JP2011079962A - Crystalline resin particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide crystalline resin particles excellent in low-temperature fixability and blocking resistance. <P>SOLUTION: The crystalline resin particles are produced by melt-kneading and pulverizing a mixture containing at least a crystalline resin (A) and wax, have a maximum peak temperature (Ta) of heat of fusion of 40-100°C and a softening point to Ta ratio (softening point/Ta) of 0.8-1.55, and satisfy the following conditions [1] and [2]: [1] G'(Ta+20)=1×10<SP>2</SP>-5×10<SP>5</SP>[Pa] and [2] G"(Ta+20)=1×10<SP>2</SP>-5×10<SP>5</SP>[Pa], wherein G' is a storage modulus, and G" is a loss modulus. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to crystalline 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, powder aggregation (blocking) tends to occur, and the preservability of the resin particles on the surface of the fixed image is deteriorated. 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 produced by melt-kneading and pulverizing a mixture containing at least a crystalline resin (A) and a wax, the maximum peak temperature (Ta) of heat of fusion being 40 to 100 ° C., and the ratio of softening point to Ta ( A crystalline resin particle having a softening point / Ta) of 0.8 to 1.55 and satisfying the following conditions.
[Condition 1] G ′ (Ta + 20) = 1 × 10 ^{2 to} 5 × 10 ⁵ [Pa]
[Condition 2] G ″ (Ta + 20) = 1 × 10 ^{2 to} 5 × 10 ⁵ [Pa]
[G ′: storage elastic modulus, G ″: loss elastic modulus]

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

Hereinafter, the crystalline resin particles of the present invention will be described in detail.
In the present invention, “crystallinity” means a ratio of softening point to maximum peak temperature of heat of fusion (softening point / maximum peak temperature of heat of fusion) of 0.8 to 1.55, and differential scanning calorimetry (DSC). ) Refers to having a clear endothermic peak rather than a stepwise endothermic change. “Non-crystalline” means that (softening point / maximum peak temperature of heat of fusion) is greater than 1.55.

  The crystalline resin particles (P) of the present invention must have a maximum peak temperature (Ta) of heat of fusion in the range of 40 to 100 ° C., preferably 45 to 80 ° C., from the viewpoint of heat-resistant storage stability. Preferably it is 50-70 degreeC.

  The ratio (softening point / Ta) between the softening point of the crystalline resin particles (P) and the maximum peak temperature (Ta) of the heat of fusion is 0.8 to 1.55 as described above, preferably 0.85. To 1.25, more preferably 0.9 to 1.2, and particularly preferably 0.9 to 1.19. If it is outside this range, the image tends to deteriorate when used as toner particles.

In the present invention, the softening point and the maximum peak temperature of the heat of fusion are values measured as follows.
<Softening point>
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. Extrude 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 graph the temperature corresponding to 1/2 of the maximum plunger descent amount And this value (temperature when half of the measurement sample flows out) is taken as the softening point.

<Maximum peak heat of fusion>
Measurement is performed using a differential scanning calorimeter (DSC) {for example, DSC210 manufactured by Seiko Denshi Kogyo Co., Ltd.}.
As a pretreatment, a sample to be used for measurement of the maximum peak temperature of heat of fusion is melted at 130 ° C., then lowered from 130 ° C. to 70 ° C. at a rate of 1.0 ° C./minute, and then from 70 ° C. to 10 ° C. The temperature is lowered at a rate of 0.5 ° C./min. Here, by DSC, the temperature is increased at a rate of temperature increase of 20 ° C./min, and the endothermic change is measured, and the graph of “endothermic amount” and “temperature” is drawn. The endothermic peak temperature at 100 ° C. is defined as “Ta *”. When there are a plurality of peaks, the peak temperature with the largest endothermic amount is Ta *. Finally, the sample is stored at (Ta * -10) ° C. for 6 hours and then stored at (Ta * −15) ° C. for 6 hours.
Next, the sample was cooled to 0 ° C. by DSC at a rate of temperature decrease of 10 ° C./min, and then the temperature was increased at a rate of temperature increase of 20 ° C./min to measure the endothermic change. The temperature corresponding to the maximum peak of the calorific value is taken as the maximum peak temperature of the heat of fusion.

In the viscoelastic properties of the crystalline resin particles (P), the storage elastic modulus G ′ at (Ta + 20) ° C. (Ta is the maximum peak temperature of heat of fusion) is in the range of 1 × 10 ^{2 to} 5 × 10 ⁵ [Pa]. Condition 1], preferably 2 × 10 ^{2 to} 3 × 10 ⁵ [Pa].
When G ′ at (Ta + 20) ° C. is less than 1 × 10 ² Pa, offset due to insufficient elasticity is likely to occur, 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.
The crystalline resin particles (P) satisfying [Condition 1] can be obtained by adjusting the ratio of the crystalline component in the resin constituting the resin particles, adjusting the resin molecular weight, or the like. For example, when the ratio of the crystalline part (b) or the ratio of the crystalline component is increased, the value of G ′ (Ta + 20) decreases. Examples of the crystalline component include polyols having a linear structure, polyisocyanates, and the like. Further, the value of G ′ (Ta + 20) is decreased by decreasing the resin molecular weight.

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 is raised to (Ta + 30) ° C. and brought into close contact with the jig, and then from (Ta + 30) ° C. to (Ta−30) ° C. at a rate of 0.5 ° C./min. The temperature was lowered, left at (Ta-30) ° C. for 1 hour, then lowered to (Ta-10) ° C. at a rate of 0.5 ° C./minute, and further left at (Ta-10) ° C. for 1 hour, After sufficient crystallization has proceeded, measurement is performed using this. The measurement temperature range is 30 ° C. to 200 ° C. By measuring the melt viscoelasticity between these temperatures, it can be obtained as a curve of temperature-G ′ and temperature-G ″.
When measuring the crystalline resin (A), the maximum peak temperature (Ta) of the melting heat of the crystalline resin particles (P) is set to the maximum peak temperature (Ta ′ of the melting heat of the crystalline resin (A). ).

