CN101331153A - Polymer particles, process for production thereof, resin compositions containing the particles, and moldings - Google Patents

Abstract

A process for the production of polymer particles having excellent powder characteristics which involves little structural restriction of the starting polymer fine particles; matte or light-diffusing resin compositions which contain the polymer particles and which are excellent in physical properties and handleability; and moldings of the compositions. The resin compositions are characterized by comprising polymer particles (C) which are obtained by mixing a latex of polymer fine particles (A) having a volume-mean particle diameter of 1 to 50[mu]m with a polymerizable monomer (B), a polymerization initiator, a suspending dispersant, and a coagulant and subjecting the obtained mixture to granulation and suspension polymerization and which have a volume-mean particle diameter of 100 to 6000[mu]m and a content of fine powder of 50[mu]m or smaller of 15 percent by weight or below and at least one base resin (D) selected from the group consisting of thermoplastic resins, thermosetting resins, and elastomers.

Description

Polymer particle and preparation method thereof and the resin combination and the formed body that contain this polymer particle

Technical field

The resin combination and the formed body that the present invention relates to polymer particle and preparation method thereof and contain this polymer particle.

Background technology

In recent years, the particulate with the particle diameter about 1～50 μ m receives publicity in a lot of fields, necessitates in this external various uses.For example can enumerate as the slipperiness imparting agent in the light diffusing agent in modifier, paint field or the various indicating meter or matting agent, the cosmetic field, the toning agent in the field of electronic copier is with the expansion of material.The application of expecting the particle of this micron order size enlarges from now on day by day.

For example, light diffusing agent refers in projection TV, liquid crystal indicator, illumination cover etc., in order to obtain light diffusing, is dispersed in specific refractory power in the transparent resin mineral-type different with this transparent resin or the particulate of organic class.

In addition, matting agent refer to obtain by resins such as acrylic resin, vinyl chloride resin, ABS resin have the purposes that the glossy moulded products is used for pool of light requirement not or matt excellence on the contrary the time, be dispersed in the mineral-type in the resin or the particulate of organic class.

As the mineral-type particulate that uses in this purposes, can enumerate median sizes such as barium sulfate, lime carbonate, quartz is the following mineral-type particulate of 10 μ m etc.Further, as the substitute of these mineral-type particulates, (for example, with reference to the patent documentations 1) such as high molecular particles that also can use vinylbenzene or substituted phenylethylene and multi-functional monomer copolymerization to obtain.

But when the above-mentioned mineral-type that generally will use so far or organic based fine particles were dispersed in the resin, the shock strength of the formed body that obtains had the situation of reduction.Therefore, there is the problem of only using in above-mentioned particulate in limited purposes.

In contrast, the reduction of the intensity of the physics of the substrate resin in order to suppress to be dispersed in high molecular particle in the substrate resin, a kind of high molecular particle is disclosed, this high molecular particle is the high molecular particle that contains core/outer cover polymer, it is characterized in that, core contains and has the elastomeric alkyl acrylate that carbonatoms is 2～8 a alkyl, and shell and matrix polymer have Combination, have about 5～40 weight % (for example, with reference to patent documentation 2) in particle.

Example as the purposes that above-mentioned high molecular particle is used for essential light diffusing discloses the use methacrylic resin as substrate resin (transparent resin), forms to contain the light diffusing agent of the outermost layer of acrylic polymers as high molecular particle.At this moment, acrylic polymers is general because the optical excellent with the affinity excellence of methacrylic resin, is expected the light-diffusing resin composition that obtains having high characteristic.

In addition, the light diffusing high molecular particle that disclose a kind of CV value spherical about being essentially, that median size is 3～20 μ m, size distribution and be below 20%, the particle more than the 75 quality % of polymer particle has the particle diameter of median size ± 10% by use, can obtain having concurrently excellent light diffusing and the photopermeability of excellence and the light diffusing sheet (for example, with reference to patent documentation 3) of outward appearance excellence

And, method as the preparation that is suitable for above-mentioned high molecular particle, following method is disclosed: at first, monomer or the monomer mixture initial stage that is divided into are added with monomer and dropping monomer, then in the water medium that contains damping fluid that is added with persulfate initiator, the above-mentioned initial stage of disposable interpolation adds with behind the monomer, keep certain hour to form seed (kind) particle, then, after in this polymeric system, adding persulfate initiator once more, get started with certain hour and drip above-mentioned dropping monomer, keep the preparation (for example, with reference to patent documentation 4) of the polymer latex of certain hour.

Further, as the method that effectively prepares the polymer particle of micron order size with simple operation with the distribution of comparison homogeneous particle diameter, disclose and to have contained polymerizable monomer, solubleness in 20 ℃ water is that the molecular weight below the 0.05 weight % is that slightly water-soluble material and the solubleness in 20 ℃ water below 20000 is the solution of the polymerization initiator below the 0.05 weight %, mix with the solution that contains emulsifying agent and/or water-soluble high-molecular compound and water, these mixtures are applied the shearing of machinery, prepare O/W type emulsion thus, carry out polymerization then, thereby the preparation volume average particle size is about the method (for example, with reference to patent documentation 5) of the polymer particle of 2～20 μ m.

And, above-mentioned high molecular particle latex, the general aggregate recovery of adopting following method as high molecular particle, described method has: polymerization finish the back by dewater, the method for dried recovered, add acid or salt, make polymer latex curdling, de-watering of slurries, exsiccant method obtaining, or spray-dired method.

But, when utilizing above-mentioned recovery method, the volume average particle size of the high molecular particle aggregate that obtains is usually less than 100 μ m, micro mist waits the situation of powder characteristics difference of goods more more, produces therefore that operability is poor, powder flies upward fierceness, operating environment variation or have the problems such as hazardous condition that cause dust explosion.

On the other hand, in order to address the above problem, disclosing by containing second-order transition temperature (below be also referred to as Tg) is the internal layer more than at least 1 layer of the acrylic polymers below 0 ℃ and to contain ratio shared in all particles be that the Tg of 1 quality %～5 quality % is the acrylic acid or the like particulate that the outermost layer of the acrylic polymers more than 50 ℃ constitutes, the volume average particle size of the aggregate by making this acrylic acid or the like particulate is 100～1000 μ m, powder characteristics can be improved, excellent operation and productivity can be realized.

But, when utilizing this method,, be difficult to adjust quality because the structural restriction of high molecular particle is big, there is the problem that only goes in the specific field.In addition, in this method, not on the books for whether being a granulated into more than the 1000 μ m.

Patent documentation 1: Japanese kokai publication sho 56-36535 communique

Patent documentation 2: TOHKEMY 2000-53841 communique

Patent documentation 3: Japanese kokai publication hei 7-234304 communique

Patent documentation 4: Japanese kokai publication hei 8-198903 communique

Patent documentation 5: Japanese kokai publication hei 10-120715 communique

Patent documentation 6: TOHKEMY 2001-294631 communique

Summary of the invention

The problem that invention will solve

The present invention, in order to solve the problems referred to above that prior art has, its purpose is, provide structural restriction less, have the preparation method of the high molecular polymer particle of excellent powder characteristics, and the extinction resin combination that operability is also excellent when containing high molecular polymer particle with excellent powder characteristics, physical properties excellent, light-diffusing resin composition, their formed body.

The method of dealing with problems

The inventor is few for the structural restriction for preparing high molecular particle, and has the polymer particle of excellent powder characteristics and found that of studying intensively repeatedly, by latex with high molecular particle, polymerizable monomer, polymerization starter, suspension dispersive agent, peptizer mixes, and carry out granulation and suspension polymerization, it is few then can to obtain structural restriction, high molecular polymer particle with excellent powder characteristics, in addition, by this high molecular polymer particle is engaged in the substrate resin, the also excellent extinction resin combination of operability when then can obtain physical properties excellent, light-diffusing resin composition, thus the present invention finished.

Promptly, polymer particle of the present invention is polymer particle (C), this polymer particle (C) is by the latex that contains the polymer particles that volume average particle size is 1～50 μ m (A), polymerizable monomer (B), polymerization starter, the system of suspension dispersive agent and peptizer is carried out granulation, and carry out the polymer particle that suspension polymerization obtains, wherein, because the volume average particle size of this polymer particle (C) is 100～6000 μ m, and the content of the micro mist that 50 μ m are following is below the 15 weight %, so forming powder flies upward few, the operability excellence, further can easily be dispersed into the unitary size of polymer particles (A), therefore be to give the excellent low gloss or the polymer particles of light diffusing to substrate resin (D).

This polymer particle of the present invention, can be by in the presence of the latex of above-mentioned polymer particles (A), add above-mentioned polymerizable monomer (B), above-mentioned polymerization starter, above-mentioned suspension dispersive agent and above-mentioned peptizer, the preparation method who carries out above-mentioned granulation and above-mentioned suspension polymerization prepares.

Promptly, polymer particle of the present invention is the preparation method by following polymer particle, and become the polymer particle that can prepare, above-mentioned granulation among the preparation method of described polymer particle is by in the presence of the latex of above-mentioned polymer particles (A), add that above-mentioned polymerizable monomer (B), above-mentioned polymerization starter, above-mentioned suspension dispersive agent and above-mentioned peptizer carry out, described granulation comprises:

Destroy above-mentioned polymer particles (A) latex emulsified state and

With above-mentioned system transition is that volume average particle size is the suspension system of 100～6000 μ m.

Wherein, serves as preferred to comprise by using the anionic species emulsifying agent prepares above-mentioned polymer particles (A) as the suspension polymerization of suspension dispersive agent step as the preparation method of the polymer particle of feature, this method can be carried out granulation to polymer particles (A) effectively, and the granulation of polymer particle (C) is had no adverse effects.

Polymer particle of the present invention (C) be preferably contain proportioning be 0.5: 99.5～95: 5 (wherein, weight ratio (A): (B)) polymer particle of the above-mentioned polymer particles (A) of scope and above-mentioned polymerizable monomer (B), can show rerum natura from high molecular particle (A), and the powder characteristics excellence.

In addition, above-mentioned polymer particles (A) is (methyl) alkyl-acrylates polymer particles, or organo-siloxanes polymer particulate, and the second-order transition temperature of the homopolymer that it is made is to be the polymer particle of feature below 0 ℃, and is preferred especially when requiring to have characteristic such as shock-resistance for the moulded products that uses resin combination manufacturing of the present invention.

Further, above-mentioned polymerizable monomer (B) is for being selected from one or more the monomer in (methyl) alkyl-acrylates monomer, aromatic ethylene base class monomer, vinyl cyanide monomer, vinyl acetate monomer and the vinyl chloride monomer, and these monomers are because excellent and preferred with the affinity of matrix resin.

Resin combination of the present invention is to contain with the polymer particle (C) of the preparation method of above-mentioned polymer particle of the present invention preparation and the resin combination of substrate resin (D), it is characterized in that above-mentioned substrate resin (D) is for being selected from least a in thermoplastic resin, thermosetting resin and the elastomerics.

Wherein, be preferably containing above-mentioned substrate resin (D) 100 weight parts and above-mentioned polymer particle (C) 0.01～500 weight part is the resin combination of feature, keeping quality is excellent and can not reduce rerum natura such as shock strength.

Further, more preferably to contain above-mentioned substrate resin (D) 100 weight parts and above-mentioned polymer particle (C) 0.1～500 weight part is the resin combination of feature.

In addition, above-mentioned substrate resin (D) is preferably at least a resin that is selected from thermoplastic resin and the thermosetting resin and is transparent resin.

More preferably above-mentioned substrate resin (D) is that the total light transmittance of the formed body of its thickness 3mm is the transparent resin more than 40%.

Further, be that the gloss reducing polymer particle is the extinction resin combination of feature preferably with above-mentioned polymer particle (C), therefore the formed body of this extinction resin combination of the present invention can be used for the purposes of requirement low gloss suitably by delustring to heavens.

The glossiness on the above-mentioned formed body surface under preferred input angle 60 degree of this formed body of the present invention is below 110.

In addition, further, be that the light diffusing polymer particles is the light-diffusing resin composition of feature preferably with above-mentioned polymer particle (C).

Wherein, as the specific refractory power of above-mentioned polymer particles (A), preferably in 1.350～1.650 scope.

In addition, the absolute value of the difference of the specific refractory power of above-mentioned polymer particles (A) and above-mentioned substrate resin (D) is preferably in 0.001～0.3 scope.

The formed body of this light-diffusing resin composition of the present invention can be used for the purposes of essential light diffusing, photopermeability suitably.

Particularly with the formed body of light-diffusing resin composition during, preferably make total light transmittance and be more than 10%, the mist degree rate is the light diffusing sheet more than 40% as light diffusing sheet.

The effect of invention

According to the preparation method of polymer particle of the present invention, can obtain structural restriction less, have a high molecular particle of excellent powder characteristics.The also excellent feature of operability when in addition, the resin combination that contains this high molecular particle has physical properties excellent.This resin combination can be suitably as the extinction resin combination of the raw material of the extinction formed body that becomes the requirement low gloss or become the light-diffusing resin composition of raw material of the light diffusing formed body of requirement light diffusing, the transparency.

Embodiment

Resin combination of the present invention can be suitably as extinction resin combination and light-diffusing resin composition etc.Below describe.And in this specification sheets, (methyl) acrylic acid or the like only otherwise specify then refers to acrylic acid or the like and/or methacrylic.

(polymer particle (C))

The polymer particle that the present invention relates to (C) is by the latex with the polymer particles (A) of volume average particle size 1～50 μ m, polymerizable monomer (B), polymerization starter, suspension dispersive agent and peptizer mix, granulation and suspension polymerization prepare, in order to realize the excellent productivity and the operability of goods, by making its volume average particle size is 100～6000 μ m, and the following micro mist amount of 50 μ m is below the 15 weight % of total amount, then can mix to form and to carry out forming process with substrate resin (D), the resin combination of the operability excellence of coating etc., by implementing this forming process, coating, can easily be dispersed into the unitary size of polymer particles (A), not only can give low gloss to substrate resin (D), light diffusing, but also the extinction resin combination or the light-diffusing resin composition of the homogeneity excellence of these characteristics in the composition can be provided.Wherein, the above-mentioned volume average particle size scope of 100～4000 μ m more preferably.In addition, the following micro mist amount of above-mentioned 50 μ m is more preferably below the 10 weight % of total amount.The following micro mist amount of 50 μ m is 15 weight % of total amount when above, and the generation frequency that powder flies upward increases, the possible variation of operability.

And, above-mentioned volume average particle size, when its value is a scope about 0.2～700 μ m, can use according to the method in the measuring method of JIS Z8901 regulation and measure, when it is worth the scope that surpasses about 700 μ m, can use observation by light microscope, try to achieve by 100 particles selecting are at random carried out image analysis.

In addition, the mensuration of above-mentioned micro mist amount for example, can be implemented according to the measuring method of JIS Z8901 regulation.

In addition, resin combination of the present invention is owing to contain this polymer particle (C) with excellent powder characteristics, therefore has excellent operation, what produce in the time of can preventing to use resin combination in the past flies upward the variation of the operating environment that is caused because of the powder of fierceness, can significantly reduce the danger of dust explosion in addition, so can significantly improve productivity.

Below there is the situation that the polymer particle (C) that uses in the above-mentioned extinction resin combination is recited as gloss reducing polymer particle (C), exists the polymer particle (C) that to use in the above-mentioned light-diffusing resin composition to be recited as light diffusing polymer particle (C) in addition, substrate resin (D) be recited as the situation of transparent resin (D).Further, constitute the substrate resin (D) of resin combination of the present invention and polymer particle (C) only otherwise the characteristic of the necessary moulded products of infringement then can use with arbitrary combination.

(substrate resin (D))

Above-mentioned substrate resin (D) forms matrix resin, is preferably to be selected from least a in common known thermoplastic resin, thermosetting resin and the elastomerics.

As above-mentioned transparent resin (D), in order to present excellent light diffusing energy, the preferred formed body of the thickness 3mm that makes by independent transparent resin (D), measure the total light transmittance that obtains according to the measuring method of JIS K7361-1 regulation and be preferably more than 40%, be preferably the transparent resin of the total light transmittance more than 80% more preferably more than 50%, especially.When to use this total light transmittance be transparent resin (D) below 40%, the transparency was poor, might not show the light diffusing energy.

And the formed body of above-mentioned 3mm thickness can obtain according to known method such as extrusion forming method, injection moulding, extrusion mouldings.For example, for the formed body that obtains by injection moulding, can measure total light transmittance by using commercially available light penetration determinator.

In addition, as this transparent resin (D), consider from the excellent aspect of wide usage, be preferably (methyl) acrylic resins such as plexiglass, methyl methacrylate-butyl acrylate copolymer resin, polycarbonate resin, styrene resins such as polystyrene, the copolymer of methyl methacrylatestyrene resin, the styrene-acrylonitrile copolymer resin, acrylonitrile-butadiene rubber-styrol copolymer (ABS) resin, vinyl chloride resin.Above-mentioned transparent resin can be used alone or in combination.But when being used in combination as if various kinds of resin, then in most cases, total light transmittance reduces, so preferred use separately.

(various additive)

And, in resin combination of the present invention, as required, for example, can suitably use softening agent, solidifying agent, dispersion agent, various flow agents, UV light absorber, viscosity modifying agent, lubricant, prevent degradation, static inhibitor, fire retardant, white dyes, fluorescence dye, pigment, tinting material, antioxidant (for example, sulfur-containing molecules, phosphoric acid ester (ホ ス Off ァ ィ ト), hindered phenol, phosphinate, phosphinate etc.) or Photostabilised dose of stablizers such as (ultra-violet stabilizers etc.), the binding property imparting agent, releasing agent, the shock-resistance activator, processing aid, whipping agent, weighting agent (for example, glass fibre etc.), supporting material, the additive that thermotolerance imparting agent etc. cooperate in common moulded products.

(extinction resin combination)

In above-mentioned extinction resin combination, gloss reducing polymer particle (C) is for the use level of substrate resin (D), usually with respect to substrate resin (D) 100 weight parts, is preferably 0.1～500 weight part, 0.1～300 weight part more preferably.Above-mentioned use level is difficult to reach the delustring level of target during less than 0.1 weight part, on the contrary, during more than 500 weight parts, the situation that exists rerum naturas such as the superficiality variation of moulded products or shock strength to reduce.

During as the extinction resin combination, when further requiring photopermeability, the specific refractory power (n of above-mentioned polymer particles (A) or gloss reducing polymer particle (C) and substrate resin (D) ²⁵ _D) the absolute value of difference be preferably below 0.01, more preferably below 0.005, more preferably below 0.002.Usually substrate resin (D) is difficult to adjust according to purposes decision, its specific refractory power of end article, and this refringence can be formed the above-mentioned scope that reaches by adjusting the polymkeric substance that constitutes polymer particles (A) or gloss reducing polymer particle (C).

Above-mentioned extinction resin combination can pass through known method, for example uses formation particles such as forcing machine, is shaped to film, sheet, tabular at an easy rate by the methods such as extrusion moulding, injection molding, calendering formation, blow molding, compressed moulding or inflation moulding that contain T pattern head method etc. again.In addition, also above-mentioned extinction resin combination directly can be extruded and covered on the base material, can obtain goods laminated into type.At this moment, never be subject to each layer rheological properties influence and obtain excellent moulded products aspect and consider, preferably use the multichannel manifold die.Further, be coated on method on the base materials such as resin or metal equably, also can make moulded products by the resin that will be dispersed with gloss reducing polymer particle (C).

This extinction formed body is by the height delustring; so can be used for the purposes of requirement low gloss; building materials such as outer wall materials, window frame, rainwater slide, various flexible pipe coatings for example; groceries such as tableware, toy; the cover tool of illumination etc.; vehicle parts such as vehicle interior trim parts, outer decorative element; house inner decoration materials such as light current parts, wallpaper, decorative sheet; dwelling house facilities such as household electrical appliance goods, OA machine, ship components, communicating machine are in the soft films such as the mulch film of upholstery parts, vehicle inside panel or protective membrane etc.

In addition, the input angle preferably measured according to the measuring method of JIS Z8741 regulation of this extinction formed body is that the glossiness on the formed body surface under 60 degree is, more preferably below 90, be preferably below 50 especially below 110.The glossiness on formed body surface surpasses at 110 o'clock might not show extinction.In other words, extinction can be estimated by glossiness.And specifically, the surface luster of formed body for example, can be used glossmeter by according to the method in the measuring method of ASTM D-523 regulation, suitably measures as glossiness.

(light-diffusing resin composition)

In above-mentioned light-diffusing resin composition, light diffusing polymer particle (C) is for the use level of transparent resin (D), usually with respect to transparent resin (D) 100 weight parts, is preferably 0.01～500 weight part, 0.05～300 weight part more preferably.

Most preferred above-mentioned use level can be decided by the characteristic (total light transmittance, specific refractory power etc.) of transparent resin (D) relation with the characteristic (total light transmittance, specific refractory power, median size etc.) of light diffusing polymer particle (C).For example, poor according to the specific refractory power of light diffusing polymer particle (C) and transparent resin (D), this difference hour, in order to obtain excellent light diffusing, preferably increase above-mentioned use level, when this difference is big, in order to obtain excellent photopermeability, preferably reduce above-mentioned use level.In addition, median size according to relative light diffusing polymer particle (C), this median size hour is in order to obtain excellent photopermeability, preferably reduce above-mentioned use level, coating for the smoothness excellence that makes the light diffusing sheet surface and light-diffusing resin composition when this median size is big is not difficult, does not preferably increase above-mentioned use level.

During as light-diffusing resin composition, the specific refractory power (n of polymer particles (A) and substrate resin (D) ²⁵ _D) the absolute value of difference be preferably 0.001～0.3 scope, more preferably 0.003～0.3 scope, more preferably 0.005～0.2 scope.Above-mentioned specific refractory power (n ²⁵ _D) be according to JIS K7142 regulation measuring method, 25 ℃ of specific refractory poweres of measuring the D line that obtains down.There is light insufficient refractive situation by light diffusing sheet in the difference of above-mentioned specific refractory power less than (±) at 0.001 o'clock, the trend enhancing that incident light directly penetrates, and existence can not be brought into play the situation of the light diffusing of excellence.In addition, above-mentioned on the contrary refringence is greater than 0.3 o'clock, and big in the refraction of the light of light diffusing sheet inside, the light of outgoing strengthens with respect to the trend that incident light reduces, the situation that exists the total light transmittance of light diffusing sheet to reduce.

Above-mentioned light-diffusing resin composition, for example, can obtain mixture by blending dispersion light diffusing polymer particle (C) in monomer, monomer mixture or the polymkeric substance of the preparation that is used for transparent resin (D) and monomeric mixture (slurry), with this mixture polymeric cast poymerization method in mold; The mixture that obtains for blending dispersion light diffusing polymer particle (C) in transparent resin (D) uses forcing machine etc. with the particle extrusion moulding or the injection molding method that form; The transparent resin (D) that maybe will be dispersed with light diffusing polymer particle (C) is coated on method on the one or both sides of tabular or membranaceous resin etc. equably and is processed into tabular.

So be processed into tabular above-mentioned light-diffusing resin composition can be used for projection TV with transmission-type screen, liquid crystal backlight with in the light diffusing sheet of light diffusing sheet or operable essential light diffusing such as illumination cover, illumination signboard, photopermeability etc.

This light diffusing sheet preferably has excellent photopermeability, light diffusing, specifically, light diffusing sheet for the thickness 3mm that measures according to JIS K7361-1, value as the total light transmittance of the index of photopermeability is preferably more than 10%, is preferably more than 40% as the value of the mist degree rate of the index of light diffusing.The value of above-mentioned total light transmittance more preferably more than 40%, more preferably more than 80%, low excessively less than 10% o'clock photopermeability, existence can not offer the situation as the use of light diffusing sheet.In addition, the value of above-mentioned mist degree rate more preferably more than 50%, more preferably more than 90%, low excessively less than 40% o'clock light diffusing, existence can not offer the situation as the use of light diffusing sheet.Self-evident ground, the photopermeability of this light diffusing sheet, light diffusing change with the difference of the specific refractory power of transparent resin (D) and the changes such as content of the light diffusing polymer particle (C) in the light diffusing sheet according to thickness, the median size of high molecular particle (A), the polymer particles (A) of light diffusing sheet.

(polymer particles (A))

The volume average particle size of above-mentioned polymer particles (A) is preferably the scope of 1～50 μ m, the more preferably scope of 1～30 μ m.The volume average particle size of polymer particles (A) is during less than 1 μ m, because relative increase, the reflection of light face long-pending along with particle surface increase relatively, so there is the trend of easy reduction of the photopermeability of the formed body that obtains by the resin combination that contains polymer particle (C) or extinction variation.On the contrary, the volume average particle size of polymer particles (A) is during greater than 50 μ m, during preparation polymer particle (C), produce scale polymerization instabilities such as (scale), powder characteristics has the trend of variation in addition, further, by the formed body that the resin combination that contains the polymer particle (C) that so obtains obtains, there is the situation of its appearance variation.

In addition, above-mentioned polymer particles (A) is preferably formed by adjusting its polymkeric substance, makes specific refractory power (n ²⁵ _D) value be 1.350～1.650 scope, 1.400～1.600 scope more preferably.

Further, above-mentioned polymer particles (A) can be single layer structure, but also can suitably adopt two-layer above multilayered structure as required, for example internal layer is by the high polymkeric substance of Tg, the outer polymkeric substance that is made of the low polymkeric substance of Tg is formed different structures, the cross-linking density of internal layer is low, outer compares the high structure of cross-linking density with internal layer, or internal layer carries out crosslinked and outer no crosslinked structure etc. according to different and different structure such as each layer cross-linking density etc.

Above-mentioned polymer particles (A) can be obtained by the general polymerizable monomer polymerization of using in emulsion polymerization, suspension polymerization.That is,, can pass through known emulsion polymerization or suspension polymerization, polymerizable monomer polymerization described later is prepared as the latex that contains above-mentioned polymer particles (A).But, consider especially preferably to prepare with suspension polymerization from the simplicity aspect of polymerization procedure.In addition, when above-mentioned polymer particles (A) is an organo-siloxanes polymer particulate described later, also can obtain by the method for forced emulsification after solution polymerization.

In addition; for the moulded products that uses resin combination of the present invention to make; when requirement has characteristics such as shock-resistance; above-mentioned polymer particles (A) is (methyl) alkyl-acrylates polymer particles or organo-siloxanes polymer particulate; because the second-order transition temperature of their homopolymer is below 0 ℃, so preferred.That is shock-resistance might variation when, wherein to use the second-order transition temperature of homopolymer be monomer more than 0 ℃.

Above-mentioned (methyl) alkyl-acrylates polymer particles is with above-mentioned (methyl) alkyl-acrylates monomer and above-mentionedly have the particulate that the multi-functional monomer polymerization of two above polymerizability unsaturated groups obtains at intramolecularly.

Above-mentioned organo-siloxanes polymer particulate, be will be selected from modification or unmodified organopolysiloxane, annular siloxane and the multi-functional silane that uses as required in the particulate that forms of more than one compound polycondensation, the content of preferred volatile low-molecular-weight siloxane is few.This organo-siloxanes polymer particulate for example, can form by the known method of putting down in writing in Japanese kokai publication hei 11-222554 communique, the TOHKEMY 2001-288269 communique.

(preparation method of polymer particles (A))

As with above-mentioned polymer particles (A) polymeric method, preferred at first preparation contains polymerizable monomer, slightly water-soluble material, oil-soluble polymerization initiator, emulsifying agent and/or contains the suspension dispersive agent of water-soluble high-molecular compound and the mixed solution of water, then, this mixed solution is applied mechanical shearing prepare O/W type emulsion, then, after importing to the O/W type emulsion that so prepares in the poly-unit, further under the intensification condition, O/W type emulsion is carried out the polymeric method.

When preparing this emulsion, in order to control O/W type particle size of emulsion, preferred use can be regulated the diverting device of shearing resistance, and the limit is regulated this intensity limit and implemented, in addition, more preferably carry out simultaneously cooling operation with the heat release that can not produce owing to this shearing initiated polymerization.Further, in order to obtain having the more O/W type emulsion of the size-grade distribution of homogeneous, emulsive film emulsion process is carried out by porous structure body limit in the preferred limit of using, particularly because the character of the film of conduct use this moment, with the wetting problem of disperse phase be important, for more easy to operate, preferably use hydrophilic film.

During this polymerization, the preferred device that uses heating cooling bodies such as having stirring mechanism and chuck carries out polymerization as poly-unit when carrying out stirring operation, in addition, carry out polymerization when more preferably heating cooling operation as required.

In addition, in order to prepare the latex of the polymer particles that volume average particle size is 1～50 μ m (A), preferably as required in polymerization and/or after the polymerization end, further add continuously or off and on and contain one or more the monomer that is selected from the above-mentioned polymerizable monomer, also can suitably use normally used chain-transfer agent in emulsion polymerization, suspension polymerization.

In addition, polymer particles (A) is being carried out effectively aspect granulation and the suspension polymerization polymer particle (C), the preferred anionic species emulsifying agent that uses is as above-mentioned suspension dispersive agent, its consumption is with respect to polymerizable monomer 100 weight parts, is preferably about 0.01～50 weight part, more preferably about 0.01～5 weight part.

But, the polymerization temperature as with above-mentioned organo-siloxanes polymer particulate polymerization the time, be preferably 0 ℃～100 ℃, more preferably below 50 ℃, more preferably below 30 ℃.In addition, preferably by add the acid be used to form acidic conditions in system, carry out the forced emulsification polymerization, the pH during this moment polymerization is preferably below 4, more preferably below 3, be preferably below 2 especially.Further, after under acidic conditions, finishing polymerization, as required with latex more than near the slaking a few hours room temperature, after making organopolysiloxane form high molecular, by adding mineral alkalis such as sodium hydroxide, potassium hydroxide, yellow soda ash, ammonia, in the organic bases such as alkylamine, alkyl ammonium hydroxide and system so that pH is 5～8, can stop the polymerization of siloxanes thus.

In addition, during above-mentioned forced emulsification polymerization, under the situation of using acid polymerizing condition, even under acidic conditions, also can preferably use the emulsifying agent of performance surfactivity ability as emulsifying agent.

Further, after above-mentioned solution polymerization, carry out preferably after in system, appending water, emulsifying agent etc., further forming desired particle diameter in the method for forced emulsification by diverting device.

(polymerizable monomer (B))

As above-mentioned polymerizable monomer (B), can use the identical polymerizable monomer of monomer that uses in the preparation with polymer particles (A), but there is no need the polymerizable monomer polymerizable monomer of the same race that uses in certain preparation of using with polymer particles (A), can suitably select according to its purposes, characteristic.For example, when polymer particle (C) for example is used as modifier, from considering with the affinity aspect of matrix resin, as polymerizable monomer (B), be preferably one or more monomers that are selected from (methyl) alkyl-acrylates monomer, aromatic ethylene base class monomer, vinyl cyanide monomer, vinyl acetate monomer and the vinyl chloride monomer.In addition, during with this polymerizable monomer (B) polymerization, can suitably use chain-transfer agent.

Proportioning (weight ratio) as above-mentioned polymer particles (A) and above-mentioned polymerizable monomer (B) is preferably 0.5: 99.5～95: 5 scope, more preferably 2: 98～85: 15 scope.During more than 99.5 weight %, because the content of polymer particles (A) is low excessively, there is the trend that is difficult to show from the rerum natura of high molecular particle (A) in polymer particles (A) less than 0.5 weight %, polymerizable monomer (B).In addition, polymer particles (A) is more than 95 weight %, polymerizable monomer (B) during less than 5 weight %, has owing to do not enter the micro mist generation that existence caused etc. of the polymer particles (A) in the polymer particle (C), the situation of the powder characteristics variation of goods.

(preparation method of polymer particle (C))

During for the above-mentioned polymer particle of preparation (C), latex, polymerizable monomer (B), polymerization starter, water-soluble polymer, the suspension dispersive agent that contains the slightly water-soluble inorganics and the peptizer blended method of above-mentioned polymer particles (A) are not limited especially, can use known tempering tank or poly-unit with stirrer etc.In addition; for the order of adding these compositions and the speed of interpolation; can be according to the composition of polymer particles (A); be muchly suitably to set perhaps according to the particle diameter of the polymer particle after granulation or the suspension polymerization (C); but consider from the production efficiency aspect; preferably in the presence of the latex of polymer particles (A), add polymerizable monomer (B), polymerization starter, suspension dispersive agent, peptizer, the method for carrying out granulation and suspension polymerization.And, for the preparation of polymer particles (A) latex and the preparation of polymer particle (C), can prepare respectively or preparation continuously.

Above-mentioned granulation refers to by the latex with polymer particles (A), polymerizable monomer (B), polymerization starter, suspension dispersive agent and peptizer mix, destroy the emulsified state of the latex of polymer particles (A), make its dispersion state change the step of the suspension system of volume average particle size 100～6000 μ m into, according to the present invention, the latex of polymer particles (A) can be changed effectively into the suspension system that volume average particle size is 100～6000 μ m by this granulation step, further, by with its suspension polymerization, can prepare polymer particle of the present invention (C) effectively.

In addition, the solid component concentration of the polymerization system behind latex, polymerizable monomer (B), polymerization starter, suspension dispersive agent and the peptizer of interpolation polymer particles (A) can suitably be set according to the viscosity of system.But when considering the viscosity of polymerization system and production efficiency, preferred solid component concentration is about 15～40 weight %.

As the polymerization starter that in the preparation of above-mentioned polymer particle (C), uses, can use the same polymerization starter of oil-soluble polymerization initiator that uses when preparing polymer particles (A).But, in the preparation of polymer particles (A) and polymer particle (C), there is no need necessarily to use polymerization starter of the same race.

Further, as the suspension dispersive agent that in the preparation of polymer particle (C), uses, can use to be selected from same compound of the water-soluble polymer that uses when preparing above-mentioned polymer particles (A) and the suspension dispersive agent in the slightly water-soluble inorganics described later.

Further, the consumption of suspension dispersive agent, the consumption that uses during by common suspension polymerization can stably carry out polymerization, but, preferably use 0.01～30 weight part, further more preferably use 0.01～20 weight part with respect to the resin solid composition of polymer particles (A) latex and total amount 100 weight parts of polymerizable monomer (B).

Peptizer as using when the preparation of above-mentioned polymer particle (C) can use acid such as being selected from hydrochloric acid, sulfuric acid, the peptizer in the salt such as calcium chloride, magnesium chloride, sodium sulfate, sal epsom, lime carbonate, lime acetate suitably.Wherein, consider from making polymer particles (A) gel aspect effectively, more preferably sodium sulfate, calcium chloride.

The consumption of above-mentioned peptizer and kind thereof can suitably be selected preferably to measure and kind because the amount of the suspension dispersive agent that uses when (A) according to the preparation polymer particles is different with kind and different.But, for example,, preferably use 0.1～20 weight part, further more preferably use 0.1～15 weight part with respect to the resin solid composition of polymer particles (A) latex and total amount 100 weight parts of polymerizable monomer (B).

And in preparation method of the present invention, when not using peptizer fully, the major part of polymer particles (A) does not enter in the polymer particle (C) and residual, because the existence of residual polymer particles (A), the filtrate after the polymerization has the trend of gonorrhoea.In addition, exist the production efficiency of polymer particle (C) to reduce or powder characteristics variation, the powder of goods flies upward the trend of fierceness, operability variation.

(example of emulsion polymerization, suspension polymerization)

And, as the object lesson of above-mentioned emulsion polymerization or suspension polymerization, preferably enumerate the method for putting down in writing in Japanese kokai publication sho 63-137911 communique, Japanese kokai publication hei 2-311685 communique, Japanese kokai publication hei 7-238200 communique, Japanese kokai publication hei 8-198903 communique, TOHKEMY 2001-294631 communique, Japanese kokai publication hei 10-87710 communique, Japanese kokai publication hei 10-120714 communique or the Japanese kokai publication hei 10-120715 communique.

(polymerizable monomer)

As above-mentioned polymerizable monomer, can for example enumerate one or more the monomer that is selected from (methyl) alkyl-acrylates monomer, aromatic ethylene base class monomer, vinyl cyanide monomer, vinyl-acetic ester and the vinylchlorid, further, can in them, append suitably, use and comprise the multi-functional monomeric monomer that intramolecularly has two above polymerizability unsaturated groups.In addition, the polymerizable monomer as with above-mentioned organo-siloxanes polymer particulate polymerization the time can be enumerated, and is preferably selected from more than one the compound in modification or unmodified organopolysiloxane, annular siloxane and the multi-functional silane.

As above-mentioned (methyl) alkyl-acrylates monomer, can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid n-octyl and (methyl) 2-EHA etc.

As above-mentioned aromatic ethylene base class monomer styrene, can enumerate alpha-methyl styrene, chlorostyrene and 1-chloro-4-methyl-benzene etc.

As the aforesaid propylene nitrile monomer, can enumerate vinyl cyanide, methacrylonitrile and ethyl acrylonitrile etc. typically.

In addition, as comprising the multi-functional monomeric monomer that intramolecularly has two above polymerizability unsaturated groups, can enumerate (methyl) allyl acrylate, dially phthalate, ethylene glycol bisthioglycolate (methyl) acrylate, 1,3 butylene glycol two (methyl) acrylate, methylene-succinic acid diallyl, Vinylstyrene, triallyl cyanurate, triallyl isocyanurate etc.

As above-mentioned modification or unmodified organopolysiloxane, be preferably the organopolysiloxane that has hydrolization group endways, partly replaced by the free radical reaction group as required of straight or branched.In addition, the content of this volatile low-molecular-weight siloxane is preferably below the 5 weight %, more preferably below the 1 weight %.Further, its weight-average molecular weight (Mw) is preferably below 20000, more preferably below 10000, more preferably below 5000, be preferably below 2500 especially.By using this raw material and selective polymerization condition, can obtain the polymer particles (A) that volatile low-molecular-weight siloxane reduces.

As the said hydrolyzed group, can enumerate hydroxyl, amino, alkoxyl group, acyloxy, ketoxime base, alkenyloxy (ァ Le ケ ノ キ シ), amide group, azyloxy etc.

As above-mentioned free radical reaction group, be preferably sulfydryl propyl group, methacryloxypropyl, acryloxy propyl group, vinyl, ethenylphenyl, allyl group etc.

As above-mentioned annular siloxane, can enumerate hexamethyl cyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentaandoxane, ten diformazan basic rings, six siloxanes, tetradecamethylcycloheptasiloxane etc.

As above-mentioned multi-functional silane, can enumerate the condenses of the above silane of the above organoalkoxysilane of trifunctional, trifunctional and have the silane compound of free radical reaction group.

Wherein, the above organoalkoxysilane of above-mentioned trifunctional is Union carbide A-162, tetrapropoxysilane etc., the condenses of the silane that trifunctional is above is a methyl orthosilicate etc., in addition, as above-mentioned silane compound, can enumerate sulfydryl propyl group dimethoxy-methyl silane, acryloxy propyl group dimethoxy-methyl silane, methacryloxypropyl dimethoxy-methyl silane, vinyl-dimethyl oxygen ylmethyl silane, ethenylphenyl dimethoxy-methyl silane etc. with free radical reaction group.

(chain-transfer agent)

As above-mentioned chain-transfer agent, it is normally used chain-transfer agent in emulsion polymerization, suspension polymerization, for example can enumerate, alkyl sulfhydryls such as uncle's lauryl mercaptan, n-dodecyl mercaptan, uncle's decyl mercaptan, positive decyl mercaptan, n-octyl mercaptan, alkyl ester mercaptan such as 2-ethylhexyl mercaptoacetate etc.

(slightly water-soluble material)

As above-mentioned slightly water-soluble material; can preferably to use solubleness in 20 ℃ water be below the 0.05 weight % and molecular weight is a material below 20000; for example; can use and be selected from the methacrylic acid stearyl; methacrylic acid dinonyl phenylesters etc. are (methyl) alkyl-acrylates monomer class that carbonatoms is 12～30 chain alkyl that has of representative; with hexadecanol; stearyl alcohol etc. are that the carbonatoms of representative is 12～22 higher alcohols; with n-Hexadecane; octadecanes etc. are the hydro carbons of representative; with the 1-chlorododecane; 1-chlorodecane etc. is the halogenated hydrocarbons of representative, or is methyl methacrylate with the segmental main component for example; AA-6 (East Asia synthetic chemical industry (strain) system) or segmental main component that end has the number-average molecular weight 6000 of methacryloyl are butyl acrylate; end has AB-6 (East Asia synthetic chemical industry (strain) system) of the number-average molecular weight 6000 of methacryloyl etc. and has (methyl) acryl for the end of representative; to the styryl alkyl; the combination of one or more in the various macromonomer classes of dihydroxyl or dicarboxyl etc. etc.

But, in the time of will being used as modifier by the polymer particle (C) that the present invention obtains, if the compound that uses non-polymerizations such as higher alcohols, hydro carbons, halogenated hydrocarbons is during as the slightly water-soluble material, owing to remain in slightly water-soluble material in the polymer particle, the reason that problem such as become then that gas when easily causing moulding sometimes takes place or oilness is too much produces.In order to address this problem, preferably use intramolecularly to have the slightly water-soluble material of the polymerizability of at least one polymerizability unsaturated group.

(oil-soluble polymerization initiator)

As above-mentioned oil-soluble polymerization initiator, can use suitably and be selected from the organo-peroxide as representative such as benzoyl peroxide, lauroyl peroxide, stearoyl, peroxidation decoyl, with 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (4-methoxyl group-2,2,2 the 4-methyl pentane nitrile), '-azo two (2-methylbutyronitrile) etc. is one or more the combination in the azo compound of representative etc.

And, even state in the use under the situation of oil-soluble polymerization initiator, in order to prevent not in containing the oil droplet of polymerizable monomer and at the aqueous phase initiated polymerization, for example, can be as required and be the water miscible stopper of representative in order to Sodium Nitrite, quinhydrones.

(suspension dispersive agent)

Above-mentioned suspension dispersive agent is used for the preparation of emulsion.

During with above-mentioned polymer particles (A) polymerization, can use known emulsifying agent and/or water-soluble high-molecular compound, for example, emulsifying agent, the water-soluble high-molecular compound that can enumerate below the two or more alone or in combination uses, in addition, the consumption that uses in the time of can be with common suspension polymerization stably prepares emulsion, and can carry out polymerization.

In addition, when preparing above-mentioned polymer particle (C), use to be selected from the water-soluble polymer of use is identical when preparing above-mentioned polymer particles (A) compound and the material in the slightly water-soluble inorganics described later.

(emulsifying agent)

As mentioned emulsifier, can enumerate anionic species emulsifying agent, nonionic class emulsifying agent etc.

As above-mentioned anionic species emulsifying agent, can enumerate carboxylic-acid emulsifying agent, sulfonic acid class emulsifying agent, sulfuric acid based emulsifying agent, succinic acids emulsifying agent, phosphoric acid class emulsifying agent etc.

As above-mentioned nonionic class emulsifying agent, can enumerate with polyoxyethylene lauryl ether etc. is the polyoxygenated alkene alkyl oxide of representative, with polyoxyethylene nonylplenyl ether etc. is the polyoxygenated alkene alkyl aryl ether of representative, is the polyoxygenated alkene high-grade aliphatic ester of representative and Arlacel-20 etc. with polyoxyethylene stearic acid ester etc.

Even as the emulsifying agent of under above-mentioned acidic conditions, also bringing into play the surfactivity ability, can enumerate, for example, the anionic species emulsifying agents such as metal-salt of the metal-salt of alkyl sulfuric ester, the metal-salt of alkylsulphonic acid, alkyl aryl sulphonic acid, in addition, preferred metal-salt is an alkali metal salt, particularly sodium salt, sylvite, wherein sodium salt more preferably most preferably is Sodium dodecylbenzene sulfonate.In addition,,, also can use above-mentioned nonionic class emulsifying agent, further also they and above-mentioned anionic species emulsifying agent also can be used except mentioned emulsifier even as the emulsifying agent of under above-mentioned acidic conditions, also bringing into play the surfactivity ability.

(water-soluble high-molecular compound)

As above-mentioned water-soluble high-molecular compound, can enumerate water-soluble polymers such as starch, gelatin, polyvinyl alcohol, Polyvinylpyrolidone (PVP), polyacrylate, poly-methyl acrylate, polyvingl ether, polyethylene oxide, methylcellulose gum, Walocel MT 20.000PV, Vltra tears, carboxymethyl cellulose, sulfonated polystyrene glycol, styrene-maleic acid copolymer and vinyl-acetic ester-maleic acid etc.

(slightly water-soluble inorganics)

As above-mentioned slightly water-soluble inorganics, can enumerate phosphate metal salt such as tricalcium phosphate, calcium phosphate powder, and magnesiumcarbonate, lime carbonate, barium carbonate, magnesium oxide, Calcium Pyrophosphate, magnesium pyrophosphate, magnesium hydroxide, aluminium hydroxide, hydroxyapatite, talcum etc.

(acidic conditions is set the acid of usefulness)

The acid of the above-mentioned acidic conditions of formation that uses when being used for above-mentioned organo-siloxanes polymer particulate polymerization can be used mineral acids such as sulfuric acid, hydrochloric acid, nitric acid.Also can use organic acids such as Witco 1298 Soft Acid, dodecyl sulphate, trifluoroacetic acid.Be that the alkyl aryl sulphonic acid of representative not only has as the function of sour composition but also has function as emulsifying agent with the Witco 1298 Soft Acid, according to circumstances only use it to get final product sometimes, so preferred the use.And be not limited thereto, these acid, emulsifying agent can be any one of independent or multiple composition combination separately.

(diverting device)

As above-mentioned diverting device, for example can use known diverting devices such as high-pressure homogenizer, equal phase mixer, ultrasonic dispersing device or impeller pump suitably, in addition, preferred outfit can be carried out the diverting device of the cooling body of above-mentioned cooling operation.Further preferred the outfit on its part is used to implement the mechanism that above-mentioned film emulsion process is used, and specifically, is equipped with the mechanism of porous structure bodies such as tabular, tubulose.

Above-mentioned porous structure body, if the porous film of aperture homogeneous and both to have made be outside these, as long as but have the structure of a large amount of pores, just do not limit especially, specifically, can enumerate hydrophilic porous matter structure or hydrophobic porous matter structure.And, as above-mentioned hydrophilic porous matter structure, can enumerate the porous glass film, hydrophilic polyfluortetraethylemicroporous (PTFE) film, the cellulose ethanoate film, nitrocellulose filter, the metal porous matter structure of hydrophilization (コ one ズ マ ゼ ラ one, ラ モ Application De ス one パ one ミ キ サ first-class) etc., as above-mentioned hydrophobic porous matter structure, can enumerate hydrophobicity PTFE film, and be undertaken that hydrophobicity processing obtains or by making hydrophobic film that film immersion obtains in medium processing such as greases etc. by above-mentioned various porous films or porous structure body being carried out surface treatment etc.

(substrate resin (D): the example of thermoplastic resin)

As the preferred thermoplastic resin that can be used as above-mentioned substrate resin (D); can enumerate aromatic polycarbonate; polycarbonate resins such as aliphatic polycarbonate; vibrin; the polyestercarbonate resin; polyphenylene oxide resin; polyphenylene sulfide; polysulfone resin; polyethersulfone resin; the polyarylene resin; polyamide resins such as nylon; polyetherimide resin; polyacetal resins such as polyoxymethylene; polyvinyl acetal resin; the polyketone resin; polyether ketone resin, polyether-ether-ketone resin, poly-aryl ketones resin; polyethers nitrile resin; liquid crystalline resin, polybenzimidazole resin, poly-secondary spot acid resin; vinylic polymers or copolymer resin; to be selected from the aromatics alkenyl compound; methacrylic ester; vinylic polymers that the polymerization of vinyl monomer of more than one in acrylate and the acrylonitrile compound or copolymerization obtain or copolymer resin, vinyl cyanide-(ethylene-propylene-diene (EPDM))-aromatics alkenyl compound copolymer resin, polyolefin resin; vinyl chloride resin, celluosic resins such as ethanoyl Mierocrystalline cellulose etc.They can use in independent or two or more mixing.

In addition; be used for essential light diffusings such as light diffusing sheet; in the time of in the purposes of perviousness; as the preferred thermoplastic resin that can be used as transparent resin (D); can enumerate aromatic polycarbonate; polycarbonate resins such as aliphatic polycarbonate; vibrin; polyvinyl acetal resin; to be selected from the aromatics alkenyl compound; methacrylic ester; vinylic polymers that the polymerization of vinyl monomer of more than one in acrylate and the acrylonitrile compound or copolymerization obtain or copolymer resin; transparency polyolefins such as polypropylene; vinyl chloride resin, transparency cellulose resins such as ethanoyl Mierocrystalline cellulose etc.They can use in independent or two or more mixing.

(polyphenylene oxide resin)

Above-mentioned polyphenylene oxide resin is homopolymer or the multipolymer shown in the following general formula 1.

[Chemical formula 1]

(general formula 1)

(in the formula, Q ¹～Q ⁴Be the group of selecting from independent hydrogen atom and alkyl separately, m represents the integer more than 30.)

As the object lesson of above-mentioned polyphenylene oxide resin, can enumerate poly-(2,6-dimethyl-1, the 4-phenylene) ether, poly-(2-methyl-6-propyl group-1,4-phenylene) ether, poly-(2,6-diethyl-1, the 4-phenylene) ether, poly-(2-ethyl-6-propyl group-1,4-phenylene) ether, poly-(2,6-dipropyl-1, the 4-phenylene) ether, (2,6-dimethyl-1,4-phenylene) ether and (2,3,6-trimethylammonium-1,4-phenylene) multipolymer of ether, (2,6-diethyl-1, the 4-phenylene) ether with (2,3,6-trimethylammonium-1, the 4-phenylene) multipolymer of ether, (2,6-dimethyl-1, the 4-phenylene) ether and (2,3,6-triethyl-1,4-phenylene) multipolymer of ether etc.

Particularly gather (2,6-dimethyl-1, the 4-phenylene) ether and (2,6-dimethyl-1,4-phenylene) ether and (2,3,6-trimethylammonium-1,4-phenylene) multipolymer of ether considers it is preferred, poly-(2 from improving the thermotolerance aspect, 6-dimethyl-1,4-phenylene) ether particularly considers it is most preferred from improving the thermotolerance aspect.

These polyphenylene oxide resins have consistency with polystyrene resin under the proportioning rate arbitrarily.The polymerization degree to the polyphenylene oxide resin that uses among the present invention does not limit especially, but preferred the use is dissolved in 100cm with resin 0.2g ³Chloroform in, the reduced viscosity that this measured in solution obtained under 25 ℃ is the polyphenylene oxide resin of 0.3～0.7dl/g.There is the situation of thermostability variation during less than 0.3dl/g in reduced viscosity, has the situation of infringement formability when surpassing 0.7dl/g.These polyphenylene oxide resins can use in independent or two or more mixing.

Above-mentioned polyphenylene oxide resin can use with other mixed with resin, preferably mixes use with polystyrene resin described later.The polyphenylene oxide resin when using with other mixed with resin and the mixture ratio of other resin can be set in known scope.

(vinyl chloride resin)

Above-mentioned vinyl chloride resin be vinyl chloride homo resin, chlorinated vinyl chloride resin, chlorinated polyethylene resin or have at least one can with two keys of chloroethylene copolymer other vinyl monomer and the copolymer resin of vinylchlorid.For above-mentioned and copolymer resin vinylchlorid, above-mentioned other vinyl monomer wherein, as its amount be preferably below the 50 weight %, more preferably below the 45 weight %, as its example, for example can enumerate ethene, propylene, vinyl-acetic ester, (methyl) vinylformic acid and ester, toxilic acid and ester thereof, vinylidene chloride, bromine ethene and vinyl cyanide.These vinyl chloride resins are by obtaining with independent vinylchlorid or with vinylchlorid and above-mentioned other vinyl monomer homopolymerization or copolymerization in the presence of radical polymerization initiator.The polymerization degree of this vinyl chloride resin is generally 400～4500, is preferably 400～1500 scope especially.

(vinylic polymers or copolymer resin)

As above-mentioned vinylic polymers or copolymer resin, can be with the dienes monomer, copolymerization such as olefin monomer and maleimide monomer, also can be further with they hydrogenation, for example can enumerate polystyrene resin, the s-polystyrene resin, plexiglass, the polychlorostyrene resin, poly-bromstyrol resin, the poly alpha methylstyrene resin, the styrene-acrylonitrile copolymer resin, the styrene-methylmethacrylate copolymer resin, acrylonitrile-styrene-methylmethacrylate copolymer resin, the styrene-maleic anhydride copolymer resin, vinylbenzene-maleimide copolymer resin, vinylbenzene-N-phenylmaleimide copolymer resin, vinylbenzene-N-phenylmaleimide-acrylonitrile compolymer resin, the methyl methacrylate-butyl acrylate copolymer resin, methyl methacrylate-ethyl acrylate copolymer resin, styrene-acrylonitrile-alpha-methyl styrene ter-polymer resin, butadiene-styrene copolymer (HIPS) resin that contains dienes composition or phenyl maleimide composition, acrylonitrile-butadiene rubber-styrol copolymer (ABS) resin, acrylonitrile-butadiene rubber-α-Jia Jibenyixigongjuwu resin, aromatics alkenyl compound-diene-vinyl cyanide-N-phenylmaleimide copolymer resin.

(polyamide resin)

As above-mentioned polyamide resin, can enumerate the polyamide resin of deriving by diamines and dicarboxylic acid, by the polyamide resin that the lactams ring-opening polymerization is obtained, by 6-aminocaprolc acid, 1, the amino undecanoic acid, 1 of 1-, polymeric amide and their multipolymer or mixture that the amino dodecylic acid of 2-etc. obtains, wherein, be preferably nylon 6, nylon 6,6, Ni Long11, nylon 12, the nylon 6 of industrial cheapness and a large amount of preparations, 10, nylon 4,6 and their multipolymer or its mixture.

As above-mentioned diamines, be aliphatics, alicyclic or aromatic diamine, can enumerate quadrol, tetramethylene-diamine, hexamethylene-diamine, decamethylene diamine, ten dimethylene diamines, 2,2,4-and 2,4,4-trimethylhexamethylenediamine, 1,3-two (amino methyl) hexanaphthene, 1,4-two (amino methyl) hexanaphthene, two (to aminocyclohexyl) methane, m-xylylene amine, to xylylene amine etc.

As above-mentioned dicarboxylic acid,, can enumerate hexanodioic acid, suberic acid, sebacic acid, cyclohexane cyclohexanedimethanodibasic, terephthalic acid, m-phthalic acid etc. for aliphatics, alicyclic or aromatic dicarboxylic acid.

As above-mentioned lactams, can enumerate ε-Ji Neixianan, omega-lauryl lactan etc.

(vibrin)

As above-mentioned vibrin, can enumerate the resin that the polycondensate of derivatives such as alkyl ester by dicarboxylic acid or dicarboxylic acid and glycol obtains, or the resin that forms of the monomer polycondensation that has the derivatives such as alkyl ester of hydroxyl and carboxylic acid or carboxylic acid in a part, have the resin that the monomer ring-opening polymerization of cyclic ester structure forms in a part.

As above-mentioned dicarboxylic acid, for example can enumerate terephthalic acid, m-phthalic acid, hexanodioic acid, sebacic acid.As above-mentioned glycol, can enumerate for example ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol.As the monomer of the derivatives such as alkyl ester that have hydroxyl and carboxylic acid or carboxylic acid in above-mentioned a part, can enumerate for example hydroxyl alkane acid such as lactic acid, hydroxy-propionic acid etc.As the monomer that has the cyclic ester structure in above-mentioned a part, can enumerate for example caprolactone etc.

Object lesson as this vibrin, can enumerate poly terephthalic acid methylene radical ester, polyethylene terephthalate, Poly(Trimethylene Terephthalate), the poly terephthalic acid tetramethylene ester, polybutylene terephthalate, poly terephthalic acid hexylene glycol ester, PEN, poly(lactic acid), polyhydroxybutyrate, polybutylene succinate, poly-epsilon-caprolactone, poly-(alpha hydroxy acid), their multipolymer and their mixture, but consider to be preferably especially polybutylene terephthalate from having excellent optical or processibility aspect among the present invention, polyethylene terephthalate, poly(lactic acid).

(polyphenylene sulfide)

As above-mentioned polyphenylene sulfide, be preferably polymkeric substance with polymerization degree 80～300 that 50 moles of % of the repeating unit shown in the following general formula 2 are above, preferred 70 moles of % are above.In addition, as copolymer composition, can enumerate the composition with the repeating unit shown in the following general formula 3, preferably these copolymer compositions are 10 moles below the %.

[Chemical formula 2]

(general formula 2)

[chemical formula 3]

Between the position key

The ortho position key

Ehter bond

The sulfone key

The biphenyl base key

The substituted benzene thioether bond

(general formula 3)

(in the formula, R represents the metal-salt of alkyl, nitro, phenyl, alkoxyl group, carboxylic acid group or carboxylic acid)

(polysulfone resin)

As containing-SO ₂The above-mentioned polysulfone resin of the polymkeric substance of-Ji, roughly be divided into aromatic species and olefines, conduct is as the polysulfone resin of substrate resin (D) among the present invention, be preferably the polysulfone resin of aromatic species, for example can enumerate the polymkeric substance that the polycondensation by dichloro diphenylsulfone obtains, the polymkeric substance that obtains by dichloro diphenylsulfone and dihydroxyphenyl propane with repeating unit shown in the following general formula 5 with repeating unit shown in the following general formula 4.Usually the former is called polyethersulfone resin, the latter is called polysulfone resin, they are useful in the present invention.

[chemical formula 4]

(general formula 4)

[chemical formula 5]

(general formula 5)

(polyetherimide resin)

As above-mentioned polyetherimide resin, can enumerate polymkeric substance with repeating unit shown in the following general formula 6 that has ehter bond and imide bond concurrently.

[chemical formula 6]

(general formula 6)

(polyvinyl acetal resin)

As above-mentioned polyvinyl acetal resin, can enumerate polyvinyl formal that polyvinyl alcohol is obtained with the aldehydes modification, polyvinyl butyral acetal etc.

(polyolefin resin)

As the said polyolefins resin, can enumerate the polymkeric substance that only obtains that polymkeric substance or multipolymer with polyethylene, polypropylene, polymethylpentene, polybutene, cycloolefin etc. are representative by alkene, but be not only them, the multipolymer of compound that also contains alkene and have the two keys of a copolymerization at least is as can be as the resin of (D) of the present invention.Have the compound of copolymerization as this and above-mentioned alkene, can enumerate (methyl) vinylformic acid and ester thereof, toxilic acid and ester thereof, maleic anhydride, vinyl-acetic ester etc.These copolymerization compounds preferably use with the ratio below the 10 weight % in resin.In addition, operable polyolefin resin comprises the multipolymer that the copolymer hydrogenating with the vinyl monomer of dienes composition and other obtains among the present invention, for example the notion of vinyl cyanide-EPDM-styrol copolymer (AES) resin etc.In addition, as the polymerization degree of this polyolefin resin, be preferably 300～6000 scope.

(polyarylene resin)

As above-mentioned polyarylene resin, can enumerate for example poly-(to phenylene), poly-(2, the inferior thienyl of 5-), poly-(1,4-naphthalene two bases) etc.

(polycarbonate resin)

Above-mentioned polycarbonate resin is that dihydric phenol and carbonyl chloride or carbonate precursor reaction obtain.

As above-mentioned dihydric phenol, be preferably two (hydroxyaryl) paraffinic hydrocarbons, can enumerate for example two (hydroxy phenyl) methane, 1,1-two (4-hydroxy phenyl) ethane, 1,2-two (4-hydroxy phenyl) ethane, 2,2-two (hydroxy phenyl) propane, 2,2-two (4-hydroxy phenyl-3-aminomethyl phenyl) propane, 2,2-two (4-hydroxyl-3, the 5-dibromo phenyl) propane, 2,2-two (4-hydroxyl-3,5-dichlorophenyl) propane, 2,2-two (hydroxy phenyl) HFC-236fa etc.

As other dihydric phenol, can enumerate 1,1-two (4-hydroxy phenyl) hexanaphthene, 1,1-two (4-hydroxy phenyl)-3,3, the 5-trimethyl-cyclohexane, 1, two (4-hydroxy phenyl) naphthenic hydrocarbon such as 1-two (4-hydroxy phenyl) cyclodecane, 1,1-two (4-hydroxy phenyl) fluorenes, 1,1-xylenol fluorenes, 1, fluorene derivativess such as 1-two phenoxyethyl alcohol fluorenes, phenyl two (hydroxy phenyl) methane, phenylbenzene two (hydroxy phenyl) methane, 1-phenyl-1,1-two (4-hydroxy phenyl) ethane etc. contains two (hydroxy phenyl) paraffinic hydrocarbons of phenyl, 4,4 '-dihydroxybiphenyl, two (4-hydroxy phenyl) ether (PVC ス (4-ヒ De ロ キ シ Off ェ ニ Le) ォ キ シ De), two (4-hydroxy phenyl) thioether, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) sulfoxide, two (4-hydroxy phenyl) ketone, quinhydrones, piperazine, the dipiperidino quinhydrones, Resorcinol etc.

These dihydric phenols can use or mix use separately.In addition, wherein, use not halogenous dihydric phenol to be thought of as preferably from security or the excellent aspect of optical characteristics.As particularly preferred dihydric phenol, be two (hydroxy phenyl) methane, 2,2 '-two (hydroxy phenyl) propane, 1,1-two (4-hydroxy phenyl) fluorenes.

As above-mentioned carbonate precursor, can enumerate dialkyl carbonates such as diaryl carbonate, methylcarbonate, diethyl carbonate such as diphenyl carbonate etc.Except this aromatic species polycarbonate resin, can also use aliphatic polycarbonate resins such as polymerized thylene carbonate ethyl ester.The polycarbonate resin that these polycarbonate resins can obtain for copolymerization dimethyl siloxane in main chain.

(polyketone)

As above-mentioned polyketone, for example can enumerate the alternating copolymer of the alternating copolymer of ethene and carbon monoxide, alpha-olefin and carbon monoxide etc.

(substrate resin (D): the example of thermosetting resin)

As the preferred thermosetting resin that can be used as above-mentioned substrate resin (D), resin combination of the present invention is used for essential light diffusing, in the time of in the purposes of photopermeability, can enumerate Resins, epoxy, polyamide-imide resin, thermosetting polyester resin (unsaturated polyester resin), silicone resin, urethane resin, (methyl) acrylic resin, fluorine-type resin etc., but in addition, thermoset substrate resin (D) as the present invention relates to can also use phenolic resin, urea resin, melamine resin, polyimide resin, Synolac, the polyvinylesters resin, polyphenyl dioctyl phthalate diallyl phthalate resin, bismaleimides-cyanate resin, furane resin, xylene resin, guanamine resin, maleic acid resin (マ レ ィ Application resin), Dicyclopentadiene (DCPD) resin and polyether resin.

Wherein, preferably contain following Resins, epoxy more than the 50 weight % with respect to the total amount of thermosetting resin, this is because these Resins, epoxy can use curing such as carboxylic acid derivative such as resol, fatty amine, aromatic amine or acid anhydrides, end-blocking carboxylic acid such as phenol phenolic varnish.Wherein, particularly because the thermotolerance raising aspect of the cured article that obtains, so more preferably use resol.

Above-mentioned Resins, epoxy is diglycidyl ether or its condenses that is selected from bis-phenol or aromatic proton replacement bis-phenol, phenolic resin varnish type epoxy resin contains more than one the Resins, epoxy in the alicyclic epoxy resin of oxidation cycloolefin structural framework in Dicyclopentadiene (DCPD) fundamental mode Resins, epoxy and a part.

(Resins, epoxy)

As the Resins, epoxy that can in above-mentioned substrate resin of the present invention (D), use, can use phenolic resin varnish type epoxy resin, biphenyl type epoxy resin or the alicyclic ring epoxide resin etc. can normally used Resins, epoxy.

Above-mentioned phenolic resin varnish type epoxy resin is phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin etc., for the novolac resin that phenols, bisphenols or aphthols and aldehydes condensation are obtained carries out the phenolic resin varnish type epoxy resin that the glycidyl etherificate obtains.

Above-mentioned biphenyl type epoxy resin for example is 2,2 ', 6,6 '-tetramethyl-bis-phenol diglycidyl ether.

Above-mentioned alicyclic epoxy resin is the alicyclic epoxy resin that contains oxidation cycloolefin structural framework in the poly epihydric alcohol base ether of polyatomic phenol, polyalcohols or their condenses, a part.

Wherein, above-mentioned polyatomic phenol is that bis-phenol, aromatic proton replace bisphenols, dihydroxyphenyl propane, Bisphenol F, bisphenol S, TriMethylolPropane(TMP) etc.

(substrate resin (D): elastomeric example)

As the preferred elastomerics that can be used as above-mentioned substrate resin (D), natural rubber or synthetic rubber are arranged, wherein, as synthetic rubber, can use butyl acrylate rubber, ethyl propenoate rubber, acrylic rubbers such as Octyl acrylate rubber, nitrile rubber such as butadiene-acrylonitrile analog copolymer, neoprene, divinyl rubber, synthetic polyisoprene, isobutene rubber, styrene butadiene rubbers, the methyl methacrylate-butyl acrylate segmented copolymer, vinylbenzene-iso-butylene segmented copolymer, styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM), urethane, chlorosulfonated polyethylene, silicon rubber (mixed milling type, room temperature vulcanized), isoprene-isobutylene rubber, viton, olefin hydrocarbons thermoplasticity elastic body, styrene analog thermoplastic elastomer, polyvinyl chloride-base thermoplastic elastomer, ammonia ester analog thermoplastic elastomer, polyamide-based thermoplastic elastomer, various elastomericss such as polyester thermoplastic elastomer or fluorine analog thermoplastic elastomer.

Embodiment

Below, enumerate specific embodiment and describe, but they all are the examples of enumerating, to content of the present invention without any qualification.

(various measuring method)

At first, the various measuring methods in hereinafter putting down in writing are described.

The mensuration of the micro mist amount that volume average particle size and 50 μ m are following, measuring method according to JIS Z8901 regulation, by observing, 100 particles selecting are at random carried out image analysis carry out with little track sreen analysis meter Model9220FRA (day machine dress (strain) system) or opticmicroscope.

In addition, the muddy degree of the filtrate after the polymerization of gloss reducing polymer particle (C) is confirmed by the filtrate observation of the qualitative filter paper No.2 that uses Advantech (ァ De バ Application テ ッ Network) Japan's (strain) system being filtered the slurry that obtains.

Photopermeability is estimated by using integrating sphere type light penetration determinator (Japanese electric look industry (strain) system NDH2000) to measure total light transmittance according to the measuring method of JIS K7361-1 regulation.

Light diffusing is estimated by using integrating sphere type light penetration determinator (Japanese electric look industry (strain) system NDH2000) to measure mist degree according to the measuring method of JIS K7136 regulation.

Glossiness is estimated by the glossiness of using glossmeter (BYK Gardner corporate system, Micro-TRI-gloss) to measure the formed body under input angle 60 degree according to the measuring method of ASTM D-523 regulation.

Gardner's shock test is according to the measuring method of ASTM D-4226 regulation, measures (unit: inch.lb/mil) under 23 ℃, the condition of relative humidity 50%, 8lbs.

Izod intensity is according to the measuring method of JIS K7110 regulation, uses No. 2 test films (mensuration (unit: kJ/m under the state of 23 ℃ of temperature, relative humidity 50% of A breach, width b=6.4 ± 0.3mm) ²).

Tensile yield strength is according to the measuring method of JIS K7160 (test film=3 shapes) regulation, measures (unit: kJ/m under 23 ℃, the condition of relative humidity 50% ²).

The operability evaluation of the powder characteristics of resin combination during by work.That is, operation almost do not have that the situation that powder flies upward is zero during resin combination, fierce situation for *.

And, below, the record of MMA represents that the record of methyl methacrylate, BA represents that the record of butyl acrylate, PMMA represents that the record of polymethylmethacrylate, MB represents that the record of methyl methacrylate-butyl acrylate multipolymer, MS represents that the record of copolymer of methyl methacrylatestyrene, PC represents that the record of polycarbonate, PVC represents that the record of polyvinyl chloride, Si represents organopolysiloxane.

In following record, preparation example 1 be embodiment 16 and 17 and comparative example 9 and 10 in the preparation example of the methyl methacrylate-butyl acrylate multipolymer (MB) that uses as substrate resin (D).

In addition, preparation example 2 is the preparation example of the shock-resistance modifying agent of use in embodiment 16 and 17, the comparative example 9 and 10.

Further, embodiment 1,2 and 3 and comparative example 1 and 2 to relate to BA be the polymer particle (A) of main component, it is the polymer particle (A) of main component that embodiment 4 relates to MMA, and embodiment 5 to relate to organopolysiloxane (Si) be the polymer particle (A) of main component, further, relate to and use each polymer particle (A) further with the preparation method of the polymer particle (C) of MMA/BA polymerization preparation.

Below, the formed body that embodiment 6～15 and comparative example 3～8 relate to light-diffusing resin composition and contain light-diffusing resin composition, embodiment 6～8 and comparative example 3,4 for utilizing the example that uses plexiglass (PMMA) to obtain moulded products as the resin combination of substrate resin (D), embodiment 9～11 and comparative example 5,6 for utilize using copolymer of methyl methacrylatestyrene resin (MS) to obtain the example of moulded products as the resin combination of substrate resin (D), and embodiment 12～15 and comparative example 7,8 for utilizing the example that uses polycarbonate resin (PC) to obtain moulded products as the resin combination of substrate resin (D).

In addition, the formed body that following examples 16～23 and comparative example 9～16 relate to the extinction resin combination and obtained by the extinction resin combination, embodiment 16 and 17 and comparative example 9 and 10 for utilize using methyl methacrylate-butyl acrylate multipolymer (MB) to obtain the example of moulded products as the resin combination of substrate resin (D), embodiment 18 and 19 and comparative example 11 and 12 for utilize using ABS resin to obtain the example of moulded products as the resin combination of substrate resin (D), embodiment 20 and 21 and comparative example 13 and 15 for utilize using hard vinyl chloride resin to obtain the example of moulded products as the resin combination of substrate resin (D), and embodiment 20 and 21 and comparative example 13 and 15 for utilizing the example that uses the flexible vinyl chloride resin to obtain moulded products as the resin combination of substrate resin (D).

Further, embodiment 6,9,12,16,18,20 and 22 for using the polymer particle (C) that obtains among the embodiment 1 to obtain the example of moulded products, embodiment 7,10,13,17,19,21 and 23 for using the polymer particle (C) that obtains among the embodiment 4 to obtain the example of moulded products, embodiment 8,11,14 and 15 for using the polymer particle (C) that obtains among the embodiment 5 to obtain the example of moulded products, comparative example 3,5 and 7 for using commercially available light diffusing agent to come replace polymeric particle (C) to obtain the example of moulded products, comparative example 9,11 and 13 for using commercially available matting agent to come replace polymeric particle (C) to obtain the example of moulded products, and comparative example 4,6,8,10,12,14 and 16 for not use polymer particle (C) to obtain the example of moulded products.

In each embodiment and comparative example, the resin combination that uses during moulding as shown in Table 1 and Table 2, the evaluation result of the moulded products that obtains is shown in table 3 and table 4.In addition, for the following record that specifies of each embodiment and each comparative example.

[table 1]

[table 2]

[table 3]

[table 4]

(preparation example 1)

The preparation of＜methyl methacrylate-butyl acrylate multipolymer (MB) 〉

By following method, the methyl methacrylate-butyl acrylate multipolymer (MB) that uses in preparation embodiment 16 and 17, the comparative example 9 and 10.

That is, in the reactor of band stirrer, add polyvinyl alcohol water solution 15 weight parts (GH-20: Japanese synthetic chemical industry (strain) system) of entry 220 weight parts and 3 weight % after, with nitrogen to replacing in the reactor.To wherein adding the monomer mixed solution that contains methyl methacrylate 90 weight parts, butyl acrylate 10 weight parts and uncle's lauryl mercaptan 0.8 weight part that are dissolved with lauroyl peroxide 0.5 weight part and benzoyl peroxide 0.5 weight part, the speed of rotation of adjusting stirrer is so that monomeric dispersion particle diameter is about 250 μ m.Then, finish polymerization, the suspension polymer of preparation polymer solids constituent concentration 30 weight % 60 ℃ following 2 hours, 70 ℃ following 2 hours, 80 ℃ following 2 hours, 90 ℃ following 1 hour stages intensification heating.With known method to the polymkeric substance that obtains wash, drying, obtain the methyl methacrylate-butyl acrylate multipolymer (MB) of pearl.

(preparation example 2)

The preparation of＜shock-resistance modifying agent 〉

By implementing following (a) and (b) and each polymerization (c) successively, the shock-resistance modifying agent of the multipolymer that uses in preparation embodiment 16 and 17, the comparative example 9 and 10 with three-decker.

(a) polymerization of innermost layer

At first; in the glass reactor, add the mixed solution that contains ion exchanged water 220 weight parts, boric acid 0.3 weight part, yellow soda ash 0.03 weight part, N-sodium N-lauroyl sarcosinate 0.09 weight part, sodium sulfoxylate formaldehyde 0.09 weight part, sodium ethylene diamine tetracetate 0.006 weight part and ferrous sulfate 7 water salt 0.002 weight part, in stream of nitrogen gas, be warming up to 80 ℃ while stirring.

In addition, preparation contains the innermost layer formation mixed solution of methyl methacrylate 24 weight parts, butyl acrylate 1 weight part, allyl methacrylate(AMA) 0.1 weight part and tertbutyl peroxide 0.1 weight part.

Then, add whole above-mentioned innermost layers in 80 ℃ the mixed solution and form, carry out polymerization in 45 minutes with 25 weight % parts in the mixed solution to above-mentioned being warming up to.

Then, appending above-mentioned innermost layer continuously with 1 hour forms with the 75 residual weight % in the mixed solution.After appending end, the N-sodium N-lauroyl sarcosinate of 0.2 weight part is appended on the limit, and the limit kept 2 hours under same temperature, finished polymerization.When the volume average particle size of the polymer particle in the crosslinked methacrylic acids polymer latex Ruzhong that so obtains, the determination of light scattering of the light by using the 546nm wavelength is 1600 In addition, the polymerisation conversion in this polymerization ((polymer output/monomer add-on) * 100) is 98%.

(b) polymerization of rubbery polymer

In stream of nitrogen gas, keep under 80 ℃ the state, after Potassium Persulphate 0.1 weight part is added in the crosslinked methacrylic acids polymer latex Ruzhong that obtains in above-mentioned (a), with appending the middle layer formation monomer mixture that contains butyl acrylate 41 weight parts, vinylbenzene 9 weight parts and allyl methacrylate(AMA) 1 weight part in 5 hours continuously.In addition, divide interpolation potassium oleate 0.1 weight part during this period three times.The middle layer form with monomer mixture append end after, finish in order to make polymerization, further add 0.05 weight part Potassium Persulphate maintenance 2 hours.The volume average particle size of the polymer particle in the rubbery polymer latex with structure that innermost layer covered by the middle layer that so obtains is 2300

Polymerisation conversion is 99%.

(c) outermost polymerization

Remain under 80 ℃ the state, after adding Potassium Persulphate 0.02 weight part in the rubbery polymer latex that in above-mentioned (b), obtains, with appending the outermost layer formation monomer mixture that contains methyl methacrylate 24 weight parts, butyl acrylate 1 weight part and uncle's lauryl mercaptan 0.1 weight part in 1 hour continuously.Outermost layer forms with appending of monomer mixture and finishes back maintenance 1 hour, obtains having the three-decker graft copolymer latex of the structure that the middle layer covered by outermost layer.The volume average particle size of the polymer particle in this three-decker graft copolymer latex is 2530

Polymerisation conversion is 99%.The three-decker graft copolymer latex that obtains saltoutd by known method solidify, thermal treatment, drying, the multipolymer with three-decker that obtains white powder is as the shock-resistance modifying agent.

(embodiment 1)

(preparation of the polymer particle of embodiment 1 (A))

The preparation homogeneous is dissolved with the mixture of butyl acrylate 6.75 weight parts, allyl methacrylate(AMA) 0.14 weight part, 1,3 butylene glycol dimethacrylate 0.04 weight part, methacrylic acid stearyl ester 0.07 weight part and lauroyl peroxide 0.2 weight part.Adding the solution that contains water 10 weight parts and Sodium dodecylbenzene sulfonate 0.02 weight part in this mixture mixes, this mixed solution is applied 10 minutes mechanical shearings by T.K. automixer (ロ ボ ミ ッ Network ス) (special machine chemical industry (strain) system) with the speed of rotation of 7000rpm, preparation O/W type emulsion.

To adding the dispersion liquid that adds the emulsion that contains this preparation in the glass reactor of water 210 weight parts, Sodium Nitrite 0.01 weight part and Sodium dodecylbenzene sulfonate 0.05 weight part is arranged, be warming up to 65 ℃ when stirring in stream of nitrogen gas, the temperature that keeps system is 65 ℃ and stirred 30 minutes.

Then, in system, add Sodium dodecylbenzene sulfonate 0.2 weight part after, with 3 hours interpolation butyl acrylate 61.4 weight parts, allyl methacrylate(AMA) 1.3 weight parts, 1,3 butylene glycol dimethacrylate 0.3 weight parts continuously.Then, the temperature that keeps system is 65 ℃ and stirred 1 hour, obtains containing the polymerization system of the latex of the polymer particles that volume average particle size is 5.1 μ m (A).

And, adding calcium chloride water in the part of this polymer particles (A) latex that takes out saltouts, polymer particles (A) the resin extrusion forming that filtration is obtained is the flat board of thickness 1mm, and the result who uses Abbe formula index meter (the ァ of Co., Ltd. go system Abb 2T) to measure 25 ℃ specific refractory power is 1.463.

(preparation of the polymer particle of embodiment 1 (C))

Then, after the polymerization system that will contain the latex of above-mentioned polymer particles (A) is cooled to 40 ℃, add entry 220 weight parts, make final solid component concentration be about 20 weight %.Then, add all be dissolved with equably methyl methacrylate 27 weight parts, butyl acrylate 3 weight parts, 2,2 '-mixture of azo (2-methylbutyronitrile) 0.3 weight part, stirred 10 minutes.Then, add polyvinyl alcohol KH-17 (Japanese synthetic chemical industry (strain) system) 0.1 weight part, stirred 20 minutes as suspension dispersive agent.Then, add sodium sulfate 7 weight parts, stir after 10 minutes, be warming up to 80 ℃ with 4 hours as peptizer.Then, the temperature that keeps system is 80 ℃ and stirred 1 hour, obtains polymer particle (C).The volume average particle size of the polymer particle that obtains (C) is 330 μ m, and the following micro mist amount of 50 μ m is 0 weight %, the filtrate water white transparency after the polymerization.

(embodiment 2)

In the preparation of polymer particles (A), except applying 2 minutes mechanical shearings with the speed of rotation of 4000rpm by T.K. automixer (ロ ボ ミ ッ Network ス), outside the preparation O/W type emulsion, prepare polymer particles (A) and polymer particle (C) by the method identical with embodiment 1.And the volume average particle size of the polymer particles that obtains (A) is 22.2 μ m, and the volume average particle size of polymer particle (C) is 360 μ m, and the following micro mist amount of 50 μ m is 0 weight %, the filtrate water white transparency after the polymerization.

(embodiment 3)

(preparation of the polymer particle of embodiment 3 (A))

Operation similarly to Example 1, preparation O/W type emulsion.Then, operation similarly to Example 1, to adding the dispersion liquid that adds the emulsion that contains this preparation in the glass reactor of water 210 weight parts, Sodium Nitrite 0.01 weight part and Sodium dodecylbenzene sulfonate 0.05 weight part is arranged, be warming up to 65 ℃ when stirring in stream of nitrogen gas, the temperature that keeps system is 65 ℃ and stirred 30 minutes.

Then, in system, add Sodium dodecylbenzene sulfonate 0.14 weight part after, with 2 hours interpolation butyl acrylate 41.9 weight parts, allyl methacrylate(AMA) 0.9 weight part, 1,3 butylene glycol dimethacrylate 0.2 weight parts continuously.Then, the temperature that keeps system is 65 ℃ and stirred 1 hour, obtains containing the polymerization system of the latex of the polymer particles that volume average particle size is 4.6 μ m (A).

(preparation of the polymer particle of embodiment 3 (C))

Then, after the polymerization system that will contain the latex of above-mentioned polymer particles (A) is cooled to 40 ℃, add entry 90 weight parts, make final solid component concentration be about 25 weight %.Then, add after sodium sulfate 2 weight parts as peptizer stir 10 minutes, add tricalcium phosphate 0.2 weight part as suspension dispersive agent.Then, add whole mixtures that is dissolved with methyl methacrylate 45 weight parts, butyl acrylate 5 weight parts, thioglycollic acid-2-ethyl hexyl ester 0.3 weight part, lauroyl peroxide 0.5 weight part equably, stirred 30 minutes.Then, add after 0.1 weight part stirs 20 minutes as the polyvinyl alcohol KH-17 of suspension dispersive agent, be warming up to 80 ℃ with 4 hours.Then, the temperature that keeps system is 80 ℃ and stirred 1 hour, obtains polymer particle (C).The volume average particle size of the polymer particle that obtains (C) is 3100 μ m, and the following micro mist amount of 50 μ m is 0 weight %, the filtrate water white transparency after the polymerization.

(embodiment 4)

(preparation of the polymer particle of embodiment 4 (A))

The preparation homogeneous is dissolved with the mixture of methyl methacrylate 64.5 weight parts, 1,3 butylene glycol dimethacrylate 2.0 weight parts, methacrylic acid dinonyl phenyl ester 3.5 weight parts and lauroyl peroxide 0.2 weight part.Adding the solution that contains water 230 weight parts, Sodium dodecylbenzene sulfonate 0.2 weight part, polyvinyl alcohol GH-23 (Japanese synthetic chemical industry (strain) system) 0.7 weight part and Sodium Nitrite 0.015 weight part in this mixture mixes, this mixed solution is applied the shearing of 20 minutes machinery, preparation O/W type emulsion by T.K. automixer (ロ ボ ミ ッ Network ス) with the speed of rotation of 6000rpm.The total transfer of dispersion liquid of O/W type emulsion that will contain this preparation is warming up to 65 ℃ when stirring in stream of nitrogen gas to the glass reactor.Then, the temperature that keeps this system is 65 ℃ and stirred 5 hours, obtains containing the polymerization system of the polymer particles that volume average particle size is 2.7 μ m (A) latex.

And, adding calcium chloride water in the part of this polymer particles (A) latex that takes out saltouts, polymer particles (A) the resin extrusion forming that filtration is obtained is the flat board of thickness 1mm, and the result who uses Abbe formula index meter (ATAGO of Co., Ltd. (ァ go) system Abb 2T) to measure 25 ℃ specific refractory power is 1.490.

(preparation of the polymer particle of embodiment 4 (C))

Then, by with the same method of preparation of the polymer particle (C) of embodiment 1, the polymer particle (C) of preparation embodiment 4.The volume average particle size of the polymer particle that obtains (C) is 210 μ m, and the following micro mist amount of 50 μ m is 2 weight %, the filtrate water white transparency after the polymerization.

(embodiment 5)

(preparation of the polymer particle of embodiment 5 (A))

To containing water 200 weight parts, Sodium dodecylbenzene sulfonate 0.5 weight part, Witco 1298 Soft Acid 1 weight part, terminal hydroxyl organopolysiloxane (Ray Dowcorning Silicone (eastern レ-ダ ゥ コ one ニ Application グ-シ リ コ one Application) Co., Ltd. system trade(brand)name: the PRX413) mixture of 100 weight parts, γ-methacryloxypropyl methyl dimethoxysilane (DSMA) 5 weight parts, apply the shearing of 5 minutes machinery, preparation O/W type silicone emulsion by T.K. automixer (ロ ボ ミ ッ Network ス) with the speed of rotation of 10000rpm.Then, this silicone emulsion is all joined apace have stirrer, reflux cooler, nitrogen are blown into mouthful, monomer appends mouthful, in the flask of thermometer.Reacted 6 hours down at 30 ℃ in the time of the stirring system.Then, be cooled to 23 ℃ and place after 20 hours, make the pH of system be back to 6.8, finish polymerization, obtain the polymer particle that volume average particle size is the organopolysiloxane of 8.6 μ m (A) latex with sodium hydroxide.

And, adding calcium chloride water in the part of this organo-siloxanes polymer particulate (A) latex that takes out saltouts, polymer particles (A) the resin extrusion forming that filtration is obtained is the flat board of thickness 1mm, and the result who uses Abbe formula index meter (ATAGO of Co., Ltd. (ァ go) system Abb 2T) to measure 25 ℃ specific refractory power is 1.402.

(preparation of the polymer particle of embodiment 5 (C))

Then, in these organo-siloxanes polymer particle (A) latex 70 weight parts (solids component), add entry, make final solid component concentration be about 20 weight %, under stream of nitrogen gas, be warming up to 40 ℃ when stirring.After arriving 40 ℃, after adding sodium sulfoxylate formaldehyde 0.1 weight part, disodium ethylene diamine tetraacetate 0.0028 weight part, ferrous sulfate 0.0007 weight part, append behind mixed methyl allyl acrylate 1.5 weight parts and isopropyl benzene hydroperoxide 0.025 weight part all, 40 ℃ are continued to stir 1 hour down.Then, add whole be dissolved with equably methyl methacrylate 27 weight parts, butyl acrylate 3 weight parts, 2,2 '-mixture of azo two (2-methylbutyronitrile) 0.3 weight part, stirred 10 minutes.Then, adding polyvinyl alcohol KH-17 (Japanese synthetic chemical industry (strain) system) 0.1 weight part stirred 20 minutes.Then, add peptizer calcium chloride 4 weight parts, stir after 10 minutes, be warming up to 80 ℃ with 4 hours.Then, the temperature that keeps system is 80 ℃ and stirred 1 hour, obtains polymer particle (C).The volume average particle size of the polymer particle that obtains (C) is 250 μ m, and the following micro mist amount of 50 μ m is 0 weight %, the filtrate water white transparency after the polymerization.

(comparative example 1)

Except in the preparation of polymer particles (A), apply outside mechanical shearing in 2 minutes, the preparation O/W type emulsion by the speed of rotation of T.K. automixer (ロ ボ ミ ッ Network ス), prepare polymer particles (A) and polymer particle (C) by the method identical with the situation of embodiment 1 with 2000rpm.The volume average particle size of the polymer particles that obtains (A) is 60 μ m.At this moment, polymerization stability is poor, produces a large amount of scales (scale) during the preparation of polymer particle (C).

(comparative example 2)

Except in the preparation of polymer particle (C), do not add outside the sodium sulfate as peptizer, prepare polymer particles (A) and polymer particle (C) by the method identical with embodiment 1.The volume average particle size of the polymer particles that obtains (A) is 5.1 μ m.But, when the preparation of polymer particle (C), have the polymer particles (A) that does not enter in a large number in the polymer particle (C).Therefore, in polymer particle (C), the content of the micro mist amount that 50 μ m are following is 90 weight %, so the product that obtains among goods powder characteristics and the embodiment 1 is compared significantly variation.

＜light-diffusing resin composition and the formed body of making by light-diffusing resin composition 〉

(embodiment 6)

Will be to plexiglass (CYRO corporate system, Acrylite (ァ Network リ ラ ィ ト) H-12, n ²⁵ _D: 1.489, the total light transmittance 92.1% of the formed body that 3mm is thick) add the mixture that polymer particle (C) 2 weight parts that obtain among the embodiment 1 and antioxidant ADEKE STAB (ァ デ カ ス Block) 2112 (rising sun electrochemical industry (strain) systems) 0.2 weight part obtain in 100 weight parts, use band venting hole single shaft forcing machine (HW-40-28:40m/m, L/D=28, field terminal tool (strain) system), under design temperature C3=200 ℃, extrude mixingly, form particle.With the particle that obtains 90 ℃ dry down more than 4 hours after, use injection moulding machine (160MSP-10 type, Mitsubishi's resin (strain) system), to obtain the flat samples of thickness 3mm barrel temperature C3=250 ℃, nozzle temperature N=255 ℃ following injection molding.In addition, under identical particleization and injection molding condition, obtain Izod strength detection test film.

(embodiment 7)

In embodiment 6, the polymer particle (C) that the polymer particles (C) that obtains in using embodiment 4 to obtain in the alternate embodiment 1, operation similarly obtains moulded products.

(embodiment 8)

Except in embodiment 6, outside the polymer particle (C) that polymer particles (C) 1 weight part that obtains among the use embodiment 5 to obtain in the alternate embodiment 1, operation similarly obtains moulded products.

(comparative example 3)

In embodiment 6, change into product industry (strain) system light diffusing agent (crosslinked polymethylmethacrylaparticles resin, tech-polymer (テ Network Port リ マ one) MBX-5, median size 5 μ m, n except using ponding ²⁵ _D: 1.490) outside the polymer particle (C) that comes to obtain in the alternate embodiment 1, operation similarly obtains moulded products.

(comparative example 4)

In embodiment 6, similarly operation obtains moulded products except not using polymer particle (C).

(embodiment 9)

With copolymer of methyl methacrylatestyrene resin (Nippon Steel's chemistry (strain) system, ESTYRENE (ェ ス チ レ Application) MSMS-600, n ²⁵ _D: the mixture of polymer particle (C) 0.2 weight part that obtains among 100 weight parts and the embodiment 1 1.530, the total light transmittance 91.1% of the formed body that 3mm is thick), use the single shaft forcing machine (HW-40-28:40m/m, L/D=28, field terminal tool (strain) system) of band venting hole, under design temperature C3=180 ℃, extrude mixingly, form particle.With the particle that obtains 80 ℃ dry down more than 3 hours after, use injection moulding machine (160MSP-10 type, Mitsubishi's resin (strain) system), barrel temperature C3=220 ℃, nozzle temperature N=225 ℃ following injection molding, obtain the flat samples of thickness 3mm.In addition, utilize identical particle, injection molding condition to obtain Izod strength detection test film.

(embodiment 10)

In embodiment 9, the polymer particle (C) that the polymer particles (C) that obtains in using embodiment 4 to obtain in the alternate embodiment 1, operation similarly obtains moulded products.

(embodiment 11)

In embodiment 9, the polymer particle (C) that polymer particles (C) 0.1 weight part that obtains in using embodiment 5 to obtain in the alternate embodiment 1, operation similarly obtains moulded products.

(comparative example 5)

In embodiment 9, change into product industry (strain) system light diffusing agent (crosslinked polymethylmethacrylaparticles resin, tech-polymer (テ Network Port リ マ one) MBX-5, median size 5 μ m, n except using ponding ²⁵ _D: 1.490) outside the polymer particle (C) that comes to obtain in the alternate embodiment 1, operation similarly obtains moulded products.

(comparative example 6)

In embodiment 9, similarly operation obtains moulded products except not using polymer particle (C).

(embodiment 12)

(Supreme Being people changes into (strain) system, Panlite (パ Application テ ィ ト) L-1225WX, n with polycarbonate resin ²⁵ _D: the mixture of polymer particle (C) 0.2 weight part that obtains among 100 weight parts and the embodiment 1 1.585, the total light transmittance 89.9% of the formed body that 3mm is thick), use the single shaft forcing machine (HW-40-28:40m/m, L/D=28, field terminal tool (strain) system) of band venting hole, under design temperature C3=260 ℃, extrude mixingly, form particle.With the particle that obtains 140 ℃ dry down more than 5 hours after, use injection moulding machine (160MSP-10 type, Mitsubishi's resin (strain) system), barrel temperature C3=265 ℃, nozzle temperature N=280 ℃ following injection molding, obtain the flat samples of thickness 3mm.In addition, utilize identical granulating, injection molding condition to obtain Izod strength detection test film.

(embodiment 13)

In embodiment 12, the polymer particle (C) that the polymer particles (C) that obtains in using embodiment 4 to obtain in the alternate embodiment 1, operation similarly obtains moulded products.

(embodiment 14)

In embodiment 12, polymer particle (C) 0.2 weight part that polymer particles (C) 0.1 weight part that obtains in using embodiment 5 to obtain in the alternate embodiment 1, operation similarly obtains moulded products.

(embodiment 15)

In embodiment 12, polymer particle (C) 0.2 weight part that polymer particles (C) 0.5 weight part that obtains in using embodiment 5 to obtain in the alternate embodiment 1, operation similarly obtains moulded products.

(comparative example 7)

In embodiment 12, change into product industry (strain) system light diffusing agent (crosslinked polymethylmethacrylaparticles resin, tech-polymer (テ Network Port リ マ one) MBX-5, median size 5 μ m, n except using ponding ²⁵ _D: 1.490) outside the polymer particle (C) that comes to obtain in the alternate embodiment 1, operation similarly obtains moulded products.

(comparative example 8)

In embodiment 12, similarly operation obtains moulded products except not using polymer particle (C).

＜extinction resin combination and the formed body that obtains by the extinction resin combination 〉

(embodiment 16)

The mixture that adds shock-resistance modifying agent 100 weight parts that obtain in polymer particle (C) 20 weight parts that obtain among the embodiment 1, the preparation example 2 and polyolefin-wax (Allied Signal Inc corporate system ACPE-629A) 0.5 weight part in methyl methacrylate-butyl acrylate multipolymer (MB) 100 weight parts that will in preparation example 1, obtain and obtain, use the single shaft forcing machine (HW-40-28:40m/m, L/D=28, field terminal tool (strain) system) of band venting hole, under design temperature C3=200 ℃, extrude mixingly, form particle.With the particle that obtains 70 ℃ dry down more than 10 hours after, use forcing machine (twin shaft コ ニ カ Le forcing machine, the smart mechanism of (strain) Japan are done made), under barrel temperature C3=175 ℃, slit die temperature=180 ℃, be shaped to the sheet of width 45mm, thickness 0.8mm.

(embodiment 17)

In embodiment 16, the polymer particle (C) that the polymer particle (C) that obtains in using embodiment 4 to obtain in the alternate embodiment 1, operation similarly obtains moulded products.

(comparative example 9)

In embodiment 16, change into the polymer particle (C) that (strain) system matting agent (BA/MMA core shell structure body particle, GBM-55, median size 8 μ m) comes to obtain in the alternate embodiment 1 except using ガ Application ッ, operation similarly obtains moulded products.

(comparative example 10)

In embodiment 16, similarly operation obtains moulded products except not using polymer particle (C).

(embodiment 18)

Will cooperate ABS resin (strange U.S. industry thigh? limited commercial firm system, PA-747S) mixture that obtains of polymer particle (C) 3 weight parts that obtain among 100 weight parts and the embodiment 1, use the equidirectional parallel biaxial extruder (JSWTEX44SS-30W-3V:40m/m, Japan's system steel (strain) system) of band venting hole, under design temperature C3=210 ℃, extrude mixing formation particle.Behind the particle drying that obtains, use injection moulding machine (160MSP-10 type, Mitsubishi's resin (strain) system), to obtain the flat samples of thickness 3mm barrel temperature C3=210 ℃, nozzle temperature N=210 ℃ following injection molding.In addition, utilize identical granulating, injection molding condition to obtain Izod strength detection test film.

(embodiment 19)

In embodiment 18, the polymer particle (C) that the polymer particle (C) that obtains in using embodiment 4 to obtain in the alternate embodiment 1, operation similarly obtains moulded products.

(comparative example 11)

In embodiment 18, except using ponding to change into the polymer particle (C) that product industry (strain) system matting agents (crosslinked polymethylmethacrylaparticles resin, tech-polymer (テ Network Port リ マ one) MBX-5, median size 5 μ m) come to obtain in the alternate embodiment 1, similarly operate and obtain moulded products.

(comparative example 12)

In embodiment 18, similarly operation obtains moulded products except not using polymer particle (C).

(embodiment 20)

To mix hard vinyl chloride resin (P=700, (strain) Bellization (カ ネ カ) system, S1007) 100 weight parts, stablizer (octyl mercaptan tin (ォ Network チ Le ス ズ メ Le カ プ チ De), the Arkema corporate system, T890S) 1.5 weight parts, softening agent (Cognis corporate system, Edenol D82) 1.5 weight parts, lubricant (Clariant corporate system, Licowax E) mixture that polymer particle (C) 3 weight parts that obtain among 0.5 weight part and the embodiment 1 obtain, by being set at 180 ℃ roller (Collin corporate system, Walzwerk200) carry out mixingly, and make sheet.

(embodiment 21)

In embodiment 20, the polymer particle (C) that the polymer particles (C) that obtains in using embodiment 4 to obtain in the alternate embodiment 1, operation similarly obtains moulded products.

(comparative example 13)

In embodiment 20, except using ganz (ガ Application ッ) to change into the polymer particle (C) that (strain) system matting agent (BA/MMA core shell structure body particle, GBM-55, median size 8 μ m) comes to obtain in the alternate embodiment 1, operation similarly obtains moulded products.

(comparative example 14)

In embodiment 20, similarly operation obtains moulded products except not using polymer particle (C).

(embodiment 22)

To mix the mixture that polymer particle (C) 5 weight parts that obtain among flexible vinyl chloride resin (P=1000, (strain) Bellization (カ ネ カ) system, S1001N) 100 weight parts, stablizer (tribasic lead sulfate, Sakai chemical industry (strain) system, TL-7000) 3 weight parts, softening agent (phthalic acid two (2-ethylhexyl)) 60 weight parts, lubricant (lead stearate, Sakai chemical industry (strain) system, SL-1000) 1 weight part and the embodiment 1 obtain, undertaken mixingly by the roller (Collin corporate system, Walzwerk200) that is set at 160 ℃, and make sheet.

(embodiment 23)

In embodiment 22, the polymer particle (C) that the polymer particle (C) that obtains in using embodiment 4 to obtain in the alternate embodiment 1, operation similarly obtains moulded products.

(comparative example 15)

In embodiment 22, except using ganz (ガ Application ッ) to change into the polymer particle (C) that (strain) system matting agent (BA/MMA core shell structure body particle, GBM-55, median size 8 μ m) comes to obtain in the alternate embodiment 1, operation similarly obtains moulded products.

(comparative example 16)

In embodiment 22, similarly operation obtains moulded products except not using polymer particle (C).

(comparison of each embodiment and each comparative example)

As shown in table 3, using volume average particle size is the operability excellence of photopermeability (total light transmittance), light diffusing (mist degree), Izod intensity and powder of embodiment 6～15 of the polymer particle of the present invention (C) of 100～6000 μ m.On the other hand, use comparative example 3,5 and 7 non-constant aspect the operability of powder of the light diffusing agent of median size 5 μ m.

As shown in table 4, using volume average particle size is the operability excellence of extinction (glossiness), intensity and powder of embodiment 16～23 of the polymer particle of the present invention (C) of 100～6000 mu m ranges.On the other hand, use comparative example 9,11,13 and 15 non-constant aspect the operability of powder of the matting agent of median size 8 μ m.

Claims (19)

1. polymer particle, it is to carry out granulation by the system of the latex that contains the polymer particles that volume average particle size is 1～50 μ m (A), polymerizable monomer (B), polymerization starter, suspension dispersive agent and peptizer, and carry out that suspension polymerization obtains, wherein

The volume average particle size of polymer particle is 100～6000 μ m, and the content of the micro mist below the 50 μ m is below the 15 weight %.

2. method for preparing the described polymer particle of claim 1, it comprises, in the presence of the latex of described polymer particles (A), add described polymerizable monomer (B), described polymerization starter, described suspension dispersive agent and described peptizer, and carry out described granulation and described suspension polymerization.

3. the described method for preparing polymer particle of claim 2, wherein, described granulation is by in the presence of the latex of described polymer particles (A), adds that described polymerizable monomer (B), described polymerization starter, described suspension dispersive agent and described peptizer carry out, and described granulation comprises:

Destroy described polymer particles (A) latex emulsified state and

With described system transition is that volume average particle size is the suspension system of 100～6000 μ m.

4. claim 2 or the 3 described methods that prepare polymer particle, it also comprises, prepares the step of described polymer particles (A) as the suspension polymerization of suspension dispersive agent by using the anionic species emulsifying agent.

5. the described polymer particle of claim 1, wherein, polymer particle contains described polymer particles (A) and the described polymerizable monomer (B) that proportioning is 0.5: 99.5～95: 5 (wherein, by weight (A): (B)) scopes.

6. the described polymer particle of claim 5, wherein, described polymer particles (A) is (methyl) alkyl-acrylates polymer particles or organo-siloxanes polymer particulate, and the second-order transition temperature of its homopolymer is below 0 ℃.

7. claim 5 or 6 described polymer particles, wherein, described polymerizable monomer (B) is one or more the monomer that is selected from (methyl) alkyl-acrylates monomer, aromatic vinyl base class monomer, vinyl cyanide monomer, vinyl acetate monomer and the vinyl chloride monomer.

8. resin combination, it contains any described polymer particle (C) and substrate resin (D) in the claim 5～7, and wherein, described substrate resin (D) is to be selected from least a in thermoplastic resin, thermosetting resin and the elastomerics.

9. the described resin combination of claim 8, it contains described substrate resin (D) 100 weight parts and described polymer particle (C) 0.1～500 weight part.

10. claim 8 or 9 described resin combinations, wherein, described substrate resin (D) is at least a resin that is selected from thermoplastic resin and the thermosetting resin, and is transparent resin.

11. any described resin combination in the claim 8～10, wherein, described substrate resin (D) is that its thickness is that the total light transmittance of the formed body of 3mm is the transparent resin more than 40%.

12. an extinction resin combination, it is any described resin combination in the claim 8～11, and wherein, described polymer particle (C) is the gloss reducing polymer particle.

13. a formed body, it is the formed body of the described resin combination of claim 12.

14. the described formed body of claim 13, wherein, the glossiness on this formed body surface under input angle 60 degree is below 110.

15. a light-diffusing resin composition, it is any described resin combination in the claim 8～11, and wherein, described polymer particle (C) is the light diffusing polymer particles.

16. the described light-diffusing resin composition of claim 15, wherein, the specific refractory power of described polymer particles (A) is in 1.350～1.650 scope.

17. claim 15 or 16 described light-diffusing resin compositions, wherein, the absolute value of the difference of the specific refractory power of described polymer particles (A) and described substrate resin (D) is in 0.001～0.3 scope.

18. a formed body, it is the formed body of any described resin combination in the claim 15～17.

19. a light diffusing sheet, it contains the described formed body of claim 18, and total light transmittance is more than 10%, the mist degree rate is more than 40%.