CN104968689A - Aggregated composite resin particles, and composition containing said particles - Google Patents
Aggregated composite resin particles, and composition containing said particles Download PDFInfo
- Publication number
- CN104968689A CN104968689A CN201480007406.0A CN201480007406A CN104968689A CN 104968689 A CN104968689 A CN 104968689A CN 201480007406 A CN201480007406 A CN 201480007406A CN 104968689 A CN104968689 A CN 104968689A
- Authority
- CN
- China
- Prior art keywords
- resin particle
- raw material
- particles
- composite aggregation
- aggregated particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
- G02B5/0236—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
- G02B5/0242—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element by means of dispersed particles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
Abstract
The purpose of the present invention is to provide aggregated composite resin particles which can be used widely in various use applications including light-scattering films, inks, paints and resin molded articles, contains less impurities, has an excellent handling property, and also has excellent light scattering performance. The present invention provides aggregated composite resin particles, in each of which a vinyl polymer is complex in a raw material aggregated particle that is an aggregate of fine resin particles, wherein some of the fine resin particles which exist in at least a surface layer part of the raw material aggregated particle are integrated together by the vinyl polymer.
Description
Technical field
The present invention relates to composite aggregation resin particle.Specifically, the present invention relates to the excellent composite aggregation resin particle of light diffusing energy and its manufacture method and the various compositions containing this particle.
Background technology
All the time, the known light diffusion film by imparting light diffusing containing organic fine particles or inorganic particles.Wherein, use the inorganic particles such as silicic acid micropowder to have following problem as the light diffusion film of light diffusing agent: the phenomenon (white blur phenomenon) that the tone producing substrate because the transparency is bad whitens fuzzy, or the rub resistance of film, strength at break are bad.
On the other hand, when using organic fine particles as light diffusing agent, compared with inorganic particles, can be bad although light diffusing can be obtained, the film that the transparency is good, transmittance is high.So, for the object of low light diffusion making up organic fine particles, such as, the light diffusing agent particle (with reference to patent documentation 1) of the light diffusing energy excellence with the structure (micro phase separation structure) making the organic fine particles of different composition be separated imperceptibly in organic fine particles inside is proposed.
But, for above-mentioned light diffusing agent particle, the particle less than 100nm contained by its inside hinder light through, have the worry of the transmitance reducing the light irradiated from backlight etc.In addition, owing to remaining the additives such as the tensio-active agent that uses in manufacturing processed in above-mentioned particle, therefore have when film forming, life-time service time occur that physical property reduces, the worry of the problem such as painted.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2012-193244 publication
Summary of the invention
the problem that invention will solve
The present invention makes based on the present situation of above-mentioned prior art, its objective is and a kind of various uses that can be widely used in light diffusion film, ink, coating, synthetic resin be representative is provided, impurity is few, treatability is excellent, composite aggregation resin particle that light diffusing can be excellent.
for the scheme of dealing with problems
The present inventor etc. study repeatedly for above-mentioned purpose, found that, making micro resin particles integrated by micro resin particles being assembled the raw material aggregated particles and the vinyl polymers compound that are formed, realizing above-mentioned purpose thus, thus completing the present invention.That is, the object of the invention is by the following method and realize.
[1] a kind of composite aggregation resin particle, it is characterized in that, it is compounded with the gathering resin particle of vinyl polymers for assembling to micro resin particles the raw material aggregated particles formed, and the aforementioned micro resin particles being at least present in skin section that described composite aggregation resin particle is in aforementioned base materials aggregated particles utilizes the state of aforementioned vinyl polymers and integration.
[2] the composite aggregation resin particle Gen Ju [1], is characterized in that, volume density is 0.20 ~ 0.50g/cm
3.
[3] according to [1] or the composite aggregation resin particle described in [2], it is characterized in that, the median size recorded by SEM image forming the micro resin particles of raw material aggregated particles is 100 ~ 600nm.
[4] according to the composite aggregation resin particle according to any one of [1] ~ [3], it is characterized in that, it is not containing emulsifying agent.
[5] according to the composite aggregation resin particle according to any one of [1] ~ [4], it is characterized in that, it is not containing aggregating agent.
[6] according to the composite aggregation resin particle according to any one of [1] ~ [5], it is characterized in that, the content of vinyl polymers is 0.1 ~ 200 % by weight of raw material aggregated particles.
[7] according to the composite aggregation resin particle according to any one of [1] ~ [6], it is characterized in that, by to use relative to total monomer weight be ethene base system monomer and 0.25 ~ 3 % by weight of 90 ~ 100 % by weight, water-soluble polymerization initiator carries out being polymerized being formed raw material aggregated particles in water, described ethene base system monomer to the solvability of water less than 3 % by weight.
[8] according to the composite aggregation resin particle according to any one of [1] ~ [7], it is characterized in that, assembling in the aqueous dispersions of the raw material aggregated particles formed containing micro resin particles, use water-soluble polymerization initiator that ethene base system monomer is polymerized, thus make aforementioned base materials aggregated particles and vinyl polymers compound and obtain.