Further, in the viscoelastic properties of the crystalline resin particles (P), the loss elastic modulus G ″ at (Ta + 20) ° C. (Ta is the maximum peak temperature of heat of fusion) is 1 × 10 ^{2 to} 5 × 10 ⁵ [Pa]. It is the range [Condition 2], preferably 5 × 10 ^{2 to} 3 × 10 ⁵ [Pa].
If G ″ at (Ta + 20) ° C. exceeds 5 × 10 ⁵ Pa, cold offset is likely to occur at low temperature fixing, and low temperature fixing properties deteriorate. Also, if it is less than 1 × 10 ² [Pa], at high temperature fixing. Viscosity is insufficient, and it becomes difficult to control the area to be fixed.
The crystalline resin particles (P) satisfying [Condition 2] can be obtained by adjusting the ratio of the crystalline component in the resin constituting the resin particles. For example, when the ratio of the crystalline part (b) or the ratio of the crystalline component is increased, the value of G ″ (Ta + 20) decreases. Examples of the crystalline component include polyols having a linear structure, polyisocyanates, and the like. It is done.

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

The crystalline resin particles (P) of the present invention contain a crystalline resin (A) and a wax.
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 (softening point / maximum peak temperature of heat of fusion) is 0. If it is .8 to 1.55, this is also a crystalline resin.

  From the viewpoint of heat-resistant storage stability, the crystalline resin (A) preferably has a maximum peak temperature (Ta ′) of heat of fusion of 40 to 100 ° C., more preferably 45 to 80 ° C., particularly preferably. 50-70 ° C.

  The ratio (softening point / Ta ′) between the softening point of the crystalline resin (A) and the maximum peak temperature (Ta ′) of heat of fusion is preferably 0.8 to 1.55, more preferably 0.85 to 1. .25, particularly preferably 0.9 to 1.2, most preferably 0.9 to 1.19. Within this range, it is easy to achieve both heat-resistant storage stability and low-temperature fixability.

In the viscoelastic property of the crystalline resin (A), the storage elastic modulus G ′ at (Ta ′ + 20) ° C. [Ta ′ is the maximum peak temperature of heat of fusion of (A)] is 50 to 1 × 10 ⁶ [Pa]. It is preferable that it is the range [condition 3] of this, More preferably, it is 100-5 * 10 < ⁵ > [Pa].
When G ′ at (Ta ′ + 20) ° C. is 50 Pa or more, fixing deterioration hardly occurs due to insufficient elasticity, 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 ′ (Ta ′ + 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 within the temperature range of (Ta ′ ± 30) ° C., preferably within the temperature range of (Ta ′ ± 20) ° C., more preferably (Ta ′ ± 15) Within the temperature range of ° C.
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.

Further, regarding the loss elastic modulus G ″ and the melting start temperature (X) of the crystalline resin (A), it is preferable to satisfy the following [Condition 4], more preferably [Condition 4-2], 4-3] is particularly preferable.
[Condition 4] | LogG ″ (X + 20) −LogG ″ (X) |> 2.0
[G ": Loss elastic modulus [Pa]]
[Condition 4-2] | LogG ″ (X + 20) −LogG ″ (X) |> 2.5
[Condition 4-3] | LogG "(X + 15) -LogG" (X) |> 2.5
When the melting start temperature (X) of (A) is within the above range and [Condition 4] is satisfied, the resin has a low viscosity reduction speed, and when toner particles are used, the low temperature side and the high temperature side of the fixing temperature region. Can obtain the same image quality. 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 range of the melting start temperature (X) and [Condition 4] can be obtained by adjusting the ratio of the crystalline component in the constituent components of (A). For example, when the ratio of the crystalline component is increased, the temperature difference between (Ta ′) and (X) is decreased.

Further, in the viscoelastic properties of the crystalline resin (A), the ratio of the loss elastic modulus G ″ at (Ta ′ + 30) ° C. to the loss elastic modulus G ″ at (Ta ′ + 70) ° C. [G ″ (Ta ′ + 30) / G “(Ta ′ + 70)] is preferably 0.05 to 50, more preferably 0.1 to 10 [Ta ′: 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 ″ (Ta + 30) / G ″ (Ta + 70)] decreases. When the molecular weight is increased, the value of [G ″ (Ta + 30) / G ″ (Ta + 70)] decreases. Examples of the crystalline component include polyols and polyisocyanates having a linear structure.

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, a block resin composed of (b) and (c) is preferable from the viewpoint of fixing. Specifically, the block resin is obtained by bonding a resin constituting the crystalline part (b) and a resin constituting the non-crystalline part (c).
In addition, the block resin is excellent in durability.

  When the crystalline resin (A) is a block resin having a crystalline part (b) and an amorphous part (c), the glass transition temperature (Tg) of (c) is preferably 40 from the viewpoint of heat-resistant storage stability. It is -250 degreeC, More preferably, it is 50-240 degreeC, Especially preferably, it is 60-230 degreeC, Most preferably, it is 65-180 degreeC. Moreover, the softening point in the flow tester measurement of (c) is preferably 100 to 300 ° C, more preferably 110 to 290 ° C, and particularly preferably 120 to 280 ° C.

The glass transition temperature (Tg) is a value measured as follows.
<Glass transition temperature>
The glass transition temperature 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 of the heat of fusion, the extension of the baseline below the maximum peak temperature in the graph of “endotherm” and “temperature” and the peak of the maximum peak from the rising part of the maximum peak The temperature corresponding to the point of intersection with the tangent indicating the maximum slope until is the glass transition temperature.

