint of fixing.
When (A) is a block resin having a crystalline part (b) and an amorphous part (c), the Mw of (b) is preferably 2000 to 80000, more preferably 4000 to 60000, and particularly preferably 6000 to 60000. 30000.
As for Mw of (c), 500-50000 are preferable, More preferably, it is 750-20000, Most preferably, it is 1000-10000.
In the present invention, the molecular weight of the resin is measured under the following conditions using gel permeation chromatography (GPC).
Device (example): HLC-8120 manufactured by Tosoh Corporation
Column (example): TSK GEL GMH6 2 [Tosoh Corporation]
Measurement temperature: 40 ° C
Sample solution: 0.25% THF solution Solution injection amount: 100 μL
Detection device: Refractive index detector Reference material: TOSANDO standard polystyrene (TSK standard POLY STYRENE) 12 points (molecular weight 500 1050 2800 5970 9100 18100 37900 96400
190000 355000 1090000 2890000)

  When the crystalline resin (A) is a block resin composed of a crystalline part (b) and an amorphous part (c), the proportion of the crystalline part (b) in the crystalline resin (A) Is preferably 50% or more, more preferably 60 to 98%, and still more preferably 63 to 96%. When the proportion of (b) is 50% or more, the crystallinity of the crystalline resin (A) is not impaired, and the low-temperature fixability is better.

When the crystalline resin (A) is a block resin composed of a crystalline part (b) and an amorphous part (c), (b) and (c) are linearly bonded in the following format. It is preferable that both ends are the resin of (b), and the average value n of the number of repeating units of {-(c)-(b)} is 0.9 to 3.5, more preferably n = 0.95 to 2.5, particularly preferably n = 1.0 to 1.5.
(B) {-(c)-(b)} n
Specifically, the above formula shows that the crystalline part (b) and the non-crystalline part (c) are (b) [n = 0], (b)-(c)-(b) [n = 1 ], (B)-(c)-(b)-(c)-(b) [n = 2], (b)-(c)-(b)-(c)-(b)-(c) -(B) means a resin linearly bonded in the form of [n = 3] or the like, and a mixture thereof (excluding those consisting only of n = 0).
When n is 3.5 or less, the crystallinity of the crystalline resin (A) is not impaired. Further, when n is 0.9 or more, the elasticity after melting of (A) is good, and when toner particles are used, hot offset hardly occurs during fixing, and the fixing temperature range becomes wider. Note that n is a calculated value obtained from the amount of raw material used [molar ratio of (b) to (c)]. Further, from the viewpoint of the crystallinity of the crystalline resin (A), it is preferable that both ends of (A) are crystalline parts (b).
When both ends are non-crystalline parts (c), the degree of crystallinity is lowered, so that the crystalline part (b) in (A) is used in order to give the crystalline resin (A) crystallinity. The ratio is preferably 75% or more.

The resin used for the crystalline part (b) will be described.
The resin used for the crystalline part (b) is not particularly limited as long as it has crystallinity. From the viewpoint of heat-resistant storage stability, the melting point is preferably in the range of 40 to 100 ° C (more preferably in the range of 50 to 70 ° C).
In the present invention, the melting point is measured with a differential scanning calorimeter {for example, DSC210, manufactured by Seiko Denshi Kogyo Co., Ltd.) similarly to the maximum peak temperature (Ta) of heat of fusion.

  The crystalline part (b) is not particularly limited as long as it has crystallinity, and may be a composite resin. Among these, polyester resins, polyurethane resins, polyurea resins, polyamide resins, polyether resins, and composite resins thereof are preferable, and linear polyester resins and composite resins containing the same are particularly preferable.

The polyester resin used as (b) is preferably a polycondensed polyester resin synthesized from an alcohol (diol) component and an acid (dicarboxylic acid) component from the viewpoint of crystallinity. However, a tri- or higher functional alcohol component or acid component may be used as necessary. As the polyester resin, in addition to the polycondensation polyester resin, a lactone ring-opening polymer and a polyhydroxycarboxylic acid are also preferable.
Examples of the polyurethane resin include a polyurethane resin synthesized from an alcohol (diol) component and an isocyanate (diisocyanate) component. However, a tri- or higher functional alcohol component or isocyanate component may be used as necessary.
Examples of the polyamide resin include a polyamide resin synthesized from an amine (diamine) component and an acid (dicarboxylic acid) component. However, a trifunctional or higher functional amine component or acid component may be used as necessary.
Examples of the polyurea resin include a polyurea resin synthesized from an amine (diamine) component and an isocyanate (diisocyanate) component. However, a trifunctional or higher functional amine component or isocyanate component may be used as necessary.
In the following description, first, a diol component, a dicarboxylic acid component, a diisocyanate component, and a diamine component (each having three or more functional groups) used for the crystalline polycondensation polyester resin, the crystalline polyurethane resin, the crystalline polyamide resin, and the crystalline polyurea resin. Each of them).

[Diol component]
As a diol component, an aliphatic diol is preferable, and it is preferable that it is C2-C36. A linear aliphatic diol is more preferred.
When the aliphatic diol is branched, the crystallinity of the polyester resin is lowered and the melting point is lowered, so that blocking resistance, image storage stability, and low-temperature fixability may be deteriorated. On the other hand, when the number of carbon atoms exceeds 36, it may be difficult to obtain practical materials.

  The content of the linear aliphatic diol in the diol component is preferably 80 mol% or more of the diol component used, and more preferably 90 mol% or more. If it is 80 mol% or more, the crystallinity of the polyester resin is improved and the melting point is increased, so that the blocking resistance and the low-temperature fixability are improved.

  Specific examples of the linear aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7. -Heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14 -Tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol and the like are exemplified, but not limited thereto. Among these, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol are preferable in view of availability.

  Other diols used as necessary include aliphatic diols other than those having 2 to 36 carbon atoms (1,2-propylene glycol, butanediol, hexanediol, octanediol, decanediol, dodecanediol, tetradecanediol, Neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc .; C4-C36 alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol) C 4 -36 alicyclic diol (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); alkylene oxide of the alicyclic diol (hereinafter abbreviated as AO) [Ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO)] adducts (addition mole number 1-30); bisphenols (bisphenol A) , Bisphenol F, bisphenol S, etc.) AO (EO, PO, BO, etc.) adduct (added mole number 2-30); polylactone diol (poly ε-caprolactone diol, etc.); and polybutadiene diol.

Furthermore, as a diol used as necessary, a diol having another functional group may be used in addition to the diol having no functional group other than the above hydroxyl group. Examples of the diol having a functional group include a diol having a carboxyl group, a diol having a sulfonic acid group or a sulfamic acid group, and salts thereof.
Diols having a carboxyl group include dialkylol alkanoic acids [things of C6-24, such as 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid. 2,2-dimethylol octanoic acid, etc.].
Examples of the diol having a sulfonic acid group or a sulfamic acid group include a sulfamic acid diol [N, N-bis (2-hydroxyalkyl) sulfamic acid (C1-6 of alkyl group) or an AO adduct thereof (EO as EO or PO). AO addition mole number 1 to 6): for example, N, N-bis (2-hydroxyethyl) sulfamic acid and N, N-bis (2-hydroxyethyl) sulfamic acid PO2 molar adduct, etc.]; bis (2 -Hydroxyethyl) phosphate and the like.
Examples of the neutralizing base of the diol having these neutralizing bases include tertiary amines having 3 to 30 carbon atoms (such as triethylamine) and / or alkali metals (such as sodium salts).
Among these, preferred are alkylene glycols having 2 to 12 carbon atoms, diols having a carboxyl group, AO adducts of bisphenols, and combinations thereof.

Examples of the polyol having 3 to 8 valences or more used as necessary include 3 to 8 or more polyhydric aliphatic alcohols having 3 to 36 carbon atoms (alkane polyols and intramolecular or intermolecular dehydrates thereof such as glycerin. , Trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerol; sugars and derivatives thereof such as sucrose and methylglucoside; and AO adducts (addition moles) of trisphenols (such as trisphenol PA) 2-30); AO addition product (addition mole number 2-30) of novolak resin (phenol novolak, cresol novolak, etc.); acrylic polyol [copolymer of hydroxyethyl (meth) acrylate and other vinyl monomer, etc.]; Etc. That.
Among these, preferred are trivalent to octavalent or higher polyhydric aliphatic alcohols and novolak resin AO adducts, and more preferred are novolak resin AO adducts.

[Dicarboxylic acid component]
Examples of the dicarboxylic acid component include various dicarboxylic acids, but aliphatic dicarboxylic acids and aromatic dicarboxylic acids are preferable, and the aliphatic dicarboxylic acids are more preferably linear carboxylic acids.

Examples of dicarboxylic acids include alkane dicarboxylic acids having 4 to 36 carbon atoms (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, etc.); alicyclic dicarboxylic acids having 6 to 40 carbon atoms. Acid [dimer acid (dimerized linoleic acid), etc.], alkenedicarboxylic acid having 4 to 36 carbon atoms (alkenyl succinic acid such as dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, maleic acid, fumaric acid) C8-36 aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, etc.) Etc.
Examples of the tri- or hexavalent or higher polycarboxylic acid used as necessary include C9-C20 aromatic polycarboxylic acids (trimellitic acid, pyromellitic acid, and the like).
In addition, as the dicarboxylic acid or the polycarboxylic acid having 3 to 6 valences or more, the above acid anhydrides or lower alkyl esters having 1 to 4 carbon atoms (methyl ester, ethyl ester, isopropyl ester, etc.) may be used. Good.
Among these dicarboxylic acids, it is particularly preferable to use an aliphatic dicarboxylic acid (especially a straight-chain carboxylic acid) alone, but an aromatic dicarboxylic acid (terephthalic acid, isophthalic acid, t-butylisophthalic acid) together with the aliphatic dicarboxylic acid. Those obtained by copolymerizing acids and their lower alkyl esters are also preferred. The copolymerization amount of the aromatic dicarboxylic acid is preferably 20 mol% or less.
Examples of the dicarboxylic acid component include, but are not limited to, the above carboxylic acids. Of these, adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, and isophthalic acid are preferable in consideration of crystallinity and availability.

[Diisocyanate component]
Examples of the diisocyanate include C6-C20 aromatic diisocyanate, C2-C18 aliphatic diisocyanate, C4-C15 alicyclic diisocyanate, and C8. To 15 araliphatic diisocyanates and modified products of these diisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, oxazolidone group-containing modified products) and the like The mixture of 2 or more types of these is mentioned. Moreover, you may use together polyisocyanate more than trivalence as needed.

Specific examples of the aromatic diisocyanate (including tri- or higher polyisocyanates) include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI). ), Crude TDI, 2,4′- and / or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde with an aromatic amine (aniline) or mixtures thereof; diamino A mixture of diphenylmethane and a small amount (for example, 5 to 20%) of a trifunctional or higher polyamine] phosgenation product: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -tri Phenylmethane triisocyanate, m- and p-isocyanate Such as preparative phenylsulfonyl isocyanate.
Specific examples of the aliphatic diisocyanate (including triisocyanate or higher polyisocyanate) include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2, 2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2 , 6-diisocyanatohexanoate and the like.
Specific examples of the alicyclic diisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2- And isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate.
Specific examples of the araliphatic diisocyanate include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.
Examples of the modified diisocyanate include urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, and oxazolidone group-containing modified product.
Specifically, modified MDI (urethane modified MDI, carbodiimide modified MDI, trihydrocarbyl phosphate modified MDI, etc.), modified products of diisocyanates such as urethane modified TDI, and mixtures of two or more thereof (for example, modified MDI and urethane modified TDI ( In combination with an isocyanate-containing prepolymer).
Of these, preferred are aromatic diisocyanates having 6 to 15 carbon atoms, aliphatic diisocyanates having 4 to 12 carbon atoms, and alicyclic diisocyanates having 4 to 15 carbon atoms, and particularly preferred are TDI, MDI, HDI, water. Attached MDI and IPDI.

[Diamine component]
Examples of diamines (including trivalent or higher polyamines used as necessary) include aliphatic diamines (C2 to C18): [1] aliphatic diamines {C2 to C6 alkylenediamines (ethylenediamine, propylenediamine, trimethylene) Diamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (C2 to C6) diamine [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]} [2] These alkyl (C1 to C4) or hydroxyalkyl (C2 to C4) substitutes [dialkyl (C1 to C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanol; Amine, 2,5-dimethyl-2,5-hexamethylenediamine, methyliminobispropylamine, etc.]; [3] Alicyclic or heterocyclic-containing aliphatic diamine {alicyclic diamine (C4 to C15) [1,3 -Diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline), etc.], heterocyclic diamine (C4-C15) [piperazine, N-aminoethylpiperazine, 1, 4-diaminoethylpiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] Undecane etc.]; [4] Aromatic ring-containing aliphatic amines (C8 to C15) (xylylenediamine, tetrachloro-p-) Siri diamine, etc.), and the like.