[9] coating composition, is characterized in that, it contains [1] ~ [8] according to any one of composite aggregation resin particle.
[10] ink composition, is characterized in that, it contains [1] ~ [8] according to any one of composite aggregation resin particle.
[11] synthetic resin, is characterized in that, it contains [1] ~ [8] according to any one of composite aggregation resin particle.
the effect of invention
Composite aggregation resin particle of the present invention has sparse aggregation structure, there is space in granule interior, and therefore the area on the surface of the per unit weight of low, the particle of pellet density is large.Therefore, higher light diffusion effect can be obtained.In addition, particle shape is irregularly shaped, therefore expects to have the light diffusing energy utilizing existing resin particle to obtain.In addition, by the micro resin particles integration utilizing vinyl polymers to make gathering, all state of aggregation can be maintained in water solvent, organic system solvent, even if therefore when such as using to middle interpolation mixing such as coating, also can obtain the film showing desired extinction effect, for process, also be not easy to produce micro mist, treatability is good.
Accompanying drawing explanation
Fig. 1 illustrates the SEM image of the raw material aggregated particles obtained in embodiment 1.
Fig. 2 illustrates the SEM image of the composite aggregation resin particle obtained in embodiment 1.
Embodiment
Below, the present invention is described in detail.The feature of composite aggregation resin particle of the present invention is, it is compounded with the gathering resin particle of vinyl polymers for assembling to micro resin particles the raw material aggregated particles formed, and the aforementioned micro resin particles being at least present in skin section that described composite aggregation resin particle is in aforementioned base materials aggregated particles utilizes the state of aforementioned vinyl polymers and integration.At this; " state of integration " does not refer to that micro resin particles is merely assembled; and referring to the state utilizing vinyl polymers that micro resin particles is bonded to each other, this state in water solvent, in organic system solvent, no matter all can maintain state of aggregation and can not the state of primary particle.
When being in this " integration state ", the outward appearance forming the micro resin particles of composite aggregation resin particle often becomes as shown in Figure 2 the unintelligible but interconnected state of the profile of micro resin particles one by one.
In addition, in composite aggregation resin particle of the present invention, " state of compound " can list following state: by raw material aggregated particles Jin Stains in the solution of vinyl polymers, thus make vinyl polymers be attached to the state of raw material aggregated particles; In the aqueous dispersions of raw material aggregated particles, the ethene base system monomer as the raw material of vinyl polymers is made to carry out being polymerized and the state etc. obtained.
In addition, the shape of composite aggregation resin particle of the present invention is irregularly shaped is desirable.At this, the shape of composite aggregation resin particle does not refer to the shape in the thin portion of composite aggregation resin particle, but using the shape of entirety as object.In addition, " irregularly shaped " refers to the state that the shape of composite aggregation resin particle is one by one different.In this condition, it is spherical shape hardly that most particle has, and has concavo-convex observing particle from a direction around the image, the i.e. particle projection that obtain.
As the yardstick representing this erose degree, the circularity defined by following formula can be used.
Circularity=(with the girth of the circle of grain projected area equal areas)/(girth of particle projection) of particle projection
The circularity of the mean value=particle of the circularity of particle projection
That is, circularity becomes 1 when positive round, increases and become smaller value along with erose degree.In composite aggregation resin particle of the present invention, as the circularity of above-mentioned particle, be preferably the scope of 0.50 ~ 0.94, be more preferably the scope of 0.70 ~ 0.90.It should be noted that, the flowing-type particle image analyser " FPIA-3000S " that this circularity such as can use SYSMEX Co., Ltd to manufacture measures.
In composite aggregation resin particle of the present invention, by being in the state that micro resin particles utilizes vinyl polymers and integration as mentioned above, thus process is easily, though in the dry state composite aggregation resin particle also not loose, molecule also do not disperse.In addition, no matter in water solvent, or in organic system solvent, all can not redispersion to molecule unit, therefore when adding and make overlay film in aqueous coating, solvent system coating etc., on the surface of composite aggregation resin particle maintaining state of aggregation, the face of various angle is intensive and exist without deflection, can obtain making the effect of the incident light scattering equably from any direction.In addition, under composite aggregation resin particle of the present invention has erose situation, also can obtain the effect making incident light to all directions scattering.And then compared with common spherical particle, volume density is also low, therefore the granule number of per unit weight becomes many, can also be formed more concavo-convex at film surface.That is, compared with the light diffusion effect of the film realized with common spherical particle, even if such as make addition become half, same light diffusion effect can also be obtained.
And then, when the vinyl polymers of compound is wetting ability, become the composite aggregation resin particle of dispersion stabilization excellence in water solvent, be applicable to adding in aqueous coating, aqueous resin etc.