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 from 2000 to 80000, more preferably from 4000 to 60000, particularly preferably from 7000 to 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 wt% 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% by weight or more, more preferably 60 to 98% by weight, still more preferably 70 to 96% by weight. When the proportion of (b) is 50% by weight or more, the crystallinity of the 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 2.0, 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). In addition, containing that whose n is 0 means containing resin which comprises a crystalline part (b) other than the block resin of (b) and (c).
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, hot offset hardly occurs at the time of fixing, and the fixing temperature region 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% by weight 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.) as is the case with the maximum peak temperature of heat of fusion.

  The crystalline part (b) is not particularly limited as long as it has crystallinity, and may be a composite resin. Of 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 the blocking resistance and the 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 lowered and the melting point is raised, 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. 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 the 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 adducts of novolak resins (phenol novolak, cresol novolak, etc.) (addition mole number 2-30); acrylic polyol [copolymers of hydroxyethyl (meth) acrylate and other vinyl monomers, etc.] ; It is.
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 the dicarboxylic acid 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- to hexa-valent 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 thereof (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modified product) 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% by weight) of a trifunctional or higher functional polyamine] phosgenation product: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ', 4 "- Triphenylmethane triisocyanate, m- and p-iso Such Anat 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.), a modified product of diisocyanate such as urethane-modified TDI, and a mixture 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, 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 polyether resins 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 have a terminal modified so as to be, for example, a carboxyl group. When 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) around 75.1 ppm, heterotactic value (H) around 75.3 ppm, and isotactic value (I) 75.5 ppm, respectively. 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 resin 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, A polyurea resin, a polyamide resin, a polyether resin, a vinyl resin, an 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 using a binder, 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 of AO adduct of hydrogenated bisphenol A, diol (ethylene glycol, propylene glycol, neopentyl glycol, butanediol, hexanediol, cyclohexanedimethanol, polyethylene glycol, polypropylene glycol, etc.) diglycidyl ether, trimethylolpropane 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. In this case, for example, the reaction is performed at a reaction temperature of 180 ° C. 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 a 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.
Of these (b1), (meth) acrylic monomers and carboxyl group-containing vinyl monomers are preferred.

  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% by weight or more, more preferably 35 to 95% by weight, particularly preferably 40 to 90% by weight. It is. Within this range, the crystallinity of the vinyl resin is not impaired and the heat resistant storage stability is good. 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% by weight, more preferably 40 to 80% by weight.
A crystalline vinyl resin is obtained by polymerizing these vinyl monomers by a known method.

The crystalline resin (A) may be used alone as the resin in the crystalline resin particles (P) of the present invention, but may be used together with an amorphous resin.
Examples of the amorphous resin include polyester resins having a number average molecular weight (hereinafter referred to as Mn) of 1,000 to 1,000,000, polyurethane resins, epoxy resins, vinyl resins, and combinations thereof. Preferred are polyester resins and vinyl resins, and more preferred are polyester resins. However, from the viewpoint of low-temperature fixability and gloss, the proportion of the crystalline resin (A) in the resin is preferably 50% by weight or more, more preferably 60% by weight or more, and further preferably 70% by weight or more.

As the wax, those having a softening point of 50 to 170 ° C. are preferable. 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, tria) Contanol), fatty acids having 30 to 50 carbon atoms (e.g., triacontane carboxylic acid), 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.

The crystalline resin particles (P) of the present invention are produced by melt-kneading a mixture containing at least the crystalline resin (A) and wax, pulverizing the solidified product, and classifying as necessary.
The mixing ratio of the crystalline resin (A) and the wax is such that the amount of the wax with respect to (A) is preferably 1 to 15% by weight, more preferably 2 to 12% by weight.

  The crystalline resin (A) and the wax may be mixed by applying a shearing force or by melting and mixing. When mixing by applying a shearing force, the crystalline resin (A) is preferably a pre-ground resin from the viewpoint of uniformly mixing and dispersing wax and the like. When the powder of (A) pulverized in advance is used, it is preferable to use a sieve or the like so that the volume average particle diameter is 100 to 5000 μm (particularly 500 to 2000 μm).

  When using a mixer that can impart shearing force to the raw material in the mixing step, the heat generation rate of the mixed raw material at the time of mixing is 3 ° C./min to 20 ° C./min, and the difference in volume average particle size before and after mixing is It is desirable to carry out under the condition of 300 to 800 μm. If the rate of heat generation is too high, the raw materials aggregate due to heat storage, and if the rate of heat generation is low, mixing and dispersion are insufficient. Moreover, if the difference between the particle sizes before and after mixing is too large, the amount of heat generated by the mixer increases. If the difference is too small, efficient dispersion is difficult and further biting failure occurs (the raw material does not sufficiently enter the screw of the kneader), which adversely affects production efficiency.

Examples of the kneader used in the step of melt-kneading the mixture obtained in the above step include a biaxial continuous extrusion kneader, a pressure kneader, and a three roll. These can also be used in the mixing step.
At that time, the discharge temperature (Ts) (° C.) of the melt-kneaded product is Ta ′ <Ts <Ta ′ + 45 [where Ta ′ is the maximum peak temperature (° C.) of the heat of fusion of the crystalline resin (A)]. Is preferably performed under such conditions, more preferably Ta ′ + 5 <Ts <Ta ′ + 40, and further preferably Ta ′ + 10 <Ts <Ta ′ + 35.

  When the discharge temperature is Ta '° C. or higher, the kneaded material containing the crystalline resin (A) and the wax is sufficiently melted, and the kneader is not loaded and kneading is easy. Further, since (A) is sufficiently melted, the function of fusing the binder resin is sufficiently exhibited at all times, additives such as pigments described later are not released, and filming hardly occurs.