As aromatic diamines (C6-C20), [1] unsubstituted aromatic diamine [1,2-, 1,3- and 1,4-phenylenediamine, 2,4′- and 4,4′-diphenylmethane Diamine, crude diphenylmethanediamine (polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4 , 4 ', 4 "-triamine, naphthylenediamine, etc .; [2] aromatic diamines having a nucleus-substituted alkyl group [C1-C4 alkyl group such as methyl, ethyl, n- and i-propyl, butyl, etc.], for example 2 , 4- and 2,6-tolylenediamine, crude tolylenediamine, die Rutorylenediamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-bis (o-toluidine), dianisidine, diaminoditolylsulfone, 1,3-dimethyl-2,4-diaminobenzene 1,3-dimethyl-2,6-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2,4-diaminobenzene 2,3-dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 3,3 ′, 5,5′-tetramethylbenzidine, 3,3 ′, 5,5 ′ -Tetramethyl-4,4'-diaminodiphenylmethane, 3,5-diethyl-3'-methyl-2 ', 4-diaminodiphenylmethane, 3,3'-diethyl-2,2 -Diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminobenzophenone, 3,3', 5,5'-tetraethyl -4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenylsulfone, etc.), and mixtures of these isomers in various proportions; [3] nuclear substitution Aromatic diamines having an electron withdrawing group (halogen such as Cl, Br, I, F; alkoxy group such as methoxy and ethoxy; nitro group) [methylenebis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2 -Chlor-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5 Dichloro-1,4-phenylenediamine, 5-nitro-1,3-phenylenediamine, 3-dimethoxy-4-aminoaniline; 4,4′-diamino-3,3′-dimethyl-5,5′-dibromo- Diphenylmethane, 3,3'-dichlorobenzidine, 3,3'-dimethoxybenzidine, bis (4-amino-3-chlorophenyl) oxide, bis (4-amino-2-chlorophenyl) propane, bis (4-amino-2- Chlorophenyl) sulfone, bis (4-amino-3-methoxyphenyl) decane, bis (4-aminophenyl) sulfide, bis (4-aminophenyl) telluride, bis (4-aminophenyl) selenide, bis (4-amino-) 3-methoxyphenyl) disulfide, 4,4'-methylenebis (2-iodoaniline), 4,4'-methyl Bis (2-bromoaniline), 4,4′-methylenebis (2-fluoroaniline), 4-aminophenyl-2-chloroaniline, etc.]; [4] aromatic diamine having a secondary amino group [above [1] To [3] wherein a part or all of —NH ₂ of the aromatic diamine is replaced by —NH—R ′ (R ′ is an alkyl group such as a lower alkyl group such as methyl or ethyl)] [4, 4 '-Di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.].

  In addition to these, the diamine component can be obtained by condensation of polyamide polyamine [dicarboxylic acid (dimer acid etc.) and excess (more than 2 mol per mole of acid) polyamine (alkylenediamine, polyalkylenepolyamine etc.). Low molecular weight polyamide polyamine, etc.], polyether polyamine [hydride of cyanoethylated polyether polyol (polyalkylene glycol, etc.), etc.].

Among crystalline polyester resins, lactone ring-opening polymerization products are monolactones having 3 to 12 carbon atoms such as β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone (the number of ester groups in the ring). Lactones such as one) can be obtained by ring-opening polymerization using a catalyst such as a metal oxide or an organometallic compound. Of these, a preferred lactone is ε-caprolactone from the viewpoint of crystallinity.
When glycol is used as the initiator, a lactone ring-opening polymer having a hydroxyl group at the terminal is obtained. For example, it can be obtained by reacting the lactone with the diol component such as ethylene glycol or diethylene glycol in the presence of a catalyst. As the catalyst, an organic tin compound, an organic titanium compound, an organic tin halide compound, and the like are common, added at a rate of about 0.1 to 5000 ppm, and preferably at 100 to 230 ° C., preferably in an inert atmosphere. By polymerizing, a lactone ring-opening polymer can be obtained. The lactone ring-opening polymer may be modified at its terminal so as to be, for example, a carboxyl group. The lactone ring-opening polymer is a thermoplastic aliphatic polyester resin having high crystallinity. As the lactone ring-opening polymer, commercially available products may be used. For example, H1P, H4, H5, H7 of PLACEL series manufactured by Daicel Corporation (all of which melting point = about 60 ° C., Tg = about −60 ° C. Highly crystalline polycaprolactone).

Among crystalline polyester resins, polyhydroxycarboxylic acid can be obtained by directly dehydrating and condensing hydroxycarboxylic acid such as glycolic acid and lactic acid (L-form, D-form, racemic form), but glycolide, lactide (L-form, A cyclic ester having 4 to 12 carbon atoms (2 to 3 ester groups in the ring) corresponding to a dehydration condensate between two or three molecules of a hydroxycarboxylic acid such as D-form or racemate) as a metal oxide or organic Ring-opening polymerization using a catalyst such as a metal compound is preferable from the viewpoint of adjusting the molecular weight. Among these, preferred cyclic esters are L-lactide and D-lactide from the viewpoint of crystallinity.
When glycol is used as an initiator, a polyhydroxycarboxylic acid skeleton having a hydroxyl group at the terminal is obtained. For example, the cyclic ester can be obtained by reacting the diol component such as ethylene glycol or diethylene glycol in the presence of a catalyst. As the catalyst, an organic tin compound, an organic titanium compound, an organic tin halide compound, and the like are common, added at a rate of about 0.1 to 5000 ppm, and preferably at 100 to 230 ° C., preferably in an inert atmosphere. A polyhydroxycarboxylic acid can be obtained by polymerization. The polyhydroxycarboxylic acid may have a terminal modified so as to be, for example, a carboxyl group.

Examples of the polyether resin include crystalline polyoxyalkylene polyols.
The method for producing the crystalline polyoxyalkylene polyol is not particularly limited, and any conventionally known method may be used.
For example, a method of ring-opening polymerization of a chiral AO with a catalyst usually used in polymerization of AO (for example, Journal of the American Chemical Society, 1956, Vol. 78, No. 18, p. 4787-4792) And a method of ring-opening polymerization of inexpensive racemic AO using a sterically bulky complex having a special chemical structure as a catalyst.
As a method using a special complex, a method in which a compound obtained by contacting a lanthanoid complex and an organoaluminum is used as a catalyst (for example, described in JP-A No. 11-12353), or bimetal μ-oxoalkoxide and a hydroxyl compound are previously used. A reaction method (for example, described in JP-T-2001-521957) is known.
Further, as a method for obtaining a polyoxyalkylene polyol having a very high isotacticity, a method using a salen complex as a catalyst (for example, Journal of the American Chemical Society, 2005, Vol. 127, No. 33, p. 11566-). 11567) is known.

For example, when a chiral AO is used and glycol or water is used as an initiator during the ring-opening polymerization, a polyoxyalkylene glycol having a hydroxyl group at the terminal and having an isotacticity of 50% or more is obtained. The polyoxyalkylene glycol having an isotacticity of 50% or more may be modified such that its terminal is, for example, a carboxyl group. If the isotacticity is 50% or more, the crystallinity is usually obtained.
Examples of the glycol include the diol component, and examples of the carboxylic acid used for carboxy modification include the dicarboxylic acid component.

As AO used for manufacture of crystalline polyoxyalkylene polyol, a C3-C9 thing is mentioned, For example, the following compounds are mentioned.
C3 AO [PO, 1-chlorooxetane, 2-chlorooxetane, 1,2-dichlorooxetane, epichlorohydrin, epibromohydrin]; C4 AO [1,2-BO, methylglycidyl ether]; C5 AO [1,2-pentylene oxide, 2,3-pentylene oxide, 3-methyl-1,2-butylene oxide]; C6 AO [cyclohexene oxide, 1,2-hexylene oxide , 3-methyl-1,2-pentylene oxide, 2,3-hexylene oxide, 4-methyl-2,3-pentylene oxide, allyl glycidyl ether]; AO [1,2-heptyl having 7 carbon atoms] Ren oxide]; AO having 8 carbon atoms [styrene oxide]; AO having 9 carbon atoms [phenyl glycidyl ether] and the like.

Of these AOs, PO, 1,2-BO, styrene oxide and cyclohexene oxide are preferred. More preferred are PO, 1,2-BO and cyclohexene oxide. From the viewpoint of the polymerization rate, PO is most preferable.
These AOs can be used alone or in combination of two or more.

  The isotacticity of the crystalline polyoxyalkylene polyol is preferably 70% or more, more preferably 80% or more, more preferably 90% or more from the viewpoint of high sharp melt property and blocking resistance of the obtained crystalline polyether resin. Most preferably, it is 95% or more.

Isotacticity is described in Macromolecules, vol. 35, no. 6, 2389-2392 (2002), and can be calculated as follows.
About 30 mg of a measurement sample is weighed into a ¹³ C-NMR sample tube having a diameter of 5 mm, and about 0.5 ml of deuterated solvent is added and dissolved to obtain an analysis sample. Here, the deuterated solvent is deuterated chloroform, deuterated toluene, deuterated dimethyl sulfoxide, deuterated dimethylformamide, or the like, and a solvent capable of dissolving the sample is appropriately selected.

¹³ C-NMR signals derived from three types of methine groups are syndiotactic value (S) in the vicinity of 75.1 ppm, heterotactic value (H) in the vicinity of 75.3 ppm, and isotactic value (I) in 75.5 ppm. Observed nearby. Isotacticity is calculated by the following calculation formula (1).
Isotacticity (%) = [I / (I + S + H)] × 100 (1)
Where I is the integrated value of the isotactic signal; S is the integrated value of the syndiotactic signal; and H is the integrated value of the heterotactic signal.

When the crystalline resin (A) is a block polymer having a crystalline part (b) and an amorphous part (c), the resin used for forming the amorphous part (c) includes a polyester resin, a polyurethane resin, Polyurea resin, polyamide resin, polyether resin, vinyl resin (polystyrene, styrene acrylic polymer, etc.), epoxy resin and the like can be mentioned, but not limited thereto.
However, the resin used for forming the crystalline part (b) is preferably a polyester resin, a polyurethane resin, a polyurea resin, a polyamide resin, or a polyether resin. The resin used for forming the crystalline part (c) is also preferably a polyester resin, a polyurethane resin, a polyurea resin, a polyamide resin, a polyether resin, and a composite resin thereof. More preferred are polyurethane resins and polyester resins.

  The composition of these non-crystalline resins is the same as that of the crystalline part (b), and the monomers used are the diol component, the dicarboxylic acid component, the diisocyanate component, the diamine component, and the AO. As a specific example, any combination may be used as long as it becomes an amorphous resin.

[Production method of block polymer]
For the block polymer composed of the crystalline part (b) and the non-crystalline part (c), the use or non-use of a binder is selected in consideration of the reactivity of each terminal functional group. Can select a binder type suitable for the terminal functional group and bond (b) and (c) to form a block polymer.
When the binder is not used, the reaction between the terminal functional group of the resin forming (b) and the terminal functional group of the resin forming (c) is advanced while heating and decompressing as necessary. In particular, in the case of a reaction between an acid and an alcohol or a reaction between an acid and an amine, the reaction proceeds smoothly when the acid value of one resin is high and the hydroxyl value or amine value of the other resin is high. The reaction temperature is preferably 180 ° C to 230 ° C.
When a binder is used, various binders can be used. It can be obtained by performing a dehydration reaction or an addition reaction using polyvalent carboxylic acid, polyhydric alcohol, polyvalent isocyanate, polyfunctional epoxy, acid anhydride or the like.
Examples of the polyvalent carboxylic acid and acid anhydride include those similar to the dicarboxylic acid component. Examples of the polyhydric alcohol include those similar to the diol component. Examples of the polyvalent isocyanate include those similar to the diisocyanate component. As the polyfunctional epoxy, bisphenol A type and -F type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, diglycidyl ethers of AO adducts of bisphenol A or -F, Diglycidyl ether and triol of diglycidyl ether and diol (ethylene glycol, propylene glycol, neopentyl glycol, butanediol, hexanediol, cyclohexanedimethanol, polyethylene glycol, polypropylene glycol, etc.) of AO adduct of hydrogenated bisphenol A Propane di and / or triglycidyl ether, pentaerythritol tri and / or tetraglycidyl ether, sorbitol hepta And / or hexaglycidyl ether, resorcin diglycidyl ether, dicyclopentadiene / phenol addition type glycidyl ether, methylene bis (2,7-dihydroxynaphthalene) tetraglycidyl ether, 1,6-dihydroxynaphthalenediglycidyl ether, polybutadiene diglycidyl ether, etc. Is mentioned.

