JP2009215414A - Resin particles - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide resin particles of core-shell type which are excellent in levelling properties during the melting and thermally adhesive properties and have an uniform particle size. <P>SOLUTION: The resin particle is a resin particle (C) of core-shell type which includes: one or more shell layers (S) in a film form comprising a polyurethane resin (U); and one core layer (Q) comprising a resin (composition) (R) mainly composed of a polyester resin (P), wherein the difference in an sp value between (U) and (P) is 0.05-2.0; the weight average molecular weight of (U) is 500-200,000; and the loss modulus G" of viscoelastic properties at 100°C at a frequency of 1 Hz is 10<SP>3</SP>-10<SP>9</SP>dyn/cm<SP>2</SP>. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to resin particles. More specifically, core-shell type resin particles composed of one or more film-like shell layers containing a polyurethane resin and one core layer mainly composed of a polyester resin, and the production thereof The present invention relates to a polyurethane resin emulsion to be used.

Core-shell type resin particles composed of a shell layer and a core layer containing polyurethane resin are known as resin particles having a uniform particle size and excellent electrical characteristics and chemical stability. (See Patent Document 1).
JP 2006-206848 A

However, the resin particles do not have sufficient leveling properties when melted, and unevenness is likely to occur on the surface during baking after electrostatic coating. Further, the heat adhesiveness was insufficient, and it could not be sufficiently adhered to the adherend unless heated to a high temperature.
The present invention has been made in view of the above circumstances in the prior art. That is, an object of the present invention is to provide core-shell type resin particles having a uniform particle size, which are excellent in leveling property at the time of melting and heat adhesiveness.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention provides a core layer of one or more shell layers (S) in the form of a film containing a polyurethane resin (U) and a resin (composition) (R) mainly composed of a polyester resin (P). (Q) is a core-shell type resin particle (C), the difference in sp value between (U) and (P) is 0.05 to 2.0, and the weight average of (U) Resin particles having a molecular weight of 500 to 200,000 and a loss elastic modulus G ″ of viscoelastic properties at 100 ° C. at a frequency of 1 Hz of 10 ³ to 10 ⁹ dyn / cm ² ; and a weight average molecular weight of 500 to 200 , 1,000, and a polyurethane resin (U) having a loss elastic modulus G ″ of a viscoelastic property at 100 ° C. at a frequency of 1 Hz of 10 ³ to 10 ⁹ dyn / cm ² is dispersed in an aqueous medium. Polyurethane resin for manufacturing shell-type resin particles Maruchon;

The resin particles of the present invention that can be obtained using the polyurethane resin emulsion for producing core / shell type resin particles of the present invention have the following effects.
1. Excellent leveling.
2. Good heat adhesion.
3. The particle size is uniform.
4). Good heat storage stability.

The resin particles (C) of the present invention are made of a resin (composition) (R) containing a polyurethane resin (U) and one or more film-like shell layers (S) and a polyester resin (P) as main components. It is a core-shell type resin particle (C) composed of one core layer (Q).
The weight ratio [(S) :( Q)] of the shell layer (S) and the core layer (Q) is (0. 0) from the viewpoint of the particle size uniformity, storage stability, fixability and the like of the resin particles (C). 1: 99.9) to (70:30) is preferable, more preferably (1:99) to (50:50), and particularly preferably (1.5: 98.5) to (30:70). . If the weight of (S) is too small, the blocking resistance may decrease. Moreover, when there is too much weight of (S), the meltability of the resin particle may fall.
(S) may be formed of three or more layers (for example, 3 to 5 layers), but one or two layers are preferable.

  In the present invention, the sp value difference between the polyurethane resin (U) and the polyester resin (P) (the calculation method of the sp value is based on Polymer Engineering and Science, February, 1974, Vol. 14, No. 2 P. 147 to 154) Is 0.05-2.0, preferably 0.07-1.8, more preferably 0.1-1.5. If the difference in sp value is larger than 2.0, the adsorptive power between (U) and (P) is weak and resin particles cannot be formed. If it is smaller than 0.05, (U) and (P) are in phase. It melts and does not become core-shell type resin particles.

The ratio of (P) as the main component in the resin (composition) (R) constituting the core layer (Q) is preferably 60 to 100%, more preferably 70 to 100%.
In the above and the following, “%” means “% by weight” unless otherwise specified.

  The weight average molecular weight (hereinafter referred to as Mw) of the polyurethane resin (U) is usually 500 to 200,000, preferably 800 to 100,000, and more preferably 1,000 to 70,000. From the viewpoint of forming the core / shell type resin particles, it is necessary to be 500 or more, and from the viewpoint of forming the shell layer (S), it is necessary to be 200,000 or less.

Mw in the present invention is measured by gel permeation chromatography (GPC). The conditions for molecular weight measurement by GPC are as follows.
Device (example): HLC-8220 manufactured by Tosoh Corporation
Column (example): Guardcolumn α, TSKgel α-M
Sample solution: 0.125% N, N-dimethylformamide (DMF) solution Injection volume: 100 μl
Flow rate: 1 ml / min Measurement temperature: 40 ° C
Detection apparatus: Refractive index detector Reference material: Tosoh standard polystyrene (TSK standard POLYSYRENE) 12 points (molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)

The loss elastic modulus G ″ of the viscoelastic property at 100 ° C. at a frequency of 1 Hz of the polyurethane resin (U) is usually 10 ³ to 10 ⁹ dyn / cm ² , preferably 5.0 × 10 ^{3 to} 5.0 ×. 10 ⁸ dyn / cm ² , more preferably 10 ⁴ to 10 ⁸ dyn / cm ² From the viewpoint of the meltability and film formation of the resin particles of the shell layer (S), it needs to be 10 ⁹ dyn / cm ² or less. There is.
The loss elastic modulus G ″ can be adjusted by the thermal characteristics such as the glass transition temperature of (U), the molecular weight of (U) and the content of urethane groups. For example, when the glass transition temperature of (U) generally increases. , G ″ increases. In general, G ″ increases as the molecular weight of (U) increases, and G ″ increases as the urethane group content increases.
The loss elastic modulus G ″ is measured using, for example, the following viscoelasticity measuring apparatus.
Apparatus: ARES-24A (Rheometric)
Jig: 25 mm parallel plate Frequency: 1 Hz
Distortion rate: 10%
Temperature increase rate: 5 ° C / min

The glass transition temperature (Tg) of the polyurethane resin (U) is preferably 30 to 100 ° C, more preferably 40 to 90 ° C. The sp value of (U) needs to have a difference in sp value from (P) of 0.05 to 2.0, but specifically, preferably 7 to 16, more preferably 8 to 14. . The softening start temperature is preferably 40 to 110 ° C, more preferably 50 to 100 ° C. The outflow temperature is preferably 60 to 150 ° C, more preferably 70 to 140 ° C. The difference between the outflow temperature and the softening start temperature is preferably 0 to 70 ° C, more preferably 20 to 60 ° C.
When the Tg, softening start temperature, and outflow temperature of (U) are equal to or higher than the lower limits of the respective temperature ranges, it is easy to produce core-shell type resin particles, and conversely, lower than the upper limits of the respective temperature ranges. , (U) has good flexibility. When the difference between the outflow temperature and the softening start temperature is 70 ° C. or less, the sharp melt property of (U) is good.
Tg in the present invention is a value obtained from DSC measurement or flow tester measurement (when it cannot be measured by DSC), and the softening start temperature and the outflow temperature are values obtained from flow tester measurement.

In the case of measurement by DSC, it is measured by a method (DSC method) prescribed in ASTM D3418-82 using DSC20 and SSC / 580 manufactured by Seiko Electronics Industry.
For the flow tester measurement, an elevated flow tester CFT500 type manufactured by Shimadzu Corporation is used. The conditions for the flow tester measurement are as follows.
Load: 30 kg / cm ² , temperature rising rate: 3.0 ° C./min,
Die diameter: 0.50 mm, Die length: 1.0 mm

  In the flow tester measurement, the point A in the flowchart shown in FIG. 1 (the temperature at which the sample begins to deform under a compressive load) is defined as the glass transition temperature (Tg), and the point B (internal void disappears and non-uniform stress distribution is obtained. The temperature of a single transparent body or phase that has a uniform appearance while holding it is the softening start temperature (Ts), point C (the piston is slightly raised due to the thermal expansion of the sample, and then the piston becomes clear again) The temperature at the point of starting to fall) is the outflow start temperature (Tfb), and point D (in the figure, 1/2 (X) of the difference between the outflow end point Smax and the minimum value Smin is obtained, and X and Smin are added) Is the outflow temperature (T1 / 2).

When adjusting the glass transition temperature (Tg), softening start temperature (Ts), and outflow temperature (T1 / 2) of (U), the molecular weight of (U) and / or the monomer composition constituting (U) It can be easily adjusted by changing. As a method for adjusting the molecular weight of (U) (the higher the molecular weight, the higher the temperature), a known method may be used, and examples thereof include adjustment of the monomer charge ratio.
In order to adjust the temperature difference between the glass transition temperature (Tg) and the outflow temperature (T1 / 2), a combination of the molecular weight of (U) and the monomer composition constituting (U) may be appropriately selected. . That is, in general, (T1 / 2) increases or decreases basically by increasing or decreasing the molecular weight of the resin, whereas Tg changes mainly by the composition and structure of the resin and is essentially independent of the molecular weight. Since the influence of the molecular weight is secondary, either the molecular weight or the monomer composition is adjusted using this point.

The content of the carboxyl group [—COOH (molecular weight 45)] in the polyurethane resin (U) is preferably 0.1 to 10% from the viewpoint of the stability of the emulsion in which (U) described later is dispersed in an aqueous medium. More preferably, it is 0.2 to 9%, and particularly preferably 0.3 to 8%.
The carboxyl group may be at least partially neutralized with a base. The base neutralization rate of the carboxyl group is preferably 20 to 100%, more preferably 40 to 100%. Even if the carboxyl group content is a carboxylate group (—COO ⁻ ) in which the carboxyl group is neutralized, the content converted from the carboxylate group to the carboxyl group is defined as the carboxyl group content.