  Further, when the discharge temperature of the kneaded resin is (Ta ′ + 45) ° C. or lower, a sufficient shearing force can be obtained during melt-kneading, and problems such as filming, black spots, and fog are less likely to occur.

The kneaded product obtained in the melt kneading step is solidified, pulverized, and classified as necessary. The solidification method may be that the discharged material obtained in the melt-kneading step is received by a pad or the like and naturally cooled, or forced cooling, for example, the discharged material is guided to a press roller or the like and forcedly cooled while applying pressure. Good. The cooling temperature is preferably (Ta′-15) ° C. or less. In the case of forced cooling, particularly when pressure is applied, the discharged melt-kneaded product is gradually cooled to a temperature of (Ta′-15) ° C. without being rapidly cooled or stretched (pressed) [preferably from the start of cooling. (Ta′-15) 30 minutes or more until reaching [° C.]]. When rapidly cooled or stretched (pressed), the crystal arrangement of the resin is disturbed, sharp melt properties are remarkably lost, and the heat-resistant storage stability of the crystalline resin particles may be lowered. In addition, problems such as insufficient dispersion of wax, wax particles with large particle diameter, rice granular dispersion, or leaf-like dispersion occur, and as a result, phenomena such as black spots and filming on the photoconductor occur during image formation. May occur.
Finally, the solidified product of the melt-kneaded product is pulverized according to ordinary means and classified as necessary to obtain the crystalline resin particles (P) of the present invention.
Examples of the pulverizer used in the above process include a supersonic jet pulverizer lab jet, and examples of the classifier include an airflow classifier and an elbow jet.

In the crystalline resin particles (P) of the present invention, additives (pigments, fillers, antistatic agents, colorants, charge control agents, ultraviolet absorbers, antioxidants, antiblocking agents, heat stabilizers, flame retardants Etc.) can be mixed. As a method for adding the additive into (P), the crystalline resin (A) and the additive may be mixed in advance and then mixed with the wax, or may be mixed when the resin and the wax are mixed.
In the present invention, the additive is not necessarily mixed when forming the crystalline resin particles (P), and may be added after forming (P). For example, after forming (P) not containing a colorant, the colorant can be added by a known dyeing method, or the additive can be impregnated with an organic solvent and / or a plasticizer.
The content of the crystalline resin (A) in the crystalline resin particles (P) of the present invention is preferably 60% by weight or more, more preferably 70% by weight or more, from the viewpoint of low-temperature fixability and gloss.

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

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

  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, and more preferably 0.5 to 10 parts, with respect to 100 parts of the resin containing the crystalline resin (A). In addition, when using magnetic powder, Preferably it is 20-150 parts, More preferably, it is 40-120 parts. Above and below, parts mean parts by weight.

  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 at the time of particle formation is based on the weight of the particles (% in the following item is% by weight), and the crystalline resin (A) is preferably 30 to 97%, more preferably 40 to 94. %, Particularly preferably 45 to 90%; wax is preferably 0.1 to 30%, more preferably 0.5 to 20%, particularly preferably 1 to 10%, and among the additives, a colorant is preferable. Is 0.05 to 60%, more preferably 0.1 to 55%, particularly preferably 0.5 to 50%; the charge control agent is preferably 0 to 20%, more preferably 0.1 to 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 the additives is preferably 3 to 70%, more preferably 4 to 58%, and particularly preferably 5 to 50%. When the composition ratio of the particles is in the above range, a particle having good chargeability can be easily obtained.

When used as a toner, the crystalline resin particles (P) are optionally coated with carrier particles {iron powder, glass beads, nickel powder, ferrite, magnetite and resin (acrylic resin, silicone resin, etc.). 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 crystalline part b)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 159 parts of sebacic acid, 11 parts of adipic acid and 108 parts of 1,4-butanediol and titanium dihydroxybis (triethanolaminate) as a condensation catalyst 0. 5 parts were added and reacted for 8 hours at 180 ° C. under a nitrogen stream while distilling off the 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 resin taken out was cooled to room temperature and then pulverized into particles to obtain a crystalline polycondensed polyester resin [crystalline part b1]. [Crystalline resin b1] of [Crystalline part b1] was obtained. [Crystalline resin b1] had a melting point of 57 ° C., Mn of 5000, Mw of 11000, and a hydroxyl value of 30.

Production Example 2 (Production of crystalline part b)
286 parts of dodecanedioic acid, 190 parts of 1,6-hexanediol and 1 part of titanium dihydroxybis (triethanolaminate) as a condensation catalyst were placed in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube. The reaction was carried out for 8 hours while distilling off the water produced under a nitrogen stream at ° C. Next, while gradually raising the temperature to 220 ° C., the reaction is carried out for 4 hours while distilling off the water produced under a nitrogen stream, and the reaction is further carried out under reduced pressure of 5 to 20 mmHg. It was. The taken-out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline polycondensed polyester resin [crystalline part b2]. [Crystalline part b2] had a melting point of 66 ° C., Mn of 4900, Mw of 10,000, and a hydroxyl value of 34.

Production Example 3 (Production of crystalline part b)
A reaction vessel equipped with a stirrer and a thermometer was charged with 66 parts of 1,4-butanediol, 86 parts of 1,6-hexanediol, and 40 parts of methyl ethyl ketone (hereinafter referred to as MEK). This solution was charged with 248 parts of hexamethylene diisocyanate (HDI) and reacted at 80 ° C. for 5 hours to obtain a MEK solution of a crystalline polyurethane resin [crystalline part b3]. [Crystalline part b3] after removing the solvent had a melting point of 57 ° C., Mn of 4500, Mw of 9700, and hydroxyl value of 36.