Among the methods for bonding (b) and (c), as an example of the dehydration reaction, both the crystalline part (b) and the non-crystalline part (c) are alcohol resins at both ends, and these are combined with a binder (for example, polyvalent). Reaction which couple | bonds with carboxylic acid) is mentioned. In this case, for example, the reaction is performed at a reaction temperature of 180 to 230 ° C. in the absence of a solvent to obtain a block polymer.
Examples of the addition reaction include a resin having a hydroxyl group at both ends of the crystalline part (b) and the non-crystalline part (c), a reaction in which these are bonded with a binder (for example, polyvalent isocyanate), and crystalline In the case where one of the part (b) and the non-crystalline part (c) is a resin having a hydroxyl group at the terminal and the other is a resin having an isocyanate group at the terminal, there is a reaction of bonding them without using a binder. . In this case, for example, both the crystalline part (b) and the non-crystalline part (c) are dissolved in a soluble solvent, and if necessary, a binder is added and reacted at a reaction temperature of 80 ° C. to 150 ° C. A block polymer is obtained.

As the crystalline resin (A), the above block polymer is preferable, but a resin having only the crystalline part (b) without the amorphous part (c) can also be used.
Examples of the composition of (A) consisting only of the crystalline part include the same as the crystalline part (b) and a crystalline vinyl resin.
As a crystalline vinyl resin, what has a vinyl monomer (m) which has a crystalline group, and the vinyl monomer (n) which does not have a crystalline group as a structural unit if necessary is preferable.

Examples of the vinyl monomer (m) include linear alkyl (meth) acrylate (m1) having 12 to 50 carbon atoms in the alkyl group (the linear alkyl group having 12 to 50 carbon atoms is a crystalline group), and the crystal And vinyl monomer (m2) having a unit of the sex part (b).
As a crystalline vinyl resin, what contains linear alkyl (meth) acrylate (m1) whose carbon number of an alkyl group is 12-50 (preferably 16-30) as a vinyl monomer (m) is further more preferable.
Examples of (m1) include linear lauryl (meth) acrylate, tetradecyl (meth) acrylate, stearyl (meth) acrylate, eicosyl (meth) acrylate, and behenyl (meth) acrylate, each of which is linear. It is done.
In the present invention, alkyl (meth) acrylate means alkyl acrylate and / or alkyl methacrylate, and the same description method is used hereinafter.

  In the vinyl monomer (m2) having a unit of the crystalline part (b), the method of introducing the unit of the crystalline part (b) into the vinyl monomer takes into account the reactivity of each terminal functional group, and the binder ( (Coupling agent) is used or not, and when it is used, the binder suitable for the terminal functional group is selected, and the crystalline part (b) is bonded to the vinyl monomer, and the crystalline part (b ) Units of vinyl monomer (m2).

  When a binder is not used when producing the vinyl monomer (m2) having the unit of the crystalline part (b), the terminal functional group of the crystalline part (b) and the terminal functional group of the vinyl monomer are heated and decompressed as necessary. Advance the reaction. Especially when the terminal functional group is a reaction between a carboxyl group and a hydroxyl group, or a reaction between a carboxyl group and an amino group, if the acid value of one resin is high and the hydroxyl value or amine value of the other resin is high, Progresses smoothly. The reaction temperature is preferably 180 ° C to 230 ° C.

When using a binder, various binders can be used according to the kind of the functional group at the terminal.
Specific examples of the binder and a method for producing the vinyl monomer (m2) using the binder include the same methods as those for producing the block polymer.

  The vinyl monomer (n) having no crystalline group is not particularly limited, and a vinyl monomer (n1) having a molecular weight of 1000 or less, which is usually used for the production of vinyl resins other than the vinyl monomer (m) having a crystalline group, And a vinyl monomer (n2) having a unit of the non-crystalline part (c).

  Examples of the vinyl monomer (n1) include styrenes, (meth) acrylic monomers, carboxyl group-containing vinyl monomers, other vinyl ester monomers, and aliphatic hydrocarbon vinyl monomers. Also good.

  Examples of styrenes include styrene and alkyl styrene having an alkyl group having 1 to 3 carbon atoms [for example, α-methyl styrene, p-methyl styrene], and styrene is preferable.

(Meth) acrylic monomers include alkyl (meth) acrylates having 1 to 11 carbon atoms in the alkyl group and branched alkyl (meth) acrylates having 12 to 18 carbon atoms in the alkyl group [for example, methyl (meth) acrylate, ethyl (Meth) acrylates, butyl (meth) acrylates, 2-ethylhexyl (meth) acrylates], alkyl groups having 1 to 11 carbon atoms hydroxylalkyl (meth) acrylates [for example, hydroxylethyl (meth) acrylates], alkyl group carbons Alkylamino group-containing (meth) acrylates having a number of 1 to 11 [for example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate], and nitrile group-containing vinyl monomers [for example, acrylonitrile, methacrylonitrile And the like.
Examples of the carboxyl group-containing vinyl monomer include monocarboxylic acids [having 3 to 15 carbon atoms such as (meth) acrylic acid, crotonic acid and cinnamic acid], dicarboxylic acids [having 4 to 15 carbon atoms such as (anhydrous) maleic acid, Fumaric acid, itaconic acid, citraconic acid], dicarboxylic acid monoester [monoalkyl (carbon number 1 to 18) ester of the above dicarboxylic acid, for example, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, itaconic acid monoalkyl ester, Citraconic acid monoalkyl ester] and the like.

Other vinyl ester monomers include aliphatic vinyl esters [4 to 15 carbon atoms, such as vinyl acetate, vinyl propionate, isopropenyl acetate], unsaturated carboxylic acid polyvalent (2 to 3 or more) alcohol esters [ C8-50, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,6 hexanediol diacrylate, Polyethylene glycol di (meth) acrylate], aromatic vinyl ester [carbon number 9 to 15, for example, methyl-4-vinylbenzoate] and the like.
Aliphatic hydrocarbon vinyl monomers include olefins [2-10 carbon atoms such as ethylene, propylene, butene, octene], dienes (4-10 carbon atoms such as butadiene, isoprene, 1,6-hexadiene) and the like. Can be mentioned.
Among these (b1), (meth) acrylic monomers and carboxyl group-containing vinyl monomers are preferable.

  In the vinyl monomer (n2) having the unit of the non-crystalline part (c), the method of introducing the unit of the non-crystalline part (c) into the vinyl monomer is the same as the vinyl monomer having the unit of the crystalline part (b). In (m2), a method similar to the method of introducing the unit of the crystalline part (b) into the vinyl monomer can be mentioned.

The proportion of the structural unit of the vinyl monomer (m) having a crystalline group in the crystalline vinyl resin is preferably 30% or more, more preferably 35 to 95%, and particularly preferably 40 to 90%. Within this range, the crystallinity of the vinyl resin is not impaired and the heat resistant storage stability is good. Further, the content of the linear alkyl (meth) acrylate (m1) having 12 to 50 carbon atoms in the alkyl group in (m) is preferably 30 to 100%, more preferably 40 to 80%.
A crystalline vinyl resin is obtained by polymerizing these vinyl monomers by a known method.

The resin particles (I) of the present invention contain an amorphous resin (B) together with a crystalline resin (A).
Even if the resin is a block body of crystalline resin and non-crystalline resin, if (softening temperature / maximum peak temperature of heat of fusion) is greater than 1.55 in differential scanning calorimetry (DSC), Is also an amorphous resin.

  From the viewpoint of heat-resistant storage stability, the amorphous resin (B) has a maximum peak temperature (TaB) of melting heat in the range of 35 to 100 ° C. (TaB) is preferably 40 to 85 ° C, more preferably 45 to 80 ° C.

The Mw of the amorphous resin (B) is preferably 4 to 5 million, more preferably 1,000 to 500,000.
The number average molecular weight (hereinafter referred to as Mn) and Mw of the amorphous resin (B) may be appropriately adjusted within a preferable range depending on the application.
For example, when the resin particle (I) is used as a slush molding resin or powder coating, the Mn of (B) is preferably 2000 to 500,000, more preferably 4000 to 200,000, and the MW is preferably 4000. ˜1 million, more preferably 8000 to 400,000.
When used as a spacer for manufacturing electronic parts such as liquid crystal displays and standard particles for electronic measuring machines, Mn in (B) is preferably 20,000 to 10,000,000, more preferably 40,000 to 2,000,000, and MW is preferably Is 40,000 to 10,000,000, more preferably 80,000 to 2,000,000. The
When used as a toner used in electrophotography, electrostatic recording, electrostatic printing, etc., the Mn of (B) is preferably 1000 to 5 million, more preferably 2000 to 500,000, and the MW is preferably 2000. ˜5 million, more preferably 4,000 to 500,000.

As the resin used for forming the amorphous resin (B), polyester resin, polyurethane resin, polyurea resin, polyamide resin, polyether resin, vinyl resin, epoxy resin, and the like are the same as the amorphous part (c). But not necessarily.
However, the resin used for forming the crystalline part (b) is preferably a polyester resin, a polyurethane resin, a polyurea resin, a polyamide resin, or a polyether resin. The resin used for forming the crystalline resin (B) is also preferably a polyester resin, a polyurethane resin, a polyurea resin, a polyamide resin, a polyether resin, and a composite resin thereof. More preferred are polyester resins and polyurethane resins.

  The composition of these non-crystalline resins (B) is the same as that of the crystalline part (b), and the monomers used are the diol component, the dicarboxylic acid component, the diisocyanate component, the diamine component, The AO is given as a specific example, and any combination may be used as long as it becomes an amorphous resin.

Difference in SP value between crystalline resin (A) and amorphous resin (B) (SP value calculation method is based on Polymer Engineering and Science, February, 1974, Vol. 14, No. 2 P. 147-154) ΔSP is 0.2 to 2.5 [(cal / cm ³ ) ^1/2 , and so on. It is preferable that it is 0.4-2.4, More preferably, it is 0.5-2.3. When ΔSP is 0.2 or more, the crystalline resin (A) and the amorphous resin (B) are hardly compatible. Therefore, due to the compatibility of (A) and (B), G ′ (TaI + 20) of the resin particles (I) becomes less than 1 × 10 ² [Pa], and as a result, fixing deterioration occurs due to insufficient elasticity, and the fixing temperature region There is no fear of narrowing.

The resin particles (I) containing the crystalline resin (A) and the amorphous resin (B) of the present invention may be produced by any method. Examples of the method for producing the resin particles (I) include the following (1) and (2), but are not limited thereto.
(1) A method in which the crystalline resin (A) and the amorphous resin (B) are melt-kneaded and then pulverized.
(2) Mixture (O1) of crystalline resin (A) and non-crystalline resin (B), or (A) and (B) with organic solvent (u) [eg ethyl acetate, methyl ethyl ketone (MEK), acetone] The organic solvent (u) solution or dispersion liquid (O2) dispersed or dissolved in is dispersed in a medium that is not compatible with them (for example, water, n-decane, liquid carbon dioxide, etc.), and in the medium ( A method of forming resin particles (I) containing A) and (B), removing a solvent from the suspension containing the obtained resin particles (I) as necessary, and further removing the medium.

  The organic solvent (u) used in the organic solvent (u) solution or dispersion (O2) of the resins (A) and (B) is a solvent that can dissolve (A) and (B) at room temperature or under heating. It does not specifically limit, Specifically, the thing of the above-mentioned and below-mentioned is illustrated. What is preferable differs depending on the types of (A) and (B), but the SP value difference between (A) and (B) is preferably 3 or less. Further, from the viewpoint of particle size uniformity of the resin particles (I), a solvent that dissolves (A) and (B) but hardly dissolves and swells the particles (D) containing the resin (d) is preferable.

  When preparing an organic solvent (u) solution or dispersion (O2) of the crystalline resin (A) and the amorphous resin (B), the crystalline resin (A) dissolved or dispersed in the organic solvent (u) It is preferable to mix the amorphous resin (B) dispersed in the organic solvent (u).