In aforementioned composite aggregation resin particle of the present invention, volume density is preferably 0.20 ~ 0.50g/cm
3, be more preferably 0.25 ~ 0.40g/cm
3.This volume density can regard the yardstick of the state of aggregation confirming micro resin particles as.If volume density is too high, then such as make be coated with membranaceous time, the concavo-convex number that surface energy is formed sometimes declines and becomes and can not obtain sufficient light diffusing energy.
In addition, the volume average particle size of composite aggregation resin particle of the present invention is preferably 3 ~ 150 μm, is more preferably 3 ~ 50 μm, more preferably 3 ~ 30 μm.If median size is less than 3 μm, then be processed as be coated with membranaceous time, sometimes make total light transmittance decline due to scattering of light, it is undesirable for needing for the purposes of light transmission for the light diffusing sheet etc. of LED.On the other hand, if median size is more than 150 μm, even if then identical to the interpolation weight in film, granule number also can reduce, and therefore sometimes becomes and can not obtain sufficient mist degree.In addition, when being coated with, become and easily produce inequality, make film coated surface become coarse, in addition, the possibility causing Physical properties of coating film to reduce uprises.
In addition, composite aggregation resin particle of the present invention does not contain aggregating agent is desirable.At this, aggregating agent refers to the additive added to make primary particle assemble, and include, for example out macromolecule aggregation agent, inorganic salts.In aggregated particles, the situation containing aggregating agent is many, if but the aggregated particles containing a large amount of aggregating agent is added in coating, then have the situation that the characteristic of coating, film is reduced.
In addition, composite aggregation resin particle of the present invention does not also contain emulsifying agent is desirable.At this, emulsifying agent refers to tensio-active agent.Emulsifying agent is added usually in polymerization process etc.If be added in coating by the aggregated particles containing a large amount of emulsifying agent, then the characteristic of coating, film is made to reduce sometimes.
The median size of the micro resin particles contained by composite aggregation resin particle of the present invention is preferably 100 ~ 600nm, is more preferably 150 ~ 500nm.If this median size is too small, then aggregation force becomes firmly, and micro resin particles gap each other disappears, and therefore volume density rises sometimes.Otherwise, if excessive, then sometimes become and cannot maintain micro resin particles state of aggregation each other.In addition, from the view point of the effect of scattering of light, be also preferably set to the median size of described scope.
In addition, the kind of the resin of micro resin particles is not particularly limited, such as select the resin little as far as possible with the refringence of the coating resin that will add composite aggregation resin particle as the resin of micro resin particles, thus the internal haze value of the film obtained reduce, the transparency improves.Otherwise the large resin of selective refraction rate variance is as the resin of micro resin particles, thus the internal haze value of the film obtained rises, the various optical characteristics such as anti-dazzle, ultraviolet scattering can be obtained.Therefore, as long as the kind of resin is at random selected according to object.It should be noted that, internal haze value described herein does not refer to and comes from the concavo-convex haze value waiting surface tissue, and refers to the haze value coming from internal structure, if above-mentioned such film, then mainly comes from the refringence of coating resin and micro resin particles.
From the view point of requiring that according to purposes characteristic is different, as the resin of micro resin particles, the vinyl resin of the abundant species of the monomer that preferably can utilize.As adopting the ethene base system monomer that can utilize during described vinyl resin, the acrylic ester monomers such as methyl acrylate, ethyl propenoate, 2-EHA, lauryl acrylate, acrylate, vinylformic acid diethylamino ethyl ester can be listed; The methacrylate ester monomers such as methyl methacrylate, β-dimethyl-aminoethylmethacrylate, lauryl methacrylate(LMA), dimethylaminoethyl methacrylate; The styrenic monomers such as vinylbenzene, p-methylstyrene; The alkyl vinyl ether such as methylvinylether, ethyl vinyl ether; The vinyl ester such as vinyl-acetic ester, vinyl butyrate system monomer; The N-alkyl such as N methacrylamide, N-ethyl acrylamide replace (methyl) acrylamide; The nitrile such as vinyl cyanide, methacrylonitrile system monomer; The polyfunctional monomers etc. such as Vinylstyrene, ethylene glycol bisthioglycolate (methyl) acrylate, polyethyleneglycol (methyl) acrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate.These monomers separately or can combine two or more and use.
The raw material aggregated particles that the present invention adopts is that above-mentioned micro resin particles is assembled and formed, such as, can obtain by adding aggregating agent in the dispersion of micro resin particles that obtains to letex polymerization and making it assemble.But, more preferably adopt the raw material aggregated particles using methyl methacrylate, ethylene glycol dimethacrylate etc. to be obtained by manufacture method described later the ethene base system monomer of the solvability of water less than 3 % by weight.Reason is any person that the raw material aggregated particles owing to being obtained by this manufacture method does not contain in emulsifying agent and aggregating agent.
In addition, if the particle diameter of micro resin particles of the present invention can be regulated by the amount etc. of emulsifying agent during polymerizing condition use emulsifying agent.Similarly, if the particle diameter of raw material aggregated particles of the present invention also can by manufacture raw material aggregated particles time polymerizing condition use aggregating agent time aggregating agent amount etc. regulate.
