WO2010140317A1 - 発泡性成形用加工性改良剤、及びこれを含有する塩化ビニル系樹脂組成物 - Google Patents
発泡性成形用加工性改良剤、及びこれを含有する塩化ビニル系樹脂組成物 Download PDFInfo
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- WO2010140317A1 WO2010140317A1 PCT/JP2010/003498 JP2010003498W WO2010140317A1 WO 2010140317 A1 WO2010140317 A1 WO 2010140317A1 JP 2010003498 W JP2010003498 W JP 2010003498W WO 2010140317 A1 WO2010140317 A1 WO 2010140317A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Definitions
- the present invention relates to a foaming processability improver and a foaming vinyl chloride resin composition containing the same.
- Vinyl chloride-based resins are widely used for molding materials, taking advantage of their properties, but have various processing problems such as thermal decomposition temperature close to the processing temperature, narrow processing width, and poor fluidity.
- thermal decomposition temperature close to the processing temperature
- narrow processing width narrow processing width
- poor fluidity e.g., thermal decomposition temperature close to the processing temperature, narrow processing width, and poor fluidity.
- gelation of vinyl chloride resin during molding processing is promoted and the appearance of the molded body is improved. It is known that it can be applied to vacuum forming and profile extrusion molding.
- one of the molding methods for vinyl chloride resin is foam molding. Attempts have been made to reduce the weight of vinyl chloride resin by using this molding method and use it as a substitute for wood.
- a foam molded article is produced by adding a high molecular weight (meth) acrylic polymer powder to a vinyl chloride resin, the melt elongation and melt strength of the vinyl chloride resin are insufficient.
- foaming cells are not sufficiently foamed, and foamed cells are not uniform.
- the vinyl chloride resin has a narrow molding processing width, it is difficult to obtain a foam molded article having an excellent appearance and a sufficient foaming ratio only by changing the processing conditions.
- (meth) acrylic polymer powders based on ultrahigh molecular weight methyl methacrylate as a main component are blended to give melt strength and a sufficient expansion ratio without deteriorating the appearance.
- Various methods for obtaining a vinyl chloride-based resin are proposed (for example, see Patent Documents 1 to 3). According to this method, it is possible to obtain a vinyl chloride-based foamed molded article having a high expansion ratio without impairing the appearance of the foamed molded article.
- the present invention is to provide a vinyl chloride resin composition for foaming that can provide excellent foaming performance and appearance of a foamed molded article by increasing the melt strength of the vinyl chloride resin composition.
- the present invention is a (meth) acrylic polymer powder having a weight average molecular weight of 2 million to 7 million, and a (meth) acrylic polymer (A) 1 having a weight average molecular weight of 1 to 300,000. (20)% by weight and (meth) acrylic polymer (B) having a weight average molecular weight of 2 million to 7 million (B) (meth) acrylic polymer powder comprising 80 to 99% by weight Processability improver.
- a preferred embodiment is the processability improver for foamable molding, wherein the primary particles have a multilayer structure, and the inner layer of the (meth) acrylic polymer (A), and the (meth) It is made into the workability improving agent for foaming molding which consists of an outer layer of an acrylic polymer (B).
- the (meth) acrylic polymer is 75 to 100% by weight of methyl methacrylate, 0 to 25% by weight of (meth) acrylic acid ester excluding methyl methacrylate, and other copolymerizable with these.
- a preferred embodiment is the processability improver for foaming molding, wherein the (meth) acrylic polymer (B) contains 75 to 100% by weight of methyl methacrylate and (meth) acrylic acid excluding methyl methacrylate.
- a processability improver for foamable molding obtained by emulsion polymerization of a monomer mixture (B) comprising 0 to 25% by weight of an ester and 0 to 5% by weight of another monomer copolymerizable therewith; It is to be.
- a preferred embodiment is the foaming processability improver, wherein the (meth) acrylic polymer (B) is 75 to 99.99999999% by weight of methyl methacrylate and excludes (meth) methyl methacrylate. It is obtained by emulsion polymerization of a monomer mixture (B) comprising 0 to 25% by weight of an acrylate ester and 0.000001 to 0.01% by weight (0.01 to 100 ppm by weight) of a polyfunctional monomer. The processability improver for foaming molding.
- a preferred embodiment is the foaming processability improver, wherein the (meth) acrylic polymer (A) comprises 10 to 100% by weight of methyl methacrylate and (meth) acrylic acid excluding methyl methacrylate.
- a processability improver for foamable molding obtained by emulsion polymerization of a monomer mixture (A) comprising 0 to 90% by weight of an ester and 0 to 5% by weight of another monomer copolymerizable therewith; It is to be.
- a preferred embodiment is the foamable molding processability improver, the (meth) acrylic polymer (A) latex obtained by emulsion polymerization of 1 to 20 parts by weight of the monomer mixture (A).
- the processability improver for foamable molding is obtained by emulsion polymerization of 80 to 99 parts by weight of the monomer mixture (B).
- the emulsifier used in the emulsion polymerization is at least one selected from alkylbenzene sulfonate, alkyl diphenyl ether disulfonate, and alkyl sarcosine.
- a preferred embodiment is to provide an expandable moldability improving agent further containing 0.2% by weight to 4.0% by weight of an emulsifier with respect to 100% by weight of the expandable moldability improving agent. .
- a preferred embodiment is the foaming processability improver, wherein the (meth) acrylic polymer powder has a volume average particle diameter of 50 ⁇ m to 300 ⁇ m, and Each particle of the powder is a porous aggregate in which primary particles having a volume average primary particle diameter of 0.12 ⁇ m to 0.70 ⁇ m are fused in a semi-molten state at a contact position between the particles. It is to be a processability improver.
- a preferred embodiment is the processability improver for foamable molding, wherein the powder of the (meth) acrylic polymer is obtained by spray-drying the polymer latex obtained by the emulsion polymerization.
- the processability improver for foaming molding is the processability improver for foaming molding.
- the present invention also relates to a vinyl chloride resin composition
- a vinyl chloride resin composition comprising 100 parts by weight of a vinyl chloride resin and 1 to 30 parts by weight of the foaming processability improver.
- the vinyl chloride resin composition using the (meth) acrylic copolymer powder of the present invention provides excellent foaming performance and foamed molded article appearance by increasing the melt strength of the vinyl chloride resin composition.
- a foamable vinyl chloride resin composition for foaming can be provided.
- the main component of the foaming processability improver of the present invention is a powder of a (meth) acrylic polymer, preferably a latex containing the (meth) acrylic polymer obtained by emulsion polymerization. It is a powder obtained by spray drying. Since the latex thus obtained by emulsion polymerization is spray-dried as it is, the foaming processability improver of the present invention has an emulsifier, preferably 0.2% when the total amount is 100% by weight. It is contained in an amount of from wt% to 4.0 wt%, more preferably from 0.3 wt% to 3.0 wt%, still more preferably from 0.5 wt% to 2.5 wt%. In most cases, the emulsifier is contained in each particle of the powder.
- (meth) acryl means acryl and / or methacryl unless otherwise specified.
- the (meth) acrylic polymer powder according to the present invention is a (meth) acrylic polymer powder having a weight average molecular weight of 2 million to 7 million, and has a weight average molecular weight of 1 to It comprises 1 to 20% by weight of 300,000 (meth) acrylic polymer (A) and 80 to 99% by weight of (meth) acrylic polymer (B) having a weight average molecular weight of 2 to 7 million.
- the powder of the (meth) acrylic polymer according to the present invention has a volume average particle diameter when each particle of the powder, that is, a powder particle is measured by a laser diffraction / scattering method. However, it is preferably from 70 ⁇ m to 250 ⁇ m from the viewpoint of making it difficult to classify it with a polyvinyl chloride resin which is also usually a powder. Further, the particle size distribution of the powder is preferably such that the number of particles of 10 ⁇ m or less is small from the viewpoint of workability and prevention of dust explosion.
- a laser diffraction / scattering method for example, MICROTRAC MT3300II (registered trademark) manufactured by Nikkiso Co., Ltd. can be used.
- the powder particles of the (meth) acrylic polymer according to the present invention have a volume average primary particle diameter of 0.12 ⁇ m to 0.70 ⁇ m fused in a semi-molten state at a contact position between the particles.
- the volume average primary particle diameter is more preferably 0.15 ⁇ m to 0.40 ⁇ m, and further preferably 0.16 ⁇ m to 0.35 ⁇ m.
- the volume average primary particle diameter is the volume average primary particle diameter of the primary particles in the powder particles of the (meth) acrylic polymer according to the present invention, and the volume average primary particle diameter is as described above.
- the particle diameter in the latex containing the (meth) acrylic polymer obtained by emulsion polymerization is preferably the same, and the particle diameter in such a latex can be measured by a dynamic light scattering method. .
- a dynamic light scattering method for example, MICROTRAC UPA150 (manufactured by Nikkiso Co., Ltd.) can be used.
- the volume average primary particle diameter is less than 0.12 ⁇ m, the primary particles inside the powder particles preferably formed by spray drying as described above, and the surfaces of the powder particles are easily fused, In some cases, the gelation promoting ability inherent in the (meth) acrylic polymer powder may be lost.
- the presence or absence of fusion between the primary particles inside the powder particles and the surfaces of the powder particles is observed by an optical microscope, and when not fused, the entire powder particles are white. However, it can be observed because it becomes transparent as the fusion proceeds. Alternatively, the fused state of the primary particles can be directly observed with a scanning electron microscope.
- the composition according to the present invention is incorporated into the composition when molding the composition containing the foaming processability improver of the present invention (
- the (meth) acrylic polymer may not be uniformly dispersed in the molecule, and fish eyes (FE) may be generated in the molded product, or gelation may be insufficiently accelerated.
- the (meth) acrylic polymer according to the present invention is 75 to 100% by weight of methyl methacrylate, 0 to 25% by weight of (meth) acrylic acid ester excluding methyl methacrylate, and copolymerizable therewith. It is obtained by emulsion polymerization of 0 to 5% by weight of other monomers, and more preferably obtained by spray drying a polymer latex obtained by emulsion polymerization.
- the (meth) acrylic polymer powder according to the present invention is a (meth) acrylic polymer powder having a weight average molecular weight of 2 million to 7 million as described above.
- the average molecular weight is a value obtained by measuring a polymer dissolved in tetrahydrofuran (THF) using a gel permeation chromatograph (GPC) and converting it to polystyrene. In this case, the powder is dissolved in THF. Is the weight average molecular weight.