Production Example 4 (Production of crystalline part b)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 159 parts of sebacic acid, 28 parts of adipic acid and 124 parts of 1,4-butanediol and 1 part of titanium dihydroxybis (triethanolaminate) as a condensation catalyst 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 220 ° C., the reaction is carried out for 4 hours while distilling off the generated water and 1,4-butanediol under a nitrogen stream, and further the reaction is carried out under a reduced pressure of 5 to 20 mmHg. When it became, 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 part b4]. [Crystalline part b4] had a melting point of 55 ° C., Mn of 8300, Mw of 20000, and a hydroxyl value of 19.

Production Example 5 (Production of crystalline resin b)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 159 parts of sebacic acid, 11 parts of adipic acid and 108 parts of 1,4-butanediol and titanium dihydroxybis (triethanolaminate) as a condensation catalyst 0. 5 parts were added and reacted for 8 hours at 180 ° C. under a nitrogen stream while distilling off the generated water. Next, while gradually raising the temperature to 225 ° C., the reaction was performed for 4 hours while distilling off the water and 1,4-butanediol produced under a nitrogen stream, and the reaction was further performed under a reduced pressure of 10 to 25 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 part b5]. The melting point of [crystalline part b5] was 56 ° C., Mn was 4100, Mw was 9200, and the hydroxyl value was 45.

Production Example 6 (Production of crystalline part b)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 159 parts of sebacic acid, 28 parts of adipic acid and 124 parts of 1,4-butanediol and 1 part of titanium dihydroxybis (triethanolaminate) as a condensation catalyst 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 mixture is reacted for 2 hours while distilling off the generated water and 1,4-butanediol under a nitrogen stream, and further reacted under a reduced pressure of 5 to 20 mmHg. When it reached 5000, it was taken out. The resin taken out was cooled to room temperature and then pulverized into particles to obtain a crystalline polycondensed polyester resin [crystalline part b6]. The melting point of [crystalline part b6] was 55 ° C., Mn was 2300, Mw was 5000, and the hydroxyl value was 83.

Production Example 7 (Production of crystalline part b)
180 parts of (S) -PO and 30 parts of KOH were placed in a 1 L autoclave and polymerized by stirring at room temperature for 48 hours. In order to melt the polymer obtained by raising the temperature to 70 ° C. and wash KOH with water, 100 parts of toluene and 100 parts of water were added, and the liquid separation was repeated three times. The toluene phase was neutralized with 0.1 mol / L hydrochloric acid, each 100 parts of water was added, and liquid separation was further performed three times. Toluene was distilled off from the toluene phase, and the resulting resin was cooled to room temperature. Then, it grind | pulverized and granulated and obtained crystalline polyether resin [crystalline part b7]. [Crystalline part b7] had a melting point of 55 ° C., Mw of 9000, a hydroxyl value of 20, and an isotacticity of 99%.

Production Example 8 (Production of crystalline part b)
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 part b8] which is a lactone ring-opening polymer. [Crystalline part b8] had a melting point of 60 ° C., Mw of 9800, and a hydroxyl value of 14.

Production Example 9 (Production of crystalline part b)
In a reaction vessel equipped with a stirrer and a dehydrator, 2 parts of ethylene glycol, 400 parts of L-lactide, 150 parts of glycolide, and 2 parts of dibutyltin oxide are charged and reacted 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 part b9] which is polyhydroxycarboxylic acid. [Crystalline part b9] had a melting point of 60 ° C., Mw of 11,200, and a hydroxyl value of 14.

Production Example 10 (Production of crystalline part b)
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 121 parts of sebacic acid, 118 parts of dimethylterephthalic acid and 124 parts of 1,6-hexanediol and titanium dihydroxybis (triethanolaminate) 1 as a condensation catalyst The reaction was allowed to proceed for 8 hours while distilling off the water produced under a nitrogen stream at 180 ° C. Next, while gradually raising the temperature to 220 ° C., the reaction is carried out for 4 hours while distilling off the generated water and 1,6-hexanediol under a nitrogen stream, and the reaction is further carried out under a reduced pressure of 5 to 20 mmHg. When it became, it took out. The resin taken out was cooled to room temperature and then pulverized into particles to obtain a crystalline polycondensed polyester resin [crystalline part b10]. The melting point of [crystalline part b10] was 53 ° C., Mw was 8000, and the hydroxyl value was 46.

Production Example 11 (Production of amorphous part c)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 831 parts of 1,2-propylene glycol (hereinafter referred to as propylene glycol), 750 parts of terephthalic acid, and 0.5% of tetrabutoxy titanate as a condensation catalyst. The reaction mixture was allowed to react for 8 hours while distilling off the methanol produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction is carried out for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and further the reaction is carried out under a reduced pressure of 5 to 20 mmHg, and the softening point becomes 87 ° C. After cooling to 180 ° C., 24 parts of trimellitic anhydride and 0.5 part of tetrabutoxy titanate were added, reacted for 90 minutes, and then taken out. The recovered propylene glycol was 442 parts. The taken-out resin was cooled to room temperature and then pulverized into particles to obtain a non-crystalline polycondensed polyester resin [non-crystalline part c1 ′]. [Amorphous part c1 ′] had Mw of 8000, Tg of 65 ° C., and a hydroxyl value of 30.

Production Example 12 (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 an amorphous polyurethane resin [amorphous part c2] having an isocyanate group at the terminal is added to a solution in which 140 parts of [crystalline part b1] are dissolved in 140 parts of MEK, and the solution is 4 at 80 ° C. By reacting for a time, an MEK solution of [crystalline resin A1] composed of a crystalline part and an amorphous part was obtained. [Crystalline Resin A1] after removing the solvent had Ta ′ of 55 ° C., Mn of 14000, and Mw of 28000.