Even if the vinyl polymers that the present invention adopts is as mentioned above in the dry state or also maintain the state of aggregation of composite aggregation resin particle of the present invention in the solvent of water system, organic system.This vinyl polymers does not preferably dissolve in the solvent of water system, organic system, when further considering the dispersion stabilization to solvent, it is desirable that good to used solvent compatibility.Therefore, when selecting vinyl polymers, such as, with reference to the solubility parameter etc. disperseing the solvent used, usually can not dissolve this point in the solvent of water system, organic system, as vinyl polymers, the material etc. selecting to have crosslinking structure can be considered.In addition, in order to obtain dispersion stabilization excellent in water solvent, as vinyl polymers, can consider to select hydrophilic material etc.
In addition, as described below, about the vinyl polymers that the present invention adopts, in the aqueous dispersions containing raw material aggregated particles, use water-soluble polymerization initiator to make ethene base system monomer polymerization, itself and raw material aggregated particles compound can be made thus.Now, as used ethene base system monomer, certainly select in the mode that can obtain the vinyl polymers of wishing compound, but also should consider the affinity of vinyl system monomer and micro resin particles.That is, when adding ethene base system monomer micro resin particles dissolve or violent swelling time, the optical characteristics such as eliminate optical property reduces sometimes.But, by introducing crosslinking structure to micro resin particles in advance, suppressing to dissolve, swelling, thus the range of choice of ethene base system monomer can be expanded.
As the vinyl polymers that the invention described above adopts, include, for example out homopolymer, the multipolymer of the ethene base system monomer that can adopt in the resin of above-mentioned micro resin particles etc.Specifically, can exemplify poly-(methyl) acrylate, polyvinyl acetate, multiple (methyl) acrylate multipolymer, polyoxyethylene glycol two (methyl) acrylate etc. by the polymkeric substance etc. of cross-linkable monomer homopolymerization or copolymerization.It should be noted that, the statement of " (methyl) vinylformic acid " represents both " methacrylic acid " and " vinylformic acid ".
In addition, make the upper limit of the amount of vinyl polymers and raw material aggregated particles compound be preferably less than 200 % by weight of raw material aggregated particles, be more preferably less than 100 % by weight, more preferably less than 50 % by weight.If vinyl polymers is more than 200 % by weight, even if then deep in raw material aggregated particles, micro resin particles gap each other is also filled up by vinyl polymers, and volume density becomes large sometimes.
On the other hand, make the lower limit of the amount of vinyl polymers and raw material aggregated particles compound be preferably more than 0.1 % by weight of raw material aggregated particles, be more preferably more than 1.0 % by weight, more preferably more than 5.0 % by weight.If vinyl polymers is less than 0.1 % by weight, then the gathering that sometimes substantially can not get being realized by vinyl polymers maintains effect, becomes and easily produces micro mist, becomes and is difficult to process.
Above-described composite aggregation resin particle of the present invention can by making raw material aggregated particles and vinyl polymers compound and obtaining.About described raw material aggregated particles, from the view point of the characteristic required by the composite aggregation resin particle of the invention described above, it is desirable that carry out assembling under the condition of shape before maintaining micro resin particles and assembling and obtain.As long as the raw material aggregated particles that the manufacture method of this raw material aggregated particles can obtain target is just not particularly limited.As an example, by making the drop of ethene base system monomer disperse in the water being dissolved with water-soluble polymerization initiator, heated/stirred, while the method for polymerization, can form raw material aggregated particles.Utilize the method, can obtain micro resin particles assemble raw material aggregated particles, and without the need to add special Do operation, additive.The raw material aggregated particles obtained like this can be adjusted to arbitrary particle diameter by pulverizing/classification.
As the ethene base system monomer used in the process, it is desirable to, ethene base system monomer to the solvability of water less than 3 % by weight, preferably less than 2 % by weight at using 20 DEG C, it is desirable to, relative to total monomer weight, use this ethene base system monomer with more than 90 % by weight, preferably more than 95 % by weight.As the typical example of this vinyl monomer, the acrylic ester monomers such as methyl acrylate, ethyl propenoate, 2-EHA, lauryl acrylate can be listed; The methacrylate ester monomers such as methyl methacrylate, β-dimethyl-aminoethylmethacrylate, lauryl methacrylate(LMA); The styrenic monomers such as vinylbenzene, p-methylstyrene; The alkyl vinyl ether such as methylvinylether, ethyl vinyl ether; The vinyl ester such as vinyl-acetic ester, vinyl butyrate system monomer; Vinylstyrene, ethylene glycol bisthioglycolate (methyl) acrylate, polyethyleneglycol (methyl) acrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate etc.If described monomer is less than 90 % by weight, then micro resin particles becomes not gathering sometimes.This is presumably because, increased by the consumption of the ethene base system monomer to the solvability of water being more than 3 % by weight, thus described monomer is preferentially polymerized, and plays the effect of dispersion agent.In addition, total monomer weight is 5 ~ 35 % by weight relative to the ratio of total charged material weight is desirable.