- the molecular weight of the (meth) acrylic polymer is required to be 2 million to 7 million, preferably 3 million to 7 million, more preferably 4 million to 7 million, and particularly preferably 5 million. ⁇ 7 million.
- the weight average molecular weight of this polymer is less than 2 million, the specific gravity of the molded product of the composition containing the foaming processability improver of the present invention may not be sufficiently lowered, or the gelling properties may be impaired. There is a case.
- the molecular weight exceeds 7 million, the surface properties of the molded article of the composition containing the foamable molding processability improver of the present invention may be deteriorated, or the gelation characteristics may be impaired. is there.
- the ratio of methyl methacrylate in the (meth) acrylic polymer is a viewpoint of sufficiently reducing the specific gravity of the vinyl chloride resin molded product obtained by blending the (meth) acrylic polymer powder of the present invention, From the viewpoint of gelling properties, it is preferably 75 to 100% by weight, more preferably 80 to 99% by weight, particularly preferably 81 to 98% by weight, and most preferably 85 to 97% by weight.
- the proportion of (meth) acrylic acid ester excluding methyl methacrylate in the (meth) acrylic polymer is that of the vinyl chloride resin molded product obtained by blending the (meth) acrylic polymer powder of the present invention. From the viewpoint of sufficiently reducing the specific gravity and from the viewpoint of gelling properties, it is preferably 0 to 25% by weight, more preferably 1 to 20% by weight, particularly preferably 2 to 19% by weight, Most preferably, it is 3 to 15% by weight.
- the proportion of the other copolymerizable monomer in the (meth) acrylic polymer is the specific gravity of the vinyl chloride resin molded product obtained by blending the (meth) acrylic polymer powder of the present invention. From the viewpoint of sufficient reduction and the viewpoint of gelling properties, the content is preferably 0 to 5% by weight, and more preferably 0 to 2% by weight.
- the (meth) acrylic polymer (A) has a weight average molecular weight of 1 to 300,000, preferably 10 to 100% by weight of methyl methacrylate and (meth) acrylic acid ester excluding methyl methacrylate It is obtained by emulsion polymerization of a monomer mixture (A) comprising 0 to 90% by weight and 0 to 5% by weight of other monomers copolymerizable therewith.
- the polymer (A) needs to have a weight average molecular weight of 10,000 to 300,000, preferably 20,000 to 250,000, more preferably 20,000 to 200,000, still more preferably 20,000 to 100,000, Particularly preferred is 20,000 to 50,000.
- the polymer (A) From the viewpoint of controlling the molecular weight of the polymer (A) within the above range, it is preferable to polymerize by adding 0.1 to 5 parts by weight of a chain transfer agent to 100 parts by weight of the monomer mixture (A). More preferably, 0.4 to 3 parts by weight, still more preferably 0.5 to 2.5 parts by weight, and particularly preferably 0.7 to 2 parts by weight are used.
- the weight average molecular weight of the polymer (A) is less than 10,000, the polymer (A) component is plated out during foam extrusion, and the composition containing the foaming processability improver of the present invention is included. In some cases, the surface property of the molded article is deteriorated. On the contrary, when the weight average molecular weight of the polymer (A) exceeds 300,000, the surface property of the molded article of the composition containing the foaming processability improver of the present invention is deteriorated, or the gelation property May be damaged.
- the proportion of methyl methacrylate in the monomer mixture (A) is preferably 10 to 100% by weight, more preferably 30 to 95% by weight, further preferably 40 to 90% by weight, and particularly preferably 40 to 70% by weight. Preferably, 40 to 60% by weight is most preferable.
- the proportion of methyl methacrylate in the monomer mixture (A) is less than 10% by weight, the surface property of the vinyl chloride resin molded product obtained by blending the (meth) acrylic polymer powder of the present invention The improvement effect may not be sufficient or the gelling properties may be impaired.
- the proportion of (meth) acrylic acid ester excluding methyl methacrylate in the monomer mixture (A) is preferably 0 to 90% by weight, more preferably 5 to 70% by weight. It is more preferably 60% by weight, particularly preferably 30 to 60% by weight, and most preferably 40 to 60% by weight. Chloride obtained by blending the processability improver for foamable molding of the present invention when the proportion of (meth) acrylic acid ester excluding methyl methacrylate in the monomer mixture (A) is less than 10% by weight. In some cases, the surface property improving effect of the vinyl-based resin molded article is not sufficient, or the gelling properties are impaired.
- the foamable molding of the present invention at the time of foam molding
- ethyl acrylate, propyl acrylate, butyl acrylate (BA) 2-ethylhexyl acrylate, octyl acrylate, ethyl methacrylate, propyl methacrylate
- BA butyl methacrylate
- BA 2-ethylhexyl acrylate
- octyl acrylate ethyl methacrylate
- propyl methacrylate propyl methacrylate
- It is preferably at least one selected from the group consisting of butyl methacrylate, more preferably at least one selected from the group consisting of BA, 2-ethylhexyl acrylate, octyl acrylate, and butyl methacrylate,
- BA 2-ethylhexyl acrylate
- octyl acrylate octyl acrylate
- the proportion of the other copolymerizable monomer in the monomer mixture (A) is preferably 0 to 5% by weight, and more preferably 0 to 2% by weight. If the proportion of other copolymerizable monomers deviates from the above range, the specific gravity when the (meth) acrylic polymer powder of the present invention is blended with a vinyl chloride resin does not decrease sufficiently, or the gel The conversion characteristics may be impaired.
- the molded product of the composition containing the foaming processability improving agent is easy to handle because the member can be made lighter as the specific gravity is low as long as the practical strength as a member is not weakened. is there.
- the (meth) acrylic polymer (B) according to the present invention has a weight average molecular weight of 2 million to 7 million, preferably 3 million to 7 million from the viewpoint of obtaining a foam having a smaller specific gravity, More preferably, it is 5 to 7 million.
- the polymer (B) From the viewpoint of controlling the molecular weight of the polymer (B) within the above range, it is preferable to polymerize by adding 200 ppm by weight or less of a chain transfer agent to 100 parts by weight of the monomer mixture (B), more preferably. 100 ppm by weight or less, more preferably 50 ppm by weight or less, particularly preferably 1 ppm by weight or less, and most preferably no chain transfer agent is used.
- the (meth) acrylic polymer (B) according to the present invention is preferably 75 to 100% by weight of methyl methacrylate, 0 to 25% by weight of (meth) acrylic acid ester excluding methyl methacrylate, and these It is obtained by emulsion polymerization of a monomer mixture (B) composed of 0 to 5% by weight of other monomers copolymerizable with.
- the proportion of methyl methacrylate in the monomer mixture (B) is preferably 75 to 100% by weight, more preferably 75 to 99.999999% by weight, and 80 to 99% by weight. Is more preferably 85 to 98% by weight, and most preferably 90 to 95% by weight.
- the proportion of methyl methacrylate in the monomer mixture (B) is less than 75% by weight, the specific gravity of the vinyl chloride resin molded product obtained by blending the (meth) acrylic polymer powder of the present invention In some cases, the decrease may be insufficient, or the gelling properties may be impaired.
- the proportion of (meth) acrylic acid ester excluding methyl methacrylate in the monomer mixture (B) is preferably 0 to 25% by weight, more preferably 1 to 20% by weight. It is more preferably 15% by weight, and particularly preferably 5 to 10% by weight. Chloride obtained by blending the (meth) acrylic polymer powder of the present invention when the proportion of (meth) acrylic acid ester excluding methyl methacrylate in the monomer mixture (B) exceeds 25% by weight. In some cases, the foamability of the vinyl resin molded article is not sufficient, the specific gravity is not sufficiently lowered, or the gelling properties are impaired.
- the proportion of the other copolymerizable monomer in the monomer mixture (B) is preferably 0 to 5% by weight, and more preferably 0 to 2% by weight. If the proportion of other copolymerizable monomers deviates from the above range, the specific gravity when the (meth) acrylic polymer powder of the present invention is blended with a vinyl chloride resin does not decrease sufficiently, or the gel The conversion characteristics may be impaired.
- the copolymerizable monomer in the monomer mixture (B) is a polyfunctional monomer based on 100% by weight of the monomer mixture (B).
- the body preferably contains 0.000001 to 0.01 wt% (0.01 to 100 wt ppm), more preferably 0.1 to 10 wt ppm, and still more preferably 0.2 to 10 wt ppm. Particularly preferred is 0.5 to 2 ppm by weight.
- the (meth) acrylic polymer according to the present invention has a weight average molecular weight of 1 to 300,000 (meth) acrylic polymer (A) of 1 to 20% by weight and a weight average molecular weight of 2 million. It is composed of 80 to 99% by weight of (meth) acrylic polymer (B) to 7 million, preferably (meth) acrylic polymer obtained by polymerizing 1 to 20 parts by weight of the monomer mixture (A). (Meth) acrylic polymer (B) obtained by polymerizing 80 to 99 parts by weight of the blend (A) and the monomer mixture (B) (however, the monomer mixture (A) and the monomer mixture) (B) total is 100 parts by weight).
- the (meth) acrylic polymer according to the present invention is the (meth) acrylic polymer (A) latex obtained by emulsion polymerization of 1 to 20 parts by weight of the monomer mixture (A).
- the primary particles are: It has a multi-layer structure, and is a multi-layer primary particle composed of an inner layer of the (meth) acrylic polymer (A) and an outer layer of the (meth) acrylic polymer (B).
- the elastic modulus of the primary particles is lowered, so that there is an effect that the primary particles are easily deformed / collapsed during molding and are easily dispersed uniformly in the vinyl chloride resin composition.
- the volume average particle diameter of the inner layer is preferably 0.03 ⁇ m to 0.4 ⁇ m, more preferably 0.04 ⁇ m to 0.15 ⁇ m.
- the monomer mixture (A) is preferably 1 to 20 parts by weight, more preferably 2 to 18 parts by weight, and particularly preferably 3 to 15 parts by weight.
- the proportion of the monomer mixture (A) used for the production of the (meth) acrylic polymer is less than 1 part by weight, the surface property of the molded body of the vinyl chloride resin composition of the present invention may deteriorate. In some cases, the specific gravity does not decrease sufficiently or the gelling properties are impaired. On the contrary, when the proportion of the monomer mixture (A) exceeds 20 parts by weight, the specific gravity of the molded body of the vinyl chloride resin composition of the present invention is not sufficiently lowered, or the gelling properties are impaired. Sometimes.
- the monomer mixture (B) is preferably 80 to 99 parts by weight, more preferably 82 to 98 parts by weight, and particularly preferably 85 to 97 parts by weight.