Examples of bases that form carboxyl group neutralized salts include ammonia, monoamines having 1 to 30 carbon atoms, quaternary ammonium, alkali metals (sodium, potassium, etc.), and alkaline earth metals (calcium salts, magnesium salts, etc.). Can be mentioned.
Examples of the monoamine having 1 to 30 carbon atoms include primary and / or secondary amines having 1 to 30 carbon atoms (ethylamine, n-butylamine, isobutylamine, etc.), and tertiary amines having 3 to 30 carbon atoms (trimethylamine, triethylamine). , Lauryl dimethylamine, etc.). Examples of the quaternary ammonium include trialkylammonium having 4 to 30 carbon atoms (such as lauryltrimethylammonium).
Among these, preferred are alkali metals, quaternary ammoniums, and monoamines, more preferred are sodium and monoamines having 1 to 20 carbon atoms, and particularly preferred are tertiary monoamines having 3 to 20 carbon atoms. It is.

In order to contain a carboxyl group (—COOH) and / or a carboxylate group (—COO ⁻ ) in (U), a compound containing a carboxyl group or a carboxylate group and an active hydrogen atom-containing group in the molecule ( It is preferable to use a1) as one of the polyol components constituting (U).
As (a1), a dialkyl alkanoic acid having 6 to 24 carbon atoms can be used. For example, 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid (DMBA), 2,2- Examples thereof include dimethylol heptanoic acid and 2,2-dimethylol octanoic acid. These salts such as salts of amines (alkanolamines such as triethylamine and triethanolamine, morpholine and the like) and / or alkali metal salts (such as sodium salt) can also be used.
Of these, DMPA and DMBA are preferred.

In order to make the carboxyl group content in (U) a desired value, it is preferable to set the charge amount of (a1) during the urethanization reaction according to the following formula.
In the following, the unit of weight is g.
Target carboxyl group content (%) = [weight corresponding to COOH based on the charged amount of (a1) / total weight of resin components] × 100
Here, when creating the polyurethane resin (U) by the method described later,
Total weight of resin component = (prepared weight other than solvent during urethanization reaction) + (total charged weight of extender, crosslinking agent and terminator described later if necessary) + [(U) emulsion is prepared. In case the weight of water acting as an extender)
It is. The weight of water acting as an extender is calculated by the following formula (2 molecules of NCO group and 1 molecule of water react).
Weight of water acting as extender = {number of residual NCO equivalents of prepolymer− (number of equivalents of amine extender + number of equivalents of crosslinker + number of equivalents of terminator)} × 18 ÷ 2
The number of equivalents is the number of moles of the molecule × the average number of functional groups per molecule.

The content of the sulfonic acid anion group (—SO ₃ ⁻ ) in the polyurethane resin (U) is preferably 0.001 to 10%. More preferably, it is 0.002-7%, Most preferably, it is 0.005-5%. When the sulfonate anion group (—SO ₃ ⁻ ) group content is 0.001% or more, the stability of the emulsion obtained by dispersing (U) in an aqueous dispersant is good, and it is 10% or less. The hygroscopicity of (U) does not increase.
In order to contain a sulfonate anion group (—SO ₃ ⁻ ) in (U), a polyol (U) is formed from a compound (a2) containing a sulfonate anion group and an active hydrogen atom-containing group in the molecule. It is preferably used as one of the components.
(A2) has preferably 3 to 50 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 4 to 15 carbon atoms.
As (a2), 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid, 3,4-dihydroxybutanesulfonic acid, 3,6-dihydroxy-2-toluenesulfonic acid and the like can be used. These salts, for example, salts of amines (triethylamine, alkanolamine, morpholine, etc.) and / or alkali metal salts (sodium salt, etc.) can also be used.
Of these, 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid and sodium 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid are preferred.

The content of urea groups [—NH—CO—N <(molecular weight 57)] in the polyurethane resin (U) is preferably 0 to 6%, more preferably 0 to 4% from the viewpoint of thermal characteristics. When the content of urea groups in (U) is 6% or less, the core-shell type resin particles (C) are excellent in heat adhesion.
Further, the content of the urethane group [—NH—COO— (molecular weight 59)] in (U) is preferably 3 to 35%, more preferably 5 to 32%, particularly preferably from the viewpoint of improving solvent resistance. Is 7-30%. When the urethane group content in (U) is 35% or less, the viscosity of (C) is good, and when it is 3% or more, (C) the resin strength is good.

In the present invention, the content of urea groups and the content of urethane groups in (U) are the N atom content determined by a nitrogen analyzer (ANTEK 7000, manufactured by Antec Corporation), and the urethane group and urea group determined by NMR. It is calculated from the ratio.
When amine compounds are used as catalysts and / or additives during the production of (U), it is necessary to subtract them. If the boiling point of the amine compound used is less than 70 ° C, the sample should be at 130 ° C. The method of measuring after drying under reduced pressure for 2 hours is mentioned. Further, when the boiling point of the amine compound used is 70 ° C. or higher, the sample is measured as it is, and the N atom content calculated from the charged amount of the amine compound is subtracted from the quantified N atom content as the N atom content. The method of doing is mentioned.
About NMR measurement, it can carry out by the method as described in "Structural study of polyurethane resin by NMR: Takeda Laboratory report 34 (2), 224-323 (1975)". That is, by measuring H ¹ -NMR, the weight ratio of urea groups and urethane groups is measured from the ratio of the integral amount of hydrogen derived from urea groups near a chemical shift of 6 ppm and the integral amount of hydrogen derived from urethane groups near a chemical shift of 7 ppm. The urea group content and the urethane group content are calculated from the weight ratio and the N atom content.
The urea group content and the urethane group content may be adjusted by appropriately adjusting the composition of raw materials and the charged equivalent.

The isocyanate group content (NCO content) in the polyurethane resin (U) is preferably 0.1% or less, more preferably 0.05% or less, particularly preferably 0% from the viewpoint of the temporal stability of (U). is there.
The isocyanate group content is determined by adding excess (1.1 to 10 times) amine (eg, di-n-butylamine) and stirring in a toluene solution at room temperature (25 ° C.) for 30 minutes. After the reaction, the remaining amine can be measured by back titrating with hydrochloric acid.

The polyurethane resin (U) can be obtained by any manufacturing method as long as it has a difference in sp value from the polyester resin (P), Mw, and loss elastic modulus G ″ at 100 ° C. at a frequency of 1 Hz. For example, it can be obtained by reacting a polyol component and a polyisocyanate component, and if necessary, a chain extender, a crosslinking agent and / or a terminator.
As (U), after reacting the polyol component and the polyisocyanate component so as to be at the end of the isocyanate group, the terminal isocyanate group of the obtained reaction product and a stopper such as monoamine and / or monoalcohol are used. Either a polyurethane resin (U1) having an isocyanate group content of 0.1% or less by reaction, or a polyurethane resin (U2) obtained by reacting a polyol component and a polyisocyanate component so as to be at the hydroxyl group terminal ) Is preferable because it is easy to adjust the content of the urea group in (U) to the above preferable range, and the thermal characteristics are improved.
Further, (U) is preferably used as an emulsion dispersed in an aqueous dispersion when the resin particles (C) of the present invention are produced.

A polyurethane produced by reacting a polyol component and a polyisocyanate component so that (U) is at the end of an isocyanate group, and then, if necessary, a termination reaction using a monoamine and / or a monoalcohol and / or a chain extension reaction. In the case of resin (U1), the production method is, for example, polyisocyanate (b); polyol component (a) other than (a1) and (a2) as a polyol component, and if necessary, a carboxyl group or One type selected from a compound (a1) containing a carboxylate group and an active hydrogen atom-containing group, a compound (a2) containing a sulfonate anion group and an active hydrogen atom-containing group in the molecule, and a terminator (e1) In addition, if necessary, an organic solvent (s) is charged, and urethane pretreatment is performed in one or more stages. After forming limer (p1) and then hydrophilizing (neutralizing) (p1), or while making it hydrophilic, chain extender (f), cross-linking agent (x) and / or terminator (e2) are optionally added. Mixed with an aqueous medium to form a polyurethane resin emulsion, until substantially free of NCO groups (isocyanate groups), chain extension with water or (f), and optionally crosslinking with (x) and / or (e2) It can be produced by performing [Stop reaction]. When the chain extender (f) and the cross-linking agent (x) are not required, the terminator (e2) is used before hydrophilizing (neutralizing) the urethane prepolymer (p1) or after hydrophilizing (neutralizing). The reaction can be carried out until NCO groups (isocyanate groups) are substantially eliminated, and then mixed with an aqueous medium to form a polyurethane resin emulsion. The isocyanate group content of (U1) is preferably 0.1% or less, more preferably 0.05% or less, and particularly preferably 0%.
As a production method of (U1), from the viewpoint of the glass transition temperature, the softening start temperature, and the outflow temperature of (U1), a method using no chain extender (f) and crosslinking agent (x) [that is, an isocyanate group terminal and A method in which the polyol component and the polyisocyanate component are reacted so that the terminal isocyanate group of the reaction product is reacted with a terminator (e2) such as monoamine and / or monoalcohol] is preferable.

  In the case of a polyurethane resin (U2) obtained by reacting a polyol component and a polyisocyanate component so that (U) is a hydroxyl group terminal, for example, a polyol other than polyisocyanate (b), (a1) and (a2) ( a) and, if necessary, a compound (a1) containing a carboxyl group or a carboxylate group and an active hydrogen atom-containing group in the molecule, a compound containing a sulfonic acid anion group and an active hydrogen atom-containing group in the molecule ( A hydroxyl group-terminated urethane prepolymer (p2) can be formed by charging one or more selected from a2) and an organic solvent (s) and performing a urethanization reaction in one or more stages. The isocyanate group content of (p2) is preferably 0.1% or less, more preferably 0.05% or less, and particularly preferably 0%. Next, (p2) is hydrophilized (neutralized) with an amine or the like as necessary to obtain (U2), and then mixed with an aqueous medium to form a polyurethane resin emulsion.

The hydroxyl value of the polyurethane resin (U) is preferably 0 to 200 (mg KOH / g, and the following hydroxyl value units are the same).
When (U) is a polyurethane resin (U1), the hydroxyl value of (U1) is preferably 0 to 2, more preferably 0 to 1, and particularly preferably 0.
When (U) is a polyurethane resin (U2), the hydroxyl value of (U2) is preferably 1 to 200, more preferably 2 to 150, and particularly preferably 3 to 100.
The hydroxyl value of (U) is measured by the method specified in JIS K0070 (1992 edition).
If the hydroxyl value of (U) is 200 mgKOH / g or less, the water resistance of (U) will be good.

As the polyisocyanate (b) for producing the urethane prepolymers (p1) and (p2), isophorone diisocyanate (hereinafter abbreviated as IPDI), hexamethylene diisocyanate (hereinafter, abbreviated as IPDI) from the viewpoint of the stability of the resulting emulsion. Abbreviated as HDI), dicyclohexylmethane diisocyanate [4,4-dicyclohexylmethane diisocyanate (hereinafter abbreviated as hydrogenated MDI)], bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, norbornane diisocyanate [2,6-norbornane diisocyanate], tetramethylene diisocyanate, hexamethylene diisocyanate, phenylene diisocyanate [1,3- and / or 1,4-phenylene diisocyanate], tollet Diisocyanate [2,4- and / or 2,6-tolylene diisocyanate (hereinafter abbreviated as TDI)] and diphenylmethane diisocyanate [2,4′- and / or 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as MDI)] It is preferable to use one or more selected from the group consisting of
Of (b), IPDI, HDI and combinations thereof are more preferable.

Examples of the polyol (a) include polyester polyols, polylactone polyols, polyether polyols, polycarbonate polyols, castor oil-based polyols, low molecular diols, and the like, and two or more kinds may be used in combination.
Of (a), preferred are polyester polyols, polyether polyols, low molecular diols, and combinations thereof.

Examples of the polyester polyol include polyesters of a polyhydric alcohol having a low molecular weight [usually, a number average molecular weight (hereinafter referred to as Mn) of 300 or less] and a polyvalent carboxylic acid or an ester-forming derivative thereof.
Examples of the low molecular weight polyhydric alcohol include 2 to 8 or more aliphatic polyhydric alcohols having a hydroxyl group equivalent of 30 to 150, and 2 to 8 or more polyhydric phenols having a hydroxyl group equivalent of 30 to 150. An alkylene oxide (hereinafter abbreviated as AO) low molar adduct can be used.
Examples of the aliphatic polyhydric alcohol include linear or branched aliphatic dihydric alcohols [(di) ethylene glycol, (di) propylene glycol, 1,2-, 1,3-, 2,3- or 1,4. -Butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,12-dodecanediol, etc. ], Alicyclic dihydric alcohol [low molecular diol having a cyclic group, such as described in JP-B No. 45-1474], aliphatic trihydric alcohol [glycerin, trimethylolpropane, trialkanolamine, etc.], and fat Alcohols of 4 to 8 or higher valences [pentaerythritol, diglycerin, triglycerin, dipe Data erythritol, sorbitol, sorbitan, and the like is sorbide, etc.].
Examples of the polyhydric phenol to which AO is added include hydroquinone, catechol, resorcin, bisphenol A, bisphenol S, bisphenol F, and the like.

  Examples of the polyvalent carboxylic acid or an ester-forming derivative thereof include aliphatic dicarboxylic acids having 2 to 20 carbon atoms (succinic acid, adipic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, etc.), alicyclic dicarboxylic acids ( Dimer acid, etc.), aromatic dicarboxylic acids having 8 to 20 carbon atoms (terephthalic acid, isophthalic acid, phthalic acid, etc.) and trivalent or higher polycarboxylic acids (trimellitic acid, pyromellitic acid, etc.), anhydrous Products such as succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, these acid halides (such as adipic acid dichloride), their low molecular weight alkyl esters (such as dimethyl succinate and dimethyl phthalate) and These combination etc. are mentioned.

  Specific examples of the polyester polyol include, for example, polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene hexa Methylene adipate diol, polydiethylene adipate diol, poly (polytetramethylene ether) adipate diol, poly (3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene sebacate Diol, polyneopentyl terephthalate diol, etc. It is. Moreover, the polyester polyol which consists of the below-mentioned aliphatic polyether polyol or aromatic ring containing polyether polyol and polyhydric carboxylic acid is also mentioned.

A polylactone polyol is a polyaddition product of a lactone to a low molecular weight polyhydric alcohol. As the lactone, a lactone having 4 to 12 carbon atoms can be used, and examples thereof include 4-butanolide, 5-pentanolide, and 6-hexanolide. It is done.
Examples of the polylactone polyol include polycaprolactone diol, polyvalerolactone diol, and polycaprolactone triol.

Examples of polyether polyols include aliphatic polyether polyols and aromatic ring-containing polyether polyols.
Examples of the aliphatic polyether polyol include an aliphatic low molecular weight active hydrogen atom-containing compound (a divalent to octavalent or higher aliphatic polyhydric alcohol having a hydroxyl group equivalent of 30 to 150, and primary or 2 as an active hydrogen atom-containing group. AO adduct of a compound containing a secondary amino group can be used.
Examples of the aliphatic polyhydric alcohol to which AO is added include those described above.
Examples of the compound containing a primary or secondary amino group to which AO is added include alkyl (1 to 12 carbon atoms) amine (monomethylamine, monoethylamine, monobutylamine, monooctylamine, etc.), and (poly) alkylenepolyamine (C2-C6 of alkylene group, C1-C4 of alkylene group, C2-C5 of polyamine) (diethylenetriamine, triethylenetetramine, etc.) etc. are mentioned.

Aromatic ring-containing polyether polyols include AO adducts of aromatic low molecular weight active hydrogen atom-containing compounds (2- to 8-valent or higher polyhydric phenols and aromatic amines having a hydroxyl equivalent weight of 30 to 150) it can.
Examples of the polyhydric phenol to which AO is added include those described above. Aromatic amines include aniline and phenylenediamine.

  As AO used for manufacture of an AO adduct, C2-C12 or more AO, for example, ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-, 2, Examples include 3- or 1,3-butylene oxide, tetrahydrofuran (THF), α-olefin oxide, styrene oxide, epihalohydrin (such as epichlorohydrin), and combinations of two or more of these (random and / or block).

Specific examples of the aliphatic polyether polyol include polyoxyethylene polyol [polyethylene glycol and the like], polyoxypropylene polyol [polypropylene glycol and the like], polyoxyethylene / propylene polyol, polytetramethylene ether glycol and the like.
As the aromatic ring-containing polyether polyol, a polyol having a bisphenol skeleton, for example, an EO2-20 mol adduct of bisphenol A [an EO2 mol adduct of bisphenol A, an EO4 mol adduct of bisphenol A, an EO6 mol adduct of bisphenol A, Bisphenol A EO 8 mol adduct, bisphenol A EO 10 mol adduct, bisphenol A EO 20 mol adduct, etc.] and bisphenol A PO 2-20 mol adduct [bisphenol A PO2 mol adduct, bisphenol A PO3 mol adduct Adduct, PO5 molar adduct of bisphenol A, etc.], and EO or PO adduct of resorcin.

  As the polycarbonate polyol, one or more alkylene diols having an alkylene group having 4 to 12 carbon atoms, preferably 6 to 10 carbon atoms, more preferably 6 to 9 carbon atoms, and a low molecular carbonate compound (for example, By condensing the alkyl group from a dialkyl carbonate having 1 to 6 carbon atoms, an alkylene carbonate having an alkylene group having 2 to 6 carbon atoms, and a diaryl carbonate having an aryl group having 6 to 9 carbon atoms while carrying out a dealcoholization reaction. The polycarbonate diol etc. which are manufactured are mentioned.

The castor oil-based polyol includes castor oil and castor oil modified with polyol or AO.
Modified castor oil can be produced by transesterification of castor oil and polyol and / or AO addition. Castor oil-based polyols include castor oil, trimethylolpropane-modified castor oil, pentaerythritol-modified castor oil, EO (4 to 30 mol) adduct of castor oil, and the like.

  Examples of the low molecular diol include alkylene diols having an alkylene group having 2 to 12 carbon atoms, such as linear alkylene diols (eg trimethylene diol, tetramethylene diol, pentamethylene diol, hexamethylene diol, heptamethylene diol, octane diol, Methylene diol, nonamethylene diol, etc.) and branched alkylene diols (eg 1,2-propylene glycol, neopentyl glycol, 2-methylpentanediol, 3-methylpentanediol, 2-methylhexanediol, 3-methylhexanediol, 2 -Methylheptanediol, 3-methylheptanediol, 4-methylheptanediol, 2-methyloctanediol, 3-methyloctanediol and 4-methyloctanediol ) It is. Particularly preferred are tetramethylene diol, pentamethylene diol, hexamethylene diol and nonamethylene diol for linear ones, 1,2-propylene glycol, neopentyl glycol, 3-methyl-1,5-pentane for branched ones. Diol and 2-methyl-1,8-octanediol.

Examples of the terminator (e1) include monoalcohols having 1 to 8 carbon atoms (such as methanol, ethanol, isopropanol, butanol, cellosolves, and carbitols), and monoamines having 1 to 10 carbon atoms (monomethylamine, monoethylamine, monobutylamine, dioxygen) Butylamine, monooctylamine, monoethanolamine, diethanolamine, etc.).
Of these, monoethylamine, monobutylamine and monoethanolamine are preferred.

The production of the urethane prepolymers (p1) and (p2) is preferably carried out at a reaction temperature of 20 ° C. to 180 ° C., more preferably 60 ° C. to 150 ° C., and the reaction time is preferably 2 to 20 hours. The production of (p1) and (p2) can be carried out in the presence or absence of an organic solvent (s) substantially nonreactive with NCO groups.
In the urethanization reaction, in order to promote the reaction, a catalyst used in a normal urethane reaction may be used if necessary. Catalysts include amine catalysts such as triethylamine, N-ethylmorpholine, triethylenediamine and cycloamidines described in US Pat. No. 4,524,104 [1,8-diaza-bicyclo (5,4,0) undecene-7. (San Apro / Manufacturing, DBU) etc.]; tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate and tin octylate; titanium-based catalysts such as tetrabutyl titanate; bismuth-based catalysts such as bismuth nitrate and triphenylbismuth .