As polymerization starter, as long as be water-soluble polymerization initiator, just can adopt the initiator of any kind such as azo system, persulphate system, peroxidation system, reducto oxydative system, can be light trigger, can also be thermal initiator.As representative examples, can 2 be listed, 2 '-Azobis (2-methylpropionamidine) dihydrochloride (2, two (the 2-methyl-prop amidine) dihydrochloride of 2 '-azo), 2,2 '-Azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride (2, two (1-imino--1-pyrrolidyl-2-methylpropane) dihydrochloride of 2 '-azo), t-Butylhydroperoxide (tertbutyl peroxide), ammonium persulphate, Potassium Persulphate, hydrogen peroxide/iron (II) ionic system etc.
Relative to total monomer weight with 0.25 ~ 3 % by weight, preferably use described water-soluble polymerization initiator to be desirable with 0.25 ~ 2 % by weight.By being set in described scope, can obtaining being in micro resin particles and there occurs the state of gathering and there is no the particle of the suitable size of consolidated block.
As above, the raw material aggregated particles that the present invention adopts can be obtained, but also can implement pulverization process to the raw material aggregated particles obtained as required, be adjusted to the particle diameter of expectation.In described pulverization process, Bu Xu Yaos the device of Te Do, can use the shredding unit that blade mill (blade mill), Banbury mixer, kneading mixer (kneader mixer), roller etc. are general.In addition, during the broken process of conducting powder, can pulverize under wetting regime after polymerization terminates etc., and not need to make particle drying in advance.
In addition, in above-mentioned manufacture method, as required, polyvinyl alcohol can be added after the stage making raw material aggregated particles be polymerized or polymerization.Thus, the dispersion stabilization of the aqueous dispersions of obtained raw material aggregated particles can be improved.As the addition of polyvinyl alcohol, it is desirable that relative to raw material aggregated particles 100 weight part, be preferably 0.001 ~ 1 weight part, be more preferably 0.01 ~ 0.1 weight part.
As mentioned above, even if the manufacture method of above-mentioned detailed description does not use emulsifying agent, aggregating agent, also can obtain the raw material aggregated particles of state of aggregation of appropriateness, therefore obtain composite aggregation resin particle of the present invention in be suitable method.But, in this manufacture method, as required, also emulsifying agent, aggregating agent can be used.
In addition, as the method making described raw material aggregated particles and vinyl polymers compound, include, for example out: in the aqueous dispersions containing raw material aggregated particles, use water-soluble polymerization initiator to make ethene base system monomer carry out the method for being polymerized.
In the process, as the aqueous dispersions containing raw material aggregated particles, the dispersion liquid of the raw material aggregated particles generated by being polymerized in the manufacture method of the raw material aggregated particles of above-mentioned detailed description directly can be used.In addition, as the method that ethene base system monomer and water-soluble polymerization initiator are added in aqueous dispersions, can disposable whole input, also can carry out polymerization and little by little drip.In addition, for the addition of ethene base system monomer, from the view point of the amount making above-mentioned vinyl polymers and raw material aggregated particles compound, as the upper limit, raw material aggregated particles is preferably less than 200 % by weight, is more preferably 100 % by weight, and more preferably less than 50 % by weight.As lower limit, raw material aggregated particles is preferably more than 0.1 % by weight, is more preferably more than 1.0 % by weight, and more preferably more than 5.0 % by weight.
It should be noted that, utilizing described method to make vinyl polymers compound tense, it is desirable that the micro resin particles of formation raw material aggregated particles has crosslinking structure.If do not have crosslinking structure, then micro resin particles is dissolved by the ethene being added base system monomer, there is the worry that can not get composite aggregation resin particle of the present invention.As the introduction method of crosslinking structure, when the manufacture method etc. of the raw material aggregated particles of above-mentioned detailed description, the method etc. of the ethene base system monomer copolymerization by having two or more vinyl can be listed.
The purposes of composite aggregation resin particle of the present invention is below described, but described purposes is an example, composite aggregation resin particle of the present invention also may be used for other widely in purposes.
Composite aggregation resin particle of the present invention can be made to contain use in coating, ink composition and synthetic resin etc.When making it contain in these, usually carry out stirring, mixing etc., in this case, composite aggregation resin particle of the present invention is substantially not loose but maintain state of aggregation, therefore can show optical characteristics as above.
As the manufacture method of coating composition of the present invention or ink composition, the method for composite aggregation resin particle of the present invention and resin glue being added in organic solvent can be listed.Above-mentioned resin glue is not particularly limited, include, for example out thermoplastic resin, heat-curing resin, light-cured resin, specifically, include, for example out acrylic resin, vibrin, polyvinyl chloride, urethane, silicone resin, melamine resin etc.It should be noted that, when giving the film transparency, being preferably applicable to using acrylic resin, vinylformic acid-silicon-type resin etc.
