TW200927830A - Resin composition and polycondensation product using the resin composition - Google Patents

Abstract

Disclosed is a resin composition wherein polymer fine particles are dispersed uniformly. Specifically disclosed is a resin composition containing a polyol and polymer fine particles each composed of an elastic core layer and a shell layer covering the elastic core layer and containing a component having a hydroxyl group. This resin composition is characterized in that the polymer fine particles are dispersed in the form of primary particles.

Description

[Technical Field] The present invention relates to a resin composition for dispersing polymer microparticles (in detail, a core-shell polymer microparticle), and a polycondensation body obtained from the resin composition . σ [Prior Art] A thermosetting resin represented by an epoxy resin, an unsaturated polyester resin, a polyimide, or a phenol resin is widely used because of its excellent heat resistance, mechanical strength, or dimensional accuracy. In various fields. For example, non-saturated polyester resins are widely used for automobile parts, train vehicle parts, electronic parts, and the like which require strength because of their excellent mechanical strength, chemical resistance, heat resistance, and privacy characteristics. ''The shape obtained by using a thermosetting resin such as unsaturated t-vine resin, the coefficient of thermal expansion is large, and the ability to relax the thermal shock stress under the environment of repeated cooling and heating, or the physical impact stress is not sufficient. Therefore, there are problems such as cracks or cracks in the valley. In order to solve the above-mentioned problems, the technique of dispersing the polymer microparticles of the core-shell structure, such as an unsaturated polyester resin, has been disclosed (see, for example, JP-A-20-284825) In the literature, in order to disperse the high-knife: U particles in the thermosetting resin or polyurethane, it is revealed that there will be more than the knives of the knives; the east's dissolution and dehydration cleaning, and a few dry to obtain multiple layers Polymer microparticles, a method of adding this to an unsaturated polyester.

2226-9866-PF 5 200927830 However, the above method, C method, because the state of polymer agglomeration is taken out of the powder by the latex, it will be: when the rubber is firmly mixed with each other, it is necessary to have a considerable machine... , (4) Disperse operation in which it is dispersed in an unsaturated state. Furthermore, it is difficult to target the dispersion of polymer microparticles. The state of the scorpion is dispersed in the unsaturated polyester, and the polymerization initiator or the emulsified "or the water-soluble inclusions such as the stabilizer" remaining in the polymer microparticles are used to form the polymer microparticles. When the polymer fine particles having such a core material are used, the quality of the thermosetting resin, the coating material, the film, and the like may be lowered. [Invention] The present invention has been made in view of the above problems, and the present invention has been made. The inventors of the present invention have found that a polymer particle having a core-shell structure prepared by a predetermined method can exhibit excellent properties in an epoxy resin. Dispersibility (for example, WO2005/G28546, W02GG4/1G8825), the technique used for the polycondensation-based polymer does not necessarily uniformly disperse the polymer fine particles. Therefore, as a result of intensive research, it has been found that a hydroxyl group is introduced into the shell layer of the polymer microparticles. Further, even if it is a polycondensation-based polymer, the polymer fine particles can be uniformly dispersed to complete the present invention. That is, the resin composition of the present invention And comprising: a polyhydric alcohol; and a polymer microparticle comprising: an elastic core layer; and a shell layer covering the elastic core layer and comprising a component having a hydroxyl group, wherein the polymer microparticle is

2226-9866-PF 6 200927830 State dispersion of primary particles. Further, in a preferred embodiment of the resin composition of the present invention, the preliminary package 3 is selected from at least one resin material selected from the group consisting of unsaturated polybasic acids and compounds of two or more isocyanate groups. According to the above configuration, since the high concentration can be promoted by the hydroxyl group introduced into the shell layer, and the compatibility or affinity of the fine particles with the polyol can be excellent, the dispersibility of the inter-microparticles in the resin composition can be excellent. Further, the introduction of the hydroxyl group of the shell layer and the measurement of the enthalpy by the polycondensation of the resin raw material (described later) may be difficult to be repelled by the polycondensate. In addition, in the present specification, "the polymer microparticles are in the form of primary particles. I. Knife release" means that the polymer microparticles are not mutually agglomerated in the resin composition, and are dispersed independently. In a preferred embodiment of the resin composition of the present invention, the high molecular fine particles are dispersed in a volume average particle diameter (Mv) / number average particle diameter (Mn) of 2 Å or less.

Further, in the resin composition of the present invention, in a preferred embodiment, the residual amount of the alkali metal ions in the resin composition is 6 〇ppm (mass ratio) or less, and a preferred embodiment is a resin combination. The residual amount of the anionic emulsifier in the product is 1 〇〇ppm (mass ratio) or less. According to the above configuration, inclusions in the resin composition of the present invention can be suppressed. Therefore, it is estimated that the polycondensate of the present invention can suppress deterioration in quality due to inclusions. A preferred embodiment of the resin composition of the present invention comprises: a water-based latex containing the above-mentioned cerium molecular microparticles, and a water of 20 Å

2226-9866-PF 7 200927830, the bath solution is 5 quality! % or more 4 Q% by mass LV AA υ 置 page set /. The following organic solvent mixing step is mixed with excess water to make the first step of the upper silicon wafer to be agglomerated, and the above-mentioned polymer material material is condensed and recovered by the liquid phase. The organic solvent is mixed to obtain the second step of the above-mentioned high-division Dandan; and the above-mentioned organic solvent is distilled off after mixing the above-mentioned right Yao's - corrective two-process and liver-on-the-organic organic agent solution with the above-mentioned multiple components. The third step is obtained. Further, in the resin composition of the present invention, a preferred embodiment thereof,

The volume average particle of the above polymer microparticles in the resin composition, (10) v number average particle diameter (Mn), and the above polymer in the aqueous latex: volume average particle diameter (Mv) / number average particle diameter (Mn) of the particles The ratio is less than ^ times. Further, the preferred embodiment is a method in which the polymer fine particles are separated and collected by liquid phase separation between the i-th step and the second step, and the solubility in water at 20 ° C is After the organic solvent of 5 mass% or more and 4 mass% or less is mixed, the mixture is further mixed with excess water to coagulate the upper molecular microparticles. In a preferred embodiment of the resin composition of the present invention, the shell layer further comprises at least one selected from the group consisting of a component having a carboxyl group and a component having a carbon-carbon double bond. According to the above configuration, the polymer fine particles are more likely to be involved in the polycondensation. Also, it may involve radical polymerization. The present invention also encompasses a polycondensate characterized by polycondensing the above resin composition. The resin composition of the present invention is a high score ‘submicron particles are primary particles

2226-9866-PF 8 200927830 The state is dispersed. Therefore, by using the β-Guanshu Yueshen composition, it is possible to obtain a polycondensate of the molecular microparticles of the homogenate of the granules without the need for a special dispersing operation. [Embodiment] The resin composition of the present invention, comprising: a propylene carbonate; and a polymer microparticle, comprising: an elastic core layer, and a shell covering the elastic core sound, ❹ 且 and comprising a component having a warp group In the layer, the polymer fine particles are dispersed in the state of primary particles. The resin composition of the present invention is described below. 1 : Polyol is used in the polyol of the present invention, which is polycondensed with an unsaturated polybasic acid to form an unsaturated polyester, or is polycondensed with a compound having more than two polyisocyanates or the like thereof to form a polyamine. Examples of the vinegar include fatty alcohols, linalool, and polymer alcohols. _

The fatty alcohol may be a divalent alcohol or a trivalent or higher alcohol (trivalent alcohol, tetravalent alcohol, etc.), and the divalent alcohol may, for example, be ethylene glycol, propylene glycol, 1,3-butanediol, or H-butanediol. a condensed diol such as h6-hexanediol or neopentyl glycol (particularly an alkanediol having a carbon number of about 1 to 6), and two or more molecules of the alkanediol (for example, 2 to δ molecules) A degree of dehydration condensate (diethylene glycol, dipropylene glycol diol, etc.) or the like. The trivalent alcohol' may, for example, be glycerin, trimethyl ketone, or tri-perihol; base ketone, 1,2,6-hexanetriol or the like (especially a triol having a degree of 3 to 1 Q). The tetravalent alcohol may, for example, beisotetraol or diglycerin. —, the galenol can be a bisphenol such as bisphenol A or bisphenol F; a biphenyl such as dihydroxy; a polyvalent phenol such as a benzophenone or a phenol aldehyde condensate;