- the proportion of the monomer mixture (B) used in the production of the (meth) acrylic polymer powder is less than 80 parts by weight, the specific gravity of the molded body of the vinyl chloride resin composition of the present invention is sufficient. In some cases, or the gelling properties may be impaired.
- it exceeds 99 parts by weight the specific gravity of the molded article of the vinyl chloride resin composition of the present invention is not sufficiently lowered, the surface property of the molded article is deteriorated, or the gelation characteristics are impaired. There is a case.
- the (meth) acrylic acid ester excluding the above-mentioned methyl methacrylate has a moderate water solubility and is suitable for emulsion polymerization.
- alkyl methacrylates having 9 or more carbon atoms such as lauryl methacrylate, stearyl methacrylate, tridecyl methacrylate, etc.
- Esters lauryl acrylate, stearyl acrylate, tridecyl acrylate, and other alkyl acrylates with 9 or more carbon atoms, glycidyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate
- glycidyl acrylate, benzyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, and the like may be used as appropriate.
- the other copolymerizable monomers are not particularly limited as long as they are other monomers copolymerizable with methyl methacrylate and (meth) acrylic acid esters other than the above-mentioned methyl methacrylate.
- Aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, chlorostyrene, vinyl styrene, and nucleus-substituted styrene, and unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile, 1,3-butanediol diacrylate, 1, 4 -Butanediol diacrylate, 1,6 hexanediol diacrylate, nonanediol diacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, and polyethylene glycol (2-23) diacrylate, polypropylene glycol (2-12) diacrylate,
- the Dioxy compounds such as poxylated (2-16) neopentyl diacrylate, alkoxylated hexanediol diacrylate, alkoxylated cyclohexanedimethanol diacrylate, ethoxylated (4-30) bisphenol A diacrylate
- the monomer mixture (B) which is a raw material of the polymer (B) according to the present invention preferably contains a polyfunctional monomer.
- the foamable molding processability improver of the present invention can be given a preferable cross-linked structure in view of the object of the present invention, and therefore, preferably a polypropylene glycol (2 to 12) diacrylate, a polypropylene glycol (2 to 12) One or more selected from the group consisting of dimethacrylate, DVB, TAIC, and TAC, more preferably TAIC.
- the said weight average molecular weight can be suitably adjusted with the polymerization conditions at the time of superposing
- the amount of polymerization initiator (catalyst) at the time of polymerization can be adjusted by the amount of chain transfer agent used for polymerization, the polymerization temperature, the monomer addition rate, and the like.
- a polymerization method for obtaining the (meth) acrylic polymer according to the present invention it is easy to control the molecular weight and particle structure, is suitable for industrial production, and is easy to apply a multistage polymerization method.
- a polymerization method and a suspension polymerization method are preferable, and an emulsion polymerization method is particularly preferable among them.
- the type of emulsifier, polymerization initiator, chain transfer agent, etc. can be set.
- emulsifier As the emulsifier, known ones such as anionic surfactants, nonionic surfactants, cationic surfactants and the like can be used, among them, from the viewpoint of excellent polymerization stability, thermal stability, and color tone, One or more selected from alkyl benzene sulfonates, alkyl diphenyl ether disulfonates, and alkyl sarcosine salts are preferable, and linear alkyl benzene sulfonates are more preferable.
- the (meth) acrylic polymer powder according to the present invention is preferably obtained by spray-drying a polymer latex obtained by emulsion polymerization. Since the emulsifier, initiator residue, and the like used during emulsion polymerization remain in the body, the processability when molding the composition containing the foaming processability improver of the present invention, and the obtained molded body The physical properties of the product may be affected. Accordingly, when the (meth) acrylic polymer powder according to the present invention is obtained by spray-drying a polymer latex obtained by emulsion polymerization, as an emulsifier used during the emulsion polymerization.
- alkylbenzene sulfonate alkyl diphenyl ether disulfonate, and alkyl sarcosine are preferable, and linear alkylbenzene sulfonate is particularly preferable.
- alkylbenzene sulfonate may include sodium decylbenzenesulfonate, sodium undecylbenzenesulfonate, sodium dodecylbenzenesulfonate, sodium tridecylbenzenesulfonate, sodium tetradecylbenzenesulfonate, and the like.
- alkyl diphenyl ether disulfonate examples include disodium dodecyl diphenyl ether sulfonate and the like.
- alkyl sarcosinate examples include sodium oleoyl sarcosinate, sodium lauroyl sarcosinate, sodium myristoyl sarcosinate, sodium palmitoyl sarcosinate, sodium stearoyl sarcosinate, and the like.
- anionic surfactant examples include fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl phosphate esters, dialkyl sulfosuccinates, and alkyl sarcosine salts.
- nonionic surfactant examples include polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, glycerin fatty acid ester and the like.
- examples of the cationic surfactant include alkylamine salts.
- Polymerization initiator As the polymerization initiator, known ones such as water-soluble and oil-soluble polymerization initiators and redox polymerization initiators can be used.
- inorganic salt polymerization initiators typified by ordinary persulfates, organic peroxides, azo compounds, etc. are exemplified, and these are used alone, or the above compounds and sulfites, hydrogen sulfites, thiosulfuric acids are used.
- a salt, a first metal salt, sodium formaldehyde sulfoxylate, and the like can be combined and used as a redox polymerization initiator.
- inorganic salt polymerization initiators that are particularly preferred as polymerization initiators include sodium persulfate, potassium persulfate, and ammonium persulfate.
- Preferred organic peroxides include t-butyl hydroperoxide, Examples thereof include cumene hydroperoxide, t-butyl peroxyisopropyl carbonate, paramentane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, benzoyl peroxide and lauroyl peroxide.
- alkyl mercaptans having 4 to 12 carbon atoms in the main chain can be suitably exemplified.
- alkyl mercaptans such as n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan (t-DM), thioglycols such as 2-ethylhexyl thioglycol and isooctyl thioglycol , Alphamethylstyrene dimer, terpinolene, etc., from the viewpoint of chain transfer efficiency, preferably one or more selected from the group consisting of alkyl mercaptans and thioglycols, more preferably t-DM. It is.
- the (meth) acrylic polymer powder according to the present invention is preferably recovered from a latex obtained by an emulsion polymerization method or a suspension polymerization method.
- a general recovery method at that time is, for example, a polymer latex containing a (meth) acrylic polymer to be recovered, an acid such as sulfuric acid, hydrochloric acid, phosphoric acid, or sodium chloride, calcium chloride, magnesium chloride, chloride.
- an electrolyte typified by a salt such as aluminum, sodium sulfate, magnesium sulfate, or aluminum sulfate
- the latex is subjected to acid coagulation or salting out, followed by heat treatment, washing, dehydration, and drying. This is a method for recovering a body-like processability improver for foam molding.
- the latex to recover the foamable processability improver of the present invention, that is, the (meth) acrylic polymer powder according to the present invention, which is the main component.
- the conditions of the spray drying are not particularly limited, but particles formed as an aggregate of latex particles remaining after water is evaporated from droplets formed when the latex is sprayed into hot air during spray drying. When the inside and the surface of the particles are fused, the gelation promoting ability inherent to the (meth) acrylic polymer powder is lost.
- the vinyl chloride resin composition of the present invention contains 100 parts by weight of a vinyl chloride resin and 1 to 30 parts by weight of the foaming processability improver of the present invention, so long as the effects of the present invention are not impaired.
- Known additives such as stabilizers, lubricants, impact modifiers, plasticizers, colorants, fillers and foaming agents may be added as appropriate.
- the (meth) acrylic polymer powder according to the present invention which is the main component of the foamable molding processability improver for the vinyl chloride resin, is blended.
- the proportion of the (meth) acrylic polymer powder is preferably 1 to 30 parts by weight, more preferably 1.5 to 25 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. In particular, the amount is most preferably 2 to 20 parts by weight.
- the blending amount of the (meth) acrylic polymer powder is less than 1 part by weight, the specific gravity of the molded body obtained from the vinyl chloride resin composition of the present invention does not decrease sufficiently, or during molding processing The gelation promoting effect may not be obtained.
- the blending amount of the (meth) acrylic polymer powder exceeds 30 parts by weight, the surface property of the vinyl chloride resin molded product is lowered or the melt viscosity is remarkably increased. A large load may be applied to other motors.
- Vinyl chloride resin As the vinyl chloride resin according to the present invention, conventionally used vinyl chloride resins can be used without particular limitation. Specifically, polyvinyl chloride, preferably a vinyl chloride copolymer comprising 80% by weight or more of vinyl chloride and 20% by weight or less of a monomer copolymerizable therewith, or post-chlorinated polyvinyl chloride, etc. It can be illustrated. Examples of the monomer copolymerizable with vinyl chloride include vinyl acetate, ethylene, propylene, styrene, vinyl bromide, vinylidene chloride, acrylic acid ester, and methacrylic acid ester. These may be used alone or in combination of two or more.
- Example 1 After mixing 140 parts by weight of water, 0.13 parts by weight of sodium dodecylbenzenesulfonate as an emulsifier, 0.1 parts by weight of sodium sulfate, and 0.05 parts by weight of sodium carbonate, and replacing with nitrogen at 80 ° C., potassium persulfate 0.035 parts by weight, 63 parts by weight of methyl methacrylate (hereinafter also referred to as MMA), 27 parts by weight of butyl acrylate (hereinafter also referred to as BA) as a part of the monomer mixture (A) with stirring, and A monomer mixture (A-1-a) comprising 0.7 parts by weight of terrestrial decyl mercaptan (hereinafter also referred to as t-DM) was continuously added over 300 minutes, and a monomer mixture ( After completion of the addition of A-1-a), polymerization was carried out by stirring for 1 hour.
- MMA methyl methacrylate
- BA butyl acrylate
- 0.3 parts by weight of sodium dodecylbenzenesulfonate was added to the first and second hours of continuous addition of the monomer mixture (A-1-a). Further, a monomer mixture (A-1-b) consisting of 7 parts by weight of MMA and 3 parts by weight of BA was continuously added as the remaining monomer mixture (A) over 30 minutes, followed by 1 hour. The polymerization reaction was terminated by stirring to obtain a latex of the polymer (A-1) as the (meth) acrylic polymer (A). The volume average particle diameter of the (meth) acrylic polymer particles in the latex was 0.092 ⁇ m.
- This latex is cooled and spray-dried at an inlet temperature of 110 ° C. and an outlet temperature of 50 ° C. with an Okawahara Kako Co., Ltd., L-12 type spray dryer, and a (meth) acrylic as a processability improver for foaming molding Polymer powder was obtained and subjected to the following test.