Above-mentioned organic solvent is not particularly limited, and include, for example out toluene, dimethylbenzene, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone, ethylene glycol monomethyl ether (methylcyclohexane), ethylene glycol monoethyl ether (ethyl cellosolve), ethyl acetate, butylacetate, Virahol, acetone, methyl-phenoxide etc.These can be used alone also can combinationally use two or more.In addition, the known various additives such as tinting material such as flow agent, surface-modifying agent, defoamer, pigment can be added in coating, ink composition.
Above-mentioned composition such as also can manufacture as follows: after dissolving resin glue in organic solvent, add composite aggregation resin particle of the present invention, use sand mill, ball mill, masher (attritor), high speed rotating whipping appts, triple-roller mill etc. to disperse equably, mix, thus manufacture.
Composite aggregation resin particle of the present invention is not limited to coating, the ink composition of solvent system as above, can also be used for various coating, the ink compositions such as solvent-free system, water-based, powder.
In addition, by be mediated by composite aggregation resin particle of the present invention in thermoplasticity or Thermocurable matrix resin and shaping, the synthetic resin containing composite aggregation resin particle can be produced.As this matrix resin, preferably use the resin that the transparencys such as plexiglass, MS resin, polycarbonate resin, vibrin are excellent, weathering resistance is good, have rigidity.
For synthetic resin of the present invention, mixing machine can be used to be mixed with composite aggregation resin particle by resin, use melting mixing machine carry out mixing after extrude, the synthetic resin of sheet can be obtained thus.In addition, after melting mixing, take out with the form of pellet, by injection molding after this beads fuse, also can obtain above-mentioned products formed thus.
Embodiment
Below, be described effect of the present invention by embodiment and comparative example, scope of the present invention is not limited to these embodiments.
(1) circularity, the volume average particle size of sample particle
Circularity, the volume average particle size of particle defined above is measured by flowing-type particle image analyser (FPIA-3000S: SYSMEX Co., Ltd manufactures).
(2) median size of micro resin particles
In the SEM image of raw material aggregated particles, at random select 20 micro resin particles, measure each diameter, calculate mean value.
(3) volume density
To the container A (cm of known volume
3) middle pack grain, measure its weight B (g), calculate volume density by following formula.
Volume density (g/cm
3)=B (g)/A (cm
3)
(4) haze value
Sample particle 12 weight part and methylethylketone 200 weight part are added in oiliness top coat coating (Acrydic (acrylic resin, resin concentration 51 % by weight): Dainippon Ink Chemicals manufactures) 100 weight parts, use homogenizer to stir 10 minutes.With bar coater by the coating composition that obtains PET film (on Cosmoshine#A4300 (thickness 100 μm: TOYOBO CO., LTD. manufacture), in the hot air dryer of 60 DEG C dry 30 minutes afterwards.By mist degree instrument (NDH 2000: Japanese electricity Se Co., Ltd. manufactures), the haze value of the film obtained is measured.
[embodiment 1]
Water 300 weight part is dropped in reactive tank, make 2 as polymerization starter, 2 '-Azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride (2, two (1-imino--1-pyrrolidyl-2-methylpropane) dihydrochloride of 2 '-azo) 0.6 weight part dissolves.Then, add methyl methacrylate 99 weight part as monomer and glycolmethacrylate 1 weight part, stir and make it react 2 hours at 45 DEG C, obtain the aqueous dispersions of raw material aggregated particles.Then, in this aqueous dispersions, the solids component of this aqueous dispersions is set to 100 weight parts, add polyoxyethylene glycol #400 dimethacrylate (manufacture of KCC of NK-ESTER 9G, Xin Zhong village) 30 weight parts and 2,2 '-Azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride (2, two (1-imino--1-pyrrolidyl-2-methylpropane) dihydrochloride of 2 '-azo) 0.3 weight part, at 45 DEG C, again make it react 2 hours.Then, after filtration, washing, drying, carrying out classification to remove big particle, obtaining the composite aggregation resin particle of embodiment 1.The characteristic of this particle will be measured and the result that obtains is shown in table 1.In addition, above-mentioned raw material aggregated particles SEM image is shown in Fig. 1, and the SEM image of composite aggregation resin particle is shown in Fig. 2.
[embodiment 2]
The gathering shape resin particle obtained embodiment 1, further with the screen sizing that mesh is thin, obtains the composite aggregation resin particle of embodiment 2.The characteristic of this particle will be measured and the result that obtains is shown in table 1.
[embodiment 3]
In embodiment 1, polyoxyethylene glycol #400 dimethacrylate 30 weight part added in aqueous dispersions to raw material aggregated particles is changed to vinyl-acetic ester 30 weight part, in addition, operate similarly to Example 1, obtain the composite aggregation resin particle of embodiment 3.The characteristic of this particle will be measured and the result that obtains is shown in table 1.
[embodiment 4]
In embodiment 1, the compounding amount of the polyoxyethylene glycol #400 dimethacrylate added in the aqueous dispersions to raw material aggregated particles is changed to 0.1 weight part by 30 weight parts, in addition, operate similarly to Example 1, obtain the composite aggregation resin particle of embodiment 4.The characteristic of this particle will be measured and the result that obtains is shown in table 1.