2226-9866-PF 9 200927830 and so on. Polypropylene glycol, polyglycerol, and polyester polyols; Polyurethane is a polymer-based alcohol, which can be obtained by using polyethylene glycol or I oxytetramethylene glycol. Alcohol polyols. These polyols may be used singly or in combination of two or more. Among the above polyols, ethylene glycol, propylene glycol, 1,4-butadiene, monoethyl ethanediol, polyethylene glycol, and polypropylene glycol are preferred. A 2: polymer microparticles 2 to 1 : an elastic core layer is too early: an elastic core layer used for the polymer microparticles of the present invention, which is a polycondensate (4) of the present invention, and has a property as a rubber. Specifically, the elastic core layer of the present invention has a gel content of 6 = preferably '8. Quality (4) is better, and the step is 9. Qualitative ❿ 95 quality "above is particularly good. Further, the term "condensation" as used in the present specification means that 5 g of crumb crumb obtained by solidification and drying is impregnated into 1. When 〇2 is left at 2 rc for 24 hours, it is divided into insoluble and soluble fractions, and 'is the ratio of the ratio of the total amount of the cereal to the soluble fraction. Further, the glass transition temperature of the elastic core layer (in the case of the case) is preferably less than or equal to C (for example: °c). 1 u can form an elastic core layer having a property as a rubber. The knives may each be selected from the group consisting of a diene monomer (conjugated diene monomer) and at least one monomer (first monomer) of the early body, 5〇% to 〇Q% by mass, and

2226-9866-PF 200927830 A rubber elastomer composed of 0 to 50% by mass of another copolymerizable vinyl monomer (second monomer); a polyoxyalkylene rubber-based elastomer; or a combination thereof. Further, the term "mercapto) acrylate in the present invention means propyl acrylate and/or methacrylate. • A diene monomer (a total of a diene mono-body) which can be used to form an elastic core layer, and examples thereof include 1,3-butadiene, isoprene, and 2-chloro-1,3-butene. Diene, 2-methyl-1,3-butadiene, and the like. These diene monomers may be used singly or in combination of two or more. It is especially preferred as 1,3-butadiene. Further, a (meth) acrylate monomer which can be used for forming an elastic core layer is exemplified by (meth)acrylic acid, (meth)acrylic acid, butyl (meth) acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)propionate (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, etc. Alkyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl (meth) acrylate Glycidyl (meth)acrylic acid glycidyl esters such as glycerol esters, (meth) propyl acrylate glyceryl alkyl esters; (meth)acrylic acid alkoxyalkyl esters; (methyl) acrylic acid olefins (meth)acrylic acid allyl alkyl ester such as propyl ester or (meth) propylene decyl allyl octylate; (meth)acrylic acid monoethylene glycol ester, (meth)acrylic acid triethylene glycol A polyfunctional (meth) acrylate such as an alcohol ester or tetraethylene glycol (meth)acrylate. These (meth) acrylate monomers may be used singly or in combination of two or more. It is particularly preferred as (mercapto)acrylic acid@, (meth)acrylic acid butyl vinegar or (meth)acrylic acid 2-ethylhexyl acrylate. The rubber elastic body which can constitute an elastic shell layer may be a copolymer of the above-mentioned first monomer 2226-9866-PF 11 200927830 and a vinyl monomer (second monomer). Examples of the vinyl monomer include vinyl arylenes such as styrene, α-mercaptostyrene, monochlorostyrene, and dichlorostyrene; vinyl carboxylic acid tears such as acrylic acid and methacrylic acid; and propylene; Vinyl cyanide such as nitrile or mercapto acrylonitrile; halogenated vinyl such as vinyl chloride, vinyl bromide or chloroprene; vinyl acetate; alkylene such as ethylene, propylene, butylene or isobutylene; A polyfunctional monomer such as diallyl phthalate, triallyl cyanurate, triallyl isocyanate or divinylbenzene. These vinyl monomers may be used singly or in combination of two or more. It is especially good with styrene. Further, the polyoxyalkylene-based elastomer which can constitute the elastic core layer may, for example, be dimethyl oxalate, diethyl oxyhydrogenation, methyl phenyl oxyhydrogen or diphenyl siloxane. A polyoxyalkylene-based polymer composed of an alkyl group or an aryl group 2 substituted with a siloxane unit. These polyoxyalkylene-based polymers may be used singly or in combination of two or more. It is particularly preferred to use dimethyloxane or diethyloxane. From the viewpoint of maintaining the dispersion stability of the polymer fine particles used in the present invention in the resin composition, the elastic core layer is introduced into the bridging structure by polymerizing the polymer component or the polyoxyalkylene polymer component. It is better. The method of introducing the bridge structure is not particularly limited, and a method generally used can be employed. For example, a method of introducing a polymer component into a bridging structure by polymerizing the above-mentioned monomer is a method of adding a bridging monomer such as a polyfunctional vinyl compound or a compound containing a thiol group to a polymer component, followed by a polymerization method, and the like. . Further, a method of introducing a polyoxyalkylene-based polymer into a bridging structure may be a method in which a polyfunctional alkoxysilane compound is used in combination at the time of polymerization; 2226-9866-PF 12 200927830 or a vinyl reactive group or a mercaptan a reactive group based on a group or the like, and a method of adding a vinyl polymerizable monomer or an organic peroxide to a radical reaction, or adding a polyfunctional compound to a polyoxyalkylene polymer A method of polymerizing a bridging monomer such as a vinyl compound or a compound containing a thiol group, followed by polymerization. Although the elastic core layer has a single layer structure, it may have a multilayer structure. Further, when the elastic core layer has a multilayer structure, the polymer compositions of the respective layers may be different. 2-2: Shell layer The shell layer of the polymer fine particles used in the present invention is composed of an elastic core layer covering member and containing a hydroxyl group component. By changing the aspect, can the polymer microparticles be improved by improving the compatibility or affinity of the polymer microparticles with the polyol? The division of the alcohol towel is difficult. Further, the polymer fine particles may also be subjected to polycondensation with an unsaturated polybasic acid or a compound having two or more different (iv) g groups. Correctly speaking, it is used to form polymer graft polymerization, shell

It is preferred that the shell layer is grafted with the elastic core layer. The monomer component of the shell layer is substantially chemically bonded to the elastic core layer and the elastic core layer. In the present invention, 7 〇 mass% or more of the polymer forming the shell layer is preferably 8% by mass or more, more preferably 9 9% by mass or more, and elastic core stratification bonding is preferred. In the specification, the method for calculating the ratio of the chemical bond between the polymer forming the shell layer and the elastic core layer is as follows: First, the water containing the polymer fine particles is cut, and the raw material is solidified and dehydrated, and finally dried to obtain a polymer fine particle powder. Test 2 咼 molecular microparticle powder 2g at 23 ° C immersed in MEK100g24 hours, 肱 (four) p

In the recovery, the MEK soluble fraction was separated from the 2226-9866-PF 13 200927830 MEK insoluble fraction. The methanol insoluble fraction was separated from the MEK soluble fraction. Then, the ratio of the MEK insoluble fraction to the methanol insoluble fraction was calculated by determining the MEK insoluble fraction. The monomer component for forming the layer may be a polymer which can be bonded to a polymer which forms an elastic core layer having a warp group. #自关结构 ^ The southern molecular microparticles used in the present invention comprise a shell layer having a component of a hydroxyl group.较佳 Preferred monomer component is a monomer having a hydroxyl group in a side chain, and examples thereof include (meth)acrylic acid 2-ethyl acetal, (meth)acrylic acid propyl vinegar, (▼-based) acrylic acid. a (meth)acrylic acid hydroxy straight chain alkyl vinegar such as -4-hydroxybutyl ester (in particular, (meth)acrylic acid is sintered by a radical bond); —(Methyl)acrylic acid methyl vinegar, (5) methyl) (tetra) acid ethyl s, etc. (meth)acrylic acid via a branched alkyl ester; from a divalent carboxylic acid (phthalic acid, etc.) and two A monoester of a polyester diol (especially a saturated polyglycol) derived from a valence alcohol (such as propylene glycol) (methicone or the like) containing a base group (meth)acrylic acid vinegar, etc. The monomer component may be used singly or in combination of two or more. In order to impart compatibility between the polymer microparticles and the polyol, or the affinity of the resin to the resin material, the function of polycondensation may be It is formed using a vehicle component having a working monomer component or having a carbon ruthenium bond, whereby it can be used in the present invention. a component having a few bases or a component having a carbon-carbon double bond Τ a high score; the body is a, optionally free from a branch forming an elastic core layer. Preferred monomer components include, for example, methyl)

2226-9866-PF 14 200927830 Acrylic acid, crotonic acid, itaconic acid, citraconic acid, maleic acid, hydrogen, oxalic acid, etc., unsaturated unsaturated acid, and such unsaturated acid anhydride. These monomer components may be used singly or in combination of two or more.