Polyamines can be used as the chain extender (f) and the crosslinking agent (x) used as necessary for the production of the polyurethane resin (U1).
Examples of the polyamine include aliphatic polyamines having 2 to 30 carbon atoms and aromatic polyamines having 6 to 30 carbon atoms.
Aliphatic polyamines include, for example, alkylene diamines such as ethylenediamine, trimethylenediamine and hexamethylenediamine; polyalkylenepolyamines such as diethylenetriamine; cyclic polyamines such as dicyclohexylmethanediamine and isophoronediamine; piperazine, N-aminoethylpiperazine and heterocyclic Polyamines. Examples of the aromatic polyamine include phenylenediamine, tolylenediamine, diethyltolylenediamine, diphenylmethanediamine, diphenyletherdiamine, polyphenylmethanepolyamine, and xylylenediamine.
The amount of (f) and (x) used is preferably from 0 to 1 for the primary and secondary amino groups of (f) and (x) with respect to 1 equivalent of the isocyanate group remaining in the prepolymer (U1). 0.0 equivalent, more preferably 0.2 to 0.6 equivalent.

  As the terminator (e2), primary monoamines having 1 to 10 carbon atoms, secondary monoamines, monoalcohols having 1 to 8 carbon atoms, and the like can be used. Monoethylamine, monobutylamine, isopropanol and n-butanol are preferred.

The production method of the resin particles (C) of the present invention is not particularly limited. For example, an emulsion of a polyurethane resin (U) and a resin (composition) (R) mainly composed of a polyester resin (P) or an organic solvent thereof And the resin (composition) (R) or an organic solvent solution thereof is dispersed in the emulsion of (U) to form resin particles from (R) in the emulsion of (U), An aqueous dispersion of the core-shell type resin particles (C) was obtained by attaching (U) to the surface of the resin particles of (R) and further forming a film of (U), and further obtaining (C ) Containing an aqueous dispersion.
When the shell layer (S) of the resin particles (C) is two or more layers, the aqueous dispersion containing the obtained core-shell type resin particles and the polyurethane resin emulsion containing (U) are mixed. It is sufficient to repeat the operation.

In the preparation of the polyurethane resin emulsion containing (U) and an aqueous medium, the temperature during mixing and reaction of (U) and the aqueous medium is preferably 10 to 60 ° C, more preferably 20 to 40 ° C. .
The amount of the aqueous medium used is an amount such that the content of (U) is preferably 5 to 60%, more preferably 8 to 50%, based on the weight of the obtained emulsion.

  Also, by preparing a solution of (p1) or (p2) in the presence of the organic solvent (s), further preparing an organic solvent solution of (U1) or (U2), and dispersing it in an aqueous medium , (U) polyurethane resin emulsion can also be produced.

As the hydrophilic solvent (s) used in the above reaction and contained in the aqueous medium, those which are substantially non-reactive with NCO groups and those which are hydrophilic (water miscible) (acetone, ethyl methyl ketone) Ketones, esters, ethers, amides, alcohols). Of these, acetone and ethyl methyl ketone are preferred.
The weight ratio of water to the hydrophilic solvent in the aqueous medium is preferably 100/0 to 50/50, more preferably 100/0 to 70/30.
When a hydrophilic solvent is used in (s) and / or the aqueous medium, these may be distilled off as necessary after the production of the polyurethane resin emulsion.

An apparatus for emulsifying and dispersing the urethane prepolymers (p1) and (p2) or their solutions in an aqueous medium is not particularly limited, and examples thereof include an emulsifier of the following method.
1) Vertical stirring method
2) Rotor-stator system [for example, “Ebara Milder” (manufactured by Ebara Corporation)]
3) Line mill method [eg line flow mixer],
4) Static tube mixing type [for example, static mixer],
5) Vibration type [for example, “VIBRO MIXER” (manufactured by Chilling Industries Co., Ltd.)]
6) Ultrasonic impact type [for example, ultrasonic homogenizer],
7) High-pressure impact type [for example, Gaurin homogenizer (Gaurin)],
8) Emulsification [for example, membrane emulsification module],
9) Centrifugal thin film contact type [for example, film mix].
Of these, 1), 2), 5), 8) and 9) are preferred.
If necessary, when performing chain extension with the chain extender (f), cross-linking with the cross-linking agent (x) and / or termination of the reaction with the terminator (e2), a continuous emulsifier [preferably 2 above], for example, Ebara Milder] is used to disperse the prepolymer (p1) in an aqueous medium, and then using a batch emulsifier [preferably 1) vertical stirring method] (f), (x) and / or ( It is preferred to add e2) and mix to react with (p1).

The pH of the polyurethane resin emulsion for producing core / shell type resin particles of the present invention in which the polyurethane resin (U) is dispersed in an aqueous dispersion medium is preferably 6 to 10, more preferably 7 to 9. The pH is measured with pHMeter M-12 (Horiba Seisakusho).
The viscosity of the polyurethane resin emulsion is preferably 20 to 1,000 mPa · s, more preferably 25 to 500 mPa · s. The viscosity can be measured with a BL type viscometer at 25 ° C.
The particle diameter of the polyurethane resin in the polyurethane resin emulsion is preferably 10 to 250 nm, more preferably 20 to 220 nm. If it is this range, the daily stability of an emulsion is good.

  The core-shell type resin particle (C) of the present invention is a resin (composition) (R) that forms a core in a polyurethane resin emulsion obtained by dispersing (U) in an aqueous dispersion medium, or an organic solvent solution thereof. Can be produced through a step of forming resin particles of (R) in the polyurethane resin emulsion and attaching the polyurethane resin (U) particles to the surface of the resin particles of (R). When the difference in sp value between (U) and (P) is 0.05 to 2.0 and the Mw of (U) is 500 to 200,000, usually, (R) is formed into a film. Core-shell type resin particles having a shell layer (S) of 2 are obtained.

Resin (composition) (R) has polyester resin (P) as a main component.
The resin other than (P) that may be contained in (R) may be a thermoplastic resin or a thermosetting resin. For example, polyurethane resin, vinyl resin, epoxy resin, polyamide resin , Polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin and the like. Two or more of these resins may be used in combination.
(P) is preferably a polyester of a polyhydric alcohol and a polyvalent carboxylic acid or an ester-forming derivative thereof.
As the polyhydric alcohol, the AO low-mole adducts of the above-mentioned aliphatic polyhydric alcohol and polyhydric phenol can be used. As the polyvalent carboxylic acid or its ester-forming derivative, those described above can be used. (P) may use 2 or more types together. When using 2 or more types of (P) together, the sp value and Tg employ an average value based on the weight ratio.

The glass transition temperature (Tg) of (P) is preferably 20 to 80 ° C, more preferably 30 to 70 ° C. When the Tg is 20 ° C. or higher, the heat resistant storage stability is good, and when it is 80 ° C. or lower, the viscosity is excellent.
The sp value of (P) needs to have a difference in sp value from (U) of 0.05 to 2.0, but specifically, it is preferably 7 to 16, more preferably 8 to 14. .
Mn of (P) is preferably 1,000 to 50,000, more preferably 1,500 to 30,000, and particularly preferably 2,000 to 10,000. Mn can be measured by GPC in the same manner as Mw. When Mn is 1,000 or more, the resin strength is improved, and when it is 50,000 or less, the viscosity is excellent.

  Examples of the organic solvent used when preparing the organic solvent solution of (P) include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic or alicyclic hydrocarbon solvents such as n-hexane, n-heptane, and cyclohexane; Ester solvents such as ethyl acetate and butyl acetate; ether solvents such as diethyl ether, tetrahydrofuran and dioxane; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone; methanol, ethanol, n-propanol and isopropanol N-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, benzyl alcohol and other alcohol solvents; dimethylformamide, dimethylacetamide and other amide solvents; N-methylpyrrolidone and other heterocyclic rings Compound solvent, as well as mixed solvents of two or more thereof.

When obtaining an aqueous dispersion from the polyurethane resin emulsion of the present invention in which the polyurethane resin (U) is dispersed in an aqueous dispersion medium and the resin (composition) (R) or an organic solvent solution thereof, a dispersion apparatus is used. May be.
The dispersing apparatus is not particularly limited as long as it is generally marketed as an emulsifier or a dispersing machine. For example, a homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK auto homomixer (specialized chemical industry) Etc.) batch type emulsifiers, Ebara Milder (made by Aihara Seisakusho Co., Ltd.), TK Philmix, TK Pipeline Homo Mixer (made by Special Machine Industries), Colloid Mill (made by Shinko Pantech Co., Ltd.), Thrasher, Continuous emulsifiers such as Trigonal wet milling machine (Mitsui Miike Chemical Co., Ltd.), Captron (Eurotech Co., Ltd.), Fine Flow Mill (Pacific Kiko Co., Ltd.), Microfluidizer (Mizuho Kogyo Co., Ltd.), Nanomizer ( Nanomizer), APV Gaurin (Gaurin) and other high pressure emulsifiers, Membrane Emulsifier (Chilling Industries) and other membrane emulsifiers Vibro Mixer (Hiyaka Kogyo) vibrating emulsifier such as, ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson Co., Ltd.). Among these, APV Gaurin, homogenizer, TK auto homomixer, Ebara milder, TK fill mix, and TK pipeline homomixer are preferable from the viewpoint of homogenizing the particle diameter.

  The core-shell type resin particles (C) are prepared by preparing an aqueous dispersion from a polyurethane resin emulsion obtained by dispersing (U) in an aqueous dispersion medium and (R) or an organic solvent solution thereof. After preparing the liquid mixture which contains (C) in it, it can isolate by removing solvents, such as an organic solvent and water, from a liquid mixture.

  Stabilize an aqueous dispersion of polyurethane resin emulsion (R) or an organic solvent solution thereof in which polyurethane resin (U) is dispersed in an aqueous dispersion medium, and apply the resin (composition) (R) to the surface of the resin particles. In order to make it easy for the particles of (U) to adhere, an emulsifier and a dispersant may be contained in the mixed solution. As the emulsifier and dispersant, a known surfactant (k) can be used.

As the surfactant (k), known ones can be widely used. Anionic surfactant (k-1), cationic surfactant (k-2), amphoteric surfactant (k-3), non-surfactant An ionic surfactant (k-4) etc. are mentioned. (K) may use 2 or more types together.
Examples of the anionic surfactant (k-1) include carboxylic acids or salts thereof, sulfate esters, carboxymethylated salts, sulfonates, phosphate esters, and the like.
Examples of the cationic surfactant (k-2) include quaternary ammonium salt surfactants and amine salt surfactants.
Examples of the amphoteric surfactant (k-3) include a carboxylate type amphoteric surfactant, a sulfate ester type amphoteric surfactant, a sulfonate type amphoteric surfactant, and a phosphate ester type amphoteric surfactant. Can be mentioned.
Examples of the nonionic surfactant (k-4) include an AO addition type nonionic surfactant and a polyvalent alcohol type nonionic surfactant.
Specific examples of these surfactants (k) include those described in JP-A-2006-206848.
The content of the surfactant (k) is preferably 0.01 to 30%, more preferably 0.1 to 20%.

In the core layer (Q) from the resin (composition) (R), additives (pigments, fillers, antistatic agents, colorants, release agents, charge control agents, ultraviolet absorbers, antioxidants, blocking agents) An inhibitor, a heat stabilizer, a flame retardant, etc.). As a method of adding the additive, it may be mixed when forming the aqueous resin dispersion in the aqueous medium, but after mixing the polyester resin (P) and the additive in advance, the mixture is added to the aqueous medium. In addition, it is more preferable to disperse.
In addition, the additive does not necessarily have to be mixed when the particles are formed in the aqueous medium, and may be added after the particles are formed. For example, after forming particles not containing a colorant, a colorant can be added by a known dyeing method, or the additive can be impregnated with an organic solvent and / or a plasticizer.
The additive may be contained in a polyurethane resin emulsion in which (U) is dispersed in an aqueous dispersion medium, and may be contained in the shell layer (S).

In addition, it is preferable to contain the wax (c) together with the polyester resin (P) in (Q) because the heat-resistant storage stability is further improved. Further, a modified wax (d) grafted with a vinyl polymer chain may be contained.
The content of (c) in the core layer (Q), that is, the resin (composition) (R) is preferably 20% or less, more preferably 1 to 15%. The content of (d) is preferably 10% or less, more preferably 0.5 to 8%. The total content of (c) and (d) is preferably 25% or less, more preferably 1 to 20%.

The wax (c) is dispersed after being previously melt-kneaded with the modified wax (d) in the absence of a solvent and / or heat-dissolved and mixed in the presence of a solvent.
Examples of the wax (c) include polyolefin wax, paraffin wax, carbonyl group-containing wax, and a mixture thereof. Among these, paraffin wax is particularly preferable. Examples of the paraffin wax include petroleum-based waxes whose main component is a linear saturated hydrocarbon having a melting point of 50 to 90 ° C. and a carbon number of 20 to 36.
Further, from the viewpoint of releasability, Mn in (c) is preferably 400 to 5000, more preferably 1000 to 3000, and particularly 1500 to 2000. In the above and below, the Mn of the wax is measured using GPC (solvent: orthodichlorobenzene, reference material: polystyrene).

  The wax (c) is dispersed in the resin (composition) (R) after being melt-kneaded in the absence of a solvent and / or heat-dissolved and mixed in the presence of a solvent with the modified wax (d) grafted with a vinyl polymer chain. Preferably it is done. By the coexistence of the modified wax (d) during the wax dispersion treatment by this method, the wax base portion of (d) is efficiently adsorbed on the surface or partly entangled in the wax matrix structure, The affinity between the surface of the wax (c) and the polyester resin (P) is improved, and (c) can be more uniformly encapsulated in the resin (composition) (R), and the dispersion state can be easily controlled. Become.

  The modified wax (d) is obtained by grafting a vinyl polymer chain onto the wax. Examples of the wax used in (d) include the same waxes as the wax (c), and preferred ones are also the same.

The amount of the wax component (including the unreacted wax) in the modified wax (d) is preferably 0.5 to 99.5%, more preferably 1 to 80%, particularly preferably 5 to 50%, and most preferably 10. ~ 30%. The Tg of (d) is preferably 40 to 90 ° C., more preferably 50 to 80 ° C., from the viewpoint of heat resistant storage stability of the resin particles.
Mn of (d) is preferably 1500 to 10,000, particularly 1800 to 9000.

The modified wax (d) is prepared by, for example, dissolving or dispersing the wax (c) in an organic solvent (for example, toluene or xylene), heating to 100 to 200 ° C., and then converting the vinyl monomer to a peroxide initiator (benzoyl peroxide, It is obtained by distilling together with ditertiary butyl peroxide, tertiary butyl peroxide benzoate, etc.) and polymerizing, and then distilling off the organic solvent.
The amount of the peroxide-based initiator in the synthesis of the modified wax (d) is preferably 0.2 to 10%, more preferably 0.5 to 5%, based on the total weight of the raw material (d).

As the peroxide polymerization initiator, an oil-soluble peroxide polymerization initiator and a water-soluble peroxide polymerization initiator are used.
Examples of the oil-soluble peroxide polymerization initiator include acetylcyclohexylsulfonyl peroxide, isobutyryl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, 2,4-dichlorobenzoyl peroxide, and t-butyl peroxide. Oxybivalate, 3,5,5-trimethylhexanonyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, stearoyl peroxide, propionitrile peroxide, succinic acid peroxide, acetyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, parachlorobenzoyl peroxide, t-butylperoxyisobuty , T-butylperoxymaleic acid, t-butylperoxylaurate, cyclohexanone peroxide, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-dibenzoylperoxyhexane, t- Butyl peroxyacetate, t-butyl peroxybenzoate, diisobutyl diperoxyphthalate, methyl ethyl ketone peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, t-butyl cumylper Oxide, t-butyl hydroperoxide, di-t-butyl peroxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, pinane hydroperoxide, 2,5-dimethylhexane-2,5- Hydroperoxide and cumene peroxide.

  Examples of the water-soluble peroxide polymerization initiator include hydrogen peroxide, peracetic acid, ammonium persulfate, potassium persulfate, and sodium persulfate.

As a method of mixing the wax (c) and the modified wax (d), [1] a method of melting and kneading at a temperature higher than the melting point of each, [2] a method of dissolving or suspending (c) and (d) in an organic solvent. After turbidity, precipitation in liquid by cooling crystallization, solvent crystallization, etc., or precipitation in gas by spray drying, etc. [3] Dissolving or suspending (c) and (d) in organic solvent And a method of mechanically wet pulverizing with a disperser. Among these, the method [2] is preferable.
As a method of dispersing the wax (c) and the modified wax (d) in the resin (composition) (R), (c), (d), and (R) may be combined with an organic solvent solution or a dispersion, respectively. Then, a method of mixing them with each other can be mentioned.

  In the present invention, the resin particles (C) are dispersed in a polyurethane resin (U) emulsion in which a resin (composition) (R) containing a polyester resin (P) as a main component or an organic solvent solution thereof is dispersed ( By forming the resin particles from (R) in the emulsion of (U), the particles of (U) are adhered to the surface of the resin particles of (R), and the core is formed by further coating (U). In the case where an aqueous dispersion of shell-type resin particles (C) is obtained and obtained by a production method in which the aqueous medium is removed from the aqueous dispersion, when the organic solvent solution of (R) is used, the organic solvent is contained in the aqueous dispersion. Preferably, 10 to 50% (especially 20 to 40%) is used, and the solvent of (U) is converted into an organic solvent only by removing the solvent at 40 ° C. or less, preferably 1% or less (particularly 0.5% or less). Dissolved into a film When aqueous dispersion of resin particles [core layer (Q)] of (R) on the surface of the (U) resin particles coating formed of (C) is obtained in many cases. However, even when the coating of (U) is not formed or when the coating of at least part of (U) is formed, the smoothness of the coating on the surface of the resin particles (C) is further improved. Therefore, when the following heating operation is performed, the shell layer (S) on the surface of the core layer (Q) can be further smoothed.

  In this case, the solid content [content of components other than water and organic solvent] in the aqueous resin dispersion is preferably adjusted to 1 to 50%, more preferably 5 to 30%. The organic solvent content (measured by gas chromatography) at this time is preferably 2% or less, more preferably 1% or less, and particularly preferably 0.5% or less. The heating conditions are not particularly limited as long as (U) is melted, but for example, under stirring, preferably 40 to 100 ° C, more preferably 60 to 90 ° C, particularly preferably 60 to 80 ° C. A method of heating for 1 to 300 minutes is preferable. Below 40 ° C, there is almost no change in surface smoothness. Moreover, when heat-processing at the temperature exceeding 100 degreeC, a shell may peel from a core.

The resin particles (C) can be obtained by removing the aqueous medium from the aqueous resin dispersion. As a method of removing the aqueous medium,
[1] A method of drying an aqueous resin dispersion under reduced pressure or normal pressure [2] A method of solid-liquid separation using a centrifuge, a spacula filter, a filter press, etc., and drying the resulting powder [3] Aqueous resin dispersion Freezing and drying the body (so-called lyophilization)
Etc. are exemplified.
In the above [1] and [2], when the obtained powder is dried, it can be performed using a known facility such as a fluidized bed dryer, a vacuum dryer, or a circulating dryer.
If necessary, it can be classified using an air classifier or the like to obtain a predetermined particle size distribution.

From the viewpoint of the particle size uniformity of the resin particles, powder flowability, storage stability, etc., the surface of the core layer (Q) is preferably 70% or more, more preferably 80% or more, particularly preferably 90% or more. It is good to be covered with the shell layer (S). The surface coverage can be determined based on the following equation from image analysis of an image obtained with a scanning electron microscope (SEM).
Surface coverage (%) = [area of the portion covered with (S) / area of the portion covered with (S) + area of the exposed portion of (Q)] × 100

The volume average particle size of the resin particles (C) of the present invention is preferably 1 to 20 μm. More preferably, it is 2-15 micrometers.
The volume average particle size is determined by a laser type particle size distribution measuring device [for example, trade name: LA-920 (manufactured by Horiba Seisakusho) or trade name: Multisizer III (manufactured by Coulter)], and laser Doppler method as an optical system It can be measured using ELS-800 (Otsuka Electronics Co., Ltd.) used.
Further, the coefficient of variation of the volume distribution of (C) is preferably 30% or less, and more preferably 0.1 to 15%, from the viewpoint of particle size uniformity.
Further, from the viewpoint of particle size uniformity, the value of [volume average particle size / number average particle size] is preferably 1.0 to 1.4, and more preferably 1.0 to 1.2.
The volume average particle diameter and the number average particle diameter can be measured simultaneously with Multisizer III (manufactured by Coulter).

The resin particle (C) of the present invention can impart desired irregularities to the particle surface by changing the coverage of the surface of the core layer (Q) by the shell layer (S). Generally, when the coverage of the (Q) surface by (S) increases, the BET specific surface area described below increases and the surface average centerline roughness Ra described below decreases.
When it is desired to improve the powder fluidity, the BET specific surface area of (C) is preferably 0.5 to 5.0 m ² / g. The BET specific surface area of the present invention is measured using a specific surface area meter such as QUANTASORB (manufactured by Yuasa Ionics) (measurement gas: He / Kr = 99.9 / 0.1 vol%, calibration gas: nitrogen).
Similarly, from the viewpoint of powder fluidity, the surface average center line roughness Ra of (C) is preferably 0.01 to 0.8 μm. Ra is a value obtained by arithmetically averaging the absolute value of the deviation between the roughness curve and its center line, and can be measured by, for example, a scanning probe microscope system (manufactured by Toyo Technica).

  The shape of the resin particles (C) of the present invention is preferably spherical from the viewpoint of powder fluidity, melt leveling properties and the like. The average circularity is preferably 0.95 to 1.00. The average circularity is more preferably 0.96 to 1.0, and particularly preferably 0.97 to 1.0. The average circularity is a value obtained by optically detecting particles and dividing by the circumference of an equivalent circle having the same projected area. Specifically, it is measured using a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation). In a predetermined container, 100 to 150 ml of water from which impure solids have been removed in advance is added, and 0.1 to 0.5 ml of a surfactant (Dry Well; manufactured by Fuji Photo Film Co., Ltd.) is added as a dispersant. Add about 1-9.5g. The suspension in which the sample is dispersed is subjected to a dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser (Ultrasonic Cleaner Model VS-150; manufactured by Wellboclear) to a dispersion concentration of 3,000 to 10,000 / μL. To measure the shape and distribution of the resin particles.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the following description, “parts” indicates parts by weight.

Production Example 1 [Production of polyurethane resin (U-1) solution]
A polyester diol composed of 3-methyl-1,5-pentanediol having a hydroxyl value of 113 and adipic acid (trade name “Kuraray polyol P-1010” manufactured by Kuraray Co., Ltd.) was added to a reactor equipped with a stirrer and a thermometer. 57 parts, 17 parts of 1,9-nonanediol, 43 parts of 2,2-dimethylolpropionic acid, 6 parts of sodium 3- (2,3-dihydroxypropoxy) -1-propanesulfonate, and 127 parts of isophorone diisocyanate Parts, 3 parts of triethylamine and 250 parts of acetone were charged while introducing nitrogen. Thereafter, the mixture was heated to 50 ° C. and subjected to urethanization reaction for 15 hours to produce an isocyanate group-terminated urethane resin solution. Next, 11 parts of n-butylamine and 29 parts of triethylamine were added and reacted at 50 ° C. for 3 hours to obtain a polyurethane resin solution. The NCO content at the end of the reaction was 0%.

Production Example 2 [Production of polyurethane resin (U-2) solution]
In a reactor equipped with a stirrer and a thermometer, 88 parts of neopentyl glycol, 4.5 parts of 2,2-dimethylolpropionic acid, sodium 3- (2,3-dihydroxypropoxy) -1-propanesulfonate 0.5 part, 157 parts hexamethylene diisocyanate, 250 parts acetone, and nitrogen were introduced. Thereafter, the mixture was heated to 50 ° C. and subjected to urethanization reaction for 10 hours to produce an isocyanate group-terminated urethane resin solution. Next, 8 parts of isopropanol and 4 parts of triethylamine were added and reacted at 50 ° C. for 7 hours to obtain a polyurethane resin solution. The NCO content at the end of the reaction was 0%.

Production Example 3 [Production of polyurethane resin (U-3) solution]
In a reactor equipped with a stirrer and a thermometer, 100 parts of ethylene oxide adduct of bisphenol A having a hydroxyl value of 276 (manufactured by Sanyo Chemical Industries, Ltd., trade name “New Pole BPE-40”), 2,2- 43 parts of dimethylolpropionic acid, 5 parts of sodium 3- (2,3-dihydroxypropoxy) -1-propanesulfonate, 64 parts of isophorone diisocyanate, 38 parts of hexamethylene diisocyanate, 3 parts of triethylamine and 250 parts of acetone Was charged while introducing nitrogen. Thereafter, the mixture was heated to 50 ° C. and subjected to a urethanization reaction over 15 hours. The NCO content at the end of the urethanization reaction was 0%. Next, 29 parts of triethylamine was added and mixed to obtain a hydroxyl group-terminated urethane resin solution.

Production Example 4 [Production of polyurethane resin (U-4) solution]
To a reactor equipped with a stirrer and a thermometer, 169 parts of polyester diol (manufactured by Toyokuni Oil Co., Ltd., trade name “HS2F-136P”) composed of neopentyl glycol having a hydroxyl value of 112 and phthalic anhydride, 2, 2 -17 parts dimethylolpropionic acid, 1 part sodium 3- (2,3-dihydroxypropoxy) -1-propanesulfonate, 63 parts isophorone diisocyanate, 13 parts triethylamine and 250 parts acetone, nitrogen was introduced While charging. Thereafter, the mixture was heated to 50 ° C. and subjected to urethanization reaction for 15 hours to obtain a hydroxyl group-terminated urethane resin solution. The NCO content at the end of the urethanization reaction was 0%.

Comparative Production Example 1 [Production of Prepolymer Solution for Comparative Polyurethane Resin (U′-5)]
A polyester diol composed of 3-methyl-1,5-pentanediol having a hydroxyl value of 56 and isophthalic acid (trade name “Kuraray polyol P-2030”, manufactured by Kuraray Co., Ltd.) was added to a reaction apparatus equipped with a stirrer and a thermometer. 49 parts, 10 parts 1,2-propylene glycol, 43 parts 2,2-dimethylolpropionic acid, 3 parts sodium 3- (2,3-dihydroxypropoxy) -1-propanesulfonate, 145 isophorone diisocyanate Parts, 10 parts of triethylamine and 250 parts of acetone, while introducing nitrogen. Thereafter, the mixture was heated to 50 ° C. and subjected to urethanization reaction for 15 hours to obtain an isocyanate group-terminated urethane prepolymer solution. The NCO content at the end of the urethanization reaction was 2.6%.

Comparative Production Example 2 [Production of Comparative Polyurethane Resin (U′-6) Solution]
In a reaction apparatus equipped with a stirrer and a thermometer, 80 parts of ethylene oxide adduct of bisphenol A having a hydroxyl value of 348 (manufactured by Sanyo Chemical Industries, Ltd., trade name “New Pole BPE-20”), 2,2- While introducing 41 parts of dimethylolpropionic acid, 6 parts of sodium 3- (2,3-dihydroxypropoxy) -1-propanesulfonate, 123 parts of isophorone diisocyanate, 10 parts of triethylamine and 250 parts of acetone, while introducing nitrogen Prepared. Thereafter, the mixture was heated to 50 ° C. and subjected to a urethanization reaction over 15 hours. The NCO content at the end of the urethanization reaction was 0%. Subsequently, 21 parts of triethylamine was added and mixed to obtain a hydroxyl group-terminated urethane resin solution.

Comparative Production Example 3 [Production of Comparative Polyurethane Resin (U′-7) Solution]
In a reactor equipped with a stirrer and a thermometer, 64 parts of neopentyl glycol, 82 parts of 2,2-dimethylolpropionic acid, 104 parts of hexamethylene diisocyanate, 31 parts of triethylamine, 250 parts of acetone, and nitrogen Prepared while introducing. Thereafter, the mixture was heated to 50 ° C. and subjected to a urethanization reaction over 15 hours. The NCO content at the end of the urethanization reaction was 0.3%. Next, 31 parts of triethylamine was added and mixed to obtain a urethane resin solution.

Production Example 5 [Production of polyurethane resin emulsion 1 and polyurethane resin (U-1)]
The polyurethane resin solution of Production Example 1 was cooled to 40 ° C. and then poured into 1800 parts of water with stirring to obtain an emulsion (polyurethane resin emulsion 1). The volume average particle diameter of this polyurethane resin emulsion measured by ELS-800 was 0.05 μm. The polyurethane resin was isolated by washing and drying to obtain a polyurethane resin (U-1). The glass transition point of the (U-1) measured by a flow tester was 60 ° C., the softening start temperature was 80 ° C., and the outflow temperature was 120. C., and the difference between the outflow temperature and the softening start temperature was 40.degree. Mw was 7,000, and the loss elastic modulus G ″ of the viscoelastic property at 100 ° C. at a frequency of 1 Hz was 10 ⁵ dyn / cm ² .

Production Example 6 [Production of polyurethane resin emulsion 2 and polyurethane resin (U-2)]
The polyurethane resin solution of Production Example 2 was cooled to 40 ° C. and then poured into 1800 parts of water with stirring to obtain an emulsion (polyurethane resin emulsion 2). The volume average particle diameter of this polyurethane resin emulsion measured by ELS-800 was 0.3 μm. The polyurethane resin was isolated by washing and drying to obtain a polyurethane resin (U-2). The glass transition point by the flow tester measurement of (U-2) was 60 ° C., the softening start temperature was 85 ° C., and the outflow temperature was 140. C., and the difference between the outflow temperature and the softening start temperature was 55.degree. Mw was 10,000, and the loss elastic modulus G ″ of the viscoelastic property at 100 ° C. at a frequency of 1 Hz was 2 × 10 ⁷ dyn / cm ² .

Production Example 7 [Production of polyurethane resin emulsion 3 and polyurethane resin (U-3)]
The polyurethane resin solution of Production Example 3 was cooled to 40 ° C., and then poured into 1800 parts of water with stirring to obtain an emulsion (polyurethane resin emulsion 3). The volume average particle diameter of this polyurethane resin emulsion measured by ELS-800 was 0.04 μm. The polyurethane resin was isolated by washing and drying to obtain a polyurethane resin (U-3). The glass transition point of the (U-3) measured by a flow tester was 55 ° C., the softening start temperature was 75 ° C., and the outflow temperature was 90 ° C. C., and the difference between the outflow temperature and the softening start temperature was 15 ° C. Mw was 3,000, and the loss elastic modulus G ″ of the viscoelastic property at 100 ° C. at a frequency of 1 Hz was 5.0 × 10 ⁶ dyn / cm ² .

Production Example 8 [Production of polyurethane resin emulsion 4 and polyurethane resin (U-4)]
After cooling the polyurethane resin solution of Production Example 4 to 40 ° C., the mixture was poured into 1800 parts of water under stirring and emulsified to obtain (polyurethane resin emulsion 4). The volume average particle diameter of this polyurethane resin emulsion measured by ELS-800 was 0.05 μm. The polyurethane resin was isolated by washing and drying to obtain a polyurethane resin (U-4). The glass transition point of the (U-4) measured by a flow tester was 80 ° C., the softening start temperature was 100 ° C., and the outflow temperature was 140. C., and the difference between the outflow temperature and the softening start temperature was 40.degree. Mw was 40,000, and the loss elastic modulus G ″ of the viscoelastic property at 100 ° C. at a frequency of 1 Hz was 10 ⁸ dyn / cm ² .

Comparative Production Example 4 [Production of Comparative Polyurethane Resin Emulsion 5 ′ and Comparative Polyurethane Resin (U′-5)]
After cooling the isocyanate group-terminated urethane prepolymer solution of Comparative Production Example 1 to 40 ° C., the mixture was poured into 1800 parts of water with stirring and emulsified, and 1.7 parts of n-butylamine, 6 parts of ethylenediamine and 23 parts of triethylamine were added. By reacting for 5 hours with stirring, (polyurethane resin emulsion 5 ′) was obtained. The volume average particle diameter of this polyurethane resin emulsion measured by ELS-800 was 0.07 μm. The polyurethane resin was isolated by washing and drying to obtain a polyurethane resin (U′-5). The glass transition point of the (U′-5) measured by a flow tester was 110 ° C., the softening start temperature was 135 ° C., and the outflow temperature. Was 210 ° C, and the difference between the outflow temperature and the softening start temperature was 75 ° C. Mw was 210,000, and the loss elastic modulus G ″ of the viscoelastic property at 100 ° C. at a frequency of 1 Hz was 10 ¹¹ dyn / cm ² .

Comparative Production Example 5 [Production of Comparative Polyurethane Resin Emulsion 6 ′ and Comparative Polyurethane Resin (U′-6)]
The polyurethane resin solution of Comparative Production Example 2 was cooled to 40 ° C. and then poured into 1800 parts of water with stirring to obtain an emulsion (polyurethane resin emulsion 6 ′). The volume average particle diameter of this polyurethane resin emulsion measured by ELS-800 was 0.06 μm. The polyurethane resin was isolated by washing and drying to obtain a polyurethane resin (U′-6). The glass transition point of (U′-6) by a flow tester measurement was 90 ° C., the softening start temperature was 120 ° C., and the outflow temperature. Was 150 ° C., and the difference between the outflow temperature and the softening start temperature was 30 ° C. Mw was 50,000, and the loss elastic modulus G ″ of the viscoelastic property at 100 ° C. at a frequency of 1 Hz was 2.0 × 10 ¹⁰ dyn / cm ² .

Comparative Production Example 6 [Production of Comparative Polyurethane Resin Emulsion 7 ′ and Comparative Polyurethane Resin (U′-7)]
The polyurethane resin solution of Comparative Production Example 3 was cooled to 40 ° C. and then poured into 1800 parts of water with stirring to obtain an emulsion (polyurethane resin emulsion 7 ′). The volume average particle diameter of this polyurethane resin emulsion measured by ELS-800 was 0.03 μm. The polyurethane resin was isolated by washing and drying to obtain a polyurethane resin (U′-7). (U′-7) The glass transition point by flow tester measurement was 45 ° C., the softening start temperature was 65 ° C., and the outflow temperature was The difference between the outflow temperature and the softening start temperature was 20 ° C. Mw was 450, and the loss elastic modulus G ″ of the viscoelastic property at 100 ° C. at a frequency of 1 Hz was 6.0 × 10 ² dyn / cm ² .

  About the polyurethane resins (U-1) to (U-4) described in Production Examples 5 to 8, and the comparative polyurethane resins (U′-5) to (U′-7) described in Comparative Production Examples 4 to 6, The results of calculating the sp value, carboxyl group content%, and sulfonic acid anion group content%, respectively, and the urea group content, urethane group content, and hydroxyl value measurement results measured by the above method were added. The results are summarized in Table 1.

Production Example 9 [Production of polyester resin (P-1)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 813 parts of 1,2-propylene glycol, 636 parts of terephthalic acid, 91 parts of adipic acid, and 3 parts of tetrabutoxy titanate as a condensation catalyst were added, The reaction was carried out for 8 hours under pressure. Next, while raising the temperature to 230 ° C., the reaction was conducted for 4 hours while distilling off 1,2-propylene glycol and water under a nitrogen stream, and further, the reaction was conducted for 5 hours under a reduced pressure of 5 to 20 mmHg. The recovered 1,2-propylene glycol was 432 parts. Subsequently, it cooled to 180 degreeC, 51 parts of trimellitic anhydride was added, it took out after reaction for 2 hours under normal pressure sealing, cooled to room temperature, pulverized and granulated (P-1). Mn of (P-1) was 3,000, and Tg was 39 ° C.

Production Example 10 [Production of polyester resin (P-2)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 67 parts of bisphenol A / PO2 molar adduct, 700 parts of bisphenol A / PO3 molar adduct, 260 parts of terephthalic acid and 1 part of dibutyltin oxide as a condensation catalyst The mixture was reacted at 230 ° C. for 5 hours at normal pressure, and further reacted for 2 hours at a reduced pressure of 10 to 15 mmHg. Subsequently, it cooled to 180 degreeC, 24 parts of trimellitic anhydride was added, it took out after reaction for 2 hours under normal pressure sealing, cooled to room temperature, pulverized and granulated (P-2). Mn of (P-2) was 2,500, and Tg was 48 ° C.

Production Example 11 [Production of Polyester Resin (P-3)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 729 parts of 1,2-propylene glycol, 683 parts of terephthalic acid, 67 parts of adipic acid, 38 parts of trimellitic anhydride and tetrabutoxytitanate 3 as a condensation catalyst A portion was added and allowed to react for 8 hours at 230 ° C. under pressure. Subsequently, it cooled to 200 degreeC and made it react for 3 hours, distilling 1,2-propylene glycol and water under the reduced pressure of 5-20 mmHg. The recovered 1,2-propylene glycol was 172 parts. After completion of the reaction, the product was taken out, cooled to room temperature, and pulverized to obtain particles (P-3). Mn of (P-3) was 7,000, and Tg was 65 ° C.

Production Example 12 (Production of wax dispersion 1)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of paraffin wax (melting point: 73 ° C.) and 33 parts of ethyl acetate are charged, heated to 78 ° C., sufficiently dissolved, and cooled to 30 ° C. in 1 hour. Wax was crystallized into fine particles and wet-pulverized with Ultraviscomyl (manufactured by Imex) to obtain (Wax Dispersion 1).

Production Example 13 (Production of polyester resin solution 1)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of a polyester resin (P-1) and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain (Polyester resin solution 1).

Production Example 14 (Production of polyester resin solution 2)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of a polyester resin (P-2) and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain (Polyester resin solution 2).

Production Example 15 (Production of polyester resin solution 3)
In a reaction vessel equipped with a thermometer and a stirrer, 10 parts of a polyester resin (P-3) and 10 parts of ethyl acetate were stirred and uniformly dispersed to obtain (Polyester resin solution 3).

Example 1
In a beaker, 97 parts of ion-exchanged water, 10.5 parts of (polyurethane resin emulsion 1), 1 part of sodium carboxymethylcellulose, and 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (manufactured by Sanyo Chemical Industries, “ELEMINOL MON-7”) ) 10 parts was added and dissolved uniformly. Then, at 25 ° C., 75 parts of (polyester resin solution 1) was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Next, this mixed solution was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised, and ethyl acetate was distilled off at 35 ° C. until the concentration reached 0.5% or less. An aqueous resin dispersion (F-1) of resin particles in which a shell layer (S) in which (U) is formed on the surface of the core layer (Q) composed of Subsequently, it was filtered and dried at 40 ° C. for 18 hours to obtain core-shell type resin particles (C-1) with a volatile content of 0.5% or less.

Example 2
In a beaker, 60 parts of (polyester resin solution 1) and 27 parts of (wax dispersion 1) are stirred at 8,000 rpm with a TK homomixer at 25 ° C., and uniformly dissolved and dispersed (resin solution 1A )
In a beaker, 97 parts of ion-exchanged water, 10.5 parts of (polyurethane resin emulsion 1), 1 part of sodium carboxymethylcellulose, and 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (manufactured by Sanyo Chemical Industries, “ELEMINOL MON-7”) ) 10 parts was added and dissolved uniformly. Then, at 25 ° C., 75 parts of (resin solution 1A) was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Next, this mixed solution was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised, and ethyl acetate was distilled off at 35 ° C. until the concentration reached 0.5% or less. An aqueous resin dispersion (F-2) of resin particles in which a shell layer (S) in which (U) is formed on the surface of the core layer (Q) composed of Subsequently, it was separated by filtration and dried at 40 ° C. for 18 hours to obtain core / shell type resin particles (C-2) with a volatile content of 0.5% or less.

Example 3
In a beaker, 97 parts of ion-exchanged water, 10.5 parts of (polyurethane resin emulsion 2), 1 part of sodium carboxymethylcellulose, and a 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (manufactured by Sanyo Chemical Industries, “Eleminol MON-7”) ) 10 parts was added and dissolved uniformly. Next, at 25 ° C., 75 parts of (polyester resin solution 2) was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Next, this mixed solution was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised, and ethyl acetate was distilled off at 35 ° C. until the concentration reached 0.5% or less. An aqueous resin dispersion (F-3) of resin particles in which a shell layer (S) in which (U) is formed on the surface of the core layer (Q) composed of Next, the mixture was filtered and dried at 40 ° C. for 18 hours to obtain core / shell type resin particles (C-3) with a volatile content of 0.5% or less.

Example 4
In a beaker, 97 parts of ion-exchanged water, 10.5 parts of (polyurethane resin emulsion 3), 1 part of sodium carboxymethylcellulose, and 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (manufactured by Sanyo Chemical Industries, “ELEMINOL MON-7”) ) 10 parts was added and dissolved uniformly. Next, at 25 ° C., 75 parts of (polyester resin solution 2) was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Next, this mixed solution was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised, and ethyl acetate was distilled off at 35 ° C. until the concentration reached 0.5% or less. An aqueous resin dispersion (F-4) of resin particles in which the shell layer (S) in which (U) was formed on the surface of the core layer (Q) composed of Subsequently, it was filtered and dried at 40 ° C. for 18 hours to obtain core / shell type resin particles (C-4) with a volatile content of 0.5% or less.

Example 5
In a beaker, 60 parts of (polyester resin solution 2) and 27 parts of (wax dispersion 1) are stirred at 8,000 rpm with a TK homomixer at 25 ° C., and uniformly dissolved and dispersed (resin solution 2A )
In a beaker, 97 parts of ion-exchanged water, 10.5 parts of (polyurethane resin emulsion 4), 1 part of sodium carboxymethylcellulose, and a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (manufactured by Sanyo Chemical Industries, “Eleminol MON-7”) ) 10 parts was added and dissolved uniformly. Next, at 25 ° C., 75 parts of (resin solution 2A) was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Next, this mixed solution was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised, and ethyl acetate was distilled off at 35 ° C. until the concentration reached 0.5% or less. An aqueous resin dispersion (F-5) of resin particles in which a shell layer (S) in which (U) was formed on the surface of the core layer (Q) composed of Subsequently, it was filtered and dried at 40 ° C. for 18 hours to obtain core-shell type resin particles (C-5) with a volatile content of 0.5% or less.

Example 6
In a beaker, 48 parts of (Polyester resin solution 2) and 12 parts of (Polyester resin solution 3) are stirred at 8,000 rpm with a TK homomixer at 25 ° C., and uniformly dissolved and dispersed (resin solution 2B )
In a beaker, 97 parts of ion-exchanged water, 10.5 parts of (polyurethane resin emulsion 4), 1 part of sodium carboxymethylcellulose, and a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (manufactured by Sanyo Chemical Industries, “Eleminol MON-7”) ) 10 parts was added and dissolved uniformly. Next, at 25 ° C., 75 parts of (resin solution 2B) was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Next, this mixed solution was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised, and ethyl acetate was distilled off at 35 ° C. until the concentration reached 0.5% or less. An aqueous resin dispersion (F-6) of resin particles in which a shell layer (S) in which (U) is formed on the surface of the core layer (Q) composed of Next, the mixture was filtered and dried at 40 ° C. for 18 hours to obtain core-shell type resin particles (C-6) with a volatile content of 0.5% or less.

Comparative Example 1
In a beaker, 97 parts of ion-exchanged water, 10.5 parts of (polyurethane resin emulsion 5 ′), 1 part of sodium carboxymethylcellulose, and a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (manufactured by Sanyo Chemical Industries, “ELEMINOL MON-7”) ]) 10 parts were added and dissolved uniformly. Then, at 25 ° C., 75 parts of (polyester resin solution 1) was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Next, this mixed solution was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised, and ethyl acetate was distilled off at 35 ° C. until the concentration reached 0.5% or less. An aqueous resin dispersion (F′-7) of resin particles in which a shell layer (S) in which (U) was formed on the surface of the core layer (Q) composed of Next, the mixture was filtered and dried at 40 ° C. for 18 hours to obtain a comparative core / shell type resin particle (C′-7) with a volatile content of 0.5% or less.

Comparative Example 2
In a beaker, 97 parts of ion-exchanged water, 10.5 parts of (polyurethane resin emulsion 6 ′), 1 part of sodium carboxymethylcellulose, and a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (manufactured by Sanyo Chemical Industries, “ELEMINOL MON-7”) ]) 10 parts were added and dissolved uniformly. Next, at 25 ° C., 75 parts of (polyester resin solution 2) was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Next, this mixed solution was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised, and ethyl acetate was distilled off at 35 ° C. until the concentration reached 0.5% or less. An aqueous resin dispersion (F′-8) of resin particles in which the shell layer (S) in which (U) was formed on the surface of the core layer (Q) composed of Subsequently, it was filtered and dried at 40 ° C. for 18 hours to obtain a comparative core / shell type resin particle (C′-8) with a volatile content of 0.5% or less.

Comparative Example 3
In a beaker, 97 parts of ion-exchanged water, 10.5 parts of (polyurethane resin emulsion 1), 1 part of sodium carboxymethylcellulose, and 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (manufactured by Sanyo Chemical Industries, “ELEMINOL MON-7”) ) 10 parts was added and dissolved uniformly. Next, at 25 ° C., 75 parts of (polyester resin solution 2) was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Next, this mixed solution was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised and ethyl acetate was distilled off at 35 ° C. until the concentration reached 0.5% or less. (P) and (U) were compatible. A comparative resin particle aqueous resin dispersion (F′-9) was obtained. Subsequently, it filtered, and it dried at 40 degreeC * 18 hours, the volatile matter was 0.5% or less, and the comparative resin particle (G-1) was obtained.

Comparative Example 4
In a beaker, 97 parts of ion-exchanged water, 10.5 parts of (polyurethane resin emulsion 5 ′), 1 part of sodium carboxymethylcellulose, and a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (manufactured by Sanyo Chemical Industries, “ELEMINOL MON-7”) ]) 10 parts were added and dissolved uniformly. Next, at 25 ° C., 75 parts of (polyester resin solution 2) was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Subsequently, this mixed solution was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised and ethyl acetate was distilled off at 35 ° C. until the concentration reached 0.5% or less, but no formation of resin particles was observed. .

Comparative Example 5
In a beaker, 97 parts of ion-exchanged water, 10.5 parts of (polyurethane resin emulsion 7 ′), 1 part of sodium carboxymethylcellulose, and a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (manufactured by Sanyo Chemical Industries, “ELEMINOL MON-7”) ]) 10 parts were added and dissolved uniformly. Then, at 25 ° C., 75 parts of (polyester resin solution 1) was added and stirred for 2 minutes while stirring the TK homomixer at 10,000 rpm. Subsequently, this mixed solution was transferred to a Kolben equipped with a stir bar and a thermometer, and the temperature was raised and ethyl acetate was distilled off at 35 ° C. until the concentration reached 0.5% or less, but no formation of resin particles was observed. .

  For Examples 1 to 6 and Comparative Examples 1 to 5, the sp value of the polyester resin (P) used for the core layer and the results of calculating the difference between the sp values of (U) and (P) were added. It was summarized in 3.

The following evaluations were performed for (C-1) to (C-6), (C′-7) to (C′-8), and (G-1). The results are shown in Table 4.
[1] Volume average particle size Dispersed in water, the volume average particle size was measured with a Coulter counter (Beckman Coulter, Inc .: Multisizer III).
[2] Particle size distribution Dispersed in water, the particle size distribution was measured with a Coulter counter (Beckman Coulter, Inc .: Multisizer III).
[3] Leveling property Electrostatic coating was applied to a zinc phosphate-treated steel standard plate manufactured by Nippon Test Panel Co., Ltd. using a commercially available corona charging spray gun so that the film pressure was 40 to 60 μm, and baked at 180 ° C. for 20 minutes. Thereafter, the surface smoothness was visually confirmed and judged according to the following criteria.
○: The surface is smooth and glossy.
X: Unevenness occurs on the surface. No gloss.
[4] Heat-resistant storage stability The sample was allowed to stand in an atmosphere of 50 ° C. for 1 day, and evaluated according to the following criteria depending on the degree of blocking.
○: Blocking does not occur.
X: Blocking occurs.
[5] Heat adhesion Electrostatic coating is applied to a standard zinc phosphate-treated steel plate manufactured by Nippon Test Panel Co., Ltd. using a commercially available corona charging spray gun so that the film pressure becomes 40-60 μm, and baked at 120 ° C. for 20 minutes. After that, a shear adhesion test was performed according to the method specified in JIS K6830. The evaluation criteria for adhesiveness are as follows.
○: Cohesive failure ×: Interface failure

  The core-shell type resin particles of the present invention, which can be obtained by using the polyurethane resin emulsion for producing core-shell type resin particles of the present invention, can be suitably used as paints, adhesives, toners, and binders for fiber processing. .

It is a conceptual diagram which shows the flowchart in the flow tester measurement of a resin particle.

Claims (8)

With one or more shell layers (S) in the form of a film containing polyurethane resin (U) and one core layer (Q) of resin (composition) (R) mainly composed of polyester resin (P) The core-shell type resin particle (C) is constructed, wherein the difference in sp value between (U) and (P) is 0.05 to 2.0, and the weight average molecular weight of (U) is 500 to 200. Resin particles having a loss elastic modulus G ″ of viscoelastic characteristics at 100 ° C. at a frequency of 1 Hz of 10 ³ to 10 ⁹ dyn / cm ² .   The resin particle according to claim 1, wherein the glass transition temperature of (P) is 20 to 80 ° C.   (U) is a resin having a glass transition temperature of 30 to 100 ° C, a softening start temperature of 40 to 110 ° C, an outflow temperature of 60 to 150 ° C, and a difference between the outflow temperature of 0 to 70 ° C and the softening start temperature. Item 3. A resin particle according to Item 1 or 2.   The resin particle according to any one of claims 1 to 3, wherein (U) is a resin containing 0.1 to 10% by weight of a carboxyl group and 0.001 to 10% by weight of a sulfonic acid anion group.   The content of urea groups in (U) is 0 to 6% by weight.   (U) has an isocyanate group content of 0.1% by weight or less, a urea group content of 0-6% by weight, a urethane group content of 3-35% by weight, and a hydroxyl value of 0-200 mgKOH / g. The resin particle according to claim 5, which is a polyurethane resin.   (C) is a mixture of an emulsion in which (U) is dispersed in an aqueous medium and a resin (composition) (R) having (P) as a main component or an organic solvent solution thereof; (R) or an organic solvent solution thereof is dispersed to form (R) resin particles in the emulsion of (U), and (U) is attached to the surface of the resin particles of (R), (U 7) is obtained by forming an aqueous dispersion of the core-shell type resin particles (C) and further removing the aqueous medium from the aqueous dispersion. Resin particles. A polyurethane resin (U) having a weight average molecular weight of 500 to 200,000 and a loss elastic modulus G ″ of viscoelastic properties at 100 ° C. at a frequency of 1 Hz of 10 ³ to 10 ⁹ dyn / cm ² is contained in an aqueous medium. A polyurethane resin emulsion for producing core / shell type resin particles, which is dispersed.