[embodiment 5]
In embodiment 1, the compounding amount of the polyoxyethylene glycol #400 dimethacrylate added in the aqueous dispersions to raw material aggregated particles is changed to 10 weight parts by 30 weight parts, in addition, operate similarly to Example 1, obtain the composite aggregation resin particle of embodiment 5.The characteristic of this particle will be measured and the result that obtains is shown in table 1.
[embodiment 6]
In embodiment 1, the compounding amount of the polyoxyethylene glycol #400 dimethacrylate added in the aqueous dispersions to raw material aggregated particles is changed to 250 weight parts by 30 weight parts, in addition, operates similarly to Example 1, obtain the particle of embodiment 6.The characteristic of this particle will be measured and the result that obtains is shown in table 1.
[embodiment 7]
In embodiment 1, after the reaction of raw material aggregated particles, add polyvinyl alcohol 0.04 weight part, in addition, operate similarly to Example 1, obtain the composite aggregation resin particle of embodiment 7.The characteristic of this particle will be measured and the result that obtains is shown in table 1.
[comparative example 1]
The aqueous dispersions of the raw material aggregated particles of embodiment 1 is directly filtered, washes, dry, classification, obtain the particle of comparative example 1.The characteristic of this particle will be measured and the result that obtains is shown in table 1.
[table 1]
As shown in table 1, in embodiment 1 ~ 7, the high and composite aggregation resin particle that micro mist is few of dispersion stabilization in solvent can be obtained.In addition, these particles are added in coatings volatile organic compounds when making film, compared with the raw material aggregated particles of comparative example 1, high fog angle value can be obtained.That is, can think, in embodiment 1 ~ 7, utilize the effect making vinyl polymers compound, even if when interpolation is mixed in coating, also maintain the state of aggregation of composite aggregation resin particle, therefore obtain high fog angle value.On the other hand, can think, in comparative example 1, owing to not making vinyl polymers compound, therefore when classification, blending time the treatability such as to disperse bad, aggregated particles is loose in a solvent, haze value step-down.It should be noted that, for the composite aggregation resin particle of embodiment 6, because the compounding quantity of vinyl polymers is many, therefore volume density is high, compared with the composite aggregation resin particle of other embodiments, and haze value step-down.
Claims (11)
1. a composite aggregation resin particle, it is characterized in that, it is compounded with the gathering resin particle of vinyl polymers for assembling to micro resin particles the raw material aggregated particles formed, and the described micro resin particles being at least present in skin section that described composite aggregation resin particle is in described raw material aggregated particles utilizes the state of described vinyl polymers and integration.
2. composite aggregation resin particle according to claim 1, is characterized in that, volume density is 0.20 ~ 0.50g/cm
3.
3. composite aggregation resin particle according to claim 1 and 2, is characterized in that, the median size recorded by SEM image forming the micro resin particles of raw material aggregated particles is 100 ~ 600nm.
4. the composite aggregation resin particle according to any one of claims 1 to 3, is characterized in that, it is not containing emulsifying agent.
5. the composite aggregation resin particle according to any one of Claims 1 to 4, is characterized in that, it is not containing aggregating agent.
6. the composite aggregation resin particle according to any one of Claims 1 to 5, is characterized in that, the content of vinyl polymers is 0.1 ~ 200 % by weight of raw material aggregated particles.
7. the composite aggregation resin particle according to any one of claim 1 ~ 6, it is characterized in that, by to use relative to total monomer weight be ethene base system monomer and 0.25 ~ 3 % by weight of 90 ~ 100 % by weight, water-soluble polymerization initiator carries out being polymerized being formed raw material aggregated particles in water, described ethene base system monomer to the solvability of water less than 3 % by weight.
8. the composite aggregation resin particle according to any one of claim 1 ~ 7, it is characterized in that, assembling in the aqueous dispersions of the raw material aggregated particles formed containing micro resin particles, use water-soluble polymerization initiator that ethene base system monomer is polymerized, thus make described raw material aggregated particles and vinyl polymers compound and obtain.
9. a coating composition, is characterized in that, it contains the composite aggregation resin particle according to any one of claim 1 ~ 8.
10. an ink composition, is characterized in that, it contains the composite aggregation resin particle according to any one of claim 1 ~ 8.