- This foamable processability improver contains 0.673% by weight of an emulsifier with respect to 100% by weight as a whole.
- Table 1 The obtained results are shown in Table 1 together with the results of the following examples and comparative examples.
- the evaluation of the surface property was carried out using 100 parts by weight of a polyvinyl chloride resin having an average degree of polymerization of 700 (Kanevinyl S-1007, manufactured by Kaneka Co., Ltd.) and an octyl tin mercapto stabilizer (TVS-8831, manufactured by Nitto Kasei Co., Ltd.).
- the foamability was evaluated by adding 10 parts by weight of the obtained powdery (meth) acrylic polymer to a vinyl chloride resin obtained in the same manner as in the surface property evaluation test, and a foaming agent (span cell #). 81 Eiwa Chemical Industry Co., Ltd.) A vinyl chloride resin composition containing 0.6 parts by weight was used.
- Example 2 After mixing 140 parts by weight of water, 0.13 parts by weight of sodium dodecylbenzenesulfonate, 0.1 parts by weight of sodium sulfate and 0.05 parts by weight of sodium carbonate, and replacing with nitrogen at 80 ° C., 0.035 weight of potassium persulfate
- a monomer mixture (A-2-a) comprising 81 parts by weight of MMA, 9 parts by weight of BA, and 0.7 parts by weight of t-DM as a part of the monomer mixture (A) with stirring for 300 minutes. In short, it was continuously added, and after completion of addition of the monomer mixture (A-2-a), the mixture was stirred for 1 hour for polymerization.
- a (meth) acrylic polymer (2) was obtained in the same manner as in Example 1 except that the latex of the polymer (A-2) was used instead of the latex of the polymer (A-1) in Example 1. Latex was obtained. The volume average particle diameter of the (meth) acrylic polymer particles in this latex was 0.172 ⁇ m.
- Example 3 After mixing 140 parts by weight of water, 0.13 parts by weight of sodium dodecylbenzenesulfonate, 0.1 parts by weight of sodium sulfate and 0.05 parts by weight of sodium carbonate, and replacing with nitrogen at 80 ° C., 0.035 weight of potassium persulfate
- a monomer mixture (A-3-a) comprising 49.5 parts by weight of MMA, 40.5 parts by weight of BA, and 0.7 parts by weight of t-DM as a part of the monomer mixture (A) with stirring. was continuously added over 300 minutes, and after the addition of the monomer mixture (A-3-a) was completed, the mixture was stirred for 1 hour for polymerization.
- a (meth) acrylic polymer (3) was prepared in the same manner as in Example 1 except that the latex of the polymer (A-3) was used instead of the latex of the polymer (A-1) in Example 1. Latex was obtained. The volume average particle diameter of the (meth) acrylic polymer particles in this latex was 0.215 ⁇ m.
- Example 4 After mixing 140 parts by weight of water, 0.13 parts by weight of sodium dodecylbenzenesulfonate, 0.1 parts by weight of sodium sulfate and 0.05 parts by weight of sodium carbonate, and replacing with nitrogen at 80 ° C., 0.035 weight of potassium persulfate A monomer mixture (A-4-a) consisting of 18 parts by weight of MMA, 72 parts by weight of BA and 0.7 parts by weight of t-DM as a part of the monomer mixture (A) with stirring for 300 minutes. In short, it was continuously added, and after completion of addition of the monomer mixture (A-4-a), polymerization was carried out by stirring for 1 hour.
- a monomer mixture (A-4-b) consisting of 2 parts by weight of MMA and 8 parts by weight of BA was continuously added as the remaining monomer mixture (A) over 30 minutes, followed by stirring for 1 hour.
- the polymerization reaction was terminated to obtain a latex of the polymer (A-4) as the (meth) acrylic polymer (A).
- the volume average particle diameter of the (meth) acrylic polymer particles in this latex was 0.108 ⁇ m.
- a (meth) acrylic polymer (4) was obtained in the same manner as in Example 1 except that the latex of the polymer (A-4) was used instead of the latex of the polymer (A-1) in Example 1. Latex was obtained. The volume average particle diameter of the (meth) acrylic polymer particles in this latex was 0.241 ⁇ m.
- Example 5 The monomer mixture (B) in Example 1 was changed to a monomer mixture (B-5) consisting of 85.5 parts by weight of MMA, 4.5 parts by weight of BA, and 0.007 parts by weight of t-DM.
- a latex of (meth) acrylic polymer (5) was obtained.
- the volume average particle diameter of the (meth) acrylic polymer particles in this latex was 0.209 ⁇ m.
- a (meth) acrylic polymer powder was obtained in the same manner as in Example 1, and subjected to the same test as in Example 1.
- Example 6 The monomer mixture (B) in Example 1 was changed to a monomer mixture (B-6) consisting of 73.8 parts by weight of MMA, 16.2 parts by weight of BA, and 0.007 parts by weight of t-DM.
- B-6 a latex of (meth) acrylic polymer (6) was obtained.
- the volume average particle diameter of the (meth) acrylic polymer particles in this latex was 0.209 ⁇ m.
- a (meth) acrylic polymer powder was obtained in the same manner as in Example 1, and subjected to the same test as in Example 1.
- Example 7 The monomer mixture (B) in Example 1 was mixed with MMA 67.5 parts by weight, BA 22.5 parts by weight, A latex of (meth) acrylic polymer (7) was obtained in the same manner as in Example 1, except that the mixture of monomers (B-7) consisting of 0.007 parts by weight of t-DM was used. The volume average particle diameter of the (meth) acrylic polymer particles in this latex was 0.209 ⁇ m. Furthermore, using this (meth) acrylic polymer (7) latex, a (meth) acrylic polymer powder was obtained in the same manner as in Example 1, and subjected to the same test as in Example 1.
- Example 8 After obtaining a latex of the polymer (A-1) in the same manner as in Example 1, the polymer (A-1) was replaced with 10 parts by weight (solid content) of the polymer (A-1) latex in Example 1. -1) 5 parts by weight of latex (solid content), and the monomer mixture (B) is a monomer comprising MMA 85.5 parts by weight, BA 9.5 parts by weight, and t-DM 0.0074 parts by weight.
- a latex of (meth) acrylic polymer (8) was obtained in the same manner as in Example 1 except that the mixture (B-8) was used. The volume average particle diameter of the (meth) acrylic polymer particles in this latex was 0.269 ⁇ m. Furthermore, using this (meth) acrylic polymer (8) latex, a (meth) acrylic polymer powder was obtained in the same manner as in Example 1, and subjected to the same test as in Example 1.
- Example 9 After obtaining a latex of the polymer (A-1) in the same manner as in Example 1, the polymer (A-1) was replaced with 10 parts by weight (solid content) of the polymer (A-1) latex in Example 1. -1) 20 parts by weight of latex (solid content), and the monomer mixture (B) was a monomer mixture (B) consisting of 72 parts by weight of MMA, 8 parts by weight of BA, and 0.0062 parts by weight of t-DM. A latex of (meth) acrylic polymer (9) was obtained in the same manner as in Example 1 except that it was changed to -9). The volume average particle diameter of the (meth) acrylic polymer particles in this latex was 0.161 ⁇ m. Furthermore, using this (meth) acrylic polymer (9) latex, a (meth) acrylic polymer powder was obtained in the same manner as in Example 1, and subjected to the same test as in Example 1.
- Example 10 Instead of the monomer mixture (A-1-a) in Example 1, a monomer comprising 63 parts by weight of MMA, 27 parts by weight of BA, and 0.4 parts by weight of t-DM in which only the amount of t-DM has been reduced.
- a latex of (meth) acrylic polymer (10) was obtained in the same manner as in Example 1 except that the mixture (A-10-a) was used.
- the volume average particle diameter of the (meth) acrylic polymer particles in the polymer (A-10) latex which is the (meth) acrylic polymer (A) was 0.088 ⁇ m.
- the volume average particle diameter of the (meth) acrylic polymer particles in the (meth) acrylic polymer (10) latex was 0.200 ⁇ m.
- a (meth) acrylic polymer powder was obtained in the same manner as in Example 1, and subjected to the same test as in Example 1.
- Example 11 instead of the monomer mixture (A-1-a) in Example 1, a monomer comprising 63 parts by weight of MMA, 27 parts by weight of BA, and 0.2 parts by weight of t-DM in which only the amount of t-DM is reduced.
- a latex of (meth) acrylic polymer (11) was obtained in the same manner as in Example 1 except that the mixture (A-11-a) was used.
- the volume average particle diameter of the (meth) acrylic polymer particles in the polymer (A-11) latex which is the (meth) acrylic polymer (A) was 0.084 ⁇ m.
- the volume average particle diameter of (meth) acrylic polymer particles in the (meth) acrylic polymer (11) latex was 0.194 ⁇ m.
- a (meth) acrylic polymer powder was obtained in the same manner as in Example 1, and subjected to the same test as in Example 1.
- Example 12 Instead of the monomer mixture (B-1) in Example 1, a monomer mixture consisting of 81 parts by weight of MMA, 9 parts by weight of BA, and 0.01 parts by weight of t-DM, in which only the amount of t-DM was increased.
- a (meth) acrylic polymer (12) was prepared in the same manner as in Example 1, except that (B-12) was used. Latex was obtained. The volume average particle diameter of the (meth) acrylic polymer particles in this latex was 0.209 ⁇ m. Further, using the latex of the (meth) acrylic polymer (12), a (meth) acrylic polymer powder was obtained in the same manner as in Example 1, and subjected to the same test as in Example 1.
- Example 13 Instead of the monomer mixture (B-1) in Example 1, a monomer mixture consisting of 81 parts by weight of MMA, 9 parts by weight of BA, and 0.015 parts by weight of t-DM in which only the amount of t-DM was increased.
- a latex of (meth) acrylic polymer (13) was obtained in the same manner as in Example 1 except that (B-13) was used.
- the volume average particle diameter of the (meth) acrylic polymer particles in this latex was 0.209 ⁇ m.
- a (meth) acrylic polymer powder was obtained in the same manner as in Example 1, and subjected to the same test as in Example 1.
- Example 14 Instead of the monomer mixture (B-1) in Example 1, a monomer mixture consisting of 81 parts by weight of MMA, 9 parts by weight of BA, and 0.003 parts by weight of t-DM in which only the amount of t-DM is reduced.
- a latex of (meth) acrylic polymer (14) was obtained in the same manner as in Example 1 except that (B-14) was used.
- the volume average particle diameter of the (meth) acrylic polymer particles in this latex was 0.210 ⁇ m.
- a (meth) acrylic polymer powder was obtained in the same manner as in Example 1, and subjected to the same tests as in Example 1.
- Example 15 Instead of the monomer mixture (B-1) in Example 1, a monomer mixture (B-15) comprising 81 parts by weight of MMA and 9 parts by weight of BA without using t-DM was used. In the same manner as in Example 1, a latex of (meth) acrylic polymer (15) was obtained. The volume average particle diameter of the (meth) acrylic polymer particles in this latex was 0.210 ⁇ m. Furthermore, using the latex of the (meth) acrylic polymer (15), a (meth) acrylic polymer powder was obtained in the same manner as in Example 1, and subjected to the same test as in Example 1.
- Example 16 After mixing 140 parts by weight of water, 0.05 parts by weight of sodium dodecylbenzenesulfonate, 0.1 parts by weight of sodium sulfate, and 0.05 parts by weight of sodium carbonate, and replacing with nitrogen at 80 ° C., 0.0024 weight of potassium persulfate
- a monomer mixture (A-14-a) consisting of 3.5 parts by weight of MMA, 1.5 parts by weight of BA and 0.09 parts by weight of t-DM as a part of the monomer mixture (A) with stirring. was continuously added over 10 minutes, and after the addition of the monomer mixture (A-14-a) was further completed, the mixture was stirred for 1.5 hours for polymerization.
- a monomer mixture (A-14-b) consisting of 3.5 parts by weight of MMA and 1.5 parts by weight of BA was continuously added over 30 minutes. The polymerization was carried out with stirring for 1.5 hours. Further, 0.5 parts by weight of sodium dodecylbenzenesulfonate was added. Subsequently, a monomer mixture (B-16) consisting of 81 parts by weight of MMA and 9 parts by weight of BA as a monomer mixture (B) was added continuously over 30 minutes and stirred for 5 hours. 0.05 part by weight of potassium persulfate was added and stirred for 1 hour to complete the polymerization reaction, thereby obtaining a latex of a (meth) acrylic polymer (16).
- the volume average particle diameter of the (meth) acrylic polymer particles in the polymer (A-16) latex which is the (meth) acrylic polymer (A) was 0.116 ⁇ m.
- the volume average particle diameter of the (meth) acrylic polymer particles in the (meth) acrylic polymer (16) latex was 0.261 ⁇ m.
- Example 1 (Comparative Example 1) Instead of the monomer mixture (A-4-a) in Example 4, a monomer mixture (A-C1-a) containing 90 parts by weight of BA and 0.7 parts by weight of t-DM without MMA And also Similar to Example 4 except that 10 parts by weight of the monomer (A-C1-b) containing no MMA was used instead of the monomer mixture (A-4-b) in Example 4. Thus, a latex of (meth) acrylic polymer (C1) was obtained. The volume average particle diameter of the (meth) acrylic polymer particles in the polymer (A-C1) latex which is the (meth) acrylic polymer (A) was 0.118 ⁇ m.
- the volume average particle diameter of the (meth) acrylic polymer particles in the latex of the (meth) acrylic polymer (C1) was 0.261 ⁇ m. Furthermore, using this (meth) acrylic polymer (C1) latex, a (meth) acrylic polymer powder was obtained in the same manner as in Example 1, and subjected to the same test as in Example 1.
- Example 1 is the same as Example 1 except that the monomer mixture (B) in Example 1 is a monomer mixture (BC2) consisting of 45 parts by weight of MMA, 45 parts by weight of BA, and 0.007 parts by weight of t-DM. Similarly, a latex of (meth) acrylic polymer (C2) was obtained. The volume average particle diameter of the (meth) acrylic polymer particles in this latex was 0.209 ⁇ m. Furthermore, using this (meth) acrylic polymer (C2) latex, a (meth) acrylic polymer powder was obtained in the same manner as in Example 1, and subjected to the same test as in Example 1.
- the monomer mixture (B) in Example 1 is a monomer mixture (BC2) consisting of 45 parts by weight of MMA, 45 parts by weight of BA, and 0.007 parts by weight of t-DM.
- a latex of (meth) acrylic polymer (C2) was obtained. The volume average particle diameter of the (meth) acrylic polymer particles in this latex was 0.209 ⁇
- Example 3 After obtaining a latex of the polymer (A-1) in the same manner as in Example 1, the polymer (A-1) was replaced with 10 parts by weight (solid content) of the polymer (A-1) latex in Example 1. -1) 40 parts by weight of latex (solid content), and the monomer mixture (B) was a monomer mixture (B) consisting of 54 parts by weight of MMA, 6 parts by weight of BA, and 0.0047 parts by weight of t-DM. A latex of (meth) acrylic polymer (C3) was obtained in the same manner as in Example 1 except that it was changed to -C3). The volume average particle diameter of the (meth) acrylic polymer particles in this latex was 0.123 ⁇ m. Furthermore, using this (meth) acrylic polymer (C3) latex, a (meth) acrylic polymer powder was obtained in the same manner as in Example 1, and subjected to the same tests as in Example 1.
- Example 4 instead of the monomer mixture (A-1-a) in Example 1, a monomer mixture (A-C4-a) comprising 63 parts by weight of MMA and 27 parts by weight of BA was used without using t-DM.
- a latex of (meth) acrylic polymer (C4) was obtained in the same manner as Example 1 except that it was used.
- the volume average particle diameter of the (meth) acrylic polymer particles in the polymer (A-C4) latex which is the (meth) acrylic polymer (A) was 0.840 ⁇ m.
- the volume average particle diameter of the (meth) acrylic polymer particles in the latex was 0.192 ⁇ m.
- a (meth) acrylic polymer powder was obtained in the same manner as in Example 1, and subjected to the same tests as in Example 1.
- Example 5 instead of the monomer mixture (B-1) in Example 1, a monomer mixture consisting of 81 parts by weight of MMA, 9 parts by weight of BA, and 0.02 parts by weight of t-DM in which only the amount of t-DM was increased.
- a (meth) acrylic polymer (C5) was prepared in the same manner as in Example 1 except that (B-C5) was used. Latex was obtained. The volume average particle diameter of the (meth) acrylic polymer particles in the (meth) acrylic polymer (C5) latex was 0.209 ⁇ m. Furthermore, using this (meth) acrylic polymer (C5) latex, a (meth) acrylic polymer powder was obtained in the same manner as in Example 1, and subjected to the same test as in Example 1.
- a monomer mixture (B) comprising a monomer mixture (B) consisting of 90 parts by weight of MMA, 10 parts by weight of BA, and 0.0078 parts by weight of t-DM as a monomer mixture (B) with stirring.
- -C6 was added over 30 minutes and stirred for 5 hours to complete the polymerization reaction, thereby obtaining a latex of (meth) acrylic polymer (C6).
- Example 7 a vinyl chloride resin composition was obtained in the same manner as in Example 1 without blending the powdery (meth) acrylic polymer, and subjected to the same test as in Example 1.
- Example 8 a vinyl chloride resin composition was obtained in the same manner as in Example 1 except that the amount of the powdery (meth) acrylic polymer was 40 parts by weight. The same test was performed.
- Example 1 and Comparative Examples 7 and 8 when the number of parts by weight of the (meth) acrylic polymer blended with respect to 100 parts by weight of the vinyl chloride resin exceeds 30 parts by weight, It turns out that specific gravity is inferior. On the contrary, when the number of parts by weight of the (meth) acrylic polymer to be blended with the vinyl chloride resin is less than 1 part by weight, it is understood that the specific gravity and gelling properties are inferior. On the other hand, when the number of parts by weight of the (meth) acrylic polymer to be blended with respect to 100 parts by weight of the vinyl chloride resin is within the range specified by the present invention, the surface properties, specific gravity, and gelation characteristics of the molded product are excellent. I understand.
- Example 17 and 18 A latex of (meth) acrylic polymer particles having the composition shown in Table 2 was prepared in the same manner as in Example 1, and ion-exchanged water was added thereto to obtain a solid content concentration of 15%, and then 100 parts by weight of polymer particles. 4% by weight (solid content) of 2.5% calcium chloride aqueous solution was added to obtain a coagulated slurry. After further adding water to a solid content concentration of 12%, the obtained coagulated slurry was heated to 95 ° C., held at 95 ° C. for 2 minutes, cooled to 50 ° C., dehydrated, and water having 5 times the amount of resin. After washing, the product was dried to obtain a (meth) acrylic polymer powder as a foaming processability improver. This was evaluated in the same manner as in Example 1. The results are summarized in Table 2.
- Example 17 From the results of Examples 17 and 18, compared with Example 1, the composition of the (meth) acrylic polymer (A) is softened by decreasing MMA and increasing BA, and increasing the amount of t-DM. In addition, the composition of the (meth) acrylic polymer (B) is hardened by increasing the MMA and decreasing the BA, and increasing the molecular weight by not using t-DM. It can be seen that a foam having a lower specific gravity than that of the vinyl chloride resin composition foam of Example 1 can be obtained by using a polymer having a branching point.