Production Example 13 (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 14 parts of 1,2-propylene glycol and allowed to react at 80 ° C. for 2 hours. Next, a solution of the amorphous polyurethane resin [amorphous part c3] having an isocyanate group at the terminal is added to a solution in which 130 parts of [crystalline resin b2] is dissolved in 130 parts of MEK, and then at 80 ° C. for 4 hours. Reaction was performed to obtain a MEK solution of [crystalline resin A2] composed of a crystalline part and an amorphous part. [Crystalline resin A2] after removing the solvent had Ta ′ of 64 ° C., Mn of 9000, and Mw of 34000.

Production Example 14 (Production of Crystalline Resin A)
A solution of 152 parts of an amorphous polyurethane resin having an isocyanate group at the end [amorphous part c3] obtained in the same manner as in Production Example 13 was dissolved in 130 parts of MEK and 130 parts of [crystalline part b3]. The solution was put into the solution and reacted at 80 ° C. for 4 hours to obtain a MEK solution of [crystalline resin A3] composed of a crystalline part and an amorphous part. [Crystalline resin A3] after removing the solvent had Ta ′ of 54 ° C., Mn of 12,000, and Mw of 37,000.

Production Example 15 (Production of crystalline resin A)
176 parts of a solution of an amorphous polyurethane resin having an isocyanate group at the end [amorphous part c2] obtained in the same manner as in Production Example 12, and 250 parts of [crystalline part b4] were dissolved in 250 parts of MEK. The solution was put into a solution and reacted at 80 ° C. for 4 hours to obtain a MEK solution of [crystalline resin A4] composed of a crystalline part and an amorphous part. [Crystalline Resin A4] after removing the solvent had Ta ′ of 55 ° C., Mn of 24,000, and Mw of 45,000.

Production Example 16 (Production of crystalline resin A)
In a reaction vessel in which a stir bar and a thermometer were set, a solution in which 190 parts of [crystalline part b1] was dissolved in 190 parts of MEK was added, and then 9 parts of tolylene diisocyanate were added and reacted at 80 ° C. for 4 hours. A MEK solution of [crystalline resin A5], which is a crystalline polyurethane resin, was obtained. After removing the solvent, [Crystalline Resin A5] had Ta ′ of 56 ° C., Mn of 31000, and Mw of 72000.

Production Example 17 (Production of crystalline resin A)
A reaction vessel equipped with a stir bar and a thermometer was charged with 63 parts of tolylene diisocyanate and 100 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 amorphous polyurethane resin [amorphous part c4] having an isocyanate group at the terminal is added to a solution in which 210 parts of [crystalline part b5] is dissolved in 210 parts of MEK, and 4 at 80 ° C. By reacting for a time, an MEK solution of [crystalline resin A6] composed of a crystalline part and an amorphous part was obtained. [Crystalline Resin A6] after removing the solvent had Ta ′ of 54 ° C., Mn of 19000, and Mw of 30000.

Production Example 18 (Production of crystalline resin A)
176 parts of a solution of an amorphous polyurethane resin having an isocyanate group at the end [amorphous part c2] obtained in the same manner as in Production Example 12, and 250 parts of [crystalline part b7] were dissolved in 250 parts of MEK. The solution was put into the solution and reacted 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 Ta ′ of 64 ° C., Mn of 15000, and Mw of 36000.

Production Example 19 (Production of crystalline resin A)
176 parts of a solution of an amorphous polyurethane resin having an isocyanate group at the end [amorphous part c2] obtained in the same manner as in Production Example 12, and 250 parts of [crystalline part b8] were dissolved in 250 parts of MEK. The solution was put into the solution and reacted at 80 ° C. for 4 hours to obtain a MEK solution of [crystalline resin A8] composed of a crystalline part and an amorphous part. After removing the solvent, [Crystalline Resin A8] had Ta ′ of 59 ° C., Mn of 10,000, and Mw of 22,000.

Production Example 20 [Production of Crystalline Resin A]
176 parts of a solution of an amorphous polyurethane resin having an isocyanate group at the end [amorphous part c2] obtained in the same manner as in Production Example 12, and 250 parts of [crystalline part b9] were dissolved in 250 parts of MEK. The solution was put into the solution and reacted at 80 ° C. for 4 hours to obtain a MEK solution of [crystalline resin A9] composed of a crystalline part and an amorphous part. [Crystalline Resin A9] after removing the solvent had Ta ′ of 60 ° C., Mn of 9000, and Mw of 21000.

Production Example 21 [Production of Crystalline Resin A]
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 acrylate of an alcohol having a chain alkyl group: Plenmer VA (manufactured by NOF Corporation), 20 parts of 2-ethylhexyl acrylate, 10 parts of methacrylic acid, 7.5 parts of azobisisobutyronitrile (AIBN), 20 ° C. The monomer solution was prepared by stirring and mixing at, and charged into the 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, [crystalline resin A10], which is a crystalline vinyl resin, was obtained. [Crystalline resin A10] had Ta ′ of 56 ° C., Mn of 68000, and Mw of 89000.

Production Example 22 [Production of Crystalline Resin A]
A reaction vessel equipped with a stir bar and a thermometer was charged with 42 parts of tolylene diisocyanate and 100 parts of MEK. This solution was charged with 31 parts of cyclohexanedimethanol and allowed to react at 80 ° C. for 2 hours. Next, a solution of the amorphous polyurethane resin [amorphous part c5] having an isocyanate group at the terminal is added to a solution in which 126 parts of [crystalline part b10] are dissolved in 140 parts of MEK, and the solution is 4 at 80 ° C. By reacting for a time, an MEK solution of [crystalline resin A11] composed of a crystalline part and an amorphous part was obtained. [Crystalline Resin A11] after removing the solvent had Ta ′ of 52 ° C., Mn of 10,000, and Mw of 22,000.

Production Example 23 [Production of Crystalline Resin A]
A reaction vessel equipped with a stir bar and a thermometer was charged with 32 parts of xylene diisocyanate and 100 parts of MEK. This solution was charged with 47 parts of a bisphenol A · EO 2 molar adduct and allowed to react at 80 ° C. for 2 hours. Next, a solution of the amorphous polyurethane resin [amorphous part c6] having an isocyanate group at the terminal is added to a solution in which 122 parts of [crystalline part b1] are dissolved in 140 parts of MEK, and the solution is 4 at 80 ° C. By reacting for a time, an MEK solution of [crystalline resin A12] composed of a crystalline part and an amorphous part was obtained. [Crystalline Resin A12] after removing the solvent had Ta ′ of 55 ° C., Mn of 14000, and Mw of 30000.

Production Example 24 [Production of Crystalline Resin A]
A reaction vessel equipped with a stir bar and a thermometer was charged with 35 parts of xylene diisocyanate and 100 parts of MEK. This solution was charged with 52 parts of a bisphenol A · EO 2-mol adduct and allowed to react at 80 ° C. for 2 hours. Next, a solution of the non-crystalline polyurethane resin [amorphous part c7] having an isocyanate group at the terminal is added to a solution in which 111 parts of [crystalline part b1] is dissolved in 140 parts of MEK, and the solution is 4 at 80 ° C. By reacting for a time, an MEK solution of [crystalline resin A13] composed of a crystalline part and an amorphous part was obtained. [Crystalline resin A13] after removing the solvent had Ta ′ of 52 ° C., Mn of 18000, and Mw of 38000.

Production Example 25 [Production of Crystalline Resin A]
A non-crystalline polycondensed polyester resin [non-crystalline part c1 ′] obtained in Production Example 11 and 100 parts of MEK were charged into a reaction vessel in which a stir bar and a thermometer were set. This solution was charged with 7 parts of xylene diisocyanate and reacted at 80 ° C. for 2 hours. Next, a solution of the [modified part c1 ′] urethane-modified product [amorphous part c1] having an isocyanate group at the terminal is added to a solution obtained by dissolving 111 parts [crystalline resin b1] in 140 parts of MEK. Then, the mixture was reacted at 80 ° C. for 4 hours to obtain a MEK solution of [crystalline resin A14] composed of a crystalline part and an amorphous part. [Crystalline Resin A14] after removing the solvent had Ta ′ of 55 ° C., Mn of 25000, and Mw of 51000.

Comparative Production Example 1 (Production of Comparative Resin A ′)
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 456 parts (9.0 moles) of bisphenol A · PO2 mole adduct, 321 parts (7.0 moles) of bisphenol A · EO2 mole adduct, terephthalate 247 parts (10.0 mol) of acid and 3 parts of tetrabutoxytitanate were added and reacted at 230 ° C. under a nitrogen stream for 5 hours while distilling off generated water. Next, the reaction was carried out under reduced pressure of 5 to 20 mmHg. When the acid value reached 2, the mixture was cooled to 180 ° C., 74 parts (2.6 mol) of trimellitic anhydride was added, and the reaction was taken out after 2 hours of reaction under normal pressure and sealed. Thus, [Comparative Resin A′1] which is an amorphous resin was obtained. Tg of [Comparative Resin A′1] was 55 ° C., Mn was 3500, and Mw was 7500.

Comparative Production Example 2 (Production of Comparative Resin A ′)
176 parts of a solution of an amorphous polyurethane resin having an isocyanate group at the end [amorphous part c2] obtained in the same manner as in Production Example 12, and 110 parts of [crystalline part b6] were dissolved in 110 parts of MEK. The solution was poured into the solution and reacted at 80 ° C. for 4 hours to obtain a MEK solution of [Comparative Resin A′2] composed of a crystalline part and an amorphous part. Ta ′ of [Comparative Resin A′2] after removing the solvent was 52 ° C., Mn was 6000, and Mw was 13000.

Comparative Production Example 3 (Production of Comparative 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 amorphous polyurethane resin having an isocyanate group at the end [amorphous part c8] was added to a solution in which 17 parts of [crystalline part b1] was dissolved in 17 parts of MEK, and the mixture was heated at 80 ° C. for 4 hours. Reaction was performed to obtain a MEK solution of [Comparative Resin A′3] composed of a crystalline part and an amorphous part. Ta ′ of [Comparative Resin A′3] after removing the solvent was 45 ° C., Mn was 12000, and Mw was 26000.

Comparative Production Example 4 (Production of Comparative Resin A ′)
9 parts of tolylene diisocyanate and 80 parts of MEK were charged into a reaction vessel equipped with a stir bar and a thermometer. This solution was charged with 48 parts of an Mw2000 polyester resin formed from bisphenol A · PO2 molar adduct and isophthalic acid and reacted at 80 ° C. for 2 hours. Next, a solution of the amorphous polyurethane resin [amorphous part c9] having an isocyanate group at the terminal is added to a solution in which 95 parts of [crystalline part b1] is dissolved in 95 parts of MEK, and the mixture is heated at 80 ° C. for 4 hours. Reaction was performed to obtain a MEK solution of [Comparative Resin A′4] composed of a crystalline part and an amorphous part. Ta ′ of [Comparative Resin A′4] after removing the solvent was 55 ° C., Mn was 4400, and Mw was 14000.

Production Example 26 (Production of crystalline resin particles P)
Each of 90 parts of the crystalline resin before kneading is mixed with 10 parts of carnauba wax or 6 parts of paraffin wax and, if necessary, 5 parts of copper phthalocyanine as a colorant, and a biaxial kneader [made by Ikegai Co., Ltd. PCM-30] and the mixture is discharged, and the temperature of the kneaded product is adjusted for 3 hours (Ta′-5) ° C. [Ta ′ is the maximum peak temperature of heat of fusion of each crystalline resin (A)], and then 25 ° C. To obtain kneaded materials (R-1) to (R-17) and comparative kneaded materials (R′-1) to (R′-4). However, the comparative kneaded product (R′-1) was based on the value of Tg instead of Ta ′ of the resin.
Table 1 below shows the component table and the discharge temperature during kneading.

  Next, the mixture was finely pulverized using a supersonic jet crusher, Labo Jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], and then classified by an airflow classifier [MDS-I, manufactured by Nippon Pneumatic Industry Co., Ltd.] Crystalline resin particles (P-1) to (P-17) of the present invention having a D50 of 8 μm and comparative resin particles (P′-1) to (P′-4) were obtained.

Examples 1-17, Comparative Examples 1-4)
Using the crystalline resin particles (P-1) to (P-17) of the present invention and the comparative resin particles (P′-1) to (P′-4), the fixability and heat resistant storage of each are described. The stability and charging characteristics were evaluated and tested by the methods described below. The results are shown in Tables 2 and 3.
In addition, the crystalline resin A and the comparative resin A ′ used in Examples 1 to 17 and Comparative Examples 1 to 4, and the crystalline part (b) and the non-crystalline part (c) constituting them, respectively. The analysis results are shown in Tables 2 and 3.
When (A) or (A ′) has an amorphous part (c), the weight average molecular weight, the glass transition temperature, and the softening point of the amorphous part are as follows when the resin that becomes the amorphous part is produced. A part was extracted and measured. However, when the non-crystalline part had an isocyanate group, the measurement was carried out after adding an equivalent amount of methanol to make the isocyanate content zero.

[Fixability]
After adding 1.0% by weight of Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd.) to the resin particles and mixing well to make uniform, this powder is uniformly placed on the paper surface so as to be 0.6 mg / cm ² (at this time) As a method of placing the powder 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 uniformly placed at the above-described weight density). The MFT (minimum fixing temperature) when passing through the pressure roller under 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 was measured.
In the MFT column “x”, 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 even when force is applied, it is difficult to disperse or does not disperse.

(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 is measured, and the charge amount of the resin particles is calculated by a conventional method. For toners, the higher the negative charge amount, the better the charging characteristics.

  As shown in Tables 2 and 3, the crystalline resin particles (Examples 1 to 17) of the present invention have significantly good results, particularly in terms of MFT, as compared with the resin particles of the comparative example. It was.

  The crystalline resin particles (P) of the present invention are excellent in fixability, sharp in particle size distribution, and excellent in 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 It is useful as electrostatic recording toner, electrostatic printing toner, standard particles for electronic measuring instruments, particles for electronic paper, medical diagnostic carriers, chromatographic fillers, particles for electrorheological fluids, and the like.

Claims (10)

A mixture containing at least a crystalline resin (A) and a wax is prepared by melt-kneading and pulverization, the maximum peak temperature (Ta) of heat of fusion is 40 to 100 ° C., and the ratio of softening point to Ta (softening point / Ta ) Is 0.8 to 1.55, and satisfies the following conditions.
[Condition 1] G ′ (Ta + 20) = 1 × 10 ^{2 to} 5 × 10 ⁵ [Pa]
[Condition 2] G ″ (Ta + 20) = 1 × 10 ^{2 to} 5 × 10 ⁵ [Pa]
[G ′: storage elastic modulus, G ″: loss elastic modulus]   The ratio of loss elastic modulus G ″ (Ta + 30) at (Ta + 30) ° C. to loss elastic modulus G ″ (Ta + 70) at (Ta + 70) ° C. [G ″ (Ta + 30) / G ″ (Ta + 70)] is 0.05 to 50 The crystalline resin particle according to claim 1. The maximum peak temperature (Ta ′) of heat of fusion of the crystalline resin (A) is 40 to 100 ° C., the ratio of the softening point to Ta ′ (softening point / Ta ′) is 0.8 to 1.55, the melting start temperature ( The crystalline resin particles according to claim 1 or 2, wherein X) is within a temperature range of (Ta ± 30) ° C and (A) satisfies the following conditions.
[Condition 3] G ′ (Ta ′ + 20) = 50 to 1 × 10 ⁶ [Pa]
[Condition 4] | LogG ″ (X + 20) −LogG ″ (X) |> 2.0
[G ′: storage elastic modulus [Pa], G ″: loss elastic modulus [Pa]]   In the melt-kneading step, the discharge temperature (Ts) (° C.) of the kneaded product is in the range of Ta ′ <Ts <Ta ′ + 45 [Ta ′: maximum peak temperature (° C.) of melting heat of crystalline resin (A)]. The crystalline resin particle according to claim 1.   The crystalline resin particles according to any one of claims 1 to 4, wherein the content of the crystalline resin (A) is 50% by weight or more.   The crystalline resin (A) is a block resin composed of a crystalline part (b) and an amorphous part (c), the weight average molecular weight of (b) is 2000 to 80000, The ratio of (b) is 50 weight% or more, The crystalline resin particle in any one of Claims 1-5. 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: 6. The crystalline resin particle according to 6.
(B) {-(c)-(b)} n   The crystalline resin particles according to claim 6 or 7, wherein the crystalline part (b) is a resin selected from polyester resins, polyurethane resins, polyurea resins, polyamide resins, polyether resins, and composite resins thereof.   The crystalline resin particle according to any one of claims 6 to 8, wherein the non-crystalline part (c) is a resin selected from a polyester resin, a polyurethane resin, a polyurea resin, a polyamide resin, a polyether resin, and a composite resin thereof. .   The crystalline resin (A) is a crystalline vinyl resin having, as constituent units, a vinyl monomer (m) having a crystalline group and, if necessary, a vinyl monomer (n) having no crystalline group. Any one of the crystalline resin particles.