11. 1 kinds of synthetic resins, is characterized in that, it contains the composite aggregation resin particle according to any one of claim 1 ~ 8.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013019516 | 2013-02-04 | ||
| JP2013-019516 | 2013-02-04 | ||
| PCT/JP2014/051902 WO2014119595A1 (en) | 2013-02-04 | 2014-01-29 | Aggregated composite resin particles, and composition containing said particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104968689A true CN104968689A (en) | 2015-10-07 |
| CN104968689B CN104968689B (en) | 2017-05-17 |
Family
ID=51262308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480007406.0A Active CN104968689B (en) | 2013-02-04 | 2014-01-29 | Aggregated composite resin particles, and composition containing said particles |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6277962B2 (en) |
| KR (1) | KR20150115727A (en) |
| CN (1) | CN104968689B (en) |
| TW (1) | TWI582154B (en) |
| WO (1) | WO2014119595A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107022220A (en) * | 2016-02-01 | 2017-08-08 | 日本爱克兰工业株式会社 | The manufacture method of composite aggregation resin particle group and the particle swarm and the composition containing the particle swarm |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016070938A (en) * | 2014-09-30 | 2016-05-09 | 敏治 吉川 | Surface reflection material for non-contact type 3d scanner |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61241310A (en) * | 1985-04-18 | 1986-10-27 | Soken Kagaku Kk | Production of emulsion of crosslinked polymer |
| JP4192245B2 (en) * | 2004-11-24 | 2008-12-10 | 国立大学法人群馬大学 | Process for producing irregular polymer particles |
| JP4853901B2 (en) * | 2005-03-01 | 2012-01-11 | 綜研化学株式会社 | Colored monodisperse particles and method for producing the same |
| JP2006335793A (en) * | 2005-05-31 | 2006-12-14 | Mitsubishi Rayon Co Ltd | Method for producing acrylic polymer powder and plastisol composition |
| JP5696918B2 (en) * | 2009-09-30 | 2015-04-08 | 日本エクスラン工業株式会社 | Aggregated resin particles, method for producing the particles, and coating composition and coating film containing the particles |
| KR102029829B1 (en) * | 2012-01-31 | 2019-10-08 | 닛폰 에쿠스란 고교 가부시키가이샤 | Composite aggregate resin particle and composition containing same particle |
-
2014
- 2014-01-22 TW TW103102203A patent/TWI582154B/en active
- 2014-01-29 WO PCT/JP2014/051902 patent/WO2014119595A1/en active Application Filing
- 2014-01-29 KR KR1020157017554A patent/KR20150115727A/en not_active Application Discontinuation
- 2014-01-29 JP JP2014559706A patent/JP6277962B2/en active Active
- 2014-01-29 CN CN201480007406.0A patent/CN104968689B/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107022220A (en) * | 2016-02-01 | 2017-08-08 | 日本爱克兰工业株式会社 | The manufacture method of composite aggregation resin particle group and the particle swarm and the composition containing the particle swarm |
| CN107022220B (en) * | 2016-02-01 | 2021-07-16 | 日本爱克兰工业株式会社 | Composite aggregated resin particle group, method for producing the particle group, and composition containing the particle group |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104968689B (en) | 2017-05-17 |
| WO2014119595A1 (en) | 2014-08-07 |
| TWI582154B (en) | 2017-05-11 |
| JP6277962B2 (en) | 2018-02-14 |
| KR20150115727A (en) | 2015-10-14 |
| JPWO2014119595A1 (en) | 2017-01-26 |
| TW201439168A (en) | 2014-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7741378B2 (en) | Porous monodispersed particles and method for production thereof, and use thereof | |
| TWI513777B (en) | Film-forming pigments and coating system including the same | |
| KR20120003434A (en) | Irregularly shaped particles and method for producing same | |
| CN106349421A (en) | Polymer microsphere and preparation method thereof | |
| JP4853901B2 (en) | Colored monodisperse particles and method for producing the same | |
| KR102029829B1 (en) | Composite aggregate resin particle and composition containing same particle | |
| CN104968689A (en) | Aggregated composite resin particles, and composition containing said particles | |
| JP5169624B2 (en) | Method for producing nano-particle composite | |
| JP6690319B2 (en) | Chromatic fine particle capsule | |
| JP5134648B2 (en) | Particles and method for producing the same | |
| JP2012140616A (en) | Acrylic fine particle and diffusion film including the same | |
| JP2013053225A (en) | Method for producing nano particle composite | |
| CN1235927C (en) | Polyacrylonitrile polymer fine particles | |
| CN107022220B (en) | Composite aggregated resin particle group, method for producing the particle group, and composition containing the particle group | |
| TW201229100A (en) | Acrylic fine particles and diffusing film including the same | |
| JP6169988B2 (en) | Black porous resin beads, method for producing the same, and glossy products using the resin beads | |
| JP2007204695A (en) | Light diffusing agent and light diffusing resin composition using the same | |
| JP6137493B2 (en) | Crosslinked fine particles, method for producing aqueous solution containing crosslinked fine particles, method for producing crosslinked fine particles, and crosslinked fine particle composition | |
| JP2012184420A (en) | Spherical cross-linked polyacrylonitrile-based fine particle having large surface area | |
| KR20120029193A (en) | Spherical polymer powder having high refractive index and preparation method thereof | |
| JP2017066363A (en) | Aggregate for dispersing resin and resin composition, and manufacturing method therefor | |
| JP2002179709A (en) | Cross-linked microparticle and anti-blocking agent using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |