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WO2005017031A1 - Composition de plastisol acrylique - Google Patents

Composition de plastisol acrylique Download PDF

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Publication number
WO2005017031A1
WO2005017031A1 PCT/JP2004/011450 JP2004011450W WO2005017031A1 WO 2005017031 A1 WO2005017031 A1 WO 2005017031A1 JP 2004011450 W JP2004011450 W JP 2004011450W WO 2005017031 A1 WO2005017031 A1 WO 2005017031A1
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WO
WIPO (PCT)
Prior art keywords
mol
fine particles
monomer
polymer
plastisol
Prior art date
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Ceased
Application number
PCT/JP2004/011450
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English (en)
Japanese (ja)
Inventor
Toshihiro Kasai
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Mitsubishi Chemical Corp
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Mitsubishi Rayon Co Ltd
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Filing date
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Application filed by Mitsubishi Rayon Co Ltd filed Critical Mitsubishi Rayon Co Ltd
Publication of WO2005017031A1 publication Critical patent/WO2005017031A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18—Spheres

Definitions

  • the present invention relates to a plastizonole composition using an acrylic polymer, and more particularly to a plastisol composition excellent in surface smoothness of a coating film and an article using the same.
  • a paste-like material obtained by dispersing fine particles of a thermoplastic polymer in a plasticizer is collectively referred to as plastizonole.
  • plastisol using a vinyl chloride polymer has been widely used as a salt visol in various industrial fields for many years. It's being used.
  • acrylic sols plastisols using acrylic polymers (hereinafter abbreviated as acrylic sols) have also been proposed, and have attracted attention as a material with excellent environmental compatibility, such as low toxic gas during incineration.
  • conditions where the surface smoothness is likely to be reduced include a case where a relatively low-polarity plasticizer is compounded and a case where an inorganic filler surface-treated with a fatty acid or the like is compounded. like this
  • Such conditions are particularly apt to concentrate, and applications include automotive undercoats and automotive body sealers.
  • an intermediate paint or a top coat is further coated on the body sealer, and the appearance of the paint is strictly evaluated. If the surface of the underlying body sealer is not sufficiently smooth, the result is As a result, the coating appearance of the top coat is low.
  • An object of the present invention is to provide an acrylic plastisol having excellent surface smoothness of a coating film while maintaining a core / shell structure of acrylic polymer fine particles having excellent basic properties of a plastisol. It is another object of the present invention to provide articles having excellent appearance quality, especially automobile undercoat / body sealers.
  • the present inventors have conducted intensive studies on the above problems, and as a result, determined that the amount of a highly polar functional group such as a carboxy group or a sulfonic acid group in a shell portion of a core / shell polymer was maintained at a certain level. It has been found that the above problem can be solved by suppressing the following. In addition, the storage stability, which tends to occur when the functional groups are reduced to a certain level or less, can be avoided by increasing the particle size of the primary particles (core / shell particles) or introducing epoxy groups. And found the present invention.
  • the present invention relates to a plastisol composition containing acrylic polymer fine particles and a plasticizer, wherein the acrylic polymer fine particles are composed of primary particles having a core / shell structure, and the average particle diameter of the primary particles is Is 400 nm or more and the monomer composition that gives the shell polymer is methinolemethallate 55 80 mol%, a carboxyl group or sulfonic acid group-containing monomer is less than 0.5 mol%, and other copolymerizable monomers.
  • a plastisol composition characterized in that it is 19.5 45 mol% (total is 100 mol%).
  • the monomer composition that gives the shell polymer of the acrylic polymer fine particles is 55-80 mol% of methyl methacrylate, and the (meth) attribute of alcohol having 2 or more carbon atoms is alcohol.
  • the acrylic polymer fine particles contain an epoxy group.
  • the improvement in the smoothness of the coating film has made it possible to apply it to high-appearance applications, such as automobile undercoats and automobile body sealers, which were difficult to achieve with conventional acrylic plastisols.
  • the acrylic polymer fine particles used in the present invention may be independent particles or an aggregate of these particles (aggregated particles), but the primary particles have a core / shell structure. is necessary. This is because, in the case of an acrylic polymer, unless the primary particles have a core / shell structure, it is not possible to achieve both storage stability and film forming properties, which are the basic performances of plastisol.
  • the monomer composition of the acrylic polymer fine particles used in the present invention that gives the polymer of the shell part is 55-80 mol% of methyl methacrylate, carboxyl group or sulfonic acid group when the total is 100 mol%. It is necessary that the contained monomer is less than 0.5 mol% and the other copolymerizable monomer is 19.5 to 45 mol%. If the ratio of methyl methacrylate is less than 55 mol%, the storage stability of plastisol will decrease, and conversely, 80 mol% If the amount exceeds the above range, adverse effects such as a decrease in the flexibility of the obtained coating film and bleeding out of the coating film plasticizer occur.
  • the ratio of the monomer containing a carboxyl group or a sulfonic acid group is 0.5 mol% or more, the storage stability of plastizonole is good regardless of the particle size of the acrylic polymer particles.
  • the surface smoothness of the coating film decreases, and the appearance of the coating film decreases.
  • methyl methacrylate is 6575 mol%
  • the carboxyl group or sulfonic acid group-containing monomer is less than 0.5 mol%
  • other copolymerizable monomers Is 24.5—35 mol. /. It is.
  • the storage stability of plastisol generally tends to decrease, but in the present invention, an acrylic polymer is used.
  • an acrylic polymer is used.
  • the average particle diameter of the primary particles of the fine particles 400 nm or more it is possible to reduce these highly polar functional group-containing monomers. If the average particle diameter is less than 3 ⁇ 400 nm, the storage stability of the plastisol is insufficient and the thickening becomes remarkable.
  • the average particle diameter means “volume average particle diameter”.
  • the “particle diameter of primary particles” refers to the particle diameter of core / shell particles.
  • the average particle size is preferably 600 nm or more, more preferably 800 nm or more. In the case of 800 nm or more, it is expected that the viscosity of plastizonole can be further reduced by simply improving the storage stability.
  • Examples of the carboxyl group- or sulfonic acid group-containing monomer used to form the shell polymer include methacrylic acid, acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and methacrylic acid.
  • These acid group-containing monomers may be in the form of a circle such as an alkali metal salt, for example, potassium salt, sodium salt, calcium salt, zinc salt, aluminum salt and the like.
  • an alkali metal salt for example, potassium salt, sodium salt, calcium salt, zinc salt, aluminum salt and the like.
  • Can be These can be in the form of a salt when polymerized in an aqueous medium, or can be in the form of a salt after polymerization.
  • copolymerizable monomers used in the range of 19.5 to 45 mol% include methinorea tallate, ethyl (meth) acrylate, n_butyl (meth) acrylate, and i_ butyl Linear alkyl alcohols such as (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and octyl (meth) acrylate (Meth) acrylates; (Meth) acrylates of cycloalkyl alcohol such as cyclohexyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Hydroxyl group-containing (meth) atalylates such as atalylate; glycidyl (meth) atalylate and other epoxy group-containing (meth) atalylate
  • the polymer of the shell part of the acrylic polymer fine particles used in the present invention it is possible to introduce these functional groups by copolymerizing monomers having various functional groups. Is preferably introduced.
  • an epoxy group When an epoxy group is introduced, it is possible to crosslink the coating film by utilizing the reactivity of the epoxy group when heating the resulting plastizol to form a gelled film, thereby increasing the mechanical strength of the coating film. Can be improved.
  • the reactivity of the epoxy group is suitable for the general conditions of heating the plastisol and is particularly useful over other reactive functional groups.
  • a reaction between epoxy groups may occur.
  • Tetrahydrofuran-insoluble matter is generated by forming a three-dimensional network structure due to the extremely high molecular weight or the presence of cross-linking, but the presence of such insoluble matter often increases the mechanical strength of the coating film. Available as needed.
  • the monomer composition that gives the polymer in the core portion of the acrylic polymer fine particles is not particularly limited as long as the (meth) acrylic ester is the main component (50 mol% or more). Can be copolymerized, and specifically, the same monomers as those exemplified as the monomer providing the shell portion can be used. However, 50% by weight of at least one kind of methacrylate or a copolymer thereof selected from ethyl methacrylate, normal butyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate, and cyclohexyl methacrylate is used. It is preferable to use a polymer containing the above.
  • Such a polymer has a high compatibility with a dialkyl phthalate plasticizer and a coating film formed from an acrylic sol containing acrylic polymer fine particles whose core is a copolymer having a copolymerization amount of the above monomer of 50% or more. Is preferable since bleed-out of the plasticizer does not occur after film formation.
  • the structure of the acrylic polymer fine particles is not particularly limited except that the primary particles have a core / shell structure, as described above, but as long as the basic performance of the plastisol is satisfied, it is intended to provide further functions. It is possible to introduce a structure similar to that described above.
  • the molecular weight of the polymer in the shell portion and the core portion of the acrylic polymer fine particles is slightly different depending on the use of the acrylic sol.
  • the weight average molecular weight of both the shell portion and the core portion is preferably 10,000 to 2,000,000.
  • the Tg of the acrylic polymer is preferably above room temperature.
  • a coating film formed from an acrylic sol made using acrylic polymer particles having a Tg of room temperature or less tends to exhibit tackiness.
  • the method for producing the acrylic polymer used in the present invention is not particularly limited, and examples thereof include an emulsion polymerization method, a soap-free polymerization method, a fine suspension polymerization method, and a dispersion polymerization method. In order to obtain a structure, an emulsion polymerization method or a soap-free polymerization method is preferable.
  • Acrylic polymer used as fine powder as a dry powder is used.
  • the detailed properties and structure are not limited.
  • a large number of primary particles obtained by polymerization can be aggregated to form aggregated particles (secondary particles), and a higher order structure is possible.
  • the primary particles are not strongly bonded to each other, but are loosely agglomerated, whereby fine and uniform dispersion of the primary particles in the plasticizer is achieved.
  • various plasticizers can be used as long as they have the ability to plasticize the acrylic polymer.
  • dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, diisononyl phthalate, phthalate Dialkyl phthalates such as diisodecyl acid; alkyl benzyl phthalates such as butyl benzyl phthalate; alkyl aryl phthalates; dibenzyl phthalate; diaryl phthalates; and triaryl phosphates such as tricresyl phosphate.
  • Phosphoric esters such as trianolyl phosphates and alkylaryl phosphates; aliphatic dibasic esters such as adipin dibutyl; ether-containing compounds such as polyethylene glycol, polypropylene glycol and dibutyl dalicol adipate; polyesters -Based plasticizer, Epoxy dung soybean Include soybean oil-based plasticizers and the like. These plasticizers can be used alone or as a mixture of two or more plasticizers.
  • plasticizers are phthalenic diesters of aliphatic alcohols having 8 to 10 carbon atoms, specifically, di-n-octyl phthalate, di-2-ethylhexyl phthalate, di_n_nonyl phthalate, di_i _Nonyl phthalate, di_n_decyl phthalate, and di_i_decyl phthalate.
  • These plasticizers are incompatible with the seal polymer of the acrylic polymer fine particles at room temperature (dissolution rate is sufficiently low), but compatible with heating (sufficiently high dissolution rate) when heated. This is because the dissolution rate balance is optimal.
  • the dissolution rate at room temperature is faster and the storage stability tends to be slightly lower. If the ester moiety has more than 10 carbon atoms, the dissolution rate during heating is higher. , There is a tendency for the gelling film formability to slightly decrease.
  • Plasticizer is acrylic It is preferable to use 50 to 300 parts by mass with respect to 100 parts by mass of the system polymer.
  • the monomer composition giving the polymer in the shell portion may be such that, as another copolymerizable monomer, (meth) acrylate of an alcohol having 2 or more carbon atoms is used. Preferably, it contains 40 mol% (the total of the monomer composition giving the polymer in the shell portion is 100 mol%).
  • (Meth) acrylates of alcohols with 2 or more carbon atoms have good compatibility with the above-mentioned plasticizers, and copolymerization of 5 mol% or more of these will make the coating film extremely flexible. . However, if the copolymerization ratio exceeds 40 mol%, the compatibility of the shell tends to be too high and the compatibility with the plasticizer tends to be too high.
  • the structure of the acrylic polymer is not particularly limited, except that the primary particles have a core / shell structure, as described above. However, as long as the basic performance of the plastisol is satisfied, the purpose is to provide further functions. It is possible to introduce a structure similar to that described above.
  • the plastisol composition of the present invention can contain any inorganic filler or the like.
  • the type of the inorganic filler is not particularly limited.
  • calcium carbonate, aluminum hydroxide, perlite, clay, colloidal silica, my powder, silica sand, diatomaceous earth, kaolin, talc, bentonite, glass powder, aluminum oxide, fly ash, shirasu Calcium carbonate is commonly used because of its high ratio, especially in terms of the force S and the amount of the balloon.
  • the surface smoothness of the coating film intended by the present invention is extremely remarkably exhibited when an inorganic filler surface-treated with a fatty acid is blended.
  • a surface-treated filler When a surface-treated filler is used, the viscosity of the plastisol composition increases or the fluidity is lost, so that the coatability is significantly reduced, and as a result, the surface smoothness of the coating film is often reduced. .
  • These phenomena are not a problem for applications that require a powerful appearance, which may not be a problem depending on the application.
  • the plastisol composition of the present invention may contain, if necessary, pigments such as titanium oxide and carbon black, various diluting solvents (aliphatic, isoparaffinic, naphthenic, etc.), antifoaming agents, fungicides, Deodorants, antibacterial agents, surfactants, lubricants, ultraviolet absorbers, fragrances, foaming agents, leveling agents, adhesives, etc. can be freely added.
  • the use of the plastisol composition of the present invention is not particularly limited, but the field of particularly high improvement effect is the use of blending a surface-treated inorganic filler as described above. This Among them, it is particularly suitable for use in automobiles that require a high degree of coating quality, and specific examples include uses such as automobile undercoats and automobile body sealers.
  • parts means “parts by mass”.
  • the evaluation of the plastisol composition and the coating film was based on the following.
  • the plastisol composition was kept warm in a constant temperature room at 25 ° C, taken out three days later, and measured for viscosity again.
  • the thickening rate of plastisol was calculated as follows, and the storage stability was evaluated.
  • the viscosity was measured with an EMD type viscometer using a cone with a 3 degree angle at a rotation speed of lOrpm with the plastisol maintained at 25 ° C.
  • Thickening rate viscosity after storage / initial viscosity X 100 (unit:%)
  • the obtained plastisol composition was cast on a Teflon-coated iron plate (thickness: lmm) so as to have a wet film thickness of 2 mm, and this was placed in a gear oven at 140 ° C. and heated for 20 minutes.
  • the obtained coating film was cut into a dumbbell shape No. 2 according to the method described in Pio ISK-7113 to obtain a test piece, and the breaking strength and the breaking elongation during the tensile test were measured by a Tensilon tester.
  • the test speed was 200 mmZ
  • the load cell rating was 980 N
  • the measured ambient temperature was 25 ° C.
  • ⁇ 1.0 or more and less than 2.0.
  • the gloss (60 degrees Daroth) of the obtained coating film was measured with a gloss meter (PB-1M, manufactured by Nippon Denshoku Industries Co., Ltd.) and used as an index of the smoothness of the coating film surface. The measurement was performed at any five different positions on the coating film, and the average value was obtained.
  • PB-1M manufactured by Nippon Denshoku Industries Co., Ltd.
  • ⁇ 60 or more.
  • the monomer mixture (Msl) (30.83 g of methyl methacrylate, 29.17 g of n-butyl methacrylate) and an emulsifier (1.0 g of sodium dioctyl sulfosuccinate per 100 g of monomer) were homogeneously mixed.
  • the dissolved mixture was added dropwise at a rate of 20 g / hr, and thereafter stirring was continued for 1 hour to obtain a core / shell polymer latex.
  • Polymer fine particles (A10) were prepared in the same manner as the preparation of polymer fine particles (A10), except that the amount of pure water initially added to the four-necked flask was 70 g. Polymer fine particles (A10) were prepared in the same manner as in the preparation of the polymer fine particles (A1). However, the monomer composition was changed to the monomer composition shown in Table 1 as a monomer mixture. The amount of the emulsifier added to the monomer mixture, the dropping rate of the mixture, the conditions for spray drying, and the like were the same as those for the polymer fine particles (A1).
  • Examples and Comparative Examples will be considered.
  • the shell polymer methyl methacrylate (MMMA) was fixed at 60 mol% and the ratio of the acid monomer was changed, and the ratio of methacrylic acid (MAA) was less than 0.5 mol%.
  • MMMA shell polymer methyl methacrylate
  • MAA methacrylic acid
  • Comparative Example 1 the storage stability of the plastisol was reduced because the ratio of the force MMA, which was the same but less than 0.5 mol%, was less than 55 mol%.
  • the ratio of the acid monomer in the shell polymer was less than 0.5 mol%, and the coating film had good smoothness.
  • the ratio of methyl methacrylate in the shell polymer is higher than in Examples 1 and 2, it is lower than 80 mol%, so that the glass transition temperature of the coating is sufficiently low, and the elongation of the coating is reduced. Good without.
  • the elongation of the coating film was decreased because the ratio of the force MMA, in which the ratio of MAA was less than 0.5 mol%, was also higher than 80 mol%.
  • Examples 5 and 6 are examples in which the composition of the polymer was changed within the scope of the present invention, and both were good without any particular problems in physical properties.
  • Comparative Example 4 is an example in which the particle size (primary particle size) of the core / shell particles is smaller than 400 nm. In this case, the obtained plastisol is immediately gelled, and the storage stability is extremely poor.
  • Example 9 is also an example in which an epoxy group is contained in the polymer.
  • the ratio of the (meth) acrylate to the alcohol having 2 or more carbon atoms constituting the core polymer is as low as less than 5 mol%, coating is performed. Although the elongation of the film is practically sufficient, it is slightly lower than those of the other examples.
  • Example 10 is an example in which a polymer having a primary particle size of 100 nm or more was used, and the configuration other than the particle size was the same as that in Example 8. In this case, the level of storage stability of plastizonore is higher.
  • Example 1 A 1 ⁇ ⁇ ⁇ ⁇ Example 2 A 2 ⁇ ⁇ ⁇ ⁇ Example 3 A 3 ⁇ ⁇ ⁇ ⁇ Example 4 A 4 ⁇ ⁇ ⁇ Example 5 A 5 ⁇ ⁇ ⁇ ⁇ Example 6 A 6 ⁇ ⁇ ⁇ Example 7 A 7 ⁇ ⁇ ⁇ ⁇ Example 8 A 8 ⁇ ⁇ ⁇ ⁇ Example 9 A 9 ⁇ ⁇ ⁇ ⁇ Example 10 A 10 0 ⁇ ⁇ ⁇ ⁇ Comparative example 1 A ll X ⁇ ⁇ ⁇ Comparative Example 2 A 1 2 ⁇ ⁇ X ⁇ Comparative Example 3 A 1 3 ⁇ ⁇ ⁇ X Comparative Example 4 A 1 4 X ⁇ ⁇ ⁇ ⁇

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de plastisol comportant de fines particules d'un polymère acrylique et d'un plastifiant, dans laquelle les fines particules de polymère acrylique comprennent des particules primaires ayant une structure noyau/enveloppe et présentant un diamètre moyen de particule supérieur ou égal à 400 nm, l'enveloppe étant composée d'un polymère formé à partir d'une composition monomère comprenant 55 à 80 %, en pourcentage molaire, de méthacrylate de méthyle, moins de 0,5 % en pourcentage molaire d'un monomère ayant un groupe carboxy ou sulfo, et 19,5 à 45 % en pourcentage molaire d'un ou de plusieurs autres monomères copolymérisables.
PCT/JP2004/011450 2003-08-15 2004-08-10 Composition de plastisol acrylique Ceased WO2005017031A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003293784A JP2005060574A (ja) 2003-08-15 2003-08-15 アクリル系プラスチゾル組成物
JP2003-293784 2003-08-15

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WO2005017031A1 true WO2005017031A1 (fr) 2005-02-24

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7741395B2 (en) 2007-08-21 2010-06-22 Eastman Chemical Company Low volatile organic content viscosity reducer
CN101328246B (zh) * 2007-06-18 2010-10-06 山东瑞丰高分子材料股份有限公司 改性纳米氧化锌与纳米碳酸钙联用的高抗冲acr树脂
CN114015243A (zh) * 2015-10-27 2022-02-08 株式会社Lg化学 增塑剂组合物和树脂组合物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH083411A (ja) * 1994-06-16 1996-01-09 Mitsubishi Rayon Co Ltd 壁紙用アクリルゾル組成物
WO2000001748A1 (fr) * 1998-07-01 2000-01-13 Mitsubishi Rayon Co., Ltd. Particules fines de polymeres acryliques et plastisols contenant de telles particules
JP2000273262A (ja) * 1999-03-19 2000-10-03 Mitsubishi Rayon Co Ltd アクリル系プラスチゾル組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH083411A (ja) * 1994-06-16 1996-01-09 Mitsubishi Rayon Co Ltd 壁紙用アクリルゾル組成物
WO2000001748A1 (fr) * 1998-07-01 2000-01-13 Mitsubishi Rayon Co., Ltd. Particules fines de polymeres acryliques et plastisols contenant de telles particules
JP2000273262A (ja) * 1999-03-19 2000-10-03 Mitsubishi Rayon Co Ltd アクリル系プラスチゾル組成物

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101328246B (zh) * 2007-06-18 2010-10-06 山东瑞丰高分子材料股份有限公司 改性纳米氧化锌与纳米碳酸钙联用的高抗冲acr树脂
US7741395B2 (en) 2007-08-21 2010-06-22 Eastman Chemical Company Low volatile organic content viscosity reducer
CN114015243A (zh) * 2015-10-27 2022-02-08 株式会社Lg化学 增塑剂组合物和树脂组合物

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