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Abstract
Description
前記粉体の各粒子が、体積平均一次粒子径が0.12μm~0.70μmの一次粒子が粒子間の接触位置で半融状態により融着した多孔質な集合体である、発泡性成形用加工性改良剤とすることである。
本発明の発泡性成形用加工性改良剤の主成分は、(メタ)アクリル系重合体の粉体であり、好ましくは、乳化重合により得られた前記(メタ)アクリル系重合体を含むラテックスを噴霧乾燥して得られる粉体である。このように乳化重合により得られた前記ラテックスをそのまま噴霧乾燥するので、本発明の発泡性成形用加工性改良剤は、その全量を100重量%としたときに、乳化剤を、好ましくは0.2重量%~4.0重量%、より好ましくは0.3重量%~3.0重量%、さらに好ましくは0.5重量%~2.5重量%含む。前記乳化剤は、前記粉体の各粒子中に含まれる場合が殆どである。なお、本発明において(メタ)アクリルとは、特に断らない限り、アクリル、及び/又は、メタクリルを意味する。
本発明に係る前記(メタ)アクリル系重合体の粉体は、重量平均分子量は200万~700万の(メタ)アクリル系重合体の粉体であり、その組成として、重量平均分子量が1~30万の(メタ)アクリル系重合体(A)1~20重量%、及び重量平均分子量が200万~700万の(メタ)アクリル系重合体(B)80~99重量%からなる。
本発明に係る前記(メタ)アクリル系重合体(A)の重量平均分子量は1~30万であり、好ましくは、メタクリル酸メチル10~100重量%、メタクリル酸メチルを除く(メタ)アクリル酸エステル0~90重量%、及びこれらと共重合可能な他の単量体0~5重量%からなる単量体混合物(A)を乳化重合して得られる。
本発明に係る前記(メタ)アクリル系重合体(B)の重量平均分子量は200万~700万であり、より比重の小さい発泡体を得る観点からは300万~700万とすることが好ましく、より好ましくは500万~700万とすることである。
本発明に係る前記(メタ)アクリル系重合体は、上述の如く、重量平均分子量が1~30万の(メタ)アクリル系重合体(A)1~20重量%、及び重量平均分子量が200万~700万の(メタ)アクリル系重合体(B)80~99重量%からなるが、好ましくは、前記単量体混合物(A)1~20重量部を重合してなる(メタ)アクリル系重合体(A)、及び前記単量体混合物(B)80~99重量部を重合してなる(メタ)アクリル系重合体(B)(ただし、単量体混合物(A)、及び単量体混合物(B)の合計は100重量部)からなる。
上述のメタクリル酸メチルを除く(メタ)アクリル酸エステルについては、適度な水溶性があり乳化重合に適している点から、メタクリル酸メチルを除いたアルキル基の炭素数が2~8のメタクリル酸エステル、及びアルキル基の炭素数1~8のアクリル酸エステルからなる群から選ばれる1種以上であることが好ましく、より具体的には、メタクリル酸アルキルエステルである、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸n-ブチル、メタクリル酸i-ブチル、及びメタクリル酸t-ブチル、メタクリル酸2-エチルへキシルメタクリル酸オクチルと、アクリル酸アルキルエステルである、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸n-ブチル、アクリル酸t-ブチル、アクリル酸2-エチルヘキシル、及びアクリル酸オクチルとからなる群から選ばれる1種以上であることが好ましい。中でも、工業的に入手しやすい観点から、特に好ましいのはメタクリル酸ブチル、及びアクリル酸ブチルである。
上述の共重合可能な他の単量体は、メタクリル酸メチル、および上述のメタクリル酸メチルを除く(メタ)アクリル酸エステルと共重合可能な他の単量体であれば特に制限されないが、例えば、スチレン、α-メチルスチレン、クロルスチレン、ビニルスチレン、及び核置換スチレン等の芳香族ビニル化合物、アクリロニトリル、及びメタクリロニトリル等の不飽和ニトリル化合物、1、3-ブタンジオールジアクリレート、1、4―ブタンジオールジアクリレート、1、6ヘキサンジオールジアクリレート、ノナンジオールジアクリレート、エチレングリコールジアクリレート、プロピレングリコールジアクリレート、及びポリエチレングリコール(2~23)ジアクリレート、ポリプロピレングリコール(2~12)ジアクリレート、プロポキシル化(2~16)ネオペンチルジアクリレート、アルコキシル化ヘキサンジオールジアクリレート、アルコキシ化シクロヘキサンジメタノールジアクリレート、エトキシ化(4~30)ビスフェノールAジアクリレート、及びトリシクロデカンジメタノールジアクリレート等のジアクリレート化合物、1、3-ブタンジオールジメタクリレート、1、4―ブタンジオールジメタクリレート、1、6ヘキサンジオールジメタクリレート、ポリエチレングリコール(2~23)ジメタクリレート、ポリプロピレングリコール(2~12)ジメタクリレート、アルコキシル化ヘキサンジオールジメタクリレート、アルコキシ化シクロヘキサンジメタノールジメタクリレート、エトキシ化(4~30)ビスフェノールAジメタクリレート、及びトリシクロデカンジメタノールジメタクリレート等のジメタクリレート化合物、トリメチロールプロパントリアクリレート、エトキシ化トリメチロールプロパントリアクリレート、プロポキシル化トリメチロールプロパントリアクリレート、及びトリス(2-ヒドロキシルエチル)イソシアヌレートトリアクリレート等のトリアクリレート化合物、トリメチロールプロパントリメタクリレート、及び三官能メタクリレートエステル等のトリメタクリレート化合物、ジビニルベンゼン(DVB)、トリアリルイソシアヌレート(TAIC)、アリルメタアクリレート、ジシクロペンタジエン、2、4、6-トリアロキシ-1、3、5トリアジン(トリアリルシアヌレート(TAC))等の架橋剤等が例示される。これらは、本発明に係る(メタ)アクリル系重合体粉体を用いた場合に、成形体の表面性、比重、ゲル化特性に関して、実用的な問題を発生しない程度に単独で又は二種以上組み合わせて適宜用いることができる。
上記重量平均分子量は、各重合体を重合する際の重合条件等により適宜調整することができる。具体的には、重合する際の重合開始剤(触媒)量の、重合に使用する連鎖移動剤量、重合温度、モノマーの追加速度等により調整することができる。
前記乳化剤としては、アニオン性界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤等の公知のものを用いることができるが、中でも、重合安定性、熱安定性、色調に優れる点から、アルキルベンゼンスルホン酸塩、アルキルジフェニルエーテルジスルホン酸塩、及びアルキルザルコシン酸塩から選ばれる1種以上が好ましく、直鎖アルキルベンゼンスルホン酸塩がより好ましい。
前記重合開始剤としては、水溶性や油溶性の重合開始剤、レドックス系の重合開始剤等の公知のものを使用することができる。たとえば、通常の過硫酸塩などに代表される無機塩系重合開始剤、有機過酸化物、アゾ化合物などが例示され、これらを単独で用いるか、または前記化合物と亜硫酸塩、亜硫酸水素、チオ硫酸塩、第一金属塩、ナトリウムホルムアルデヒドスルホキシレートなどを組み合わせ、レドックス系重合開始剤として用いることもできる。
前記連鎖移動剤としては公知のものを用いることができ、たとえば、主鎖の炭素数が4~12のアルキルメルカプタンを好適に例示できる。具体的には、n-オクチルメルカプタン、t-オクチルメルカプタン、n-ドデシルメルカプタン、t-ドデシルメルカプタン(t-DM)などのアルキルメルカプタン類、2-エチルヘキシルチオグリコール、イソオクチルチオグリコール等のチオグリコール類、アルファメチルスチレンダイマー、ターピノーレン等を挙げることができるが、連鎖移動効率の観点から、好ましくはアルキルメルカプタン類、及びチオグリコール類からなる群から選ばれる1種以上が好ましく、より好ましくはt-DMである。
本発明に係る前記(メタ)アクリル系重合体粉体は、上述したように好ましくは乳化重合法、懸濁重合法により得られたラテックスから回収される。
本発明の塩化ビニル系樹脂組成物は、塩化ビニル系樹脂100重量部、及び本発明の前記発泡性成形用加工性改良剤1~30重量部を含むが、本発明の効果を損なわない限り、安定剤、滑剤、衝撃改良剤、可塑剤、着色剤、充填剤、発泡剤等の公知の添加剤を適宜加えてもよい。
前記本発明に係る塩化ビニル系樹脂としては、従来から使用されている塩化ビニル系樹脂を特に制限無く使用できる。具体的には、ポリ塩化ビニル、好ましくは80重量%以上の塩化ビニルとこれと共重合可能な単量体20重量%以下からなる塩化ビニル系共重合体、あるいは後塩素化ポリ塩化ビニルなどを例示することができる。前記の塩化ビニルと共重合可能な単量体としては、例えば、酢酸ビニル、エチレン、プロピレン、スチレン、臭化ビニル、塩化ビニリデン、アクリル酸エステル、メタクリル酸エステルなどを例示することができる。これらは単独で用いてもよく2種以上併用してもよい。
水140重量部、乳化剤であるドデシルベンゼンスルホン酸ナトリウム0.13重量部、硫酸ナトリウム0.1重量部、及び炭酸ナトリウム0.05重量部を混合し、80℃で窒素置換した後に、過硫酸カリウム0.035重量部、次いで攪拌しながら単量体混合物(A)の一部としてメタクリル酸メチル(以下、MMAともいう)63重量部、アクリル酸ブチル(以下、BAともいう)27重量部、及びターシャリードデシルメルカプタン(以下、t-DMともいう)0.7重量部からなる単量体の混合物(A-1-a)を300分間を要して連続添加し、更に単量体の混合物(A-1-a)の添加終了後、1時間攪拌して重合を行った。また単量体の混合物(A-1-a)の連続添加1時間目、2時間目にそれぞれドデシルベンゼンスルホン酸ナトリウム0.3重量部を添加した。そこに更に、残りの単量体混合物(A)としてMMA7重量部、及びBA3重量部からなる単量体の混合物(A-1-b)を30分間を要して連続添加した後、1時間攪拌して重合反応を終了させて(メタ)アクリル系重合体(A)として重合体(A-1)のラテックスを得た。ラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.092μmであった。
分子量は、システム:東ソー製HLC-8220、カラム:東ソー製TSKgel SuperHZM-H(×2本)、溶媒:THFを用いて測定し、重量平均分子量はポリスチレン換算で求めたものを用いた。
表面性の評価は、押出シートの目視でおこなった。評価用の試料は、パラレル押出機(Haake社製PolyLab System)を用いて、成形条件C1/C2/C3/D:165/170/175/190(℃)、スクリュー回転数50rpm、フィーダー回転数140rpmにて、押出成形を実施し、得られた成形体を用い、この成形体表面の表面性を測定した。この押出シートを観察し、表面にフローマークやダイラインが見られないものを5、フローマークやダイラインが若干見られるものを4、フローマークやダイラインが見られるが実用上問題ないものを3、フローマークやダイラインが発生して実用上問題のあるものを2、フローマークやダイラインが著しく発生しているものを1として、5段階で評価した。
発泡性の評価は、押出シートの比重を測定しておこなった。評価用の試料は、パラレル押出機(Haake社製)を用いて、成形条件C1/C2/C3/D:165/170/175/190(℃)、スクリュー回転数50rpm、フィーダー回転数140rpmにて押出成形を実施し、得られた成形体の比重を東洋精機社製DENSIMETER-Hを用いて測定した。
水140重量部、ドデシルベンゼンスルホン酸ナトリウム0.13重量部、硫酸ナトリウム0.1重量部、炭酸ナトリウム0.05重量部を混合し、80℃で窒素置換した後に、過硫酸カリウム0.035重量部、次いで攪拌しながら単量体混合物(A)の一部としてMMA81重量部、BA9重量部、及びt-DM0.7重量部からなる単量体混合物(A-2-a)を300分間を要して連続添加し、更に単量体混合物(A-2-a)の添加終了後、1時間攪拌して重合を行った。また単量体の混合物(A-2-a)の連続添加1時間目、3時間目にそれぞれドデシルベンゼンスルホン酸ナトリウム0.3重量部を添加した。そこに更に、残りの単量体混合物(A)としてMMA9重量部、及びBA1重量部からなる単量体混合物(A-2-b)を30分間を要して連続添加した後、1時間攪拌して重合反応を終了させて(メタ)アクリル系重合体(A)として重合体(A-2)のラテックスを得た。このラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径0.074μmであった。
水140重量部、ドデシルベンゼンスルホン酸ナトリウム0.13重量部、硫酸ナトリウム0.1重量部、炭酸ナトリウム0.05重量部を混合し、80℃で窒素置換した後に、過硫酸カリウム0.035重量部、次いで攪拌しながら単量体混合物(A)の一部としてMMA49.5重量部、BA40.5重量部、及びt-DM0.7重量部からなる単量体混合物(A-3-a)を300分間を要して連続添加し、更に単量体混合物(A-3-a)の添加終了後、1時間攪拌して重合を行った。また単量体の混合物(A-3-a)の連続添加1時間目、3時間目にそれぞれドデシルベンゼンスルホン酸ナトリウム0.3重量部を添加した。そこに更に、残りの単量体混合物(A)としてMMA5.5重量部、及びBA4.5重量部からなる単量体混合物(A-3-b)を30分間を要して連続添加した後、1時間攪拌して重合反応を終了させて(メタ)アクリル系重合体(A)として重合体(A-3)のラテックスを得た。このラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.095μmであった。
水140重量部、ドデシルベンゼンスルホン酸ナトリウム0.13重量部、硫酸ナトリウム0.1重量部、炭酸ナトリウム0.05重量部を混合し、80℃で窒素置換した後に、過硫酸カリウム0.035重量部、次いで攪拌しながら単量体混合物(A)の一部としてMMA18重量部、BA72重量部、及びt-DM0.7重量部からなる単量体混合物(A-4-a)を300分間を要して連続添加し、更に単量体混合物(A-4-a)の添加終了後、1時間攪拌して重合を行った。そこに更に、残りの単量体混合物(A)としてMMA2重量部、及びBA8重量部からなる単量体混合物(A-4-b)を30分間を要して連続添加した後、1時間攪拌して重合反応を終了させて(メタ)アクリル系重合体(A)として重合体(A-4)のラテックスを得た。このラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.108μmであった。
実施例1における単量体混合物(B)を、MMA85.5重量部、BA4.5重量部、及びt-DM0.007重量部からなる単量体の混合物(B-5)としたこと以外は実施例1と同様にして、(メタ)アクリル系重合体(5)のラテックスを得た。このラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.209μmであった。更に、この(メタ)アクリル系重合体(5)のラテックスを用いて実施例1と同様にして(メタ)アクリル系重合体の粉体を得て、実施例1と同様の試験に供した。
実施例1における単量体混合物(B)を、MMA73.8重量部、BA16.2重量部、及びt-DM0.007重量部からなる単量体の混合物(B-6)としたこと以外は実施例1と同様にして、(メタ)アクリル系重合体(6)のラテックスを得た。このラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.209μmであった。更に、この(メタ)アクリル系重合体(6)のラテックスを用いて実施例1と同様にして(メタ)アクリル系重合体の粉体を得て、実施例1と同様の試験に供した。
実施例1における単量体混合物(B)を、MMA67.5重量部、BA22.5重量部、
及びt-DM0.007重量部からなる単量体の混合物(B-7)としたこと以外は実施例1と同様にして、(メタ)アクリル系重合体(7)のラテックスを得た。このラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.209μmであった。更に、この(メタ)アクリル系重合体(7)のラテックスを用いて実施例1と同様にして(メタ)アクリル系重合体の粉体を得て、実施例1と同様の試験に供した。
実施例1と同様にして前記重合体(A-1)のラテックスを得た後、実施例1における重合体(A-1)のラテックス10重量部(固形分)に代えて、重合体(A-1)のラテックス5重量部(固形分)を用い、また、単量体混合物(B)をMMA85.5重量部、BA9.5重量部、及びt-DM0.0074重量部からなる単量体の混合物(B-8)としたこと以外は実施例1と同様にして、(メタ)アクリル系重合体(8)のラテックスを得た。このラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.269μmであった。更に、この(メタ)アクリル系重合体(8)のラテックスを用いて実施例1と同様にして(メタ)アクリル系重合体の粉体を得て、実施例1と同様の試験に供した。
実施例1と同様にして前記重合体(A-1)のラテックスを得た後、実施例1における重合体(A-1)のラテックス10重量部(固形分)に代えて、重合体(A-1)のラテックス20重量部(固形分)を用い、また、単量体混合物(B)をMMA72重量部、BA8重量部、及びt-DM0.0062重量部からなる単量体の混合物(B-9)としたこと以外は実施例1と同様にして、(メタ)アクリル系重合体(9)のラテックスを得た。このラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.161μmであった。更に、この(メタ)アクリル系重合体(9)のラテックスを用いて実施例1と同様にして(メタ)アクリル系重合体の粉体を得て、実施例1と同様の試験に供した。
実施例1における単量体混合物(A-1-a)に代えて、そのt-DMの量のみを減らしたMMA63重量部、BA27重量部、及びt-DM0.4重量部からなる単量体の混合物(A-10-a)を用いたこと以外は実施例1と同様にして、(メタ)アクリル系重合体
(10)のラテックスを得た。(メタ)アクリル系重合体(A)である重合体(A-10)ラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.088μmであった。また(メタ)アクリル系重合体(10)ラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.200μmであった。更に、この(メタ)アクリル系重合体(10)のラテックスを用いて実施例1と同様にして(メタ)アクリル系重合体の粉体を得て、実施例1と同様の試験に供した。
実施例1における単量体混合物(A-1-a)に代えて、そのt-DMの量のみを減らしたMMA63重量部、BA27重量部、及びt-DM0.2重量部からなる単量体の混合物(A-11-a)を用いたこと以外は実施例1と同様にして、(メタ)アクリル系重合体
(11)のラテックスを得た。(メタ)アクリル系重合体(A)である重合体(A-11)ラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.084μmであった。また(メタ)アクリル系重合体(11)ラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.194μmであった。更に、この(メタ)アクリル系重合体(11)のラテックスを用いて実施例1と同様にして(メタ)アクリル系重合体の粉体を得て、実施例1と同様の試験に供した。
実施例1における単量体混合物(B-1)に代えて、そのt-DMの量のみを増やした
MMA81重量部、BA9重量部、及びt-DM0.01重量部からなる単量体の混合物(B-12)を用いたこと以外は実施例1と同様にして、(メタ)アクリル系重合体(12)
のラテックスを得た。このラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.209μmであった。更に、この(メタ)アクリル系重合体(12)のラテックスを用いて実施例1と同様にして(メタ)アクリル系重合体の粉体を得て、実施例1と同様の試験に供した。
実施例1における単量体混合物(B-1)に代えて、そのt-DMの量のみを増やした
MMA81重量部、BA9重量部、及びt-DM0.015重量部からなる単量体の混合物(B-13)を用いたこと以外は実施例1と同様にして、(メタ)アクリル系重合体
(13)のラテックスを得た。このラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.209μmであった。更に、この(メタ)アクリル系重合体(13)のラテックスを用いて実施例1と同様にして(メタ)アクリル系重合体の粉体を得て、実施例1と同様の試験に供した。
実施例1における単量体混合物(B-1)に代えて、そのt-DMの量のみを減らした
MMA81重量部、BA9重量部、及びt-DM0.003重量部からなる単量体の混合物(B-14)を用いたこと以外は実施例1と同様にして、(メタ)アクリル系重合体
(14)のラテックスを得た。このラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.210μmであった。更に、この(メタ)アクリル系重合体(14)のラテックスを用いて実施例1と同様にして(メタ)アクリル系重合体の粉体を得て、実施例1と同様の試験に供した。
実施例1における単量体混合物(B-1)に代えて、t-DMを含まない、MMA81重量部、及びBA9重量部からなる単量体の混合物(B-15)を用いたこと以外は実施例1と同様にして、(メタ)アクリル系重合体(15)のラテックスを得た。このラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.210μmであった。更に、この(メタ)アクリル系重合体(15)のラテックスを用いて実施例1と同様にして(メタ)アクリル系重合体の粉体を得て、実施例1と同様の試験に供した。
水140重量部、ドデシルベンゼンスルホン酸ナトリウム0.05重量部、硫酸ナトリウム0.1重量部、炭酸ナトリウム0.05重量部を混合し、80℃で窒素置換した後に、過硫酸カリウム0.0024重量部、次いで攪拌しながら単量体混合物(A)の一部としてMMA3.5重量部、BA1.5重量部、及びt-DM0.09重量部からなる単量体混合物(A-14-a)を10分間を要して連続添加した後、更に単量体混合物(A-14-a)の添加終了後、1.5時間攪拌して重合を行った。そこに更に、残りの単量体混合物(A)としてMMA3.5重量部、及びBA1.5重量部からなる単量体混合物(A-14-b)を30分間を要して連続添加した後、1.5時間攪拌して重合を行った。さらに、ドデシルベンゼンスルホン酸ナトリウム0.5重量部を添加した。そこに引き続き、単量体混合物(B)としてMMA81重量部、及びBA9重量部からなる単量体の混合物(B-16)を30分間を要して連続添加し、5時間攪拌した後、更に過硫酸カリウム0.05重量部を添加し、1時間攪拌して重合反応を終了させて(メタ)アクリル系重合体(16)のラテックスを得た。また単量体の混合物(B-16)の連続添加後の0.5時間目、1時間目、1.5時間目にそれぞれドデシルベンゼンスルホン酸ナトリウム0.5重量部を添加した。(メタ)アクリル系重合体(A)である重合体(A-16)ラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.116μmであった。また(メタ)アクリル系重合体(16)ラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.261μmであった。
実施例4における単量体混合物(A-4-a)に代えて、MMAを含まない、BA90重量部、及びt-DM0.7重量部からなる単量体の混合物(A-C1-a)を用い、また、
実施例4における単量体混合物(A-4-b)に代えて、MMAを含まない、BA10重量部の単量体(A-C1-b)を用いたこと以外は、実施例4と同様にして、(メタ)アクリル系重合体(C1)のラテックスを得た。(メタ)アクリル系重合体(A)である重合体(A-C1)ラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.118μmであった。また(メタ)アクリル系重合体(C1)のラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.261μmであった。更に、この(メタ)アクリル系重合体(C1)のラテックスを用いて実施例1と同様にして(メタ)アクリル系重合体の粉体を得て、実施例1と同様の試験に供した。
実施例1における単量体混合物(B)を、MMA45重量部、BA45重量部、及びt-DM0.007重量部からなる単量体の混合物(B-C2)としたこと以外は実施例1と同様にして、(メタ)アクリル系重合体(C2)のラテックスを得た。このラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.209μmであった。更に、この(メタ)アクリル系重合体(C2)のラテックスを用いて実施例1と同様にして(メタ)アクリル系重合体の粉体を得て、実施例1と同様の試験に供した。
実施例1と同様にして前記重合体(A-1)のラテックスを得た後、実施例1における重合体(A-1)のラテックス10重量部(固形分)に代えて、重合体(A-1)のラテックス40重量部(固形分)を用い、また、単量体混合物(B)をMMA54重量部、BA6重量部、及びt-DM0.0047重量部からなる単量体の混合物(B-C3)としたこと以外は実施例1と同様にして、(メタ)アクリル系重合体(C3)のラテックスを得た。このラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.123μmであった。更に、この(メタ)アクリル系重合体(C3)のラテックスを用いて実施例1と同様にして(メタ)アクリル系重合体の粉体を得て、実施例1と同様の試験に供した。
実施例1における単量体混合物(A-1-a)に代えて、t-DMを使用せず、MMA63重量部、及びBA27重量部からなる単量体の混合物(A-C4-a)を用いたこと以外は実施例1と同様にして、(メタ)アクリル系重合体(C4)のラテックスを得た。(メタ)アクリル系重合体(A)である重合体(A-C4)ラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.840μmであった。またこのラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.192μmであった。更に、この(メタ)アクリル系重合体(C4)のラテックスを用いて実施例1と同様にして(メタ)アクリル系重合体の粉体を得て、実施例1と同様の試験に供した。
実施例1における単量体混合物(B-1)に代えて、そのt-DMの量のみを増やした
MMA81重量部、BA9重量部、及びt-DM0.02重量部からなる単量体の混合物(B-C5)を用いたこと以外は実施例1と同様にして、(メタ)アクリル系重合体(C5)
のラテックスを得た。この(メタ)アクリル系重合体(C5)ラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.209μmであった。更に、この(メタ)アクリル系重合体(C5)のラテックスを用いて実施例1と同様にして(メタ)アクリル系重合体の粉体を得て、実施例1と同様の試験に供した。
水140重量部、ドデシルベンゼンスルホン酸ナトリウム0.05重量部、硫酸ナトリウム0.1重量部、及び炭酸ナトリウム0.05重量部を混合し、70℃で窒素置換した後に、過硫酸カリウム0.005重量部、次いで攪拌しながら単量体混合物(B)としてMMA90重量部、BA10重量部、及びt-DM0.0078重量部からなる単量体の混合物(B)からなる単量体の混合物(B-C6)を30分間を要して添加し、5時間攪拌して重合反応を終了させて(メタ)アクリル系重合体(C6)のラテックスを得た。また単量体の混合物(B-C6)の連続添加後の0.5時間目、1時間目、3時間目にそれぞれドデシルベンゼンスルホン酸ナトリウム0.5重量部を添加した。このラテックス中の(メタ)アクリル系重合体粒子の体積平均粒子径は0.211μmであった。
実施例1において、粉体状の(メタ)アクリル系重合体を配合せずに、実施例1と同様にして塩化ビニル系樹脂組成物を得て、実施例1と同様の試験に供した。
実施例1において、粉体状の(メタ)アクリル系重合体の配合量を40重量部としたこと以外は、実施例1と同様にして塩化ビニル系樹脂組成物を得て、実施例1と同様の試験に供した。
実施例1と同様にして表2の組成の(メタ)アクリル系重合体粒子のラテックスを作製し、そこに、イオン交換水を加えて固形分濃度15%とした後、重合体粒子100重量部に対して、2.5%塩化カルシウム水溶液を4重量部(固形分)加えて凝固スラリーを得た。さらに水を加えて固形分濃度12%とした後、得られた凝固スラリーを95℃まで加熱し、95℃で2分間保持した後、50℃まで冷却して脱水、樹脂量の5倍の水で洗浄後、乾燥させて発泡性成形用加工性改良剤として(メタ)アクリル系重合体の粉体を得た。これを実施例1と同様にして、評価した。結果を表2にまとめて示す。
Claims (12)
- 重量平均分子量が200万~700万の(メタ)アクリル系重合体の粉体であって、重量平均分子量が1~30万の(メタ)アクリル系重合体(A)1~20重量%、及び重量平均分子量が200万~700万の(メタ)アクリル系重合体(B)80~99重量%からなる(メタ)アクリル系重合体の粉体、を含む発泡性成形用加工性改良剤。
- 請求項1に記載の発泡性成形用加工性改良剤であって、前記一次粒子が、多層構造を有し、かつ、前記(メタ)アクリル系重合体(A)の内層、及び前記(メタ)アクリル系重合体(B)の外層からなる、発泡性成形用加工性改良剤。
- 請求項1、又は2に記載の発泡性成形用加工性改良剤であって、前記(メタ)アクリル系重合体が、メタクリル酸メチル75~100重量%、メタクリル酸メチルを除く(メタ)アクリル酸エステル0~25重量%、及びこれらと共重合可能な他の単量体0~5重量%を乳化重合して得られる(メタ)アクリル系重合体である、発泡性成形用加工性改良剤。
- 請求項3に記載の発泡性成形用加工性改良剤であって、前記(メタ)アクリル系重合体(B)が、メタクリル酸メチル75~100重量%、メタクリル酸メチルを除く(メタ)アクリル酸エステル0~25重量%、及びこれらと共重合可能な他の単量体0~5重量%からなる単量体混合物(B)を乳化重合して得られる、発泡性成形用加工性改良剤。
- 請求項3、又は4に記載の発泡性成形用加工性改良剤であって、前記(メタ)アクリル系重合体(B)が、メタクリル酸メチル75~99.999999重量%、メタクリル酸メチルを除く(メタ)アクリル酸エステル0~25重量%、及び多官能性単量体0.000001~0.01重量%(0.01~100重量ppm)からなる単量体混合物(B)を乳化重合して得られる、発泡性成形用加工性改良剤。
- 請求項3~5のいずれかに記載の発泡性成形用加工性改良剤であって、前記(メタ)アクリル系重合体(A)が、メタクリル酸メチル10~100重量%、メタクリル酸メチルを除く(メタ)アクリル酸エステル0~90重量%、及びこれらと共重合可能な他の単量体0~5重量%からなる単量体混合物(A)を乳化重合して得られる、発泡性成形用加工性改良剤。
- 請求項3~6のいずれかに記載の発泡性成形用加工性改良剤であって、前記単量体混合物(A)1~20重量部を乳化重合して得られる前記(メタ)アクリル系重合体(A)ラテックスの存在下に、前記単量体混合物(B)80~99重量部を乳化重合して得られる、発泡性成形用加工性改良剤。
- 請求項7に記載の発泡性成形用加工性改良剤であって、前記乳化重合で使用する乳化剤が、アルキルベンゼンスルホン酸塩、アルキルジフェニルエーテルジスルホン酸塩、及びアルキルザルコシン酸塩から選ばれる1種以上である、発泡性成形用加工性改良剤。
- 請求項7、又は8に記載の発泡性成形用加工性改良剤であって、該発泡性成形用加工性改良剤100重量%に対して、さらに、乳化剤を0.2重量%~4.0重量%含む発泡性成形用加工性改良剤。
- 請求項7~9のいずれかに記載の発泡性成形用加工性改良剤であって、前記(メタ)アクリル系重合体の粉体の体積平均粒子径が、50μm~300μmであり、かつ、
該粉体の各粒子が、体積平均一次粒子径が0.12μm~0.70μmの一次粒子が粒子間の接触位置で半融状態により融着した多孔質な集合体である、発泡性成形用加工性改良剤。 - 請求項10に記載の発泡性成形用加工性改良剤であって、前記(メタ)アクリル系重合体の粉体が、前記乳化重合で得られた重合体ラテックスを噴霧乾燥して得られてなる、発泡性成形用加工性改良剤。
- 塩化ビニル系樹脂100重量部、及び請求項1~11のいずれかに記載の発泡性成形用加工性改良剤1~30重量部を含有する、塩化ビニル系樹脂組成物。
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Publication number | Priority date | Publication date | Assignee | Title |
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JPWO2010061630A1 (ja) * | 2008-11-28 | 2012-04-26 | 三菱レイヨン株式会社 | 発泡成形用加工助剤、発泡成形用塩化ビニル系樹脂組成物及び発泡成形体 |
JP5636673B2 (ja) * | 2008-11-28 | 2014-12-10 | 三菱レイヨン株式会社 | 発泡成形用塩化ビニル系樹脂組成物及び発泡成形体 |
JP2018537567A (ja) * | 2015-12-18 | 2018-12-20 | ローム アンド ハース カンパニーRohm And Haas Company | 潤滑性を有する溶融強度加工助剤として多段コポリマーを含有する熱可塑性組成物 |
JP7025330B2 (ja) | 2015-12-18 | 2022-02-24 | ローム アンド ハース カンパニー | 潤滑性を有する溶融強度加工助剤として多段コポリマーを含有する熱可塑性組成物 |
KR20190007922A (ko) * | 2017-07-14 | 2019-01-23 | 주식회사 엘지화학 | 아크릴계 공중합체 제조방법, 아크릴계 공중합체, 및 이를 포함하는 수지 조성물 |
KR102088755B1 (ko) * | 2017-07-14 | 2020-03-13 | 주식회사 엘지화학 | 아크릴계 공중합체 제조방법, 아크릴계 공중합체, 및 이를 포함하는 수지 조성물 |
US10703839B2 (en) | 2017-07-14 | 2020-07-07 | Lg Chem, Ltd. | Method for preparing acrylic copolymer, acrylic copolymer and resin composition comprising the copolymer |
Also Published As
Publication number | Publication date |
---|---|
CN102414264B (zh) | 2014-06-11 |
JPWO2010140317A1 (ja) | 2012-11-15 |
EP2439232B1 (en) | 2016-02-10 |
CN102414264A (zh) | 2012-04-11 |
EP2439232A1 (en) | 2012-04-11 |
US8664338B2 (en) | 2014-03-04 |
EP2439232A4 (en) | 2013-02-27 |
US20120142796A1 (en) | 2012-06-07 |
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