Further, the monomer component having a carbon-carbon double bond may also be a monomer component which has a carbon-carbon double bond in a side chain, and may be, for example, two. Ethylene glycol (meth)acrylate, diethylene glycol di(decyl)acrylate, triethylene glycol di(decyl)acrylate, tetraethylene glycol di(decyl)acrylate, triene Isocyanate, triallyl cyanurate, diallyl phthalate, divinylbenzene. The shell layer may be formed by containing other monomer components in addition to the above monomers. The other monomer component may, for example, be a (meth) acrylate, an aromatic vinyl compound, a vinyl cyanide compound, a (meth) acrylamide derivative, a maleimide derivative, or a vinyl ether. Wait. Other monomer components such as # may be used singly or in combination of two or more. The (fluorenyl) acrylate may, for example, be methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate or 2-ethylhexyl acrylate. Alkyl methacrylate; (meth) acrylate-2 - aminoethyl K mercapto) acryl glycerin vinegar. The aromatic vinyl compound may, for example, be a styrene-substituted styrene such as styrene or a methyl styrene; or a styrene-substituted styrene such as styrene-vinyl chlorostyrene. It is a cyanide-based compound 'packaged') acrylonitrile and substituted acrylonitrile. Further, the (meth) acrylamide amide is, for example, a (meth) acrylamide (including an N-substituted product). Malay I sub-organisms, including, for example, maleimide maleate (including substitutions). Vinyl ether, can be used as a weight reduction % & glyceryl vinyl ether, allyl vinyl

2226-9866-PF 35 200927830 Ether, etc. For example, 1% by mass of θBerry/〇 or more (more preferably 5% by mass or more), 60-mass, having a right-handed component of the monomer component of the base group, for example, for forming a full-early component of the shell layer. I% or less (more preferably 5 〇 mass% or less) and j is better. The content of the monomer component having a hydroxyl group is less than 1% by mass, and the compatibility or affinity of the polymer microparticles with the polymer is not sufficiently provided, and the material or the resin material is involved in the polymerization. The situation of the function of condensation. In addition, if the rate of the female φ- odd 3 is more than 60% by mass, the polymerization system is unstable, and there is a problem that the problem of clogging and smashing is easy to occur. The shell layer of the present invention has a ratio of axe core layer/shell ratio (mass ratio) to a fissure core layer/shell ratio (mass ratio) of 40/60 to 95/5 in the Du-n target area of 4, The range of 50/50~90/10 is better 'further with 60/40~88/12 Minghao® from Z's 4th better. The elastic core/shell ratio is deviated from 40/60 and the elastic field shore + is reduced, and the ratio of the a layer is lowered, which tends to reduce the effect of the polycondensate on the toughness improvement. In addition, when the ratio of the shell is reduced from 9b/5, the proportion of the shell layer is reduced, so that the polymer particles are used in the day-to-day traffic, and the sputum is taken, and the stagnation of the valley is not concentrated. . Moreover, the beneficial method obtains the possibility of the physical properties of the place + ... and the caretaker. 2-3: Method for Producing Polymer Microparticles The polymer microparticles of the core-shell structure can be produced by a known method, for example, emulsion polymerization, suspension polymerization, or microsuspension polymerization. Among them, from the viewpoint of controlling the structure of the south molecular microparticles, it is preferable to use a cut/μ to take a human/ 曰 砚 anvil to ritual polymerization (especially multistage emulsification polymerization). An emulsifier (dispersant) which can be used for emulsion polymerization, which may be an alkyl or arylsulfonic acid represented by dioctylthio-acid 'dodecylbenzene benzoic acid; or an alkyl or aryl ether; Rareic acid; an alkyl or aryl sulphate represented by t-decyl sulphate; succinyl or propyl sulphate; or aryl or aryl substituted sulphate; alkane 2226-9866-PF 16 200927830 aryl or aryl ether Substituted phosphoric acid; n-alkyl or aryl creatinine represented by dodecyl creatinine; alkyl or aryl carboxylic acid represented by oleic acid or stearic acid; alkyl or aryl ether carboxylate Various acids such as acids; alkalis of acid acids: anionic emulsifiers (dispersants) such as salts or ammonium salts; alkyl or aryl substitutions; nonionic emulsifiers (dispersants) such as polyethylene glycol; A dispersing agent such as a polyvinyl alcohol, an alkyl-substituted cellulose, a polyvinylpyrrolidone, a polyacrylic acid derivative or the like. These emulsifiers (dispersants) may be used singly or in combination of two or more. . ❹ As long as the dispersion stability of the polymer microparticles to the aqueous emulsion is not affected, the amount of the emulsifier (dispersant) used is as small as possible. Further, an emulsifier (dispersant), the higher the water solubility, the better. When the water solubility is high, the emulsifier (dispersant) can be easily washed by water, and the adverse effect on the finally obtained polycondensate can be easily prevented. The particle size of the fine particles of the f molecule can be set to obtain the aqueous emulsion 2, 4 Q, and the industrial productivity is also considered, and the volume average particle diameter (μ v) is 0.03 (four) or more (to 〇〇 5 " m or more is better), 丄 (four) or less (except for ©, _# m is preferred). In addition, the volume average particle diameter (5) of the polymer fine particles can be measured by using QTRACK UPA15Q (Nikkiso Co., Ltd.). 3: Resin composition The hydrazine molecular fine particles of the present invention have excellent compatibility with a polyol and affinity because a hydroxyl group is introduced into the shell layer. Therefore, the polymer microparticles are dispersed in the state of primary particles in the resin composition. 4. Resin composition containing a resin raw material The resin composition of the present invention, the composition of which may further comprise: unsaturated

2226-9866-PF 17 200927830 A polybasic acid, and one selected from the group consisting of two or more. One type of tree 曰 曰 获 获 获 、 , , , , , , , , 枓碏 多元 多元 多元 多元 多元 多元 多元 多元 多元 多元 多元 多元 多元 多元 多元 多元 多元 多元 多元 多元 多元 多元 多元 多元 多元 多元 多元 多元 多元 多元 多元 多元 多元 多元A saturated polyester resin composition, each of which is an ancient eight-, cyanogenic group. Further, the present invention adjusts the molecular microparticle phase-complexes to be mutually agglomerated and separately dispersed, and does not entangle the polycondensate obtained in the resin composition, and the ancient resin is used in the resin group. Disperse and uniformly improve the characteristics (quality) of the polycondensate. The composition of the knife can be used for the composition of the polymer, which will involve the polymer microparticles; the tree scorpion microparticles of the present invention are condensed by the polycondensation tree " Preventing the high-concentration of the composition from the polycondensation obtained by the description of the wax composition comprising the wax material. Rep. 4-1: Unsaturated polybasic acid Unsaturated polybasic acid, which will form a saturated polybasic acid, and may be, for example, - μ f 4b _. Maleic anhydride, my acid, itaconic acid #. Nightmare Small saturated polybasic acid, which can be used alone or in combination of two or more. A compound having two or more isocyanate groups has two or more lyophiles; a compound of ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium The cyanide and the compound can also be made into a non-isocyanate having a polymerizable unsaturated double bond, an unsaturated 哿 _ _ _ _ a -, bismuth citrate. These compounds may be used alone or in combination of two or more. use'

The mono-isocyanuric acid vinegar may, for example, be benzene diisocyanate vinegar (m), 4,4, 〜α diyl arylene-isocyanate (Xie), xylene diisocyanate, L-naphthalene diiso Aromatic 2226-9866-PF 18 200927830 diisocyanate of cyanic acid vinegar (卯D, 1,4-phenylene diisocyanate θ, tetradecyl dimethyl sulfenyl diisocyanate (TMXDI); 6-hexamethylene diisocyanate (HD I), cyclohexane-1,3-diylbis(methylene) diisocyanate (IhXDI), 4,4'-dicyclohexylmethylene diisocyanate (UDI), two Isophorone isocyanate (ipdi), hydrazine, 4_cyclohexyl diisocyanate (CHDI), norbornene diisocyanate (NBDI), aliphatic and alicyclic diisocyanate, etc. e 聚 polyisocyanate, Examples are TMP TMP (trimethylol propyl ether) adduct, TDI trimeric isocyanate, HDI biuret, hd I uretdione, HDI trimeric isocyanate, IpM trimer Isocyanate or the like. The oxime-type unsaturated diisocyanate or unsaturated polyisocyanate may, for example, be an isocyanate group of a polyisocyanate, and may be unsaturated. a (poly)condensate of a hydroxyl group of an unsaturated diol compound such as an ester, etc. 4 A method of preparing a resin composition of 3 parts of a fat raw material, comprising a resin composition of a resin raw material, which can be used for a polymer fine particle in a polyterpene alcohol The polyol solution (described later) dispersed in the state of the primary particles is mixed with the resin raw material, or the surface of the polyol solution is obtained on the way of the preparation step of the polyol solution, and the molecular microparticles, the day ^ t / , the day, the addition (described later), it is prepared by blending with a polyol and a resin material. The composition of the polymer is easily dispersed in the tree, and it is distributed in the tree. 'It is possible to omit the special dispersion operation which has been carried out in the process of dispersing the polymer material smoldering in the resin composition, and the granules in the granules. : In the polyol solution prepared by the top material, it is preferably 3% by mass or more; and the upper portion is preferably 2% by mass or more, more preferably, and further preferably 4 Å to 400% by mass or less. Quality (9) below Berry ° is better) Good. The polymer microparticles

2226-9866-PF 19 200927830 When the content is less than 1% by mass, the polycondensate of the present invention obtained by using a polyol solution has insufficient effect on the impact of the impact, and has a low shrinkage effect. situation. When the content of the polymer fine particles exceeds 60% by mass, the polycondensate of the present invention may not have sufficient heat resistance. 5: The degree of dispersion of the south molecular microparticles is in the present invention, and the polymer microparticles have a volume average particle diameter (Mv) / number average particle diameter (Mn) of 2 Å or less in the resin composition. Preferably, it is preferably 1.8 or less, and more preferably h 7 or less. When the volume average particle diameter (Mv) / number average particle diameter (Mn) is a resin composition dispersed in excess of 2 Å, even if a polycondensate is obtained from the resin composition, it is difficult to obtain a meaningful effect of adding polymer microparticles (for example, resistance Punch I, etc.). Further, in the present specification, the volume average particle diameter (Mv)/number average particle diameter (Μη) is measured by using MIKCROTRACK UPA (manufactured by Nikkiso Co., Ltd.), respectively, to determine the polymer microparticles in the resin combination. The volume average particle diameter (5) and the number average particle diameter (10) in the product were determined by dividing the volume average particle 2 = by the number average particle diameter (?η). 6. Residual amount of alkali metal ion and anionic emulsifier The following:: The resin composition of the bright, the residual amount of the alkali metal ion is preferably 60 gram or less, and more preferably 5 〇 Dr) m w nr * # M. Further, the residual amount of the anionic emulsifier is preferably eight or less at T: '90 ppm or less. It is preferably in the form of polymer microparticles, two or two; the emulsifier or dispersant used at the time of manufacture, having a water-soluble poly port. Water-soluble inclusions such as initiators and reducing agents, especially metal

2226-9866-PF 20 200927830 Ionic or anionic emulsifier. Or residual 卩m “After the residual metallization, the amount of ritualizing agent is reduced to a tree below the established concentration... The quality of the alkali metal ion or the negative ion is reduced. a <combination of the body ^ in this specification, resin combination The amount of residual metal ions in the solution is determined by adding a light analysis to the resin composition. In addition, the frequency of the anionic emulsifier in the tree sputum composition is determined by the following: 2nd boat 輙义> 4th 7~存里, / After the organic solvent solution after the step is dried, the ethanol solution obtained by extracting the ionic emulsifier with ethanol is used to monitor the wavelength ratio by using methylene group. The color quantitative method is used for the determination of the polyol solution. The preparation method of the polyol solution of the present invention, in particular, the polyol composition obtained by dispersing the polymer fine particles in a polyhydric alcohol, The preparation includes an aqueous emulsion containing polymer microparticles (in detail, a reaction mixture obtained by emulsion polymerization to produce polymer microparticles©), and a solubility in water of 2 ° C is 5 mass% to 40 ^% below After the organic solvent is mixed, the mixture is further mixed with excess water to cause a second step of aggregating the molecular fine particles; and the agglomerated polymer fine particles are separated and recovered from the liquid phase, and then mixed with an organic solvent to obtain the organic solvent to the molecular fine particles. The second step of the solution; and further, the third step of distilling off the organic solvent after mixing the organic solvent solution with the polyol, wherein the volume average particle diameter of the polymer microparticles in the polyol solution is (Mv) / number average particle size (Mn), the volume average particle size (Mv) / number average particle of the polymer microparticles in the waterborne gum

2226-9866-PF 21 200927830 The ratio of the diameter (Μη) is preferably 2 times or less. It is preferably 18 times or less, further preferably 1.7 times or less, and further preferably 丨.4 times 〇. By the constitution, it is possible to easily obtain a polymer solution in which polymer microparticles - two human particles are dispersed. Further, a polyol solution having an alkali metal ion concentration of less than or equal to the following, and having an anionic emulsifier of less than 10 〇ppm (mass ratio). In the following, the modulation method will be described in more detail. η 明 明 π π 醇 醇 7-1 7-1 7-1 : Step 1 of the first step 'including mixing: for 2 (rc water solubility is 5 quality ... above 4. mass% or less (especially 30% by mass or less) The organic solvent and the operation of the aqueous emulsion containing the cerium alkali particles obtained by emulsion polymerization. By using the organic solvent, the above-mentioned mixing and adding water (described later) will be separated, and When the solubility of the loose organic solvent in which the polymer fine particles are aggregated to the extent of the interface is less than 5% by mass, the mixing with the aqueous emulsion containing the polymer fine particles may be slightly difficult. χ, the solubility exceeds 40. In the second step (described later), it is difficult to separate and collect the polymer fine particles from the liquid phase (mainly in the aqueous phase). The organic solubility in the second generation is 5 mass% or less. The solvent may, for example, be a class such as methyl ethyl ketone or the like; a vinegar such as formic acid formazan, acetic acid vinegar or acetic acid; an ether such as diethyl ether, ethylene glycol, or tetrahydropyran; Acetals such as aldehydes; isobutanol, Butanol and the like alcohols and the like. Such organic solvents may be used alone, or two or more together discipline.

2226-9866-PF 22 200927830 The organic solvent of the step 1 is as long as it is 5% by mass or more of the water in the 20T: ☆ solution. For example, a... can be a mixed organic solution, methyl propyl ketone, diethyl _, methyl isobutyl ketone, ... t ketone, etc., class; diethylene carbonate, butyl vinegar , acetic acid propylene vinegar, butyl acetate 莫 μ Gu #., ρ, ρ (9), diisopropyl ether, dibutyl ether and other ethers; pentane: _ heptane, octane and other aliphatic hydrocarbons; Benzene, toluene, diterpene benzene, right I, and broad cheek; low-water soluble glutinous agents such as methylene chloride and chloroform, such as sulfonium hydride, cyclohexylamine, etc.; Internal vinegar, E.2 2 early: acetic acid vinegar, etc., L, ethylene glycol monomethyl ether, such as isopropanol, third butanol, etc.; tetrahydro (tetra) and other high water organic solvents are suitable for more than Mixed organic solvent. When T 1 is less, the solvent is added to the liquid phase (mainly in the aqueous phase) of the second step described later.) The 易 point of the valley is easy to remove, and the water is higher than the water. The amount of the organic solvent to be mixed is 100 ❹Θ for the aqueous latex: Ρ is 5° or more in mass (especially 6G mass or more) and 250 or less (especially when the mass is less than 5 〇 mass) There is a case where the organic solvent is mixed, and it is difficult to form a polymer micro-secondary or aggregated body contained in the aqueous latex. Further, the organic solvent is mixed in an amount of more than 3 Å. The amount of water required for agglomeration is increased, and there is a case where the manufacturing efficiency is lowered. In the mixing operation of the upper water and the organic solvent, the conventional S can be used, for example, the general equipment having the position of the (four) wing can be used, Use a hybrid m mixer (in the piping - part group)

2226-9866-PF 23 200927830 Into the stirring device) and so on. In the first step, after the operation of mixing the aqueous emulsion with the organic solvent, the operation of adding excess water to the mixture is further included. Thereby, the mixture phase is separated, and the polymer fine particles can be agglomerated in a relaxed state. Further, the electrolyte of the water-soluble emulsifier or dispersion enthalpy used in the preparation of the aqueous emulsion, the water-soluble polymerization initiator, or the reducing agent may be dissolved in the aqueous phase. 100 parts of the above-mentioned organic solvent used in the mixing of the water-based emulsions, in an amount of 40 f or more (especially 6 parts by mass or more) of '300 mass parts or less (especially 25 parts by mass or less) ) is better. When the amount of water mixed is less than 40 parts by mass, it is difficult to cause the polymer fine particles to aggregate and form. In addition, when the amount of the water is more than 3 parts by mass, the concentration of the organic solvent in the agglomerated high-sized fine particles is lowered, which is the second step described later: the redispersion of the polymer particles to be agglomerated takes a long time, etc. There are cases where the dispersion of 2 molecular microparticles is reduced. _Two Ο 1 The mixing of water ‘In order to prevent the part of the polymer granules, it is preferable to use a flow which can impart the same fluidity. Specifically, it can be exemplified by the following: (4): Continuous operation. Further, the method of adding water may be a method of continuously adding = 10,000 or a method of adding one breath. 4 7-2: Step 2 The step is to take the aggregated polymer microparticles from the liquid phase and wait for the operation of the molecular microparticle additive. Sa ° Separation and removal of emulsified 9-layer wood by polymer microparticles, which can remove water-soluble inclusions such as ceremonial agents. .

2226-9866-PF 24 200927830 It is possible to use a method in which a liquid-phase network separates and collects agglomerated polymer microparticles from a liquid phase. For example, since agglomerated polymer microparticles generally have a suspension in a liquid phase, stirring is used in the first step. In the case of the tank, it is discharged from the bottom of the agitation tank (mainly in the water phase), or filtered using a filter paper, a filter cloth or a coarse mesh screen. The amount of the organic solvent contained in the aggregate of the polymer fine particles is 3% by mass or more based on the total mass of the high eight" microparticles (particularly, the % mass center: the mass is 75 mass% or less (particularly 7 mass%) In the organic soil, if the mass of the polymer is less than 5%, there is a case where the polymer microparticle additive is further divided into a long-term time, or an uncomfortable agglomerate is generated. When the content of the organic solvent is not equal to the mass%, the water is more dissolved. #1丄—13 is over 75, and the second is cold and cold; the other solvent remains and remains, and the Chu is suddenly the original g-aggregated polymer microparticles. The situation. No, the 'in this specification' is contained in the high amount of solvent. The organic matter of the polymer is cut into agglomerates for about u minutes, and the body is precisely and quantitatively obtained by the coffee C ❹ dose. The amount of the condensate of the 栌柞 ^ ^ ^ 含 含 含 含 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 高分子 高分子 高分子 高分子 高分子 高分子 高分子 高分子 高分子 高分子 高分子 高分子 高分子 高分子 高分子 高分子 高分子 高分子 高分子 高分子 高分子 高分子 高分子 高分子The state of the stand is redispersed in an organic solvent. ' Λ ,缰 1 =k The organic solvent used in the second step, the organic solvent exemplified. When the organic solvent is distilled off by using the shutdown step, the organic solvent used in the first step can be used together with water, which will be described later. Essence, but it can be contained in polymers

2226-9866-PF 25 200927830 The moisture of the microparticles is used for the first step; the organic solvent used in the second step is also different from the organic solvent in the second step, and the redispersion in the body is more certain. It is better to turn the κ agent into the same species. In the amount of the organic solvent, the amount of the organic fine particles used in the first step of the organic solvent is 1 〇◦ mass portion or more. The mass part is right 媸, -, °° (more preferably 10 〇〇 mass part or less). © Less than 40 lb. I, there are polymer particles that are difficult to ^ ^ times are still merging, molecular microparticles remain in blocks, unn W ~ Barrier. x 'The amount of organic solvent mixed exceeds... Bay:: The third step is to evaporate the organic solvent by the third step described later...: The energy of the big cockroach and the large-scale device are not economical. In the present invention, between the first step and the second step, when the agglomerated portion is separated from the liquid phase by the liquid phase, the solubility in the water at 2 Gt is again 5 mass% or more and 4 degrees. After the organic solvent is mixed, the step of mixing the excess polymer with the excess water to make the polymer microparticles agglomerate is preferably carried out, thereby making it possible to make the water-soluble inclusions of the emulsifier temple contained in the polymer microparticle additive. The residual amount is lower. Again, the water used here, = as It is preferred to use the organic solvent-containing water exemplified in the step! 7-3: Step 3, step 3, comprising: the organic solvent in the organic solvent solution of the polymer microparticles obtained in the second step is a polyol Replacement operation. By the operation, the polymer microparticles can be dispersed, and the emulsifier and the like are clipped.

2226-9866-PF 26 200927830 Polyol solution with a small amount of debris remaining. Further, the remaining water can be azeotropically distilled off. The amount of the polyol used in the third step can be appropriately adjusted in accordance with the concentration of the polymer fine particles in the final desired polyol solution. For example, for the mass portion of the polymer fine particles, the mass portion is 6 〇 (more preferably the HO mass portion or more), and the mass portion is 99 〇〇 or less (preferably 3 (four)). ❹ ‘ ‘ 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤 鹤. For example, = tank = a mixture of organic solvent solution and polyol, heated in decompression tank! Dry gas and the above mixture, the flow contact structure is extruded; p type = the continuous method of the machine; use the method of having the devolatilizer = two "two-stop cultivating tank", etc. The range is suitable for selection and the amount of the obtained polyol solution is not selected, and the volatile matter remaining in the polyol solution according to the polyol solution can be selected. - 0 The purpose of use is in the range of no problem. 8: Polycondensate in the present invention, ~ Human body: The tree of the present invention:: = group: the state of the polycondensate obtained by the material is dispersed, so that the borrower and the knife are uniformly dispersed by the sub-particles: the polycondensation is known The non-condensed body in the polymer polycondensate is easily obtained. Hereinafter, the unsaturated polyester and the polyurethane in the present invention will be described. 8 - 1 . Unsaturated polyester The unsaturated flat I of the present invention Know that the use of unsaturated polybasic acid as a resin

2226-9866-PF 27 200927830 f is obtained by polycondensation with a polyol. In this case, since the polymer microparticles are involved in the polymerization of the unsaturated polymer in the outermost layer of the polymer microparticles, the polymer microparticles are not easily condensed by the polycondensate. In order to obtain an unsaturated polyacetate, the method of polycondensing the resin composition of the present invention is used. For example, the resin composition is placed in the reaction, and the nitrogen is added to the first 1 to 2 small days*] 7 n ❹ 升 升 m A 9nny j day can be 17 (M8 〇r reaction, which takes several hours. At the same time, since the condensed water will azeotrope with the multi-drug and go out of the system, the polyhydric alcohol will be recovered from the hydrazine and the knives will be removed. A small amount of the sample is taken out in the reaction, and the measurement is carried out (15-30) 8^^ l ^ - 仏, until it becomes the desired acid price)% 彳〒 加热 heating. The reaction solution w, ^ ^ ^ L ^ is reduced from the dish to 1 001 before and after the addition of the inhibiting agent (for example, to the stupid two - etc., after adding... this bowl of second-instar B is suspected) A vinyl monomer (for example, Benzene Temple) is made into an unsaturated polyester. The obtained unsaturated polyester resin hard machine peroxide catalyst (for example, peroxyethylene, unsaturated polyester is added with a mixing accelerator as needed (example 2 == benzoyl peroxide, etc.), and it can be hardened at room temperature or heat-hardened. . & money or ring-burning acid, etc.), the resulting unsaturated polyester resin (hardened), viable-reinforced plastic (10) (10) mixture, or: 箄 also:: in the fiber bath unit or septic tank, etc. The construction of the table materials 'conveying machines, electronic parts and so on. /_L α boat or yacht, etc. 8-2 : Polyurethane The polyurethane of the present invention uses "cyano I δ day as a resin raw material,

2226-9866-PF 28 200927830 is obtained by polycondensation with a polyol. At this time, the outermost ancient, the first, Ding Tianwan, in the abortion layer of the molecular microparticles have a hydroxyl group, the polymer microparticles also involve 盥 & ψ m ^ mm- 4. Xingfi vinegar A, ·, It is difficult to cause the polymer microparticles to be precipitated from the polycondensate. In order to obtain a polyurethane, the resin composition of the present invention can be used in a method of A / 士 no ^ from D < Wanfa, • : + . For example, a foam (foam), a resin composition, a bridging agent (water, etc.), 3 a touch of a touch (amine or organotin compound, hydrazine, package (c〇2, fluorocarbon, methylene ketone) - Livestock, corpse - pentane, sputum, sputum size regulator (silicone resin or emulsifier, etc.), etc. ❹ 发泡 于 Μ Μ Μ Μ 。 。 。 。 。 。 。 。 。 。 寺With the method of thermosetting polyurethane, the resin of the present invention which is sufficiently dehydrated can be extended, and the hardened TM single method or pre-form: the heat-hardening polymerization of the present invention Ammonia series, not only with heat::; 3 can be hardened by ultraviolet rays or electron lines. The polyurethane of the present invention can be used for various types of beads, elastomers, adhesives, coatings and the like. For example, m ^ ® m ϋ * can be obtained as a binder for carbon fiber, glass fiber, aramid fiber, etc., and is made of fiber-reinforced plastic (10). Furthermore, the use of polyurethane is preferred; ‘unsaturated polyurethane is preferred. /. W Ν·, and &curable polymerization can also be used in the field of solder resist resistance of printed boards and the like. 'Requires crack resistance, high gloss, low yield. [Examples] Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but only

2226-9866-PF 29 200927830 The invention is not limited to the above, and may be appropriately modified and implemented in accordance with the scope of the present invention, which is included in the technical scope of the present invention. In addition, in the following examples and comparative examples, "part" and "%" mean mass parts or mass%. Evaluation Method First, the evaluation methods of the polyol solutions produced in the examples and the comparative examples will be described below. ❹ [Residual amount of anionic emulsifier] The residual amount of the anionic emulsifier is the method of the examples and the comparative examples, and the amount of the emulsifier remaining in the organic solvent solution of the polymer fine particles before mixing with the polyol is as follows In the measurement method, the mass ratio (ppm) contained in the system after the polyol solution was prepared by using the total amount of the emulsifier used for the production of the polymer fine particles as 1% by mass was determined. [1 -1 ] The analysis sample is a method described in the following examples and comparative examples, and 5 ml of an organic solvent solution of the polymer fine particles before mixing with the polyol is added, and after drying, 50 ml of ethanol is placed in a beaker. After stirring for 1 minute, the supernatant was used as an analysis sample. 1 [1 - 2 ] Measurement by methyl blue method 30 ml of water, 1 〇 ml of an alkaline sodium borate solution, and 5 ml of a thiol blue solution (0.025 mass% aqueous solution) were placed in a separatory funnel. Add 2 ml of chloroform and shake for 3 to 5 minutes to separate the chloroform layer. The addition of chloroform and removal is repeated until the chloroform layer is not colored. Next, dilute sulfuric acid (2.9% by mass aqueous solution) 3mi, chloroform 20ml' of the analysis sample prepared by the above [1-1] 2m bub 3~5 minutes

2226-9866-PF 30 200927830 After the clock, the chloroform layer was measured by a spectrophotometer (product name: UV-2200, manufactured by Shimadzu Corporation) at an absorption wavelength of 65 〇 nm to determine the anionic emulsification in an organic solvent solution. The residual amount of the agent. Further, the alkaline sodium borate solution was prepared by mixing sodium tetraborate decahydrate and a 19 mass% aqueous solution 5 〇〇 ffli - 〇. 4 mass% sodium hydroxide solution 500 ml. [2] Analysis of the residual amount of metal ions [2-1] Pretreatment 0 Add sulfuric acid and nitric acid to the polyterpene alcohol solution, and pressurize the acid using a microwave decomposing device (product name: MLS-1 200MEGA 'MILESTONE GENERAL· company) break down. [2-2] Electrolyte amount analysis by ICP mass spectrometry (Icp_MS quantification) HP-45 00 type manufactured by Yokogawa Analytical Systems was used, and co was used as an internal standard under cold plasma conditions, and the absolute line method was used. By analyzing the amount of Na ions (Na+) and the amount of κ ions (κ + ) φ by high-frequency inductive plasma luminescence analysis, in the present invention, the obtained analytical values (Na+ amount and Κ+ amount) are combined. As a residual metal ion test. [3] Determination of the average particle size and the degree of dispersion. The volume average particle diameter (Μν) and the number average particle diameter (Μη) of the polymer fine particles dispersed in the aqueous latex and the polyol solution are based on UPA150 (Nikkiso Co., Ltd.) System) measurement. The aqueous emulsion is diluted with deionized water. As for the polyhydric alcohol solution, the polyol and the hydrazine constituting the polyol are used as the measurement sample. The measurement is performed by measuring the refractive index of water, or the refractive index of the polyol used, and the refractive index of each ruthenium molecular microparticle.

2226-9866-PF 31 200927830 600 seconds, adjust the sample concentration by setting the Signal Level to _ 6~0. The degree of dispersion was obtained by calculating Mv/Mn from the values of Μν and Μη. Production Example 1 of Water-Soluble Latex Containing Polymer Microparticles 1 -1 : An elastic core layer is formed in a glass reactor having a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, a monomer and an emulsifier addition device, and is placed therein. Ionized water 18 〇Beibu, dipotassium phosphate 〇.〇3 mass parts, potassium dihydrogen phosphate 〇·25 mass parts,

Ethylenediamine tetraacetate dihydrate (EDTA) 〇〇〇 2 mass fraction, ferrous sulfate, 7 water and salt (Fe) 0. 〇〇1 mass fraction, sodium sulfoxylate sodium sulfonate (SFS) 〇. 〇 4 mass parts 5 parts of sodium lauryl sulfate (SLS), and the temperature was raised to 45 ° C while stirring in a nitrogen stream. Next, 70 parts by mass of n-butyl acrylate (BA), a mass fraction of styrene (ST) 13, and allyl methacrylate 2 were peroxidized. The monomer mixture composed of the mass portion of 〇2 is instilled. Further, while the monomer mixture was added, the mass portion W of the 胄i was prepared as a 5 mass% aqueous solution, and the mass portion was continuously added for 5 hours. 1 - 2 : The formation of the shell layer is continued by the addition of the monomer mixture for 1 hour, and then the mass portion of BA2, decyl decanoate (MMA), 1 〇 mass portion, thiol acrylate = = (hemA) 3 f quantity, & CHP 〇. Q1 mass part of the mixture of 90 minutes to choose, 夭丄 里 _ _ add. After the end of the addition, the addition of the CHp portion was further carried out, and the polymerization was completed after stirring for 1 hour. The single conversion rate was 99.3%. &The mouth of the knife The volume average particle size (MV) of the polymer microparticles contained in the di-t-gel is the volume average particle diameter of the molecular microparticles of the raw rubber.

2226-9866-PF 32 200927830 (Mv) is 0.20// πι. Production Example 2 of Water-Soluble Latex Containing Bismuth Molecular Particles 2-1: Formation of Elastic Nucleation Layer In a 100 L pressure-resistant polymerization machine, a ZU0 Berry portion, a tripotassium phosphate, a ?3 shell portion, and potassium dihydrogen phosphate were introduced. .25 mass parts, · 〇〇 2 quality Jin Department, • Fe 0.001 mass part, and dodecyl benzene sulfonate (clear _5 mass part, after fully mixing nitrogen to remove oxygen, In the middle of the input of di-bare e aBD) 100 quality, heating up to 45t. The pentamidine hydrogen peroxide (php) was charged to 0.015 mass portions, and then the SFS 〇4 mass portion was introduced to start polymerization. = The 4th hour of the start of the 'People's PHPG.G1 f, edta〇〇〇i5 > Bay! Department, and FeO.OOl quality department. The residual monomer 仏 depressurization r was removed by devolatilization during the polymerization for 1 hour, and the polymerization was terminated. The polymerization conversion ratio was 97·(10), and the volume average particle diameter of the obtained BD rubber latex was 〇. I 〇 #(1). 2 - 2 : The shell layer is formed in a 3L glass container, and is placed in the above-mentioned rubber latex ι 48 〇 mass portion (containing 480 mass parts of ruthenium rubber particles, 丨 · 5 mass % SDS as an emulsifier for rubber solid content) and pure 440 mass parts of water were stirred with 7 〇〇c while replacing with nitrogen. After adding a mass fraction of azobisisobutyronitrile (ΑΙΒΝ) to 1.2 mass, a mixture of ST 42 mass fraction, ΜΜΑ 42 mass fraction, and 36 mass fraction of 4-hydroxybutyl acrylate (4-oxime) was continuously used for 2 hours. Add graft polymerization. After the end of the addition, the mixture was stirred for 2 hours to complete the reaction, and an aqueous emulsion of polymer microparticles was obtained. 8%。 Polymerization conversion rate was 99.8%. 2~3: Volume average particle diameter of polymer microparticles in aqueous latex (Μν) The average particle diameter of polymer microparticles contained in the obtained aqueous latex is 2226-9866-PF 33 200927830 (Mv) is 〇. 11 # m. Production Example 3 of Water-Soluble Latex Containing Bismuth Molecular Particles 3-1 : The elastic core layer was formed in a 100 L pressure-resistant polymerization machine, and a mass of 2 〇〇 mass, a potassium triphosphate 0.03 mass, and potassium dihydrogen phosphate were added. 25 mass parts, edta〇〇〇2 mass parts, Fe0. 0 01 shellfish, and 12 yards of sodium benzoate () u mass part, after the nitrogen is completely replaced by agitation, the oxygen is removed The bd U quality department and the ST 25 quality department heat up to the TOEIC. The pHp was put into the mass fraction, and then 3 was added to start the polymerization at 0.04 mass. The fourth smallest % from the start of the polymerization is put into the php 〇. 01 mass, EDTA 〇. 〇〇 15 mass, and Fe 0. 〇〇 1 Berry. The residual monomer was removed by devolatilization under reduced pressure during the second hour of polymerization to terminate the polymerization. The polymerization conversion ratio was 98%, and the volume average particle diameter of the obtained st_rib rubber latex was 〇.1〇 A m. 3-2: Formation of shell

In a 3 L glass container, the above-mentioned rubber latex 丨 3 〇〇 mass portion (including 420 mass parts of ST-BD rubber particles, 15% by mass of SDS as an emulsifier for the solid content of the rubber) and 44 〇 mass parts of pure water were placed. The mixture was stirred at 7 ° C with nitrogen substitution. After adding ΑΙΒΝ1·2 mass part, ST96 mass part, 4_hba 3曰0 mass part, acrylonitrile (AN) 36 mass part, methyl acrylic acid (mixture of _ 爪 罝 & & & 连续 连续 连续 连续 连续 连续 3 3 After the end of the addition, the mixture is further mixed for 2 hours to complete the reaction, and the aqueous emulsion of the polymer microparticles is obtained. The polymerization conversion ratio is 99.5%. The volume average particle diameter (Mv) is 3:3. The polymer microparticles in the aqueous latex are contained in the polymer latex in the obtained aqueous latex.

2226-9866-PF 34 200927830 (Mv) is a production example of a water-based emulsion containing polymer microparticles. 4:1: The shell layer is formed in a 3L glass container, and the BI) rubber latex/gel obtained in the above Production Example 2 is placed. Elastic core layer) 1480 mass parts (including 480 parts of BD rubber particles, . 5.3 mass % SDS as an emulsifier for rubber solids) and 440 mass parts of pure water 'with nitrogen substitution 7 〇t: stirring . After adding the aibn i.2 mass part _, the mixture of ST 42 mass part, Li A 42 mass part, 4-HBA 18 mass part, and allyl methacrylate (ALMA) 18 mass part was continuously added and grafted for 2 hours. polymerization. After the end of the addition, the mixture was further stirred for 2 hours to complete the reaction, and an aqueous emulsion of polymer microparticles was obtained. 5%。 Polymerization conversion rate was 99. 5%. 4-2: volume average particle diameter (Mv) of the polymer microparticles in the aqueous latex § square; the volume average particle diameter (Mv) of the polymer microparticles in the aqueous emulsion to be applied is 〇. 11 # m. Production Example 5 of the aqueous emulsion containing the polymer fine particles Ρ 5 - 1 : The shell layer was formed in a 3 L glass container, and the rubber latex (elastic core layer) obtained in the above Production Example 2 was placed in a mass of 1480 parts (including the rubber particles). The 48 〇 mass part, the solid content of the rubber contains 5.6 mass% SDS as an emulsifier) and the pure water 440 λ liter 4, and the nitrogen is replaced by nitrogen at 70 ° C. After the addition of a I BN 1. 2 mass fraction, the mixture of the ST 60 mass fraction and the MMA 60 mass fraction was continuously added for graft polymerization for 2 hours. After the end of the addition, the mixture was further stirred for 2 hours to complete the reaction, and the aqueous emulsion of the polymer fine particles was applied. 3%。 Polymerization conversion rate was 99.3%. 5 2. Volume average particle size (Mv) of molecular microparticles in aqueous latex

2226-9866-PF 35 200927830 The volume average particle diameter (Mv) of the polymer fine particles contained in the obtained aqueous latex was 0.11 m. Production Example 6 of the aqueous emulsion containing the polymer microparticles 6 -1 : The shell layer was formed in a 3 L glass container, and the BD rubber latex (elastic core layer) obtained in the above Production Example 2 was placed in a mass portion of 14 8 0 (including BD rubber particles). 48 0 mass parts, the solid content of the rubber contains 1.5 mass % SDS as an emulsifier) and the pure water 440 mass part 'with nitrogen substitution 7 (rc stirring. After adding ΑίΒΝ 12 mass parts, the ST 51 mass part 3%。 Polymerization conversion rate of 99. 3%. The polymerization of the polymer emulsion was 99.3%. 6 2 . The volume average particle size (Mv) of the micro-particles in the aqueous latex. The volume average particle size (Μν) of the polymer particles in the raw rubber is 0.11 ". m〇❹ Example 1 A 144 mass portion of methyl ethyl ketone (MEK) was introduced into a 1 L mixing tank of 25 〇, and the mixture was stirred and put into the mass portion of the production example i. The aqueous emulsion 126 of the granules was supplied at a speed of supply: _ 2° 〇 mass portion 8〇 mass fraction/min of floating condensation After the slurry of the body is stopped, the stirring is quickly stopped, and the suspension portion obtained by the suspension unit is provided in the mixing tank, and the liquid crystal 350 mass fine particle additive is chased into the discharge port. The body (the organic solvent of the polymer particles is dissolved in the 9 Q mass part) to obtain the molecular weight of the organic solvent solution.

2226-9866-PF 36 Polypropylene glycol (PPG) 57 mass parts of 200927830, after mixing, the MEK decompression chamber was removed to obtain a PPG solution (polyol solution 1) of polymer microparticles. The polyol solution 1 is white translucent. As shown in Table 1, the average particle diameter of the polymer fine particles dispersed in the polyol solution 1 was measured by MICROTRACK UPA, Μν = 0.26 // m, Μη = 0. 20 " m, Mv /Mn=l. 30, it is understood that the polymer fine particles are uniformly dispersed. Further, the results of measuring the residual amount of the anionic emulsifier and the residual amount of the alkali metal ions were 78 ppm and 38 ppm, respectively. [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Southern molecular microparticle elastic core layer BA ST ALMA BD BD ST BD BD Shell having an OH group component having a C00H group having a c=c bond Composition HEMA 4-HBA 4-HBA MAA 4-HBA ALMA 4-HBA ALMA Other ingredients MMA BA ST MMA ST AN ST MMA ST MMA Volume average particle size in aqueous latex Mv("m) 0.20 0.11 0.11 0.11 0 . 11 Number average particle size in aqueous latex Μη ( /ζιη) 0.18 0.09 0.09 0.09 0. 09 Dispersion of polymer microparticles in aqueous latex (Mv/Mn) (A) 1.11 1.20 1.20 1.20 1.20 Polyol PPG Volume average particle size of PPG BG PPG IG in polyol solution Mv ( //m) 0. 26 0.18 0.20 0.18 0.19 Number average particle size in polyol solution Μη (in m) 0.20 0.12 0.14 012 0. 12 Dispersion of polymer microparticles in polyol solution (Mv/Mn) (B) 1.30 1.50 1.43 1.50 1.58 Rate of change of dispersion (8) / (A) 1.17 1.25 1.19 1.25 1.32 Residual amount of anionic emulsifier (ppm) 78 82 67 75 71 Residual metal ion residue (ppm) 38 48 36 43 33 Polyol solution No. 1 2 3 4 5 2226-9866-PF 37 200927830 Example 2 In the first embodiment, the aqueous emulsion of the polymer microparticles obtained in the production example 1 was used in addition to the aqueous emulsion of the polymer microparticles obtained in Production Example 2. In the same manner as in Example i, a solution of polymer fine particles (polyol solution 2) was obtained. The polyol solution 2 was white translucent. As shown in Table 1, the average particle size of the polymer fine particles dispersed in the polyol solution 2 was obtained. The diameter is determined by the result of MICR 〇 TRACK upA,

When Mn = 0.12 / /m and Mv / Mn = i 5 , it was found that the polymer fine particles were uniformly dispersed. Further, the results of measuring the residual amount of the anionic emulsifier and the residual amount of the alkali metal ions were 82 ppm and 48 ppm, respectively. (Example 3) A mass fraction of 126 parts by mass of ketone ketone (MEK) was introduced into a 1 L mixing tank of 25 C, and the mass fraction of the aqueous emulsion 126 of the polymer fine particles obtained in Production Example 3 was stirred. After uniformly mixing, the spleen k ^ was charged at a supply rate of 80 parts by mass of water of 20 parts by mass. The end of the supply of the German, m Gu l Cheng 1 丨 φ (after a rapid stirring, to obtain a slurry containing the suspension of the political polymer. 1 time, leaving the Μ ” 迢 迢 减 ” ” 迢 迢 迢 迢 迢350 ΐ 由 排出 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 Obtain the organic solvent solution of the polymer micro-teacher in the sentence eight and the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ After the house was distilled off, a BG solution (polyol solution 3) of high-resolution knife microparticles was obtained. The polyol solution 3 was white translucent. As shown in Table 1, the polymer microparticles dispersed in the polyol solution 3 were micro.

2226-9866-PF 38 200927830

The average particle size of the particles is known by MICR0TRACK .43, and the polymer particles are known.

Mv-〇. 20" m, Μη = 0. 14" m, the child is evenly dispersed. The residual amount of the anion emulsifier and the residual amount of the metal ion were measured and found to be 67 ppm and 36 ppm, respectively. Example 4 In the same manner as in Example 1, except that the aqueous emulsion of the polymer fine particles obtained in the production example i was replaced with the aqueous emulsion of the polymer fine particles obtained in Production Example 4, the polymer fine particles were obtained. ppG solution (polyol solution 4). The polyol solution 4 is white translucent. The average particle diameter of the polymer microparticles dispersed in the polyol solution 4 as shown in Table 1 is determined by MICR0TRACK ϋρΑ, Μν = 0·18 // m, Μη = 0·12# m, Μν/ Μη=1. 50, it is understood that the polymer fine particles are uniformly dispersed. Further, the results of measuring the residual amount of the anionic emulsifier and the residual amount of the alkali metal ions were 75 ppm and 43 ppm, respectively. (Example 5) A Pg solution (polyol solution 5) of polymer microparticles was obtained in the same manner as in Example 4 except that propylene glycol (pc) was used instead of the PPG of Example 4. The polyol solution 5 is white translucent. As shown in Table 1, 'the average particle diameter of the polymer fine particles dispersed in the polyol solution 5 is measured by MICROTRACK UPA, Mv = 0.99 / m, Μη = 〇·m, Mv/Mn = l. 58, it is known that the polymer particles are uniformly dispersed. 2226-9866-PF 39 200927830 The results of measuring the residual amount of anionic emulsifier and the residual amount of alkali metal ions were 71 ppm and 33 ppm, respectively. Comparative Example 1 A PPG solution of polymer microparticles was obtained in the same manner as in Example 2 except that the aqueous emulsion of the polymer microparticles obtained in Production Example 2 of Example 2 was used in the same manner as in Example 2 except for the aqueous emulsion of the polymer microparticles obtained in Production Example 5. (Polyol solution 6). The polyol solution 6 was white turbid. As shown in Table 2, the average particle diameter of the polymer micro-particles dispersed in the polyol solution 6 was measured by MICROTRACK UPA, Mv = 0.82 / zm, Mn = 0.25 " m, Μν / Μη = 3.28, it is understood that the polymer fine particles are aggregated and are not uniformly dispersed. [Table 2] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Molecular fine particle elastic core layer BD BD BD BD Shell having a 0H group component having a (3)0H group having a c=c bond component ALMA 4-HBA 4 -HBA .Other components ST MMA ST MMA ST MMA ST MMA Volume average particle size in aqueous latex MvCym) 0.11 0.11 0.11 0.11 Number average particle size in aqueous latex Mn( //m) 0. 09 0.09 0.09 0.09 Dispersion of polymer microparticles in aqueous latex (Mv/Mn) (A) 1.20 1.20 1.20 1.20 Polyol PPG PPG PPG PPG Volume average particle size in polyol solution Mv ( //m) 0.82 - - - Diversified Number average particle size in alcohol solution Mn( ytzm) 0.25 1 - Dispersion of polymer microparticles in polyol solution (Mv/Mn) (B) 3. 28 (coagulation) Gelatinous (coagulated) gel Shape (coagulation) gel (coagulation) rate of change of dispersion 2. 73 - ~ 2226-9866-PF 40 200927830

92 45 T

—————- IBV (A) M±SibS5#* (ppm) Residual amount (DDm) - chromophore-filled liquid No. Comparative Example 2 The aqueous emulsion of the polymer microparticles obtained in the production example 2 of Example 2 was replaced. In the same manner as in Example 2, except that the aqueous emulsion of the polymer fine particles obtained in Example 6 was used, a ppG solution (many 7 L of the alcohol solution 7) of the polymer fine particles was obtained. The polyol solution 7 was white turbid and gelled. As shown in Table 2, the average particle diameter of the polymer fine particles dispersed in the polyol solution 7 could not be measured by MICROTRACK UPA, and it was found that the polymer fine particles were aggregated and were not uniformly dispersed. Comparative Example 3 In a 1 L mixing tank at 25 ° C, 50 parts by mass of the aqueous emulsion of the polymer micro-pole obtained in Production Example 2 was placed, and 35 mass% of calcium chloride CaC 12 water-cooled liquid 13 Generate agglomerates. The slurry containing the coagulum was heated at 801: with stirring, and then cooled to room temperature. The slurry was filtered and dehydrated by a filter having a suction bottle, and then the agglomerates were dried in a box dryer at (C) C for 24 hours to obtain a dry powder of polymer fine particles. The mass fraction of PPG 60 was put into the mass of 30 parts of the dry powder, and after mixing, ultrasonic wave separation (20 kHz) was carried out for 1 hour to obtain a ppG solution (polyol solution 8) containing polymer fine particles. The polyol solution 8 was in the form of a white opaque gel/%. As shown in Table 2, the average particle diameter of the polymer fine particles dispersed in the polyol solution 8 could not be uniformly dispersed by the aggregation of the MICROTRACKUPiV fine particles. Further, the measurement of the amount of the residual amount of the alkali metal ions was measured and found to be 178 ppm.

2226-9866-PF 41 200927830 Comparative Example 4 The 1 L mixing tank of 2 5 C was placed in a mass of 5 Å of the aqueous emulsion of the polymer fine particles obtained in Production Example 2, and mixed with a mass of PPG 450 under stirring. Heat with stirring to bring the internal temperature to 1 30. (: Ground retention, by taking water to obtain a PPG solution (polyol solution 9) of polymer microparticles. The polyterpene alcohol solution 9 is a white opaque gel. As shown in Table 2, 'dispersed in the plural The average particle diameter of the polymer fine particles in the alcohol solution 9 cannot be measured by MICROTRACK UPA, and it is understood that the polymer is not uniformly dispersed by the particles being condensed by the particles. The result of measuring the residual amount of the metal ions is 7〇〇. From the results of Examples 1 to 5 of Table 1, it is understood that the polymer microparticles of the present invention have high dispersibility and low inclusions (anionic emulsifiers and alkali metal ions). The polyol solution of the present invention can easily obtain a resin composition in which polymer fine particles are uniformly dispersed, and a polycondensate. Further, from Examples 1 to 5 of Table 1, comparison with Comparative Examples 1 and 2 of Table 2, It is understood that when the shell layer of the polymer microparticles is not contained in the component having no hydroxyl group, the dispersibility of the polymer microparticles in the obtained polyol solution is remarkably lowered. Further, compared with Examples 1 to 5 of Table 1 and Table 2 Comparison of Example 3, it can be seen that When the molecular fine particles are solidified into a dry powder, it is difficult to obtain a polyol solution in which the polymer fine particles are uniformly branched. Further, from the comparison of Examples 1 to 5 of Table 1 with Comparative Example 4 of Table 2, it is understood that polymer fine particles are not used. When the additive is used to prepare a polyol solution, it is understood that the polymer microparticles are not uniformly dispersed. χ, contained in the polyol solution

2226-9866-PF 42 200927830 Inclusions are significantly more. [Industrial Applicability] The resin composition of the present invention can be suitably used in the production of a polycondensate in which polymer microparticles are uniformly dispersed. [Simple description of the diagram] . M. ^ [Description of main component symbols] * **>

2226-9866-PF 43

Claims (1)

200927830 X. Patent Application: 1 · A resin composition comprising: a polyol; and a polymer microparticle comprising: an elastic core layer, and a coating of the elastic core layer and comprising a component having a warp group In the shell layer, the polymer fine particles are dispersed in the state of primary particles. © at least one resin material selected from the compounds. 2. The resin composition according to claim 1, further comprising a free-unsaturated polybasic acid, and two or more isocyanate groups. The resin composition according to claim 1, wherein The above-mentioned commercial molecular fine particles are dispersed in a volume average particle diameter (MV) / number average particle diameter (Mn) of 2.0 or less. 4. The resin composition according to claim 1, wherein the metal ion residual amount is 6 Q PPJJJ (mass ratio) or less. The resin composition according to claim 1, wherein the residual amount of the anionic emulsifier is 1,000,000 ppm (mass ratio) or less. 6. The resin composition according to claim 2, wherein the preparation comprises: the aqueous emulsion having the above-mentioned cerium molecular microparticles, and the pair of particles. After the water solubility of cerium is 5% by mass or more and 40%, the mixture is further mixed with water, and the first step is performed; the organic solvent having a mass of 5% by mass or less is mixed, and the polymer microparticles agglomerated by the polymer microparticles are separated by the liquid phase. After recycling, once again 2226-9866-PF 44 2nd step of 200927830; and a third step of distilling the organic solvent and the above organic solvent to remove the organic solvent. 7. The resin composition according to claim 6, wherein the volume average particle diameter (Mv) / number average particle diameter of the polymer microparticles in the resin composition is the polymer microparticles in the aqueous latex. The ratio of the volume average particle diameter (Mv) / number average particle diameter (Mn) is 2 times or less. The resin composition according to claim 6, wherein the polymer fine particles are separated and collected by liquid phase separation between the first step and the second step, and the polymer particles are separated again. When the solubility of water in t: is 有机 mass% or more and 4 〇 mass% or less of the organic solvent is mixed, the step of mixing with the excess water is carried out to coagulate the polymer fine particles. The resin composition according to claim 1, wherein the shell layer further comprises at least one selected from the group consisting of a component having a carboxyl group and a component having a carbon-carbon double bond. And a resin composition according to any one of the items 2 to 9 of the present invention. 11. The resin composition according to claim 3, wherein the metal ion residual amount is 60 ριηη (mass ratio) or less. The resin composition according to claim 11, wherein the residual amount of the anionic emulsifier is 10 Oppm (mass ratio) or less. 13. The resin composition according to claim 12, wherein the composition comprises: 2226-9866-PF 45 200927830 3 is an aqueous latex having the above-mentioned local molecular microparticles, and the pair is 2 Å. In the first step of mixing the organic fine solvent having a solution degree of 5% by mass or more and 40% by mass or less, and further mixing the excess polymer particles to form agglomerated polymer fine particles; After the liquid phase separation and recovery, the second step of obtaining the organic solvent solution of the polymer fine particles is further mixed with the organic solvent; and the organic solvent solution is mixed with the polyol, and the organic solvent is distilled off. Step 3. 14. The resin composition according to claim 13, wherein the volume average particle diameter (MV) / number average particle diameter (Mn) of the polymer microparticles in the resin composition 16 is in the aqueous latex. The ratio of the volume average particle diameter (Mv)/number average particle diameter of the polymer fine particles is not more than the ratio. The resin composition according to claim 14, wherein the ruthenium molecular microparticles separated and recovered by liquid phase separation are carried out once or more between the first step and the second step, and again For 2 〇. After the organic solvent having a solubility of cerium is 5 mass% or more and 4 mass% or less, the mixture is mixed with excess water, and the polymer fine particles are agglomerated. 16. The resin composition according to claim 15, wherein the shell layer comprises at least one selected from the group consisting of a component having an anthracene group and a component having a carbon double bond. A polycondensate characterized by a resin condensate according to item 16 of the polycondensation application. 2226-9866-PF 46 200927830 V VII. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the representative figure is simple: No. 8. If there is a chemical formula in this case, please reveal the best display. Chemical formula of the invention: no 2226-9866-PF 4