  In the resin particles (I) of the present invention, it is preferable that the crystalline resin (A) and the amorphous resin (B) are phase-separated. Therefore, the above-described methods (1) and (2) for producing the resin particles Is preferable to the manufacturing method (2). The crystalline resin (A) used in the production method (2) is more preferably dispersed as resin particles in the organic solvent (u). Further, when the mixture (O1) of (A) and (B) or the organic solvent (u) solution or dispersion (O2) thereof is dispersed in the medium, the particles (D) described below are dispersed in the medium in advance. It is preferable to keep it. This is because the particles (D) are adsorbed to the generated oil droplets containing (A) and (B), and the oil droplets are easily stabilized.

The particles (D) used in the above-mentioned particle formation method can form fine particles in the medium, and are adsorbed to oil droplets containing the crystalline resin (A) and the amorphous resin (B). Any material can be used. Therefore, the material forming the particles (D) may be the resin (d) or the inorganic compound (e).
The resin (d) forming the particles (D) includes vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate. Examples thereof include resins. As (d), two or more of the above resins may be used in combination.
Examples of the inorganic compound (e) include silica, alumina, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate and the like, and two or more kinds may be used in combination.
Of these, calcium carbonate, vinyl resin, polyester resin, polyurethane resin, polyamide resin, polyurea resin, epoxy resin, and combinations thereof are preferable from the viewpoint of low-temperature fixability. More preferred are calcium carbonate from which particles (D) can be easily removed finally, or vinyl resin, polyester resin, and polyurethane resin that can be easily designed as a crystalline resin. Particularly preferably, the alkyl (meth) acrylate (d1) and the perfluoroalkyl (alkyl) (meth) acrylate (d2) in which the crystalline alkyl group has 8 to 50 carbon atoms are used as part of the monomer for addition copolymerization. ) Is a vinyl resin from the viewpoint of easy introduction of structural units. As a resin other than the vinyl resin, after synthesizing a vinyl polymer having the structural units (d1) and (d2), a reaction such as esterification or amidation is performed, or other than the above vinyl resins having a vinyl group A resin obtained by copolymerizing (d1) and (d2) with the above resin is also particularly preferred.

  Hereinafter, vinyl resin, polyester resin, polyurethane resin, polyamide resin, polyurea resin and epoxy resin, which are preferable resins, will be described in detail.

  The vinyl resin is a polymer obtained by homopolymerization or copolymerization of a vinyl monomer, and an alkyl (meth) acrylate (d1) and a perfluoroalkyl (alkyl) (meth) acrylate having an alkyl group having 8 to 50 carbon atoms as a structural unit. Those in which the vinyl monomer (d2) is introduced into the structural unit are particularly preferred.

Storage stability under high temperature and high humidity is improved by containing alkyl (meth) acrylate (d1) and perfluoroalkyl (alkyl) (meth) acrylate (d2) having 8 to 50 carbon atoms in the alkyl group. . Further, by containing (d2), the chargeability of the resin particles (I) of the present invention under high temperature and high humidity is also improved.
The alkyl (meth) acrylate (d1) having 8 to 50 carbon atoms in the alkyl group has a linear or branched alkyl group. Specific examples thereof include 2-ethylhexyl (meth) acrylate and dodecyl (meta). ) Acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, eicosyl (meth) acrylate, behenyl (meth) acrylate, and 2-decyltetradecyl (meth) acrylate. (D1) may be a single monomer or a combination of plural monomers. Among these, behenyl (meth) acrylate is preferable.
The content of the structural unit (d1) in the resin (d) is preferably 30 to 90%, more preferably 40 to 90%, and particularly preferably 50 to 80%. When the content of (d1) is 30% or more, it has crystallinity and is sharp-melted, so that it has excellent storage stability and low-temperature fixability, and good charging characteristics under high temperature and high humidity.
The perfluoroalkyl (alkyl) (meth) acrylate (d2) is preferably an even number having 2 to 12 carbon atoms in the perfluoroalkyl group, and preferably 0 to 3 carbon atoms in the (alkyl) portion. Specific examples include (2-perfluoroethyl) ethyl (meth) acrylate, (2-perfluorobutyl) ethyl (meth) acrylate, (2-perfluorohexyl) ethyl (meth) acrylate, (2-perfluorooctyl). ) Ethyl (meth) acrylate, (2-perfluorodecyl) ethyl (meth) acrylate, and (2-perfluorododecyl) ethyl (meth) acrylate.
Of these, more preferred are (2-perfluorohexyl) ethyl (meth) acrylate, (2-perfluorooctyl) ethyl (meth) acrylate, and (2-perfluorodecyl) ethyl (meta) from the viewpoint of chargeability. ) Acrylate, (2-perfluorododecyl) ethyl (meth) acrylate.
Perfluoroalkyl (alkyl) (meth) acrylate (d2) may be a single monomer or a combination of a plurality of monomers.
In addition, the said (meth) acrylate means an acrylate and / or a methacrylate, and the same description method is used hereafter.
The content of the structural unit (d2) in the resin (d) is preferably 0.001 to 30%, more preferably 0.05 to 25%, particularly preferably 0.01 to 10%, and most preferably 0. .1-5%. When the content of (d2) is 0.001% or more, the charging characteristics under high temperature and high humidity are good.
The content of constituent units of monomers other than (d1) and (d2) in (d) is preferably 50% or less, particularly preferably 30% or less. When the content of the monomer other than (d1) and (d2) is 50% or less, the crystallinity is increased and the storage stability is improved.

  Examples of vinyl monomers other than alkyl (meth) acrylate (d1) and perfluoroalkyl (alkyl) (meth) acrylate (d2) having an alkyl group with 8 to 50 carbon atoms include the following (1) to (10). It is done.

(1) Vinyl hydrocarbon:
(1-1) Aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, other α-olefins, etc .; alkadienes such as butadiene, Isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene.
(1-2) Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene, etc .; terpenes such as pinene, limonene, indene etc.
(1-3) Aromatic vinyl hydrocarbons: Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substitution products such as α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene , Isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, trivinyl benzene, etc .; and vinyl naphthalene.

(2) Carboxyl group-containing vinyl monomer and metal salt thereof:
C3-C30 unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and anhydrides thereof and monoalkyl (carbon number 1-8) esters thereof such as (meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate Carboxylic group-containing vinyl monomers such as esters, fumaric acid, fumaric acid monoalkyl esters, crotonic acid, itaconic acid, itaconic acid monoalkyl esters, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl esters, and cinnamic acid. In addition, the said (meth) acrylic acid means acrylic acid and / or methacrylic acid, and the same description method is used hereafter. From the viewpoint of improving hydrolysis resistance, the alkyl chain constituting the monoalkyl (C1-24) ester preferably has a branched structure.

(3) Sulfonic group-containing vinyl monomer, vinyl sulfate monoester product and salts thereof:
Alkene sulfonic acids having 2 to 14 carbon atoms such as vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfonic acid; and alkyl derivatives having 2 to 24 carbon atoms such as α-methyl styrene sulfonic acid Sulfo (hydroxy) alkyl- (meth) acrylate or (meth) acrylamide, such as sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino-2 , 2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, 3- (Meth) acrylamide-2- Droxypropanesulfonic acid, alkyl (C3-18) allylsulfosuccinic acid, poly (n = 2-30) oxyalkylene (ethylene, propylene, butylene: single, random or block) sulfuric acid of mono (meth) acrylate Esters [poly (n = 5-15) oxypropylene monomethacrylate sulfate, etc.], polyoxyethylene polycyclic phenyl ether sulfate, and sulfates represented by the following general formulas (1-1) to (1-3) or Sulfonic acid group-containing monomers; and salts thereof.

O- (AO) nSO ₃ H
｜
_{CH 2 = CHCH 2 -OCH 2 CHCH} 2 O-Ar-R (1-1)

CH = CH-CH ₃
｜
R-Ar-O- (AO) nSO 3 H (1-2)

CH ₂ COOR '
｜
HO ₃ SCHCOOCH ₂ CH (OH) CH ₂ OCH ₂ CH═CH ₂ (1-3)

(In the formula, R represents an alkyl group having 1 to 15 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and when n is plural, they may be the same or different, and when they are different, they may be random or block. Ar represents a benzene ring, n represents an integer of 1 to 50, and R ′ represents an alkyl group having 1 to 15 carbon atoms which may be substituted with a fluorine atom.

(4) Phosphoric acid group-containing vinyl monomer and salt thereof:
(Meth) acryloyloxyalkyl (C1 to C24) phosphoric acid monoester, for example, 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, (meth) acryloyloxyalkyl (C1-24) Phosphonic acids, such as 2-acryloyloxyethylphosphonic acid.

  Examples of the salts (2) to (4) include metal salts, ammonium salts, and amine salts (including quaternary ammonium salts). Examples of the metal forming the metal salt include Al, Ti, Cr, Mn, Fe, Zn, Ba, Zr, Ca, Mg, Na, and K. Alkali metal salts and amine salts are preferred, and sodium salts, magnesium salts, aluminum salts, tertiary monoamines having 3 to 20 carbon atoms, and diamine salts are more preferred.

(5) Hydroxyl group-containing vinyl monomer:
Hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1- Buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, etc.

(6) Nitrogen-containing vinyl monomer:
(6-1) Amino group-containing vinyl monomer: aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, ( (Meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N- Arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, salts thereof, etc. (6-2) Amido group Vinyl monomers: (meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N′-methylene-bis (meth) acrylamide, cinnamic amide N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl N-vinylacetamide, N-vinylpyrrolidone, etc. (6-3) Nitrile group-containing vinyl monomers: (meth) acrylonitrile, cyanostyrene (6-4) Quaternary ammonium cation group-containing vinyl monomers: dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, die Ruaminoechiru (meth) acrylamide, quaternized product of tertiary amine group-containing vinyl monomers such as diallylamine (methyl chloride, dimethyl sulfate, benzyl chloride, which was quaternized with quaternizing agents such as dimethyl carbonate)
(6-5) Nitro group-containing vinyl monomer: nitrostyrene, etc.

(7) Epoxy group-containing vinyl monomer:
Glucidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide, etc.

(8) Halogen element-containing vinyl monomers other than (d2):
Vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene, etc.

(9) Vinyl esters other than (d1) and (d2), vinyl (thio) ethers, vinyl ketones, vinyl sulfones:
(9-1) Vinyl esters such as vinyl butyrate, vinyl acetate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl ( (Meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl α-ethoxy acrylate, alkyl (meth) acrylate having an alkyl group having 1 to 7 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate Butyl (meth) acrylate, etc.], dialkyl fumarate (dialkyl fumarate ester) (two alkyl groups are linear, branched or alicyclic having 2 to 8 carbon atoms) Dialkyl maleate (dialkyl maleate) (two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms), poly (meth) Vinyl monomers having a polyalkylene glycol chain such as aryloxyalkanes [diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.] [polyethylene glycol [Mn300] mono (meth) acrylate, polypropylene glycol (Mn500) monoacrylate, methyl alcohol EO 10 mol adduct (meth) acrylate, lauryl alcohol EO 30 mol adduct (meth) acrylate, etc.], poly (meth) acrylates [multivalent Alcohol poly ( Meth) acrylate: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.].
(9-2) Vinyl (thio) ether, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxy butadiene, vinyl 2- Butoxyethyl ether, 3,4-dihydro1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, vinyl 2-ethylmercaptoethyl ether, acetoxystyrene, phenoxystyrene, etc. (9-3) Vinyl ketones such as vinyl Methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone;
Vinyl sulfone, such as divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide, etc.

(10) Other vinyl monomers:
Isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, etc.

  As the copolymer of the vinyl monomer, a polymer obtained by copolymerizing any one of the above (1) to (10) or (d1) and (d2) with a binary number or more in an arbitrary ratio. Examples include (2-perfluorododecyl) ethyl (meth) acrylate-behenyl (meth) acrylate copolymer, (2-perfluorododecyl) ethyl (meth) acrylate-behenyl (meth) acrylate- (meth) acrylic. Acid ester copolymer, (2-perfluorododecyl) ethyl (meth) acrylate-behenyl (meth) acrylate- (meth) acrylic acid- (meth) acrylic acid ester copolymer, (2-perfluorododecyl) ethyl ( (Meth) acrylate-behenyl (meth) acrylate-acrylonitrile copolymer, (2-perfluoro Dodecyl) ethyl (meth) acrylate-behenyl (meth) acrylate-maleic anhydride copolymer, (2-perfluorododecyl) ethyl (meth) acrylate-behenyl (meth) acrylate- (meth) acrylic acid copolymer, 2-perfluorododecyl) ethyl (meth) acrylate-behenyl (meth) acrylate-styrene copolymer, (2-perfluorododecyl) ethyl (meth) acrylate-behenyl (meth) acrylate-hydroxyethyl (meth) acrylate copolymer Examples thereof include (2-perfluorododecyl) ethyl (meth) acrylate-behenyl (meth) acrylate-acrylonitrile-maleic anhydride- (meth) acrylic acid ester acid-hydroxyethyl (meth) acrylate copolymer.

  For example, when the resin particles (I) of the present invention are produced in an aqueous medium, the resin (d) needs to form the particles (D) in water and must not be completely dissolved in water. It is. Therefore, when the vinyl resin is a copolymer, the ratio of the hydrophobic monomer and the hydrophilic monomer constituting the vinyl resin depends on the type of monomer selected, but generally the hydrophobic monomer may be 10% or more. Preferably, it is 20% or more. When the ratio of the hydrophobic monomer is less than 10%, the vinyl resin becomes water-soluble, and the particle size uniformity of (I) may be impaired. Here, the hydrophilic monomer means a monomer that dissolves in water at an arbitrary ratio, and the hydrophobic monomer means another monomer (a monomer that is basically not miscible with water).

  In addition, a composite resin obtained by urethanizing a vinyl resin containing a hydroxyl group-containing vinyl monomer as a structural unit with a polyester resin having a hydroxyl group or a polyurethane resin having an amine as a composite with a vinyl resin and another resin It may be.

  The polyester resin, polyurethane resin, polyamide resin and polyurea resin used as the resin (d) can form particles (D) in the medium, and oil droplets of the crystalline resin (A) and the amorphous resin (B). Any composition may be used as long as it adsorbs to the surface. Examples of the constituent monomer include the monomers described above.

  Examples of the epoxy resin used as the resin (d) include polyepoxide ring-opening polymer, polyepoxide and active hydrogen-containing compound {water, polyol [the diol component, etc.], dicarboxylic acid component, diamine component, polythiol, etc.} Examples include adducts or cured products of polyepoxides and acid anhydrides of dicarboxylic components.

Examples of the polythiol include alkanedithiol having 2 to 36 carbon atoms (ethylene dithiol, 1,4-butanedithiol, 1,6-hexanedithiol, etc.) and the like.
The polyepoxide is not particularly limited as long as it has two or more epoxy groups in the molecule. A thing preferable as a polyepoxide has 2-6 epoxy groups in a molecule | numerator from a viewpoint of the mechanical property of hardened | cured material. The epoxy equivalent (molecular weight per epoxy group) of the polyepoxide is preferably 65 to 1000, and more preferably 90 to 500. When the epoxy equivalent is 1000 or less, the crosslinked structure becomes dense, and the physical properties such as water resistance, chemical resistance and mechanical strength of the cured product are improved. On the other hand, it is easy to synthesize an epoxy equivalent of 65 or more. It is.

  Examples of the polyepoxide include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds, and aliphatic polyepoxy compounds. Examples of aromatic polyepoxy compounds include glycidyl ethers and glycidyl ethers of polyhydric phenols, glycidyl aromatic polyamines, and glycidylated products of aminophenols. Examples of glycidyl ethers of polyphenols include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, and tetrachlorobisphenol A. Diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyldi Glycidyl ether, tetramethylbiphenyl diglycidyl ester Ter, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolylbisphenol A glycidyl ether, trismethyl -Tret-butyl-butylhydroxymethane triglycidyl ether, 9,9'-bis (4-hydroxyphenyl) furorange glycidyl ether, 4,4'-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4 , 4′-oxybis (1,4-phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, Of glycol ether of enolic or cresol novolak resin, glycidyl ether of limonene phenol novolak resin, diglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, phenol and glyoxal, glutaraldehyde, or formaldehyde Examples thereof include polyglycidyl ethers of polyphenols obtained by condensation reactions, polyglycidyl ethers of polyphenols obtained by condensation reactions of resorcin and acetone, and the like. Examples of the glycidyl ester of polyhydric phenol include diglycidyl phthalate, diglycidyl isophthalate, and diglycidyl terephthalate. Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidylxylylenediamine, N, N, N ′, N′-tetraglycidyldiphenylmethanediamine and the like. Furthermore, as an aromatic polyepoxy compound, triglycidyl ether of P-aminophenol, diglycidyl urethane compound obtained by addition reaction of tolylene diisocyanate or diphenylmethane diisocyanate and glycidol, glycidyl obtained by reacting polyol with the above two reactants Also included are diglycidyl ethers of AO (EO or PO) adducts of group-containing polyurethane (pre) polymers and bisphenol A. Heterocyclic polyepoxy compounds include trisglycidyl melamine; alicyclic polyepoxy compounds include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, Ethylene glycol bisepoxy dicyclopentyl ale, 3,4-epoxy-6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) Examples include adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine, dimer acid diglycidyl ester, and the like. The alicyclic polyepoxy compound also includes a hydrogenated product of the aromatic polyepoxy compound; examples of the aliphatic polyepoxy compound include polyglycidyl ethers of polyhydric aliphatic alcohols and polyglycidyl polyhydric fatty acids. Examples include ester bodies and glycidyl aliphatic amines. Polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether and polyglycerol polyglycidyl ether Can be mentioned. Examples of polyglycidyl ester of polyvalent fatty acid include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimelate and the like. Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine. The aliphatic polyepoxy compound also includes a (co) polymer of diglycidyl ether and glycidyl (meth) acrylate. Of these, preferred are aliphatic polyepoxy compounds and aromatic polyepoxy compounds. Two or more polyepoxides may be used in combination.

  The maximum peak temperature (Tad) of the heat of fusion of the resin (d) used for the particles (D) is from the viewpoint of the particle size uniformity, powder flowability, heat resistance during storage, and stress resistance of the resin particles (I). The temperature is preferably 0 ° C to 300 ° C, more preferably 20 ° C to 250 ° C, and particularly preferably 40 ° C to 200 ° C. If the (Tad) of the resin (d) is lower than the temperature at which the resin dispersion is produced in the medium, the effect of preventing coalescence or preventing splitting is reduced, and the effect of increasing the uniformity of the particle diameter is obtained. Get smaller.

  From the viewpoint of reducing dissolution or swelling of the particles (D) with respect to water or the organic solvent (u) used at the time of dispersion, the molecular weight, SP value, crystallinity, It is preferable to appropriately adjust the molecular weight between cross-linking points.

  The Mn of the resin (d) is preferably 2 to 5 million, more preferably 2000 to 500000. The SP value is preferably 7 to 18, and more preferably 8 to 14. The melting point (measured by DSC) of the resin (d) is preferably 50 ° C. or higher, more preferably 80 ° C. or higher. When it is desired to improve the heat resistance, water resistance, chemical resistance, particle size uniformity, etc. of the resin particles (I), a crosslinked structure may be introduced into the resin (d). Such a cross-linked structure may be any cross-linked form such as covalent bond, coordinate bond, ionic bond, hydrogen bond, and the like. The molecular weight between crosslinking points when a crosslinked structure is introduced into the resin (d) is preferably 30 or more, and more preferably 50 or more.

Although the method of making resin (d) into the dispersion liquid by which particle | grains (D) were disperse | distributed in a medium is not specifically limited, The following [1]-[8] is mentioned.
[1] A method of directly producing a dispersion of particles (D) in the case of a vinyl resin, using a monomer as a starting material, and a polymerization reaction such as a suspension polymerization method, an emulsion polymerization method, a seed polymerization method or a dispersion polymerization method .
[2] In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer, etc.) or a solvent solution thereof is dispersed in a medium in the presence of an appropriate dispersant, and then A method for producing a dispersion of particles (D) by heating to a temperature or adding a curing agent to cure.
[3] In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, and epoxy resin, a precursor (monomer, oligomer, etc.) or a solvent solution thereof (preferably liquid) may be liquefied by heating. ) A suitable emulsifier is dissolved therein, and then a medium is added to carry out phase inversion emulsification.
[4] A resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc. The same applies to the polymerization reaction in the following section). The resin particles are obtained by pulverizing using a mechanical rotary type or jet type fine pulverizer and then spheroidizing, and then dispersing in a medium in the presence of an appropriate dispersant.
[5] A method of obtaining resin particles by spraying a resin solution prepared by previously dissolving a resin prepared by a polymerization reaction in a solvent in a mist, and then dispersing the resin particles in a medium in the presence of an appropriate dispersant.
[6] Add a poor solvent to a resin solution prepared by dissolving a resin prepared in advance in a solvent, or cool a resin solution previously dissolved in a solvent to precipitate resin particles, and then remove the solvent. Then, after obtaining resin particles, the resin particles are dispersed in a medium in the presence of an appropriate dispersant.
[7] A method in which a resin solution in which a resin prepared by a polymerization reaction is dissolved in a solvent is dispersed in a medium in the presence of an appropriate dispersant, and the solvent is removed by heating or decompression.
[8] A method in which a suitable emulsifier is dissolved in a resin solution prepared by previously dissolving a resin prepared by a polymerization reaction in a solvent, and then a medium is added to perform phase inversion emulsification.

In the above methods [1] to [8], as the emulsifier or dispersant used in combination, a known surfactant (s), water-soluble polymer (t) and the like can be used. Moreover, an organic solvent (u), a plasticizer (v), etc. can be used together as an auxiliary agent for emulsification or dispersion.
It does not specifically limit as surfactant (s), Anionic surfactant (s-1), Cationic surfactant (s-2), Amphoteric surfactant (s-3), Nonionic surfactant ( s-4). The surfactant (s) may be a combination of two or more surfactants.

As the anionic surfactant (s-1), a carboxylic acid or a salt thereof, a sulfate ester salt, a salt of a carboxymethylated product, a sulfonate salt, a phosphate ester salt, or the like is used.
Examples thereof include inorganic acid salts or organic acid salts such as additives.
As the cationic surfactant (s-2), a quaternary ammonium salt type surfactant, an amine salt type surfactant and the like can be used.
Examples of the amphoteric surfactant (s-3) include a carboxylate type amphoteric surfactant, a sulfate ester type amphoteric surfactant, a sulfonate type amphoteric surfactant and a phosphate ester type amphoteric surfactant. Can be used.
As the nonionic surfactant (s-4), an AO addition type nonionic surfactant and a polyvalent alcohol type nonionic surfactant can be used.
Specific examples of these surfactants (s) include those described in JP-A-2002-284881.

  Examples of the water-soluble polymer (t) include cellulose compounds (for example, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose and saponified products thereof), gelatin, starch, dextrin, gum arabic, chitin , Chitosan, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, acrylic acid (salt) -containing polymer (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, in the sodium hydroxide part of polyacrylic acid) Sodium hydroxide, acrylic acid ester copolymer), styrene-maleic anhydride copolymer sodium hydroxide Beam (partial) neutralization product, water-soluble polyurethane (polyethylene glycol, reaction products of polycaprolactone diol with polyisocyanate and the like) and the like.

The organic solvent (u) used in the present invention may be added to the medium to be emulsified and dispersed in the emulsified dispersion [the crystalline resin (A) and the non-crystalline resin (B) as described above]. It may be added to the containing oil phase (O2)].
Specific examples of the organic solvent (u) include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetralin; aliphatic or alicyclic hydrocarbon solvents such as n-hexane, n-heptane, mineral spirit and cyclohexane; Halogen solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, perchloroethylene; esters or esters such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate Ether solvents; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl , Ketone solvents such as di-n-butyl ketone and cyclohexanone; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol and benzyl alcohol; dimethylformamide; Examples include amide solvents such as dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide; heterocyclic compound solvents such as N-methylpyrrolidone; and mixed solvents of two or more of these.

Even if the plasticizer (v) is added to the medium as needed during the emulsification dispersion, the emulsified dispersion [the oil phase (O2) containing the crystalline resin (A) and the amorphous resin (B)] It may be added to [Medium].
As a plasticizer (V), it is not limited at all, The following are illustrated.
(V1) Phthalates [dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, etc.];
(V2) Aliphatic dibasic acid ester [di-2-ethylhexyl adipate, 2-ethylhexyl sebacate, etc.];
(V3) trimellitic acid ester [tri-2-ethylhexyl trimellitic acid, trioctyl trimellitic acid, etc.];
(V4) Phosphate ester [triethyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate, etc.];
(V5) fatty acid ester [butyl oleate and the like];
(V6) and a mixture of two or more of these.

  The particle size of the particles (D) is usually from the particle size of the resin particles (I0) containing the crystalline resin (A) obtained by removing the particles (D) from the resin particles (I) and the amorphous resin (B). From the viewpoint of particle size uniformity, the value of the particle size ratio [volume average particle size of particles (D)] / [volume average particle size of resin particles (I)] is in the range of 0.001 to 0.3. Is preferred. When the particle size ratio is smaller than 0.3, (D) is efficiently adsorbed on the surface of (I0), so that the obtained particle size distribution of (I) tends to be narrow.

  The volume average particle diameter of the particles (D) can be appropriately adjusted within the above range of the particle diameter ratio so as to be a particle diameter suitable for obtaining the resin particles (I) having a desired particle diameter. The volume average particle diameter of the particles (D) is generally preferably 0.0005 to 30 μm. More preferably, it is 0.01-20 micrometers, Most preferably, it is 0.02-10 micrometers. However, for example, when it is desired to obtain resin particles (I) having a volume average particle diameter of 1 μm, the range is preferably 0.0005 to 0.3 μm, particularly preferably 0.001 to 0.2 μm, and 10 μm resin particles ( In the case of obtaining I), preferably 0.005 to 3 μm, particularly preferably 0.05 to 2 μm, and 100 μm of resin particles (I) are preferably 0.05 to 30 μm, particularly preferably. Is 0.1-20 μm. The volume average particle size can be measured with a laser type particle size distribution analyzer LA-920 (manufactured by Horiba) or Multisizer III (manufactured by Coulter).

In the preferable production method (2) of the resin particle (I) of the present invention, when the particle (D) is used, a mixture (O1) (melt) of the crystalline resin (A) and the amorphous resin (B). And a liquid dispersion (W) that is incompatible with (O1) of the particles (D) containing the resin (d) and / or the inorganic compound (e), and (W ), (O1) was dispersed, and resin particles (I0) containing (A) and (B) were formed in the dispersion (W), and (D) adhered to the surface of (I0). A dispersion (X) of resin particles (I) is obtained.
Alternatively, the organic solvent (u) solution or dispersion (O2) of (A) and (B) is compatible with (O2) of the particles (D) containing the resin (d) and / or the inorganic compound (e). (O2) is dispersed in (W), and resin particles (I0) containing (A) and (B) are formed in the dispersion (W). Thus, a dispersion (X) of resin particles (I) having (D) attached to the surface of (I0) is obtained.

  The amount of the medium dispersion liquid (W) of the particles (D) is preferably 50 to 2000 parts, more preferably 100 to 1000 parts with respect to 100 parts in total of the crystalline resin (A) and the amorphous resin (B). is there. If it is 50 parts or more, the dispersed state of (A) and (B) is good. It is economical that it is 2000 parts or less. Above and below, parts mean parts by weight.

In the case where the mixture (O1) of the resins (A) and (B) or the organic solvent (u) solution or dispersion (O2) thereof is dispersed in the dispersion (W), a dispersion device can be used.
The dispersing apparatus to be used is not particularly limited as long as it is generally marketed as an emulsifier or a dispersing machine. For example, a homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK auto homomixer (special machine) Batch type emulsifier such as Ebara Milder (manufactured by Ebara Seisakusho), TK Fillmix, TK Pipeline Homomixer (made by Special Machine Industries), colloid mill (made by Shinko Pantech), Continuous emulsifiers such as slasher, trigonal wet pulverizer (manufactured by Mitsui Miike Chemical Co., Ltd.), Captron (manufactured by Eurotech), fine flow mill (manufactured by Taiheiyo Kiko Co., Ltd.), microfluidizer (manufactured by Mizuho Kogyo Co., Ltd.), High pressure emulsifiers such as Nanomizer (made by Nanomizer), APV Gaurin (made by Gaurin), membrane emulsifier (made by Chilling Industries Co., Ltd.), etc. Membrane emulsification machine, Vibro Mixer (Hiyaka Kogyo) vibrating emulsifier such as, ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson Co., Ltd.). Among these, APV Gaurin, homogenizer, TK auto homomixer, Ebara milder, TK fill mix, and TK pipeline homomixer are preferable from the viewpoint of uniform particle size.

The viscosity of the mixture (O1) of the resin (A) and (B) or the organic solvent (u) solution or dispersion (O2) thereof is preferably from 10 to 50,000 mPa · s (from the viewpoint of particle size uniformity. (Measured with a B-type viscometer), more preferably 100 to 10,000 mPa · s.
The temperature at the time of dispersion is preferably 0 to 150 ° C. (under pressure), more preferably 5 to 98 ° C. When the viscosity of the dispersion is high, it is preferable to carry out emulsification dispersion by lowering the viscosity to the above preferred range by increasing the temperature.

The resin particles (I) of the present invention can be obtained by removing the organic solvent (u) and the medium from the dispersion (X) of the resin particles (I).
As a method of removing the organic solvent (u) and the medium from the dispersion (X),
[1] A method of drying a resin dispersion under reduced pressure or normal pressure [2] A method of solid-liquid separation with a centrifuge, a spacula filter, a filter press, etc., and drying the resulting powder [3] A resin dispersion Method of freezing and drying (so-called freeze drying)
Etc. are exemplified.
In the above [1] and [2], when the obtained powder is dried, it can be performed using a known facility such as a fluidized bed dryer, a vacuum dryer, or a circulating dryer.
Moreover, it can classify | classify using a wind classifier etc. as needed, and can also be set as predetermined particle size distribution.

In resin particles (I) [including (I0) and / or particles (D)] containing a crystalline resin (A) and an amorphous resin (B), additives (pigments, fillers, antistatic agents) Agents, coloring agents, mold release agents, charge control agents, ultraviolet absorbers, antioxidants, antiblocking agents, heat stabilizers, flame retardants, etc.) may be mixed. As a method of adding an additive into (I0) or (D), the dispersion (X) containing the resin particles (I) may be mixed in a medium, but it may be mixed in advance. After mixing (A), amorphous resin (B), their organic solvent (u) solution or dispersion (O2), or resin (d) and an additive, the mixture is added and dispersed in the medium. Is more preferable.
Further, the additive is not necessarily mixed when forming the resin particles (I) in the medium, and may be added after the particles are formed. For example, after forming particles containing no colorant, a colorant may be added by a known dyeing method, or the additive may be impregnated with the organic solvent (u) and / or the plasticizer (v). it can.

From the particle size uniformity, the value of [volume average particle size / number average particle size] of the resin particles (I) is preferably 1.0 to 1.4, more preferably 1.0 to 1.2. Is more preferable.
The volume average particle size of (I) varies depending on the use, but is generally preferably 0.1 to 300 μm. The upper limit is more preferably 250 μm, particularly preferably 200 μm, most preferably 50 μm, and the lower limit is further preferably 0.5 μm, particularly preferably 1 μm.
The volume average particle size and the number average particle size can be measured simultaneously with Multisizer III (manufactured by Coulter).

The resin particles (I) of the present invention are paint additives, adhesive additives, cosmetic additives, paper coating additives, slush molding resins, powder coatings, electronic component manufacturing spacers, and catalysts. Carrier, electrophotographic toner base particle, electrostatic recording toner base particle, electrostatic printing toner base particle, electronic measuring instrument standard particle, electronic paper particle, medical diagnostic carrier, chromatographic filler, electrorheological fluid It can be used for various applications such as particles.
For example, the crystalline resin (A) and the non-crystalline resin (B) and a colorant are mixed, and if necessary, a charge control agent, a release agent, a fluidizing agent, and the like are contained as toner resin particles. Can be used.

  As the colorant, all of dyes and pigments used as toner colorants can be used. Specifically, carbon black, iron black, Sudan black SM, first yellow G, benzidine yellow, solvent yellow (21, 77, 114, etc.), pigment yellow (12, 14, 17, 83, etc.), Indian first orange, Irgasin Red, Paranitaniline Red, Toluidine Red, Solvent Red (17, 49, 128, 5, 13, 22, 48, 2 etc.), Disperse Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B lake, methyl violet B lake, phthalocyanine blue, solvent blue (25, 94, 60, 15.3, etc.), pigment blue, brilliant green, phthalocyanine green, oil yellow GG, Kayaset YG, o Mentioned tetrazole brown B and oil pink OP etc. These may be used alone or in admixture of two or more thereof. Further, if necessary, magnetic powder (a powder of a ferromagnetic metal such as iron, cobalt, nickel, or a compound such as magnetite, hematite, ferrite) can also be included as a colorant. The content of the colorant is preferably 0.1 to 40 parts, more preferably 0.5 to 10 parts, with respect to 100 parts of the resin containing the crystalline resin (A) and the amorphous resin (B). is there. In addition, when using magnetic powder, Preferably it is 20-150 parts, More preferably, it is 40-120 parts.

  As the release agent, those having a softening temperature of 50 to 170 ° C. are preferable, and polyolefin wax, natural wax (for example, carnauba wax, montan wax, paraffin wax and rice wax), aliphatic alcohol having 30 to 50 carbon atoms ( For example, triacontanol and the like, fatty acids having 30 to 50 carbon atoms (e.g., triacontanecarboxylic acid and the like), and mixtures thereof. Polyolefin waxes include (co) polymers [obtained by (co) polymerization] of olefins (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and mixtures thereof). And olefin (co) polymer oxides with oxygen and / or ozone, maleic acid modifications of olefin (co) polymers [eg maleic acid and its derivatives (maleic anhydride, Modified products such as monomethyl maleate, monobutyl maleate and dimethyl maleate), olefins and unsaturated carboxylic acids [such as (meth) acrylic acid, itaconic acid and maleic anhydride] and / or unsaturated carboxylic acid alkyl esters [(meta ) Alkyl acrylate (alkyl 1 to 1 carbon atoms) 8) Copolymers with esters and alkyl maleates (alkyl esters having 1 to 18 carbon atoms), etc., and polymethylene (such as Fischer-Tropsch wax such as sazol wax), fatty acid metal salts (such as calcium stearate), Fatty acid ester (behenyl behenate etc.) is mentioned.

  As charge control agents, nigrosine dyes, triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium base-containing polymers, metal-containing azo dyes, copper phthalocyanine dyes , Salicylic acid metal salts, boron complexes of benzylic acid, sulfonic acid group-containing polymers, fluorine-containing polymers, halogen-substituted aromatic ring-containing polymers, metal complexes of salicylic acid alkyl derivatives, cetyltrimethylammonium bromide, and the like.

  As a fluidizing agent, colloidal silica, alumina powder, titanium oxide powder, calcium carbonate powder, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, Examples thereof include diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, and barium carbonate.

  The composition ratio of the toner resin particles is preferably 30 to 97%, more preferably 40%, based on the weight of the resin particles (I), the total of the crystalline resin (A) and the amorphous resin (B). ~ 95%, particularly preferably 45 to 92%; the colorant is preferably 0.05 to 60%, more preferably 0.1 to 55%, particularly preferably 0.5 to 50%; The release agent is preferably 0-30%, more preferably 0.5-20%, particularly preferably 1-10%; the charge control agent is preferably 0-20%, more preferably 0.1-10. %, Particularly preferably 0.5 to 7.5%; the fluidizing agent is preferably 0 to 10%, more preferably 0 to 5%, particularly preferably 0.1 to 4%. The total content of additives is preferably 3 to 70%, more preferably 4 to 58%, and particularly preferably 5 to 50%. When the composition ratio of the resin particles is in the above range, a resin having good chargeability can be easily obtained.

When used for toner, the resin particles (I) are, if necessary, carrier particles {iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite whose surface is coated with resin (acrylic resin, silicone resin, etc.) } Can be used as a developer of an electric latent image. Further, instead of the carrier particles, an electric latent image can be formed by friction with a charging blade or the like.
The electric latent image is fixed on a support (paper, polyester film, etc.) by a known hot roll fixing method or the like.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto.

Production Example 1 (Production of amorphous part c)
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 74 parts of bisphenol A · EO 2 molar adduct, 32 parts of isophthalic acid and 1 part of dibutyltin oxide as a condensation catalyst were placed at 230 ° C. under normal pressure. The reaction was continued for 2 hours, and further under reduced pressure of 10 to 15 mmHg for 2 hours. Subsequently, it cooled to 180 degreeC, took out after reaction for 2 hours under normal pressure sealing, cooled to room temperature, grind | pulverized and granulated, and obtained the amorphous polycondensation polyester resin [amorphous part c1]. [Non-crystalline part c1] had a Mw of 5500 and a hydroxyl value of 41.

Production Example 2 (Production of crystalline part b and crystalline resin A)
In a reactor equipped with a condenser, stirrer and nitrogen inlet tube, 159 parts sebacic acid, 11 parts adipic acid, 108 parts 1,4-butanediol, and titanium dihydroxybis (triethanolamate) 0 as condensation catalyst .5 parts was added and reacted at 180 ° C. under a nitrogen stream for 8 hours while distilling off generated water. Next, while gradually raising the temperature to 225 ° C., the reaction is carried out for 4 hours while distilling off the generated water and 1,4-butanediol under a nitrogen stream, and the reaction is further carried out under a reduced pressure of 5 to 20 mmHg. When it became 10,000, it took out. The taken-out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline polycondensed polyester resin [crystalline resin A1 / crystalline part b1]. [Crystalline resin A1 / crystalline part b1] had a TaA of 57 ° C., a softening temperature of 59 ° C., an Mw of 11000, and a hydroxyl value of 30.

Production Example 3 (Production of crystalline part b and crystalline resin A)
In a reaction vessel equipped with a stirrer and a dehydrator, 2 parts of 1,4-butanediol, 650 parts of ε-caprolactone, and 2 parts of dibutyltin oxide are added, and the reaction is carried out at 150 ° C. for 10 hours under normal pressure and nitrogen atmosphere. went. Further, the obtained resin was cooled to room temperature and then pulverized into particles to obtain a crystalline polyester resin [crystalline resin A2 / crystalline part b2] which is a lactone ring-opening polymer. [Crystalline resin A2 / crystalline part b2] had a TaA of 60 ° C., a softening temperature of 67 ° C., an Mw of 6000, and a hydroxyl value of 50.

Production Example 4 (Production of crystalline resin A)
A reaction vessel equipped with a stirrer and a dehydrator is charged with 420 parts of terephthalic acid, 180 parts of isophthalic acid, 400 parts of 1,5-pentanediol, and 2 parts of dibutyltin oxide, and dehydrated at normal pressure and 230 ° C. for 5 hours. Then, dehydration reaction was performed for 5 hours under a reduced pressure of 0.5 kPa. Further, the obtained resin was cooled to room temperature and then pulverized into particles to obtain a crystalline polycondensed polyester resin [crystalline resin A3]. [Crystalline Resin A3] had a TaA of 85 ° C., a softening temperature of 100 ° C., an Mw of 9000, and a hydroxyl value of 28.

Production Example 5 (Production of crystalline resin A)
A reaction vessel equipped with a stir bar and a thermometer was charged with 44 parts of tolylene diisocyanate and 100 parts of MEK. This solution was charged with 32 parts of cyclohexanedimethanol and reacted at 80 ° C. for 2 hours. Next, a solution of the non-crystalline polyurethane resin having an isocyanate group at the end [non-crystalline part c2] is added to a solution in which 140 parts of [crystalline resin A1 / crystalline part b1] are dissolved in 140 parts of MEK. And a reaction at 80 ° C. for 4 hours to obtain a MEK solution of [crystalline resin A4] composed of a crystalline part and an amorphous part. After removal of the solvent, [Crystalline Resin A4] had a TaA of 55 ° C., a softening temperature of 59 ° C., and an Mw of 28000.

Production Example 6 (Production of crystalline resin A)
A reaction vessel equipped with a stir bar and a thermometer was charged with 44 parts of tolylene diisocyanate and 100 parts of MEK. This solution was charged with 32 parts of cyclohexanedimethanol and reacted at 80 ° C. for 2 hours. Next, a solution of the non-crystalline polyurethane resin having an isocyanate group at the terminal [non-crystalline part c2] is added to a solution in which 140 parts of [crystalline resin A2 / crystalline part b2] are dissolved in 140 parts of MEK. And a reaction at 80 ° C. for 4 hours to obtain a MEK solution of [crystalline resin A5] composed of a crystalline part and an amorphous part. After removing the solvent, [Crystalline Resin A5] had TaA of 58 ° C., a softening temperature of 61 ° C., and Mw of 21000.

Production Example 7 (Production of crystalline resin A)
A reaction vessel equipped with a stir bar and a thermometer was charged with 43 parts of tolylene diisocyanate and 100 parts of MEK. This solution was charged with 33 parts of cyclohexanedimethanol and allowed to react at 80 ° C. for 2 hours. Next, a solution of an amorphous polyurethane resin having an isocyanate group at the end [amorphous part c3] is added to a solution in which 140 parts of [crystalline resin A1 / crystalline part b1] are dissolved in 140 parts of MEK. And a reaction at 80 ° C. for 4 hours to obtain a MEK solution of [crystalline resin A6] composed of a crystalline part and an amorphous part. After removal of the solvent, [Crystalline Resin A6] had a TaA of 57 ° C., a softening temperature of 59 ° C., and an Mw of 26000.

Production Example 8 (Production of crystalline resin A)
A reaction vessel equipped with a stir bar and a thermometer was charged with 38 parts of tolylene diisocyanate and 100 parts of MEK. This solution was charged with 27 parts of cyclohexanedimethanol and allowed to react at 80 ° C. for 2 hours. Next, a solution of the non-crystalline polyurethane resin [non-crystalline part c4] having an isocyanate group at the terminal is added to a solution in which 151 parts of [crystalline resin A1 / crystalline part b1] are dissolved in 140 parts of MEK. And a reaction at 80 ° C. for 4 hours to obtain a MEK solution of [crystalline resin A7] composed of a crystalline part and an amorphous part. After removing the solvent, [Crystalline Resin A7] had a TaA of 52 ° C., a softening temperature of 59 ° C., and an Mw of 30000.

Production Example 9 (Production of crystalline resin A)
Next, 10 parts of tolylene diisocyanate and 30 parts of MEK were charged into a reaction vessel equipped with a stirring bar and a thermometer. A solution prepared by dissolving 68 parts of [noncrystalline part c1] in 45 parts of MEK was added to this solution and reacted at 80 ° C. for 2 hours. Next, this solution is added to a solution in which 133 parts of [crystalline resin A1 / crystalline part b1] are dissolved in 135 parts of MEK and reacted at 80 ° C. for 4 hours. A MEK solution of [crystalline resin A8] constituted was obtained. After removing the solvent, [crystalline resin A8] had a TaA of 55 ° C., a softening temperature of 57 ° C., and an Mw of 27,000.

Comparative Production Example 1 (Production of Comparative Crystalline Resin A ′)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 100 parts of sebacic acid, 52 parts of adipic acid and 64 parts of 1,4-butanediol, 60 parts of 1,3-propylene glycol and titanium dihydroxy as a condensation catalyst 1 part of bis (triethanolaminate) was added, and the mixture was charged and reacted at 180 ° C. under a nitrogen stream for 8 hours while distilling off the generated water. Next, while gradually raising the temperature to 210 ° C., the reaction was carried out for 2 hours while distilling off the generated water, 1,4-butanediol and 1,3-propylene glycol under a nitrogen stream, and further under reduced pressure of 5 to 20 mmHg. It was taken out when Mw became about 5000. The taken-out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline polycondensed polyester resin [Comparative crystalline resin A′9 / crystalline part b′1]. [Comparative crystalline resin A′9 / crystalline part b′1] had a Ta of 28 ° C., a softening temperature of 33 ° C., an Mw of 5000, and a hydroxyl value of 83.

Comparative Production Example 2 (Production of Comparative Crystalline Resin A ′)
In a reaction vessel equipped with a stirrer and a dehydrator, 250 parts of terephthalic acid, 290 parts of adipic acid, 460 parts of 1,6-hexanediol, and 2 parts of dibutyltin oxide as a condensation catalyst were placed at 230 ° C. under normal pressure. After the time dehydration reaction, the dehydration reaction was performed under a reduced pressure of 0.5 kPa for 5 hours. Further, the obtained resin was cooled to room temperature and then pulverized into particles to obtain a crystalline polycondensed polyester resin [crystalline resin for comparison A′10]. [Comparative crystalline resin A′10] had Mw of 7000, Ta of 105 ° C., softening temperature of 115 ° C., and hydroxyl value of 35.

Comparative Production Example 3 (Production of Comparative Crystalline Resin A ′)
A reaction vessel equipped with a stir bar and a thermometer was charged with 59 parts of tolylene diisocyanate and 80 parts of MEK. This solution was charged with 46 parts of cyclohexanedimethanol and reacted at 80 ° C. for 2 hours. Next, a solution of the non-crystalline polyurethane resin having an isocyanate group at the terminal [non-crystalline part c′1] is added to 95 parts of MEK 95 parts [crystalline resin A′9 for comparison / crystalline part b′1] 95 parts. Was added to the solution in which the solution was dissolved and reacted at 80 ° C. for 4 hours to obtain a MEK solution of [crystalline resin for comparison A′11] composed of a crystalline part and an amorphous part. [Comparative crystalline resin A′11] after removing the solvent had Ta of 68 ° C., softening temperature of 85 ° C., and Mw of 26000.

Production Example 10 (Production of Amorphous Resin B)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 67 parts of bisphenol A / PO2 molar adduct, 700 parts of bisphenol A / PO3 molar adduct, 260 parts of terephthalic acid and 1 part of dibutyltin oxide as a condensation catalyst The mixture was reacted at 230 ° C. for 5 hours at normal pressure, and further reacted for 2 hours at a reduced pressure of 10 to 15 mmHg. Next, the mixture was cooled to 180 ° C., 24 parts of trimellitic anhydride was added, the reaction was taken out for 2 hours under normal pressure sealing, and the mixture was taken out, cooled to room temperature, pulverized and granulated, and non-crystalline polycondensed polyester resin [non-crystalline resin B1] was obtained. [Amorphous resin B1] had an Mw of 5500 and TaB of 52 ° C.

Production Example 11 (Production of Amorphous Resin B)
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, 701 parts (1,8 mol) of 1,2-propylene glycol, 716 parts (7.5 mol) of dimethyl terephthalate, 180 parts of adipic acid ( 2.5 mol), and 3 parts of titanium terephthalate as a condensation catalyst were allowed to react at 180 ° C. for 8 hours while distilling off the produced methanol under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction is carried out for 4 hours while distilling off 1,2-propylene glycol and water produced under a nitrogen stream, and further the reaction is carried out under a reduced pressure of 5 to 20 mmHg. When it reached 150 ° C., it was taken out. The recovered 1,2-propylene glycol was 316 parts (8.5 mol). The taken-out resin was cooled to room temperature and then pulverized into particles to obtain a non-crystalline polycondensed polyester resin [non-crystalline resin B2]. [Amorphous resin B2] had TaB of 48 ° C. and Mw of 10,000.
In addition, the number of moles in () means a relative molar ratio (mole part) (the same applies hereinafter).

Comparative Production Example 4 (Production of comparative non-crystalline resin B ′)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 701 parts (1,8.8 mol) of 1,2-propylene glycol, 286 parts (3.0 mol) of dimethyl terephthalate, 432 parts of adipic acid ( 6.0 mol), and 3 parts of titanium terephthalate as a condensation catalyst were added and reacted at 180 ° C. for 8 hours while distilling off the produced methanol under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction is carried out for 4 hours while distilling off 1,2-propylene glycol and water produced under a nitrogen stream, and further the reaction is carried out under a reduced pressure of 5 to 20 mmHg. When it reached 90 ° C., it was taken out. The recovered 1,2-propylene glycol was 316 parts (8.5 mol). The taken-out resin was cooled to room temperature and then pulverized into particles to obtain an amorphous polycondensed polyester resin [non-crystalline resin for comparison B′3]. [Comparative Amorphous Resin B′3] had a Ta of 28 ° C. and an Mw of 11,000.

Production Example 12 (Production of Colorant Dispersion)
In a beaker, 20 parts of copper phthalocyanine, 4 parts of a colorant dispersant (Solspers 28000; manufactured by Avicia Co., Ltd.) and 76 parts of ethyl acetate were stirred and uniformly dispersed. [Colorant dispersion 1] was obtained. The volume average particle diameter of [Colorant Dispersion Liquid 1] measured by LA-920 was 0.3 μm.

Production Example 13 (Production of modified wax)
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 454 parts of xylene and 150 parts of low molecular weight polyethylene (Sanwa Kasei Kogyo Co., Ltd. sun wax LEL-400: softening temperature 128 ° C.) were added, and after nitrogen substitution, 170 parts were obtained. The temperature was raised to 0 ° C. and dissolved sufficiently, and a mixed solution of 595 parts of styrene, 255 parts of methyl methacrylate, 34 parts of di-t-butylperoxyhexahydroterephthalate and 119 parts of xylene was added dropwise at 170 ° C. over 3 hours for polymerization. And kept at this temperature for 30 minutes. Next, the solvent was removed to obtain [modified wax 1]. The SP value of the graft chain of [modified wax 1] was 10.35 (cal / cm ³ ) ^1/2 , Mn was 1870, Mw was 5190, and Tg was 56.9 ° C.

Production Example 14 (Production of wax dispersion)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of paraffin wax (melting point: 73 ° C.), 1 part of [modified wax 1] and 33 parts of ethyl acetate are added, heated to 78 ° C. and sufficiently dissolved. After cooling to 30 ° C. over time, the wax was crystallized into fine particles and further wet-pulverized with Ultraviscomyl (manufactured by IMEX) to obtain [Wax Dispersion 1].

Production Example 15 (Production of crystalline resin dispersion)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Crystalline Resin A1], 5 parts of MEK and 5 parts of ethyl acetate are heated to 78 ° C., stirred and uniformly dispersed, and heated to 78 ° C. Then, the solution is cooled to 30 ° C. in 1 hour to crystallize [Crystalline Resin A1] into fine particles, and then wet pulverized with Ultraviscomyl (manufactured by IMEX). Obtained.

Production Example 16 (Production of crystalline resin dispersion)
Instead of [Crystalline Resin A1], [Crystalline Resin A2] to [Crystalline Resin A8] are used in the same manner as in Production Example 15, except that [Crystalline Resin Dispersion A2] to [Crystalline Resin Dispersion] are used. Liquid A8] was obtained.

Comparative Production Example 5 (Production of comparative crystalline resin dispersion)
Instead of [Crystalline Resin A1], [Comparative Crystalline Resin A′9] to [Comparative Crystalline Resin A′11] are used in the same manner as in Production Example 15, except that [Comparative Crystalline Resin A1] is used. Dispersions A′9] to [Crystalline resin dispersion A′11 for comparison] were obtained.

Production Example 17 (Production of amorphous resin solution)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of [Amorphous Resin B1], 5 parts of MEK and 5 parts of ethyl acetate are added, heated to 70 ° C., stirred and uniformly dispersed, and further cooled to room temperature. [Amorphous resin solution B1] was obtained.

Production Example 18 (Production of amorphous resin solution)
[Amorphous resin solution B2] was obtained in the same manner as in Production Example 17, except that [Amorphous resin B2] was used instead of [Amorphous resin B1].

Comparative Production Example 6 (Production of comparative non-crystalline resin solution)
[Comparative Amorphous Resin B′3] was obtained in the same manner as in Production Example 17 except that [Comparative Amorphous Resin B′3] was used instead of [Amorphous Resin B1].

Production Example 19 <Production of Resin (d)>
A reaction vessel equipped with a stirrer, heating / cooling device, thermometer, dropping funnel, and nitrogen blowing tube was charged with 500 parts of toluene, and another glass beaker was charged with 350 parts of toluene and behenyl acrylate (22 carbon atoms directly). 120 parts of an alcohol acrylate premer VA (manufactured by NOF Corporation)), 22.5 parts of methyl methacrylate, 7.5 parts of (2-perfluorodecyl) ethyl acrylate (manufactured by Wako Pure Chemical Industries), AIBN ( Azobisisobutyronitrile) 10 parts was charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After substituting the gas phase portion of the reaction vessel with nitrogen, the monomer solution was added dropwise at 80 ° C. over 2 hours in a sealed state, and after aging at 85 ° C. for 2 hours from the end of the addition, toluene was added at 130 ° C. for 3 hours. After removing under reduced pressure, a crystalline resin (d-1) was obtained. The crystallinity of this resin was 60%, the melting point was 60 ° C., and Mn was 8,000.

Production Example 20 <Preparation of Nonaqueous Dispersion (W) of Particle (D)>
After mixing 700 parts of normal hexane and 300 parts of crystalline resin (d-1), pulverization was performed using zirconia beads having a particle diameter of 0.3 mm in a bead mill (Dynomill Multilab: manufactured by Shinmaru Enterprises). A milky white fine particle dispersion [fine particle dispersion W1] was obtained. The volume average particle size of this dispersion was 0.4 μm.

Production Example 21 (Production of aqueous dispersion (W) of particles (D))
60 parts of calcium carbonate (average particle size: 0.18 μm) coated with an acrylic acid-maleic acid copolymer (Mn: 10000), an average degree of polymerization of 800 to 900, and an etherification degree of 0.70 to 0.80 [Particulate dispersion W2] was obtained by dispersing 2 parts of carboxymethyl cellulose and 238 parts of ion-exchanged water with an Ebara milder at 25 ° C. for 5 hours.

Example 1
In a beaker, 10 parts of [Crystalline resin dispersion A1], 50 parts of [Amorphous resin solution B1], 27 parts of [Wax dispersion 1] and 10 parts of [Colorant dispersion 1] are placed at 50 ° C. Then, the mixture was stirred at 8,000 rpm with a TK homomixer and uniformly dissolved and dispersed to obtain [resin solution 1].
In a beaker, 97 parts of ion-exchanged water, 30.5 parts of [fine particle dispersion W2] and 1 part of sodium carboxymethylcellulose were uniformly dissolved. Then, at 25 ° C., 75 parts of [resin solution 1] was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Subsequently, this mixed liquid was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised and ethyl acetate and MEK were distilled off at 35 ° C. until the concentration became 0.5% or less. X1) was obtained. Next, an aqueous hydrochloric acid solution was added to the aqueous resin dispersion (X1) to PH = 1.5, then an aqueous sodium hydroxide solution was added to PH = 9.0, and an aqueous hydrochloric acid solution was added to PH = 4.5. Stir for 1 hour. This was further cooled to room temperature, filtered, and dried at 40 ° C. for 18 hours to obtain resin particles (I-1) having a volume average particle size of 6.3 μm by Multisizer III (hereinafter the same).

Examples 2-10
Instead of [Resin Solution 1], [Resin Solution 2] to [Resin Solution 10] were produced using the number of parts shown in Table 1 below, and the volume average was obtained in the same manner as in Example 1 except that it was used. Resin particles (I-2) to (I-10) having a particle diameter of 6.1 to 6.3 μm were obtained.

Example 11
Into a beaker, 120 parts of normal decane and 45 parts of [fine particle dispersion W1] were added and mixed with a homomixer (manufactured by Primix) for 10 seconds at a rotational speed of 16000 rpm. The dispersion was obtained by dispersing for 1 minute. Further, the dispersion was desolvated with an evaporator at 40 ° C. and 0.01 MPa, followed by filtration and drying to remove the solvent in the system, and resin particles (I-11 having a volume average particle diameter of 6.1 μm). )

Comparative Examples 1-6
Instead of [Resin Solution 1], [Comparative Resin Solution 1 ′] to [Comparative Resin Solution 6 ′] were produced using the number of parts shown in Table 1 below, and Example 1 was used except that it was used. Similarly, comparative resin particles (I′-12) to (I′-17) having a volume average particle diameter of 6.1 to 6.3 μm were obtained.

Measurement Example of Physical Properties Fixing property (minimum fixing temperature) and heat resistance of resin particles (I-1) to (I-11) of the present invention and comparative resin particles (I′-12) to (I′-17), respectively. Storage stability and charging characteristics were measured by the methods described below. The results are shown in Tables 2 and 3.
Tables 2 and 3 show the results of analyzing the crystalline resin A and the amorphous resin B used in Examples 1 to 11 and Comparative Examples 1 to 6, respectively.

[Minimum fixing temperature (MFT)]
After adding 1.0% Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd.) to the resin particles and mixing well, the powder is uniformly placed on the paper surface so as to be 0.6 mg / cm ² (at this time As a method for placing the body on the paper surface, a printer from which the heat fixing machine is removed is used (other methods may be used as long as the powder can be placed uniformly at the above-mentioned weight density). The MFT (minimum fixing temperature) was measured when passing through a roller under the conditions of a fixing speed (heating roller peripheral speed) of 213 mm / sec and a fixing pressure (pressure roller pressure) of 5 kg / cm ^2. In the MFT column, “x” indicates that there is no fixing area.

[Heat resistant storage stability]
Resin particles were allowed to stand for 15 hours in a dryer controlled to 50 ° C., and evaluated according to the following criteria based on the degree of blocking.
○: Blocking does not occur.
Δ: Blocking occurs, but disperses easily when force is applied.
X: Blocking occurs and does not disperse even when force is applied.

(Charging characteristics)
In a 50 cc glass bottle with a stopper, 0.5 g of resin particles and 10 g of iron powder (“F-150” manufactured by Nippon Iron Powder Co., Ltd.) are precisely weighed, stoppered and placed in an atmosphere of 23 ° C. and 50% RH. Set in a turbula shaker mixer (manufactured by Willy a Baschofen) and stir for 2 minutes at 90 rpm. 0.2 g of the mixed powder after stirring was loaded into a blow-off powder charge measuring device (TB-203, manufactured by Kyocera Chemical Co., Ltd.) in which a 20 μm stainless wire mesh was set, and the blow pressure was 10 KPa and the suction pressure was 5 KPa. Then, the charge amount of the residual iron powder was measured, and the charge amount of the resin particles was calculated by a conventional method. For toner, the higher the negative charge amount, the better the charging characteristics. If it is −25 μC / g or less, it is judged that the charging characteristics are good.

  As shown in Tables 2 and 3, the resin particles of the present invention (Examples 1 to 11) are both markedly superior in both MFT and heat-resistant storage stability as compared with the resin particles of Comparative Examples. Good results were obtained.

  The resin particles of the present invention have excellent fixability, a sharp particle size distribution, and excellent chargeability. For this purpose, coating additives, adhesive additives, cosmetic additives, paper coating additives, slush molding resins, powder coatings, spacers for manufacturing electronic components, catalyst carriers, electrophotographic toners Useful as base particles for electrostatic recording, base particles for electrostatic recording toner, base particles for electrostatic printing toner, standard particles for electronic measuring instruments, particles for electronic paper, medical diagnostic carrier, chromatographic filler, particles for electrorheological fluid, etc. It is.

Claims (6)

Resin particles (I) containing a crystalline resin (A) and an amorphous resin (B), the maximum peak temperature (TaA) of melting heat of the crystalline resin (A) is 40 to 100 ° C., the softening temperature To TaA (softening temperature / TaA) is 0.8 to 1.55, the maximum peak temperature (TaB) of heat of fusion of the amorphous resin (B) is 35 to 100 ° C., and the crystalline resin ( A) is a resin selected from polyester resins, polyurethane resins, and composite resins thereof, and the crystalline resin (A) is composed of a crystalline part (b) and an amorphous part (c). Resin particles characterized in that the proportion of (b) in (A) in the case of resin is 50% by weight or more, and the resin particles (I) satisfy the following conditions.
[Condition 1] G ′ (TaI + 20) = 1 × 10 ^{2 to} 5 × 10 ⁵ [Pa]
[Condition 2] G ″ (TaI + 20) = 1 × 10 ^{2 to} 5 × 10 ⁵ [Pa]
[G ′: storage elastic modulus (Pa), G ″: loss elastic modulus (Pa), TaI: resin particle
Maximum peak temperature of melting heat of child (I) (° C.)]   The total content of the crystalline resin (A) and the amorphous resin (B) in the resin particles (I) is 50% by weight or more, and the weight of the crystalline resin (A) and the amorphous resin (B) The resin particles according to claim 1, wherein the ratio (A) / (B) is 0.05 or more and less than 4.   The resin particle according to claim 1 or 2, wherein a difference ΔSP in SP value between the crystalline resin (A) and the amorphous resin (B) is 0.2 to 2.5. The resin particle according to any one of claims 1 to 3, wherein the melting start temperature (X) of the crystalline resin (A) is within a temperature range of (TaA ± 30) ° C, and (A) satisfies the following condition.
[Condition 3] G ′ (TaA + 20) = 50 to 1 × 10 ⁶ [Pa]
[Condition 4] | LogG ″ (X) −LogG ″ (X + 20) |> 2.0
[G ′: storage elastic modulus (Pa), G ″: loss elastic modulus (Pa), TaA: crystallinity
Maximum peak temperature of heat of fusion of resin (A) (° C.)]]   The crystalline resin (A) is a block resin composed of a crystalline part (b) and an amorphous part (c), and the weight average molecular weight of (b) is 2000 to 80000. Any one of the resin particles. The crystalline resin (A) is a resin in which a crystalline part (b) and an amorphous part (c) are linearly bonded in the following format, and n is 0.9 to 3.5: 5. The resin particle according to 5.
(B) {-(c)-(b)} n