WO2014027421A1 - シリコーン樹脂縮重合体粒子とポリ塩化ビニルとの反応物、該反応物の製造方法、塩化ビニル樹脂組成物並びに塩化ビニル樹脂組成物の製造方法 - Google Patents
シリコーン樹脂縮重合体粒子とポリ塩化ビニルとの反応物、該反応物の製造方法、塩化ビニル樹脂組成物並びに塩化ビニル樹脂組成物の製造方法 Download PDFInfo
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- WO2014027421A1 WO2014027421A1 PCT/JP2012/070915 JP2012070915W WO2014027421A1 WO 2014027421 A1 WO2014027421 A1 WO 2014027421A1 JP 2012070915 W JP2012070915 W JP 2012070915W WO 2014027421 A1 WO2014027421 A1 WO 2014027421A1
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- vinyl chloride
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- silicone resin
- chloride resin
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
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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
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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
- 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
- C08L51/08—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 otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
- C08L51/085—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 otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
Definitions
- the present invention relates to a vinyl chloride resin composition capable of obtaining a molded article excellent in impact resistance, heat resistance and chemical resistance, and a method for producing the vinyl chloride resin composition.
- the present invention also relates to a reaction product of the silicone resin condensation polymer particles and polyvinyl chloride blended in the vinyl chloride resin composition and a method for producing the reaction product.
- Vinyl chloride resin is generally excellent in mechanical strength, weather resistance and chemical resistance. For this reason, the vinyl chloride resin is processed into various molded products and is used in many fields. However, the vinyl chloride resin has a problem that its impact resistance is relatively low when used for hard applications. Therefore, it has been studied to improve the impact resistance of the vinyl chloride resin.
- Patent Document 1 discloses a vinyl chloride resin obtained by graft copolymerization of an acrylic copolymer and vinyl chloride.
- Patent Document 2 discloses a vinyl chloride resin obtained by suspension polymerization of vinyl chloride in the presence of a block copolymer having a polyorganosiloxane unit and a (meth) acrylic acid ester polymer unit. Yes.
- Patent Document 3 100 parts by weight of a post-chlorinated polyvinyl chloride resin having a chlorine content of 62 to 70% by weight and an average degree of polymerization of 600 to 1000, and 15 to 25 parts by weight of a multi-component acrylic rubber resin And 1 to 10 parts by weight of an acrylic processing aid.
- the impact resistance of a molded product using the vinyl chloride resin can be increased to some extent by reducing the amount of block copolymer due to the presence of polyorganosiloxane units, and fatigue strength can be increased. It can be held to some extent.
- the heat resistance cannot be sufficiently increased.
- both the heat resistance and impact resistance of a molded article using the composition can be improved to some extent.
- the acrylic rubber itself deteriorates with respect to an acid or alkaline chemical solution, the chemical resistance of the obtained molded product is lowered.
- a limited object of the present invention is to provide a reaction product of silicone resin polycondensation polymer particles and polyvinyl chloride capable of imparting heat resistance, and a method for producing the reaction product.
- the present invention also relates to a vinyl chloride resin composition containing a reaction product of the above-mentioned silicone resin condensation polymer particles and polyvinyl chloride, and a method for producing the vinyl chloride resin composition, which has improved impact resistance and chemical resistance. It aims at providing the manufacturing method of the vinyl chloride resin composition which can obtain the outstanding molded article, and a vinyl chloride resin composition.
- a limited object of the present invention is a vinyl chloride resin composition containing a reaction product of the above-mentioned silicone resin condensation polymer particles and polyvinyl chloride, and a method for producing the vinyl chloride resin composition, which is also excellent in heat resistance. It is an object of the present invention to provide a vinyl chloride resin composition and a method for producing the vinyl chloride resin composition capable of obtaining a molded product.
- a reaction product obtained by reacting a material containing silicone resin condensation polymer particles and a vinyl chloride monomer wherein the silicone resin condensation polymer particles are represented by the following formula (1):
- a reaction product of a silicone resin condensation polymer particle and polyvinyl chloride, which is a silicone resin condensation polymer particle obtained by reacting a mixed material containing the third organosilicon compound to be reacted (hereinafter referred to as a reaction product X) May be abbreviated as).
- R1 and R2 each represent a phenyl group or an alkyl group having 1 to 3 carbon atoms, and m represents an integer of 1 to 20.
- R3 represents a hydrogen atom or a methyl group
- R4 and R5 each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
- p represents an integer of 0 to 3
- q represents 0 to Represents an integer of 2.
- R6 and R7 each represents an alkyl group having 1 to 3 carbon atoms.
- R8 represents an alkyl group having 1 to 3 carbon atoms.
- the silicone resin condensation polymer particles have a structural unit represented by the formula (1) and are 100 weights of the first organosilicon compound that is siloxane. 3 parts by weight or more, 7 parts by weight or less of the second organosilicon compound represented by the formula (2), and the third organosilicon compound represented by the formula (3A) or the formula (3B) Silicone resin polycondensation particles obtained by reacting a mixture containing 2 parts by weight or more and 10 parts by weight or less.
- the silicone resin condensation polymer particles include a first organosilicon compound having a structural unit represented by the formula (1) and being siloxane;
- R9 to R11 each represents an unsaturated hydrocarbon group or an alkyl group having 1 to 3 carbon atoms
- R12 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
- R13 to R18 each represents an unsaturated hydrocarbon group or an alkyl group having 1 to 3 carbon atoms.
- R19 to R21 each represents an unsaturated hydrocarbon group or an alkyl group having 1 to 3 carbon atoms.
- the silicone resin condensation polymer particles have a structural unit represented by the formula (1) and are 100 weights of the first organosilicon compound that is siloxane. 0.5 part by weight or more and 10 parts by weight or less of the second organosilicon compound represented by the formula (2) and the third organic represented by the formula (3A) or the formula (3B) 0.5 parts by weight or more and 10 parts by weight or less of the silicon compound, and 0.25 parts by weight or more of the fourth organosilicon compound represented by the formula (4A), the formula (4B), or the formula (4C). It is the silicone resin condensation polymer particle obtained by making the mixed material containing below a weight part react.
- the reactant is a content of the silicone resin condensation polymer particles in a total of 100% by weight of the silicone resin condensation polymer particles and the vinyl chloride monomer.
- the reactant is a content of the silicone resin condensation polymer particles in a total of 100% by weight of the silicone resin condensation polymer particles and the vinyl chloride monomer. Is 2 wt% or more and 20 wt% or less, and the vinyl chloride monomer content is 80 wt% or more and 98 wt% or less.
- the reactant is a content of the silicone resin condensation polymer particles in a total of 100% by weight of the silicone resin condensation polymer particles and the vinyl chloride monomer. Is 20% by weight or more and 95% by weight or less, and the content of the vinyl chloride monomer is 5% by weight or more and 80% by weight or less.
- the second organosilicon compound represented by the formula (2) is vinyltriethoxysilane or vinyltrimethoxysilane.
- the reactant reacts with a material containing the silicone resin condensation polymer particles and the vinyl chloride monomer, and then is washed with a solvent. Has been obtained.
- the silicone resin polycondensation polymer is obtained by reacting a material containing the silicone resin polycondensation polymer particles and the vinyl chloride monomer and then washing with a solvent to obtain the reactant.
- a method for producing a reaction product of particles and polyvinyl chloride is provided.
- a vinyl chloride resin composition comprising a reaction product of the above-mentioned silicone resin condensation polymer particles and polyvinyl chloride, and a vinyl chloride resin or a chlorinated vinyl chloride resin.
- the content of the reaction product of the silicone resin condensation polymer particles and polyvinyl chloride, and the total of the vinyl chloride resin and the chlorinated vinyl chloride resin is 2.0: 98.0 to 60.0: 40.0 by weight.
- the content of particles derived from the silicone resin condensation polymer particles is 1.6% by weight or more and 51% by weight or less.
- the vinyl chloride resin composition contains the chlorinated vinyl chloride resin, and the chlorine content is 56.5% by weight or more and 65.5% by weight. It is as follows.
- the reactant and the vinyl chloride resin or chlorine are obtained using the reactant obtained by reacting the material containing the silicone resin condensation polymer particles and the vinyl chloride monomer.
- a method for producing a vinyl chloride resin composition comprising a step of obtaining a vinyl chloride resin composition containing the reactant and the vinyl chloride resin or the chlorinated vinyl chloride resin by blending with a chlorinated vinyl chloride resin Is done.
- the reactant and the chlorinated vinyl chloride resin are blended, and the reactant and the chlorinated vinyl chloride resin are contained.
- a vinyl chloride resin composition having a chlorine content of 56.5 wt% or more and 65.5 wt% or less is obtained.
- the method for producing the vinyl chloride resin composition comprises reacting a material containing the silicone resin condensation polymer particles and the vinyl chloride monomer. And a step of obtaining the reactant.
- the reaction product of the silicone resin condensation polymer particles and polyvinyl chloride according to the present invention is a reaction product obtained by reacting a material containing silicone resin condensation polymer particles and a vinyl chloride monomer.
- the condensation polymer particles include a first organosilicon compound having a structural unit represented by formula (1) and being siloxane, a second organosilicon compound represented by formula (2), and a formula (3A).
- reaction product of silicone resin condensation polymer particles and polyvinyl chloride The reaction product of the silicone resin condensation polymer particles and polyvinyl chloride according to the present invention is obtained by reacting a material containing silicone resin condensation polymer particles (hereinafter sometimes abbreviated as particle A) and a vinyl chloride monomer. (Hereinafter, may be abbreviated as “Reactant X”).
- the reactant X includes particles derived from the particles A (hereinafter referred to as particles B, for example, particles bonded to polyvinyl chloride). In the reactant X, for example, the particles B are dispersed.
- the silicone resin condensation polymer particle A includes a first organosilicon compound having a structural unit represented by the following formula (1) and being siloxane, and a second organosilicon represented by the following formula (2).
- R1 and R2 each represent a phenyl group or an alkyl group having 1 to 3 carbon atoms, and m represents an integer of 1 to 20. m may be an integer of 2 or more. When m is 2 or more, the plurality of R1s and the plurality of R2s may be the same or different.
- R3 represents a hydrogen atom or a methyl group
- R4 and R5 each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
- p represents an integer of 0 to 3
- q represents 0 to Represents an integer of 2.
- the plurality of R4 may be the same or different.
- q is 0 or 1
- the plurality of R5 may be the same or different.
- R6 and R7 each represents an alkyl group having 1 to 3 carbon atoms. Several R7 may be the same and may differ.
- R8 represents an alkyl group having 1 to 3 carbon atoms. Several R8 may be the same and may differ.
- the reactant X according to the present invention has the above-described configuration, it is possible to impart excellent impact resistance and chemical resistance by using the reactant X. That is, by using the vinyl chloride resin composition containing the reactant X, a molded article excellent in impact resistance and chemical resistance can be obtained. In the present invention, both impact resistance and chemical resistance can be improved.
- the reactant X according to the present invention has the above-described configuration, it is possible to impart excellent heat resistance (thermal stability) by using the reactant X. That is, by using the vinyl chloride resin composition containing the reactant X, a molded article having excellent heat resistance can be obtained. In the present invention, all of impact resistance, heat resistance, and chemical resistance can be improved.
- silicone resin condensation polymer particles that are generally difficult to disperse in polyvinyl chloride can be present in the state of reactant X in a well dispersed state in polyvinyl chloride.
- the conventional silicone resin condensation polymer particles tend to be fused between the silicone resin condensation polymer particles, the silicone resin condensation polymer particles are used to further improve the impact resistance. It is difficult to blend a large amount in polyvinyl chloride (for example, 20% by weight or more).
- the specific particles A fusion between the particles A can be prevented, and the particles A can be dispersed at a high density in polyvinyl chloride.
- the silicone resin condensation polymer particle A includes a first organosilicon compound having a structural unit represented by the above formula (1) and being siloxane, and a second organosilicon represented by the above formula (2).
- Silicone resin condensation polymer particles obtained by reacting a mixed material containing an organosilicon compound are preferred.
- R9 to R11 each represents an unsaturated hydrocarbon group or an alkyl group having 1 to 3 carbon atoms
- R12 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
- R13 to R18 each represents an unsaturated hydrocarbon group or an alkyl group having 1 to 3 carbon atoms.
- R19 to R21 each represents an unsaturated hydrocarbon group or an alkyl group having 1 to 3 carbon atoms.
- the plurality of R19, the plurality of R20, and the plurality of R21 may be the same or different.
- the fusion between the particles A is effective by using the fourth organosilicon compound represented by the above formula (4A), the above formula (4B), or the above formula (4C).
- the particles A can be present in a well dispersed state in the polyvinyl chloride.
- the impact resistance, heat resistance and chemical resistance of the molded article using the vinyl chloride resin composition containing the reactant X according to the present invention are more effective. Can be increased. That is, by using the vinyl chloride resin composition containing the reactant X, it is possible to obtain a molded product that is more excellent in impact resistance, heat resistance, and chemical resistance. By using the fourth organosilicon compound, all of impact resistance, heat resistance, and chemical resistance can be further improved.
- first organosilicon compound having the structural unit represented by the above formula (1) and being siloxane include linear siloxane and cyclic siloxane.
- the first organosilicon compound is preferably polysiloxane.
- M in the above formula (1) is preferably an integer of 2 to 20.
- the first organosilicon compound is preferably a cyclic siloxane, and more preferably a cyclic polysiloxane.
- the cyclic siloxane include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, and octaphenyl.
- cyclotetrasiloxane hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasilox
- the 1st organosilicon compound which has a radically polymerizable unsaturated double bond for the purpose of copolymerizing with a vinyl chloride monomer.
- the said 1st organosilicon compound only 1 type may be used and 2 or more types may be used together.
- the second organosilicon compound represented by the above formula (2) it is possible to bond polyvinyl chloride and silicone, which originally have no or low affinity. Further, the second organosilicon compound disperses the particles B derived from the particles A in the reactant X, and the acid or alkali chemical liquid enters the gap between the particles B and the resin in the molded product. Play a role to suppress.
- the second organosilicon compound represented by the above formula (2) examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylethyldiethoxysilane, allyltrimethoxysilane, allyltriethoxy. Examples include silane and allyltripropoxysilane.
- the organosilicon compound represented by the above formula (2) is vinyltrimethoxysilane or vinyltrimethoxysilane. More preferably, it is ethoxysilane.
- the said 2nd organosilicon compound only 1 type may be used and 2 or more types may be used together.
- the amount of the second organosilicon compound used when obtaining the particles A is not particularly limited.
- the amount of the second organosilicon compound used is preferably 0.5 parts by weight or more, more preferably 2 parts by weight or more, with respect to 100 parts by weight of the first organosilicon compound. More preferably, it is 3 parts by weight or more, preferably 10 parts by weight or less, more preferably 7 parts by weight or less, and still more preferably 5 parts by weight or less.
- the amount of the second organosilicon compound used is equal to or more than the lower limit, the particles A can be easily combined with the vinyl chloride monomer.
- the vinyl chloride resin composition peeling is less likely to occur at the interface between the particle B derived from the particle A and the resin. For this reason, it becomes easy to disperse
- the amount of the second organosilicon compound used is less than or equal to the above upper limit, the entanglement of the polyvinyl chloride bonded to the particles B is reduced when the vinyl chloride resin composition is thermoformed, Unevenness is less likely to occur on the surface, and the appearance of the molded product is improved.
- the third organosilicon compound represented by the above formula (3A) or the above formula (3B) has a role of adjusting the hardness of the particles A and B and expressing the impact resistance of the molded product, Acts as a cross-linking agent.
- a third organosilicon compound represented by the above formula (3A) may be used, or a third organosilicon compound represented by the above formula (3B) may be used. .
- the third organosilicon compound represented by the above formula (3A) or the above formula (3B) include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and And methyl triisopropoxysilane.
- the said 3rd organosilicon compound only 1 type may be used and 2 or more types may be used together.
- the amount of the third organosilicon compound used for obtaining the particles A is not particularly limited.
- the amount of the third organosilicon compound used is preferably 0.5 parts by weight or more, more preferably 2 parts by weight or more, with respect to 100 parts by weight of the first organosilicon compound. More preferably, it is 3 parts by weight or more, preferably 10 parts by weight or less, more preferably 7 parts by weight or less.
- the amount of the third organosilicon compound used is equal to or greater than the lower limit, when the vinyl chloride resin composition is thermoformed, the particles B are not easily deformed and the particles B are not easily separated from the polyvinyl chloride. The surface of the molded product is less likely to be uneven, and the appearance of the molded product is improved.
- the amount of the third organosilicon compound used is less than or equal to the above upper limit, in the polymerization reaction for obtaining the particles A, the viscosity is hardly excessively high, the polymerization is facilitated, and the rubber component is difficult to cure. The impact resistance of the molded product can be increased.
- the fourth organosilicon compound represented by the above formula (4A), the above formula (4B), or the above formula (4C) it is difficult to cause fusion that was originally likely to occur between the silicone resin condensation polymer particles. be able to.
- a fourth organosilicon compound represented by the above formula (4A) may be used, or a fourth organosilicon compound represented by the above formula (4B) may be used.
- a fourth organosilicon compound represented by the above formula (4C) may be used.
- the fourth organosilicon compound represented by the above formula (4A), the above formula (4B) or the above formula (4C) is bonded to the silanol group present on the surface of the particle A, and the siloxane bond between the particles. It acts as a surface treatment agent for preventing the formation of.
- the unsaturated hydrocarbon group is preferably a vinyl group, an allyl group or a phenyl group.
- the unsaturated hydrocarbon group may be a vinyl group or an allyl group, or may be a phenyl group.
- the unsaturated hydrocarbon group may be a vinyl group or an allyl group.
- the fourth organosilicon compound represented by the above formula (4A), the above formula (4B) or the above formula (4C) include trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane and the like as monoalkoxysilane compounds.
- the disiloxane compound include hexamethyldisiloxane
- examples of the disilazane compound include hexamethyldisilazane.
- the said 4th organosilicon compound only 1 type may be used and 2 or more types may be used together.
- the amount of the fourth organosilicon compound used when obtaining the particles A is not particularly limited.
- the amount of the fourth organosilicon compound used is preferably 0.25 parts by weight or more, more preferably 1.5 parts by weight with respect to 100 parts by weight of the first organosilicon compound.
- the amount is preferably 10 parts by weight or less, more preferably 5 parts by weight or less.
- the amount of the fourth organosilicon compound used is not less than the above lower limit, when the vinyl chloride resin composition is thermoformed, the particles B are easily dispersed in the resin, and impact resistance is exhibited.
- the usage-amount of the said 4th organosilicon compound is below the said upper limit, when the said vinyl chloride resin composition is heat-molded, the lubricity of the particle
- the method for obtaining the above-mentioned silicone resin condensed polymer particles (particle A) is not particularly limited, and examples thereof include suspension polymerization method, emulsion polymerization method, micro suspension polymerization method, solution polymerization method and bulk polymerization method.
- the emulsion polymerization method or the microsuspension polymerization method is preferred because the particle size of the particles A is easy to control and the impact resistance of the molded article is good.
- the polymerization for obtaining the particles A includes all copolymerization such as random copolymerization, block copolymerization, and graft copolymerization.
- the emulsion polymerization method or the micro suspension polymerization method Conventionally known methods can be adopted as the emulsion polymerization method or the micro suspension polymerization method.
- an emulsion dispersant, a polymerization initiator, a pH adjuster, an antioxidant, or the like may be used as necessary.
- the above emulsifying dispersant is used for improving the dispersion stability of the monomer component in the emulsion and performing the polymerization efficiently.
- the emulsifying dispersant is not particularly limited, and examples thereof include anionic surfactants, nonionic surfactants, partially saponified polyvinyl alcohol, cellulose dispersants, and gelatin.
- the emulsifying dispersant is preferably alkylbenzene sulfonic acid. Alkylbenzenesulfonic acid can also be used as a polymerization initiator. As for the said emulsifying dispersant, only 1 type may be used and 2 or more types may be used together.
- the polymerization initiator is not particularly limited, and examples thereof include acids such as sulfuric acid, hydrochloric acid and alkylbenzene sulfonic acid, and alkalis such as sodium hydroxide and potassium hydroxide. Of these, alkylbenzenesulfonic acid that can be used as an emulsifier is preferred. As for the said polymerization initiator, only 1 type may be used and 2 or more types may be used together.
- the type of the emulsion polymerization method is not particularly limited, and examples thereof include a batch polymerization method, a monomer dropping method, and an emulsion dropping method.
- the monomer dropping method pure water, an emulsifying dispersant and a polymerization initiator are placed in a jacketed polymerization reactor, oxygen is removed and pressurized under a nitrogen stream, and the reactor is kept at a predetermined temperature while stirring. In this method, after the temperature is raised, a mixed monomer is dropped dropwise in a certain amount.
- a mixed monomer, an emulsifying dispersant, and pure water are stirred to prepare an emulsified monomer in advance, and then pure water and a polymerization initiator are placed in a jacketed polymerization reactor and stirred under a nitrogen stream.
- This is a method in which oxygen removal and pressurization are performed, and the temperature inside the reactor is raised to a predetermined temperature, and then the above-mentioned emulsified monomer is dropped in a predetermined amount for polymerization.
- the emulsion dropping method if a method of adding a part of the emulsified monomer at the initial stage of polymerization and then dropping the remaining emulsified monomer is used, the amount of the emulsified monomer to be added is changed, thereby changing the amount of the particles A.
- the particle size can be easily controlled.
- a polymerization apparatus usually used for polymerization may be used, and the shape, material, etc. of the polymerization apparatus are not particularly limited.
- the reaction for obtaining the particles A is preferably performed in the presence of an acid or alkali catalyst.
- the reaction temperature is not particularly limited, and the reaction temperature may be changed in multiple stages along the way.
- the reaction temperature is preferably 30 to 100 ° C.
- the reaction temperature is more preferably 70 to 95 ° C.
- the reaction time is not particularly limited, but it is preferable to carry out the reaction for 2 to 6 hours in order to sufficiently proceed the ring-opening reaction.
- the reaction temperature is used. Is preferably 0 to 60 ° C.
- the reaction temperature is kept at 30 to 50 ° C.
- the reaction time is not particularly limited, it is preferable to carry out the reaction for 3 to 12 hours in order to sufficiently increase the molecular weight after the reaction of the first organosilicon compound.
- the molecular weight after the reaction of the first organosilicon compound is sufficiently increased, and the reaction efficiency between the main chain of the produced polymer and the second, third, and fourth organosilicon compounds is increased.
- the reaction time can be shortened to some extent, it is preferable that the reaction is carried out at 70 to 95 ° C. for 2 to 5 hours and then further reacted at 30 to 50 ° C. for 3 to 8 hours.
- the average particle diameter of the particles A and the particles B is not particularly limited.
- the average particle diameter of the particles A and the particles B is preferably 0.1 ⁇ m or more, more preferably 0.14 ⁇ m or more, and preferably 0.5 ⁇ m or less.
- the average particle diameter is not less than the above lower limit, the impact resistance of the molded product is further enhanced.
- the average particle size is not more than the above upper limit, the tensile strength of the molded product is further improved.
- the solid content ratio of the particles A obtained after completion of the reaction is not particularly limited. From the viewpoint of enhancing the productivity of the particles A and the stability of the polymerization reaction, the solid content ratio of the particles A obtained after the completion of the reaction is preferably 10% by weight or more, and preferably 50% by weight or less.
- a protective colloid may be used for the purpose of improving the mechanical stability of the particles A.
- the reaction between the particles A and polyvinyl chloride is preferably performed in the presence of a radical polymerization catalyst.
- the particles B are dispersed.
- the particles B are bonded to, for example, polyvinyl chloride.
- a vinyl monomer copolymerizable with the vinyl chloride monomer may be used.
- the material may contain a vinyl monomer copolymerizable with a vinyl chloride monomer.
- the vinyl monomer copolymerizable with the vinyl chloride monomer is not particularly limited, and examples thereof include vinyl acetate, alkyl (meth) acrylate, alkyl vinyl ether, ethylene, vinyl fluoride, and maleimide.
- vinyl monomer only 1 type may be used and 2 or more types may be used together.
- the blending ratio of the silicone resin condensation polymer particles (particle A) and the vinyl chloride monomer is not particularly limited.
- the content of the particle A is 2% by weight or more and 95% by weight or less in a total of 100% by weight of the particle A and the vinyl chloride monomer, and the vinyl chloride monomer
- the content of is preferably 5% by weight or more and 98% by weight or less.
- the content of the particles A in the total 100% by weight of the particles A and the vinyl chloride monomer in the material for obtaining the reactant X Is preferably 2 wt% or more and 20 wt% or less, and the vinyl chloride monomer content is preferably 80 wt% or more and 98 wt% or less.
- the particles A in 100% by weight of the particles A and the vinyl chloride monomer in total in the case where the first, second, third and fourth organosilicon compounds are used, in the material for obtaining the reactant X, the particles A in 100% by weight of the particles A and the vinyl chloride monomer in total.
- the vinyl chloride monomer content is preferably 5 wt% or more and 80 wt% or less.
- the content of the particle A is 15% by weight or more and 75% by weight or less in the total 100% by weight of the particle A and the vinyl chloride monomer, and the chloride
- the vinyl monomer content may be 25 wt% or more and 85 wt% or less, the particle A content is 15 wt% or more and 30 wt% or less, and the vinyl chloride monomer content is 70 wt%. % By weight or more and 85% by weight or less may be used.
- the present invention relates to a molded product such as a hard vinyl chloride tube or a molded product.
- a molded product such as a hard vinyl chloride tube or a molded product.
- the impact resistance of the molded product is further increased.
- the mechanical strength of the molded product is further increased.
- the total amount of the particles A and the vinyl chloride monomer is 100% by weight.
- the content is preferably 3% by weight to 16% by weight, and the vinyl chloride monomer content is preferably 84% by weight to 97% by weight.
- the particles are contained in a total of 100% by weight of the particles A and the vinyl chloride monomer. More preferably, the content of A is 50% by weight or more and 85% by weight or less, and the content of the vinyl chloride monomer is 15% by weight or more and 50% by weight or less.
- the reactant X obtained by reacting the particles A and the vinyl chloride monomer with such a preferable content molding of a vinyl chloride resin composition that is further excellent in impact resistance, heat resistance, and chemical resistance. Goods can be obtained.
- the content of the particles A is not less than the above lower limit, it is easy to further increase the chlorine content in the vinyl chloride resin composition according to the present invention, and the heat resistance of the molded product can be further increased.
- the content of the particles A is not more than the above upper limit, the particles B are more easily dispersed in the reactant X, and the impact resistance of the molded product can be further enhanced.
- vinyl chloride monomer is graft-copolymerized on the particles A.
- the weight fraction (wt%) per 1 wt% of the unit silicone resin condensation polymer particles (particle B) of vinyl chloride molecules graft-copolymerized and chemically bonded to the particles B is defined as the graft ratio.
- the graft ratio in the reactant X is preferably 0.4% by weight or more.
- the graft ratio in the reactant X is 0.4% by weight or more, the polyvinyl chloride is difficult to peel off from the surface of the particles B, and the particles B are easily dispersed uniformly in the polyvinyl chloride. X and the impact resistance of the molded product can be further enhanced.
- the graft ratio in the reaction product X is 0.4% by weight or more, entry of the chemical solution into the interface can be suppressed under the condition of contacting with the chemical solution such as acid or alkali, and performance deterioration due to the chemical solution can be suppressed.
- the reactant X containing polyvinyl chloride and the particle B deterioration due to hydrogen chloride generated due to photodegradation of polyvinyl chloride can be suppressed. For this reason, the weather resistance of the reactant X is increased.
- the graft copolymerization method is not particularly limited, and examples thereof include suspension polymerization method, emulsion polymerization method, solution polymerization method and bulk polymerization method. Among these, the suspension polymerization method is preferable.
- a dispersant or an oil-soluble polymerization initiator may be used.
- the dispersant By using the dispersant, the dispersion stability of the particles A in the material can be improved, and the graft copolymerization of vinyl chloride can proceed efficiently.
- the dispersant is not particularly limited.
- poly (meth) acrylate, (meth) acrylate / alkyl acrylate copolymer, methylcellulose, ethylcellulose, hydroxypropylmethylcellulose, polyethylene glycol, polyvinyl acetate, and parts thereof examples thereof include saponified products, gelatin, polyvinyl pyrrolidone, starch, and a maleic anhydride / styrene copolymer.
- the said dispersing agent only 1 type may be used and 2 or more types may be used together.
- the oil-soluble polymerization initiator is not particularly limited.
- the oil-soluble polymerization initiator is preferably a radical polymerization initiator.
- examples of the oil-soluble polymerization initiator include lauroyl peroxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, dioctyl peroxydicarbonate, t-butyl peroxyneodecanoate and ⁇ -cumyl peroxy.
- organic peroxides such as neodecanoate, and azo compounds such as 2,2-azobisisobutyronitrile and 2,2-azobis-2,4-dimethylvaleronitrile.
- the said oil-soluble polymerization initiator only 1 type may be used and 2 or more types may be used together.
- a scale inhibitor When graft copolymerizing vinyl chloride, a scale inhibitor, a pH adjuster or an antioxidant may be used for the purpose of reducing the amount of deposits adhering to the polymerization tank during the polymerization. It is particularly preferable to use a scale inhibitor. Furthermore, if necessary, the polymerization apparatus may be changed depending on the inside of the polymerization tank, the shape and material of the stirring blade and baffle plate, and the polymerization conditions such as the stirring speed may be changed. It is preferable to use a scale inhibitor when the material containing the particles A and the vinyl chloride monomer is reacted.
- the scale inhibitor is not particularly limited.
- the scale inhibitor include polyhydric phenols obtained by a condensation reaction of one or two or more compounds selected from polyaminobenzene, polyhydric phenol, aminophenol, alkyl-substituted phenol and the like.
- the scale inhibitor may be diluted with water or an organic solvent. As for the said scale inhibitor, only 1 type may be used and 2 or more types may be used together.
- the suspension polymerization method for example, the following method can be used.
- Dispersion solution containing pure water, the dispersant, the oil-soluble polymerization initiator, particles A, and, if necessary, a water-soluble thickener and a polymerization degree regulator in a polymerization vessel equipped with a temperature controller and a stirrer And air is removed from the inside of the polymerization vessel by a vacuum pump.
- vinyl chloride and optionally other vinyl monomers are placed in the polymerization vessel.
- the temperature in the reaction vessel is increased, and the polymerization reaction of the material is allowed to proceed at a desired polymerization temperature to perform graft copolymerization.
- the polymerization temperature is preferably 30 to 90 ° C.
- the polymerization time is preferably 2 to 20 hours.
- the temperature in the reaction vessel that is, the polymerization temperature can be controlled by changing the jacket temperature.
- the above-mentioned reactant X can be obtained by removing a vinyl monomer containing unreacted vinyl chloride as a main component and performing dehydration and drying.
- the blending ratio of the particle A and the vinyl chloride monomer used in the polymerization reaction does not correspond to the content of the particle B derived from the particle A and the content of polyvinyl chloride obtained by polymerizing the vinyl chloride monomer. Sometimes. This is because some particles A and some vinyl chloride monomers exist in an unreacted state and are discharged after polymerization.
- the polymerization degree of polyvinyl chloride obtained by the above polymerization reaction is preferably 400 or more, more preferably 500 or more, preferably 3000 or less, more preferably 1400 or less.
- molding the said vinyl chloride resin composition can be further improved as a polymerization degree is more than the said minimum and below the said upper limit. Furthermore, it is possible to obtain a molded product that is more excellent in impact resistance and heat resistance.
- the reaction product X is preferably obtained by reacting a material containing the silicone resin condensation polymer particles A and the vinyl chloride monomer and then washing with a solvent.
- a solvent After reacting the material containing the silicone resin condensation polymer particles A and the vinyl chloride monomer, It is preferable to obtain the reactant X by washing with a solvent.
- By performing the cleaning using a solvent it is possible to impart even more excellent impact resistance. That is, by using the vinyl chloride resin composition containing the reactant X washed with a solvent, a molded article having more excellent impact resistance can be obtained.
- the reason why the impact resistance is increased by the cleaning using the solvent is considered to be that a silicone component that does not sufficiently develop the impact resistance is removed from the reactant X.
- the solvent examples include aliphatic solvents, ketone solvents, aromatic solvents, ester solvents, ether solvents, alcohol solvents, paraffin solvents, petroleum solvents, and the like.
- the said solvent only 1 type may be used and 2 or more types may be used together.
- Examples of the aliphatic solvent include cyclohexane, methylcyclohexane, and ethylcyclohexane.
- Examples of the ketone solvent include acetone and methyl ethyl ketone.
- Examples of the aromatic solvent include toluene and xylene.
- Examples of the ester solvent include ethyl acetate, butyl acetate and isopropyl acetate.
- Examples of the ether solvent include tetrahydrofuran (THF) and dioxane.
- Examples of the alcohol solvent include ethanol and butanol.
- Examples of the paraffinic solvent include paraffin oil and naphthenic oil.
- Examples of the petroleum solvent include mineral terpenes and naphtha.
- reaction product after reaction is put in a solvent.
- the reaction product generally swells.
- the said reaction product X can be obtained by taking out the reaction product put into the solvent by filtration.
- the reaction product may be washed by applying a solvent to the reaction product.
- the solvent is preferably an organic solvent, preferably an ether solvent, and preferably a solvent having an ether bond. It is preferable that the second and third organosilicon compounds are soluble, and the first, second, third and fourth organosilicon compounds can be dissolved at 23 ° C. Is preferred, and tetrahydrofuran is particularly preferred.
- the vinyl chloride resin composition according to the present invention contains the reaction product X of the above-mentioned silicone resin condensation polymer particles A and polyvinyl chloride, and a vinyl chloride resin or a chlorinated vinyl chloride resin.
- the vinyl chloride resin composition according to the present invention may contain only a vinyl chloride resin, may contain only a chlorinated vinyl chloride resin, or contains both a vinyl chloride resin and a chlorinated vinyl chloride resin. May be.
- the vinyl chloride resin is not chlorinated.
- the vinyl chloride resin does not include chlorinated vinyl chloride resin.
- the degree of polymerization of the vinyl chloride resin is not particularly limited, but is preferably about 500 to 1000 in order to achieve sufficient gelation from the viewpoint of developing impact resistance during melt kneading.
- As for the said vinyl chloride resin only 1 type may be used and 2 or more types may be used together.
- the chlorinated vinyl chloride resin is preferably a post-chlorinated vinyl chloride resin.
- the post-chlorinated vinyl chloride resin refers to a resin obtained by chlorinating the vinyl chloride resin after obtaining the vinyl chloride resin. There is no restriction
- the degree of polymerization of the chlorinated vinyl chloride resin is not particularly limited, but is preferably about 500 to 1000 in order to achieve sufficient gelation to exhibit impact resistance during melt kneading. As for the said chlorinated vinyl chloride resin, only 1 type may be used and 2 or more types may be used together.
- the vinyl chloride resin composition contains the chlorinated vinyl chloride resin
- the vinyl chloride resin composition does not contain or contains the vinyl chloride resin. In order to adjust the chlorine content and workability, two or more chlorinated vinyl chloride resins can be used.
- the chlorine content in the vinyl chloride resin composition according to the present invention is preferably 56.5% by weight or more, and preferably 65.5% by weight or less.
- the chlorine content is the weight fraction of chlorine atoms in the total weight of the vinyl chloride resin composition.
- the chlorine content is 56.5% by weight or more, the strength and heat resistance of the molded product are further improved.
- the chlorine content is 65.5% by weight or less, the impact resistance of the molded product is further improved.
- the chlorine content in the vinyl chloride resin composition is more preferably 58.5% by weight or more, more preferably 63.0% by weight. It is as follows.
- the method for making the chlorine content in the vinyl chloride resin composition above the lower limit and below the upper limit is not particularly limited.
- the vinyl chloride resin composition has a chlorine content of 64.0% by weight or more and 70.5% by weight or less. It preferably contains some chlorinated vinyl chloride resin.
- the chlorine content in the chlorinated vinyl chloride resin is equal to or higher than the lower limit, the heat resistance of the molded product is further increased.
- the chlorine content in the chlorinated vinyl chloride resin is not more than the above upper limit, the vinyl chloride resin composition is easily melted, and the impact resistance of the molded product can be further enhanced.
- the chlorine content in the chlorinated vinyl chloride resin is preferably 65% by weight or more, and preferably 68.5% by weight or less.
- the content of the reactant X and the total content of the vinyl chloride resin and the chlorinated vinyl chloride resin are 2.0: 98.0 to 60. It is preferably 0: 40.0, and more preferably 3.0: 97.0 to 42.0: 58.0. If the content of the reactant X and the total content of the vinyl chloride resin and the chlorinated vinyl chloride resin are within the above range, the chlorine content in the vinyl chloride resin composition is within an appropriate range.
- the impact resistance, heat resistance and chemical resistance of the molded product can be improved in a well-balanced manner.
- the content of the particles B derived from the particles A is preferably 1.6% by weight or more, more preferably 1.8% by weight or more, and still more preferably 2. It is 4% by weight or more, preferably 51% by weight or less, more preferably 36% by weight or less.
- the content of the particles B derived from the particles A may be 2.6% by weight or more, 9% by weight or less, and 6.3% by weight. It may be the following.
- the content of the particles B is not less than the above lower limit, the impact resistance of the molded product is further increased.
- the content of the particles B is not more than the above upper limit, the heat resistance of the molded product is further improved.
- the total amount of the vinyl chloride resin and the chlorinated vinyl chloride resin may be vinyl chloride resin, or the total amount may be chlorinated vinyl chloride resin.
- the method for producing a vinyl chloride resin composition according to the present invention uses the reactant X obtained by reacting the material containing the silicone resin condensation polymer particles A and the vinyl chloride monomer, and the reactant X And the vinyl chloride resin or the chlorinated vinyl chloride resin, and a step of obtaining a vinyl chloride resin composition containing the reactant and the chlorinated vinyl chloride resin.
- the method for producing a vinyl chloride resin composition according to the present invention preferably further comprises a step of obtaining a reaction product X by reacting a material containing the silicone resin condensed polymer particles A and the vinyl chloride monomer.
- the reaction product X may be obtained without being synthesized, and the obtained reaction product X may be used to obtain a polyvinyl chloride resin composition.
- the product X may be synthesized and a polyvinyl chloride resin composition may be obtained using the synthesized reactant X.
- the reactant X and the chlorinated vinyl chloride resin are blended, the reactant X and the chlorinated vinyl chloride resin are contained, and chlorine is contained. It is preferable to obtain a vinyl chloride resin composition having a rate of 56.5 wt% or more and 65.5 wt% or less. In this case, the vinyl chloride resin may not be used and may be used.
- a scale inhibitor when the material containing the silicone resin condensation polymer particles A and the vinyl chloride monomer are reacted. By using a scale inhibitor, it is possible to suppress the generation of deposits in the polymerization tank and allow the reaction to proceed more efficiently.
- a molded product can be obtained by molding the vinyl chloride resin composition according to the present invention.
- the method for producing a molded product includes a step of extruding the above-described vinyl chloride resin composition using a molding machine.
- a molding machine having a resin retaining portion in which resin stays in a resin flow path as the molding machine.
- the molded article is preferably a tube.
- additives such as a heat stabilizer, a stabilizing aid, a lubricant, a processing aid, an antioxidant, a light stabilizer, a filler, and a pigment are added as necessary. It may be added.
- the heat stabilizer is not particularly limited. Organotin stabilizers such as tin laurate polymers, lead-based stabilizers such as lead stearate, dibasic lead phosphite and tribasic lead sulfate, calcium-zinc stabilizers, barium-zinc stabilizers, and And barium-cadmium stabilizer. As for the said heat stabilizer, only 1 type may be used and 2 or more types may be used together.
- the stabilizing aid is not particularly limited, and examples thereof include epoxidized soybean oil, epoxidized linseed oil, epoxidized tetrahydrophthalate, epoxidized polybutadiene, and phosphate ester. Only 1 type may be used for the said stabilization adjuvant, and 2 or more types may be used together.
- the lubricant is not particularly limited, and examples thereof include montanic acid wax, paraffin wax, polyethylene wax, stearic acid, stearyl alcohol, and butyl stearate. As for the said lubricant, only 1 type may be used and 2 or more types may be used together.
- the processing aid is not particularly limited, and examples thereof include an acrylic processing aid that is an alkyl acrylate / alkyl methacrylate copolymer having a weight average molecular weight of 100,000 to 2,000,000.
- Specific examples of the processing aid include n-butyl acrylate / methyl methacrylate copolymer and 2-ethylhexyl acrylate / methyl methacrylate / butyl methacrylate copolymer.
- the said processing aid only 1 type may be used and 2 or more types may be used together.
- the antioxidant is not particularly limited, and examples thereof include phenolic antioxidants. As for the said antioxidant, only 1 type may be used and 2 or more types may be used together.
- the light stabilizer is not particularly limited, and examples thereof include UV absorbers such as salicylic acid esters, benzophenones, benzotriazoles, and cyanoacrylates, and hindered amine light stabilizers.
- UV absorbers such as salicylic acid esters, benzophenones, benzotriazoles, and cyanoacrylates
- hindered amine light stabilizers As for the said light stabilizer, only 1 type may be used and 2 or more types may be used together.
- the filler is not particularly limited, and examples thereof include calcium carbonate and talc. As for the said filler, only 1 type may be used and 2 or more types may be used together.
- the pigment is not particularly limited, and examples thereof include organic pigments such as azo-based, phthalocyanine-based, selenium-based and dye lake-based, and oxide-based, molybdenum chromate-based, sulfide-selenide-based and ferrocyanide-based. And inorganic pigments. As for the said pigment, only 1 type may be used and 2 or more types may be used together.
- a plasticizer may be added to the vinyl chloride resin composition for the purpose of improving processability during molding.
- the plasticizer is not particularly limited, and examples thereof include dibutyl phthalate, di-2-ethylhexyl phthalate, and di-2-ethylhexyl adipate.
- the said plasticizer only 1 type may be used and 2 or more types may be used together.
- thermoplastic resin different from the vinyl chloride resin and different from the chlorinated vinyl chloride resin may be added to the vinyl chloride resin composition as necessary.
- the said thermoplastic resin only 1 type may be used and 2 or more types may be used together.
- the method of mixing the additive or plasticizer with the vinyl chloride resin composition is not particularly limited, and examples thereof include a method using hot blending and a method using cold blending.
- the method for molding the vinyl chloride resin composition is not particularly limited, and examples thereof include an extrusion molding method, an injection molding method, a calendar molding method, and a press molding method.
- the molding machine used when molding the vinyl chloride resin composition of the present invention is not particularly limited.
- An extruder etc. are mentioned.
- the above-mentioned vinyl chloride resin composition can be processed with good fluidity by blending the above-mentioned lubricant, stabilizer or pigment used for molding into the above-mentioned vinyl chloride resin composition.
- the vinyl chloride resin composition according to the present invention is excellent in impact resistance, heat resistance and chemical resistance. Furthermore, the vinyl chloride resin composition is also excellent in weather resistance. Moreover, the vinyl chloride resin composition has a very good balance of impact resistance, heat resistance and chemical resistance.
- the vinyl chloride resin composition according to the present invention is very useful particularly for pipes and tanks in which chemicals are used at high temperatures. Furthermore, the above-mentioned vinyl chloride resin composition can be suitably used for a hard vinyl chloride pipe, a plate, or the like that requires impact resistance, heat resistance, etc., taking advantage of the above characteristics.
- Examples 1 to 10 (1) Manufacture of silicone resin condensation polymer particle A After mixing the compounding component (1) shown in the following Tables 1 and 2 with the compounding amounts shown in the following Tables 1 and 2, emulsification at 8000 rpm using a homogenizer. I let you. Next, the mixture was put into a polymerization tank and stirred, and then the gas layer in the polymerization tank was replaced with nitrogen. Thereafter, the temperature in the polymerization tank was raised to 85 ° C. and reacted for 5 hours, and then the temperature in the polymerization tank was lowered to 50 ° C. over 30 minutes and then reacted at 50 ° C. for 6 hours.
- the compounding component (2) shown in the following Tables 1 and 2 was added to the polymerization tank and reacted for 2 hours. Thereafter, a 10% by weight aqueous sodium hydroxide solution was added to adjust the pH to 6-8, and silicone resin condensation polymer particles A having a solid content concentration of about 16-20% by weight were obtained.
- Example 11 to 13 The reaction was carried out in the same manner as in Example 1 except that the types and blending amounts of the blending components used in the production of the silicone resin condensation polymer particles A and the reactant X were changed as shown in Table 2 below. Product X was obtained. In Examples 11 to 13, the blending component (2) shown in Table 2 below was not blended.
- a vinyl chloride resin composition was obtained by blending the chlorinated vinyl chloride resin, polyvinyl chloride (vinyl chloride resin), and particles B so that the contents thereof were as shown in Table 2 below.
- Silicone resin condensation polymer particle A solid content concentration (% by weight) (CA) / B ⁇ 100 Formula (W)
- the content E of polyvinyl chloride was determined from the content D of the silicone resin condensation polymer particles B.
- Example 14 and 15 (1) Production of Silicone Resin Condensed Polymer Particle A After blending the blending component (1) shown in Table 3 below in the blending amount shown in Table 3 below, the mixture was emulsified at 8000 rpm using a homogenizer. Next, the mixture was put into a polymerization tank and stirred, and then the gas layer in the polymerization tank was replaced with nitrogen. Thereafter, the temperature in the polymerization tank was raised to 85 ° C. and reacted for 5 hours, and then the temperature in the polymerization tank was lowered to 50 ° C. over 30 minutes and then reacted at 50 ° C. for 6 hours.
- the compounding component (2) shown in the following Table 3 was added to the polymerization tank and reacted for 2 hours. Thereafter, a 10% by weight aqueous sodium hydroxide solution was added to adjust the pH to 6-8, and silicone resin condensation polymer particles A having a solid content concentration of about 16-20% by weight were obtained.
- reaction product before washing Into a reaction vessel (polymerizer) equipped with a stirrer and a jacket, the compounding component (3) shown in Table 3 below was charged all at once. Thereafter, the air in the reaction vessel was discharged with a vacuum pump, and further, vinyl chloride as the blending component (4) shown in Table 3 below was added while stirring. Next, the jacket temperature was controlled, polymerization was started at the polymerization temperature shown in Table 3 below, and the reaction was confirmed to be completed by reducing the pressure in the reaction vessel to a predetermined pressure, and the reaction was stopped. Thereafter, unreacted vinyl chloride was removed, and dehydration and drying were performed to obtain a reaction product (reacted product before washing) of the silicone resin condensation polymer particles A and polyvinyl chloride.
- Example 16 (1) Production of Silicone Resin Condensed Polymer Particle A After blending the blending component (1) shown in Table 3 below in the blending amount shown in Table 3 below, the mixture was emulsified at 8000 rpm using a homogenizer. Next, the mixture was put into a polymerization tank and stirred, and then the gas layer in the polymerization tank was replaced with nitrogen. Thereafter, the temperature in the polymerization tank was raised to 85 ° C. and reacted for 5 hours, and then the temperature in the polymerization tank was lowered to 50 ° C. over 30 minutes and then reacted at 50 ° C. for 6 hours.
- the compounding component (2) shown in the following Table 3 was added to the polymerization tank and reacted for 2 hours. Thereafter, a 10% by weight aqueous sodium hydroxide solution was added to adjust the pH to 6-8, and silicone resin condensation polymer particles A having a solid content concentration of about 16-20% by weight were obtained.
- Examples 17 to 38 (1) Production of Silicone Resin Condensed Polymer Particles A
- the formulations shown in Tables 4 to 6 below were mixed in the amounts shown in Tables 4 to 6, and then emulsified at 8000 rpm using a homogenizer. Next, the mixture was put into a polymerization tank and stirred, and then the gas layer in the polymerization tank was replaced with nitrogen. Thereafter, two temperature conditions (pattern ⁇ : the internal temperature of the polymerization tank was raised to 85 ° C., reacted for 3 hours, the temperature in the polymerization tank was lowered to 50 ° C. over 30 minutes, and then 4.
- the reaction was allowed to proceed for 5 hours; the pattern ⁇ : the temperature in the polymerization tank was raised to 90 ° C. and the reaction was performed for 6 hours). Thereafter, a 10% by weight aqueous sodium hydroxide solution was added to adjust the pH to 6-8, and silicone resin condensation polymer particles A having a solid content concentration of about 16-20% by weight were obtained.
- Charpy impact value at 0 ° C. A resin material in which 1.0 part by weight of an organic tin stabilizer and 0.3 part by weight of polyethylene wax is mixed with 100 parts by weight of the reactant X is roll-kneaded at 195 ° C. for 3 minutes. Further, press molding was performed at 200 ° C. for 3 minutes to produce a press plate having a thickness of 3 mm. Using the obtained press plate as a measurement sample, a No. 1 test piece / A notch was used as an edgewise impact test piece in accordance with JIS K7111, and the Charpy impact value was measured. After the measurement sample was stored for 12 hours in a thermostatic bath at 0 ° C., the measurement was performed at 23 ° C. within 10 seconds after the measurement sample was taken out.
- This vinyl chloride composition material is supplied to a biaxial counter-rotating extruder (manufactured by Brabender) having a diameter of 20 mm and molded so that the resin temperature is 195 ° C., and the width is 30 mm, the thickness is 3 mm, and the length is A plate-shaped molded product of about 100 mm was obtained. The appearance of the obtained molded product was visually evaluated and judged according to the following three criteria.
- Example 51 A reactant X and a vinyl chloride resin composition were obtained in the same manner as in Example 41 except that no scale inhibitor was used in the production of the reactant X.
- Example 52 The reaction was carried out in the same manner as in Example 39 except that the type and amount of the compound used in the production of the silicone resin condensation polymer particles A and the reaction product X were changed as shown in Table 10 below. Product X was obtained.
- Synthesis of post-chlorinated vinyl chloride resin Into a reaction vessel equipped with a stirrer and a jacket, a mixture excluding vinyl chloride shown in Table 10 below was charged all at once. Thereafter, the air in the reaction vessel was discharged with a vacuum pump, and 100 parts by weight of vinyl chloride was added while stirring. Subsequently, the jacket temperature was controlled, polymerization was started at an internal temperature of 57.5 ° C., and the reaction was confirmed to be completed by the pressure inside the reaction vessel decreasing to 0.7 MPa, and the reaction was stopped. Thereafter, unreacted vinyl chloride was removed, and dehydration and drying were performed to obtain a vinyl chloride resin.
- the chlorine content of the vinyl chloride resin in the reactor is calculated from the hydrogen chloride concentration generated in the reaction tank.
- the chlorination content reaches 63.5% by weight, the supply of chlorine gas is stopped and the chlorination reaction is started. finished.
- nitrogen gas was blown into the reaction tank to remove unreacted chlorine, and the resulting resin was washed with water, dehydrated and dried to obtain a powdered post-chlorinated vinyl chloride resin.
- the obtained chlorinated vinyl chloride resin had a chlorine content of 63.5% by weight and a degree of polymerization of 1020.
- the obtained reactant X and the above-mentioned post-chlorinated vinyl chloride resin are contained in the following vinyl chloride resin composition in which the contents of the post-chlorinated vinyl chloride resin, polyvinyl chloride and particles B are shown in Table 10 below. Thus, a vinyl chloride resin composition was obtained.
- Example 53 The reaction was carried out in the same manner as in Example 39 except that the type and amount of the compound used in the production of the silicone resin condensation polymer particles A and the reaction product X were changed as shown in Table 10 below. Product X was obtained.
- Synthesis of post-chlorinated vinyl chloride resin Into a reaction vessel equipped with a stirrer and a jacket, a mixture excluding vinyl chloride shown in Table 10 below was charged all at once. Thereafter, the air in the reaction vessel was discharged with a vacuum pump, and 100 parts by weight of vinyl chloride was added while stirring. Subsequently, the jacket temperature was controlled, polymerization was started at an internal temperature of 57.5 ° C., and the reaction was confirmed to be completed by the pressure inside the reaction vessel decreasing to 0.7 MPa, and the reaction was stopped. Thereafter, unreacted vinyl chloride was removed, and dehydration and drying were performed to obtain a vinyl chloride resin.
- the obtained chlorinated vinyl chloride resin had a chlorine content of 71.5% by weight and a degree of polymerization of 960.
- the obtained reactant X and the above-mentioned post-chlorinated vinyl chloride resin are contained in the following vinyl chloride resin composition in which the contents of the post-chlorinated vinyl chloride resin, polyvinyl chloride and particles B are shown in Table 10 below. Thus, a vinyl chloride resin composition was obtained.
- Examples 39, 40 and 42 to 50 a vinyl chloride resin composition was obtained in the same manner except that no scale inhibitor was used in the production of the reactant X, and Examples 39, 40, When the same evaluation as in 42 to 50 was performed, the evaluation result was the same except that the amount of deposits in the polymerization vessel increased.
- Example 46 The vinyl chloride resin composition obtained in Example 46 was prepared. This vinyl chloride resin composition and various compounding agents shown in Table 11 below were blended and mixed while being heated from room temperature (23 ° C.) to 110 ° C. with a Henschel mixer, and then cooled to 50 ° C. with a cooling mixer. A blended powder was obtained.
- Extruder SLM50 (2-axis different direction conical extruder) manufactured by Nagata Manufacturing Co., Ltd.
- Resin retention part Resin breaker, 1 sheet, resin flow surface chrome plating Mold: Pipe mold, outlet portion outer radius 13.33 mm, outlet portion inner radius 10 mm, resin flow surface chrome plating, three bridges Extrusion amount: 30 kg / h
- Resin temperature 200 ° C (temperature at the mold inlet)
- Rotation speed 20-25rpm
- Mold temperature D1: 190 ° C.
- D2 205 ° C.
- D3 210 ° C. (tip parallel part)
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Abstract
Description
前記式(2)中、R3は水素原子又はメチル基を表し、R4及びR5はそれぞれ水素原子又は炭素数1~3のアルキル基を表し、pは0~3の整数を表し、qは0~2の整数を表す。
前記式(3A)中、R6及びR7はそれぞれ炭素数1~3のアルキル基を表す。
前記式(3B)中、R8は炭素数1~3のアルキル基を表す。
(シリコーン樹脂縮重合体粒子とポリ塩化ビニルとの反応物)
本発明に係るシリコーン樹脂縮重合体粒子とポリ塩化ビニルとの反応物は、シリコーン樹脂縮重合体粒子(以下、粒子Aと略記することがある)と塩化ビニルモノマーとを含む材料を反応させることにより得られる反応物(以下、反応物Xと略記することがある)である。上記反応物Xにおいては、粒子Aに由来する粒子(以下、粒子Bと記載することがある、例えばポリ塩化ビニルに結合した粒子)が含まれる。上記反応物Xでは、例えば、上記粒子Bが分散されている。
上記式(2)中、R3は水素原子又はメチル基を表し、R4及びR5はそれぞれ水素原子又は炭素数1~3のアルキル基を表し、pは0~3の整数を表し、qは0~2の整数を表す。qが2であるとき、複数のR4は同一であってもよく、異なっていてもよい。qが0又は1であるとき、複数のR5は同一であってもよく、異なっていてもよい。
上記式(3A)中、R6及びR7はそれぞれ炭素数1~3のアルキル基を表す。複数のR7は同一であってもよく、異なっていてもよい。
上記式(3B)中、R8は炭素数1~3のアルキル基を表す。複数のR8は同一であってもよく、異なっていてもよい。
本発明に係る塩化ビニル樹脂組成物は、上述したシリコーン樹脂縮重合体粒子Aとポリ塩化ビニルとの反応物Xと、塩化ビニル樹脂又は塩素化塩化ビニル樹脂とを含有する。本発明に係る塩化ビニル樹脂組成物は、塩化ビニル樹脂のみを含んでいてもよく、塩素化塩化ビニル樹脂のみを含んでいてもよく、塩化ビニル樹脂と塩素化塩化ビニル樹脂との双方を含んでいてもよい。
(1)シリコーン樹脂縮重合体粒子Aの製造
下記の表1,2に示した配合成分(1)を下記の表1,2に示した配合量で混合した後、ホモジナイザーを用いて8000rpmで乳化させた。次いで、重合槽内に投入し、攪拌し、続いて、重合槽内の気層部分を窒素で置換した。その後、重合槽内の温度を85℃に昇温して5時間反応させ、次に重合槽内の温度を30分かけて50℃まで低下させた後、50℃で6時間反応させた。その後、下記の表1,2に示した配合成分(2)を重合槽内に添加し、2時間反応させた。その後、10重量%の水酸化ナトリウム水溶液を添加してpHを6~8に調整し、固形分濃度約16~20重量%のシリコーン樹脂縮重合体粒子Aを得た。
攪拌機及びジャケットを備えた反応容器(重合器)内に、下記の表1,2に示した配合成分(3)を一括で投入した。その後、真空ポンプで反応容器内の空気を排出し、更に、攪拌しながら下記の表1,2に示した配合成分(4)である塩化ビニルを投入した。次いで、ジャケット温度を制御して、下記の表1,2に示す重合温度にて重合を開始し、反応容器内の圧力が所定圧力まで低下することで反応の終了を確認し、反応を停止した。その後、未反応の塩化ビニルを除去し、更に、脱水及び乾燥を行うことで、シリコーン樹脂縮重合体粒子Aとポリ塩化ビニルとの反応物Xを得た。
得られた反応物Xと後塩素化塩化ビニル樹脂(徳山積水工業社製「HA-58K:塩素含有率67.3重量%,重合度1000タイプ」)とを、得られる塩化ビニル樹脂組成物における後塩素化塩化ビニル樹脂とポリ塩化ビニル(塩化ビニル樹脂)と粒子Bとの含有量が下記の表1,2に示す量となるように配合して、塩化ビニル樹脂組成物を得た。
シリコーン樹脂縮重合体粒子Aの製造及び反応物Xの製造の際に用いた配合成分の種類及び配合量を下記の表2に示すように変更したこと以外は実施例1と同様にして、反応物Xを得た。なお、実施例11~13では、下記の表2に示した配合成分(2)を配合しなかった。
(1)シリコーン樹脂縮重合体粒子Aの粒子径
シリコーン樹脂縮重合体粒子Aの粒子径を光散乱粒度計(光散乱粒度計DLS-7000:大塚電子社製)にて測定した。
予め重量を測定したアルミニウム製容器(重量Ag)内に、シリコーン樹脂縮重合体粒子Aを約5g(重量Bg)を秤量して入れた後、70℃で24時間乾燥した。乾燥後、アルミニウム製容器を含む残留固形分の重量を測定し(重量Cg)、下記式(W)により、シリコーン樹脂縮重合体粒子Aの固形分濃度を算出した。
反応物X中のポリ塩化ビニルの重合度をJIS K6720-2に準拠して測定した。なお、発生した不溶解物は濾別し、可溶解分のみを用いて測定した。
反応物X中の塩素重量含有率(Cl%)をJIS K7229に準拠して、電位差滴定法にて測定した。この塩素重量含有率(C=Cl%/100)から下記式(X)により、シリコーン樹脂縮重合体粒子Bの含有量Dを算出した。
塩化ビニル樹脂組成物を約10g(以下、W1gとする)を秤取し、テトラヒドロフラン(THF)100mL中で50時間攪拌混合した。その後、THFに不溶解部分を遠心分離操作により、THF溶液部分より沈降分離し、不溶解部分を70℃で24時間乾燥した。得られた乾燥物の重量を秤量(以下、W2gとする)し、更に塩素含有率(以下、C%とする)を定量した。これらの結果より、下記式(Y)により、シリコー樹脂縮重合体粒子Bの含有量Fを算出した。
塩化ビニル樹脂組成物における塩素重量含有率(Cl%)をJIS K7229に準拠して、電位差滴定法にて測定した。
塩化ビニル樹脂組成物100重量部に対して、有機錫系安定剤2.0重量部及びポリエチレンワックス0.5重量部を混合した樹脂材料を200℃で3分間ロール混練し、更に、205℃で3分間プレス成形して厚さ3mmのプレス板を作製した。得られたプレス板を測定試料として、JIS K7111に準拠してエッジワイズ衝撃試験片で1号試験片・Aノッチで試験片を作製し、シャルピー衝撃値を測定した。23℃の恒温槽で測定試料を12時間保管した後、23℃で測定を行った。
シャルピー衝撃値を測定する際に作製したプレス板を測定試料として、プラスチックの引張試験方法(JIS K7113)に則り、1号形試験片で10mm/分で引張降伏強さを測定した。測定温度は23℃とし、引張抗張力の単位は(MPa)とした。
シャルピー衝撃値を測定する際に作製したプレス板を測定試料として、JIS K7206(荷重5kgf)に準拠して測定した。
上記塩化ビニル樹脂組成物100重量部に、有機錫系安定剤1.0重量部及びポリエチレンワックス0.3重量部を添加し、混合した樹脂材料を用意した。この樹脂材料を195℃で3分間ロール混練し、更に、200℃で3分間プレス成形して、厚さ3mmのプレス板を作製した。得られたプレス板を2.5cm角に切り取り、端面を研磨して浸漬用サンプルを得た。予め、浸漬用サンプルの重量(Ag)を秤量した後、97%硫酸を入れたガラス容器内に、浸漬用サンプルを入れ、該浸漬用サンプルの全面が97%硫酸に漬かるように上からガラス製の落し蓋をして、密閉した。その後、浸漬用サンプルが97%硫酸に浸漬した状態で14日間放置した。14日後、浸漬サンプルを取り出し、軽く水洗した後、表面の水分を拭取って、浸漬後のサンプルの重量(Bg)を秤量した。これらの結果から下記式(Z)により、97%硫酸浸漬・重量変化率を算出した。
97%硫酸浸漬・重量変化率(%)=(B-A)/A×100・・・式(Z)
(1)シリコーン樹脂縮重合体粒子Aの製造
下記の表3に示した配合成分(1)を下記の表3に示した配合量で混合した後、ホモジナイザーを用いて8000rpmで乳化させた。次いで、重合槽内に投入し、攪拌し、続いて、重合槽内の気層部分を窒素で置換した。その後、重合槽内の温度を85℃に昇温して5時間反応させ、次に重合槽内の温度を30分かけて50℃まで低下させた後、50℃で6時間反応させた。その後、下記の表3に示した配合成分(2)を重合槽内に添加し、2時間反応させた。その後、10重量%の水酸化ナトリウム水溶液を添加してpHを6~8に調整し、固形分濃度約16~20重量%のシリコーン樹脂縮重合体粒子Aを得た。
攪拌機及びジャケットを備えた反応容器(重合器)内に、下記の表3に示した配合成分(3)を一括で投入した。その後、真空ポンプで反応容器内の空気を排出し、更に、攪拌しながら下記の表3に示した配合成分(4)である塩化ビニルを投入した。次いで、ジャケット温度を制御して、下記の表3に示す重合温度にて重合を開始し、反応容器内の圧力が所定圧力まで低下することで反応の終了を確認し、反応を停止した。その後、未反応の塩化ビニルを除去し、更に、脱水及び乾燥を行うことで、シリコーン樹脂縮重合体粒子Aとポリ塩化ビニルとの反応生成物(洗浄前の反応物)を得た。
得られた反応生成物5g(用いた洗浄前の反応生成物の量)を、THF300mL中に浸漬して、23℃で12時間撹拌した。その後に、膨潤した反応生成物を、金網(400メッシュ、SUS316)を用いてろ過により取り出して、乾燥を行うことで、シリコーン樹脂縮重合体粒子Aとポリ塩化ビニルとの反応物Xを得た。得られた反応物Xの下記式(K)より求められるゲル分率は、下記の表3に示す値であった。
ゲル分率=(得られた反応物Xの量(g))/(用いた洗浄前の反応生成物の量(g)) ・・・式(K)
得られた反応物Xと後塩素化塩化ビニル樹脂(徳山積水工業社製「HA-58K:塩素含有率67.3重量%,重合度1000タイプ」)とを、得られる塩化ビニル樹脂組成物における後塩素化塩化ビニル樹脂とポリ塩化ビニル(塩化ビニル樹脂)と粒子Bとの含有量が下記の表3に示す量となるように配合して、塩化ビニル樹脂組成物を得た。
(1)シリコーン樹脂縮重合体粒子Aの製造
下記の表3に示した配合成分(1)を下記の表3に示した配合量で混合した後、ホモジナイザーを用いて8000rpmで乳化させた。次いで、重合槽内に投入し、攪拌し、続いて、重合槽内の気層部分を窒素で置換した。その後、重合槽内の温度を85℃に昇温して5時間反応させ、次に重合槽内の温度を30分かけて50℃まで低下させた後、50℃で6時間反応させた。その後、下記の表3に示した配合成分(2)を重合槽内に添加し、2時間反応させた。その後、10重量%の水酸化ナトリウム水溶液を添加してpHを6~8に調整し、固形分濃度約16~20重量%のシリコーン樹脂縮重合体粒子Aを得た。
攪拌機及びジャケットを備えた反応容器(重合器)内に、下記の表3に示した配合成分(3)を一括で投入した。その後、真空ポンプで反応容器内の空気を排出し、更に、攪拌しながら下記の表3に示した配合成分(4)である塩化ビニルを投入した。次いで、ジャケット温度を制御して、下記の表3に示す重合温度にて重合を開始し、反応容器内の圧力が所定圧力まで低下することで反応の終了を確認し、反応を停止した。その後、未反応の塩化ビニルを除去し、更に、脱水及び乾燥を行うことで、シリコーン樹脂縮重合体粒子Aとポリ塩化ビニルとの反応物Xを得た。
得られた反応物Xと後塩素化塩化ビニル樹脂(徳山積水工業社製「HA-58K:塩素含有率67.3重量%,重合度1000タイプ」)とを、得られる塩化ビニル樹脂組成物における後塩素化塩化ビニル樹脂とポリ塩化ビニル(塩化ビニル樹脂)と粒子Bとの含有量が下記の表3に示す量となるように配合して、塩化ビニル樹脂組成物を得た。
実施例14~16で得られた反応物X及び塩化ビニル樹脂組成物について、実施例1と同様の評価を実施した。
結果を下記の表3に示す。
(1)シリコーン樹脂縮重合体粒子Aの製造
下記の表4~6に示した配合物を表4~6に示した配合量で混合した後、ホモジナイザーを用いて8000rpmで乳化させた。次いで、重合槽内に投入し、攪拌し、続いて、重合槽内の気層部分を窒素で置換した。その後、2つの温度条件(パターンα:重合槽の内温を85℃昇温して3時間反応後、重合槽内の温度を30分かけて50℃まで低下させた後、50℃で4.5時間反応させる;パターンβ:重合槽内の温度を90℃まで昇温して6時間反応させる)のうち、いずれかのパターンで重合を進行させた。その後、10重量%の水酸化ナトリウム水溶液を添加してpHを6~8に調整し、固形分濃度約16~20重量%のシリコーン樹脂縮重合体粒子Aを得た。
攪拌機及びジャケットを備えた反応容器内(重合器)に、下記の表4~6に示す塩化ビニルを除く配合物を一括投入した。その後、真空ポンプで反応容器内の空気を排出し、更に、攪拌しながら塩化ビニルを投入した。次いで、ジャケット温度を制御して、下記の表4~6に示す重合温度にて重合を開始し、反応容器内の圧力が所定圧力まで低下することで反応の終了を確認し、反応を停止した。その後、未反応の塩化ビニルを除去し、更に、脱水及び乾燥を行うことで、シリコーン樹脂縮重合体粒子Aとポリ塩化ビニルとの反応物Xを得た。
得られた反応物Xと後塩素化塩化ビニル樹脂(徳山積水工業社製「HA-58K:塩素含有率67.3wt%,重合度1000タイプ」、「HA-54H:塩素含有率65.4wt%,重合度1000タイプ」、または、「HA-54F:塩素含有率64.0wt%,重合度1000タイプ」)とを、得られる塩化ビニル樹脂組成物における後塩素化塩化ビニル樹脂とポリ塩化ビニルと粒子Bとの含有量が下記の表4~6に示す量となるように配合して、塩化ビニル樹脂組成物を得た。
シリコーン樹脂縮重合体粒子の製造及び反応物の製造の際に用いた配合物の種類及び配合量を下記の表7に示すように変更したこと以外は実施例17と同様にして、反応物X及び塩化ビニル樹脂組成物を得た。
実施例17~38及び比較例1~3で得られた反応物X及び塩化ビニル樹脂組成物について、実施例1と同様にして、上述した(1),(2),(3),(4),(5),(8),(10)の評価項目について評価を実施した。さらに、下記の(11,(12),(13)の評価項目について評価を実施した。
上記反応物Xを約10g(以下、W1gとする)を秤取し、テトラヒドロフラン(THF)100mL中で50時間攪拌混合した。その後、THFに不溶な部分を200メッシュの金網でTHF溶液部分より分離し、70℃で一昼夜乾燥した。得られた乾燥物の重量を秤量(以下、W2gとする)し、更に塩素含有率(以下、C%とする)を定量した。これらの結果より、上記式(X)により求めたシリコーン樹脂縮重合体粒子Bの含有量D(重量%)と下記式(L)により、グラフト率を算出した。
グラフト率(重量%)=[{(C×W2/56.8)×100}/{W1-W2(1-C/56.8)}]/X ・・・式(L)
上記反応物X100重量部に対して、有機錫系安定剤1.0重量部及びポリエチレンワックス0.3重量部を混合した樹脂材料を195℃で3分間ロール混練し、更に、200℃で3分間プレス成形して厚さ3mmのプレス板を作製した。得られたプレス板を測定試料として、JIS K7111に準拠してエッジワイズ衝撃試験片で1号試験片・Aノッチで試験片を作製し、シャルピー衝撃値を測定した。0℃の恒温槽で測定試料を12時間保管した後、測定試料を取り出してから10秒以内に23℃で測定を行った。
上記反応物X100重量部に、安定剤として有機錫系安定剤であるジオクチル錫メルカプト1重量部と、滑剤としてポリエチレンワックス0.5重量部と、エステル系ワックス0.5重量部と、PMMA系加工助剤1.5重量部とを添加し、スーパーミキサー(100L、カワタ社製)にて、攪拌、混合して、塩化ビニル組成物材料を得た。
○:表面が平滑である
△:表面に凹凸があるものの、該凹凸が小さい
×:表面の凸凹があり、該凹凸がかなり大きい
(1)シリコーン樹脂縮重合体粒子Aの製造
下記の表8,9に示した配合物を表8,9に示した配合量で混合した後、ホモジナイザーを用いて8000rpmで乳化させた。次いで、重合槽内に投入し、攪拌し、続いて、重合槽内の気層部分を窒素で置換した。その後、重合槽内の温度を85℃に昇温して3時間反応させ、次に重合槽内の温度を30分かけて50℃まで低下させた後、50℃で4.5時間反応させた。その後、10重量%の水酸化ナトリウム水溶液を添加してpHを6~8に調整し、固形分濃度約16~20重量%のシリコーン樹脂縮重合体粒子Aを得た。
攪拌機及びジャケットを備えた反応容器(重合器)内に、スケール防止剤であるポリアリルフェノール水溶液を塗布し、下記の表8,9に示す塩化ビニルを除く配合物を一括投入した。その後、真空ポンプで反応容器内の空気を排出し、更に、攪拌しながら塩化ビニルを投入した。次いで、ジャケット温度を制御して、下記の表8,9に示す重合温度にて重合を開始し、反応容器内の圧力が所定圧力まで低下することで反応の終了を確認し、反応を停止した。その後、未反応の塩化ビニルを除去し、更に、脱水及び乾燥を行うことで、シリコーン樹脂縮重合体粒子Aとポリ塩化ビニルとの反応物Xを得た。
得られた反応物Xと後塩素化塩化ビニル樹脂(徳山積水工業社製「HA-58K:塩素含有率67.3重量%,重合度1000タイプ」、「HA-54H:塩素含有率65.4重量%,重合度1000タイプ」、または、「HA-54F:塩素含有率64.0重量%,重合度1000タイプ」)とを、得られる塩化ビニル樹脂組成物における後塩素化塩化ビニル樹脂とポリ塩化ビニルと粒子Bとの含有量が下記の表8,9に示す量となるように配合して、塩化ビニル樹脂組成物を得た。
反応物Xの製造の際にスケール防止剤を用いなかったとこと以外は実施例41と同様にして、反応物X及び塩化ビニル樹脂組成物を得た。
実施例39で得られたシリコーン樹脂縮重合体粒子Aを用意した。該粒子Aと後塩素化塩化ビニル樹脂(徳山積水工業社製「HA-58K:塩素含有率67.3重量%,重合度1000タイプ」)とを、得られる塩化ビニル樹脂組成物における後塩素化塩化ビニル樹脂と粒子Aとの含有量が下記の表10に示す量となるように配合して、塩化ビニル樹脂組成物を得た。
シリコーン樹脂縮重合体粒子Aの製造及び反応物Xの製造の際に用いた配合物の種類及び配合量を下記の表10に示すように変更したこと以外は実施例39と同様にして、反応物Xを得た。
攪拌機及びジャケットを備えた反応容器内に、下記の表10に示す塩化ビニルを除く配合物を一括投入した。その後、真空ポンプで反応容器内の空気を排出し、更に、攪拌しながら塩化ビニル100重量部を投入した。次いで、ジャケット温度を制御して、内温57.5℃にて重合を開始し、反応容器内の圧力が0.7MPaまで低下することで反応の終了を確認し、反応を停止した。その後、未反応の塩化ビニルを除去し、更に、脱水及び乾燥を行うことで、塩化ビニル樹脂を得た。
シリコーン樹脂縮重合体粒子Aの製造及び反応物Xの製造の際に用いた配合物の種類及び配合量を下記の表10に示すように変更したこと以外は実施例39と同様にして、反応物Xを得た。
攪拌機及びジャケットを備えた反応容器内に、下記の表10に示す塩化ビニルを除く配合物を一括投入した。その後、真空ポンプで反応容器内の空気を排出し、更に、攪拌しながら塩化ビニル100重量部を投入した。次いで、ジャケット温度を制御して、内温57.5℃にて重合を開始し、反応容器内の圧力が0.7MPaまで低下することで反応の終了を確認し、反応を停止した。その後、未反応の塩化ビニルを除去し、更に、脱水及び乾燥を行うことで、塩化ビニル樹脂を得た。
実施例39~53及び比較例4で得られた反応物X及び塩化ビニル樹脂組成物について、実施例1と同様にして、上述した(1),(2),(3),(4),(5),(7),(8),(9),(10)の評価項目について評価を実施した。さらに、下記の(14)の評価項目について評価を実施した。
重合器内部の付着物量を全て取りきることは困難なため、目視で相対評価した。付着物が多い順に1、2、3、4、5と判定した。判定結果の数字が大きいほど、付着物量が少ないことを示す。
〔配合〕
実施例46で得られた塩化ビニル樹脂組成物を用意した。この塩化ビニル樹脂組成物と下記の表11に示す各種配合剤とを配合し、ヘンシェルミキサーで室温(23℃)から110℃まで昇温しながら混合した後、クーリングミキサーで50℃まで冷却して、配合粉を得た。
上記配合粉を用い、かつ樹脂滞留部を樹脂流路に有する押出機(成形機)を用いて、以下の押出条件で押出成形し、成形品である管を得た。
樹脂滞留部:樹脂ブレーカー、1枚、樹脂流動面クロムメッキ
金型:パイプ用金型、出口部外半径13.33mm、出口部内半径10mm、樹脂流動面クロムメッキ、3本ブリッジ
押出量:30kg/h
樹脂温度:200℃(金型入口部での温度)
回転数:20~25rpm
金型温度:D1:190℃、D2:205℃、D3:210℃(先端平行部)
押出機出口と金型との間の樹脂流路に樹脂ブレーカーを設けずに、樹脂滞留部を有さない成形機を用いたこと以外は成形品の作製例1と同様にして、成形品である管を得た。
得られた成形品である管の断面を1000番紙ヤスリで研磨し、管肉厚部の混練レベルを目視評価した。その結果、成形品の作製例1で得られた管における混練レベルは、成形品の作製例2で得られた管における混練レベルよりも良好であることを確認した。
Claims (17)
- シリコーン樹脂縮重合体粒子と塩化ビニルモノマーとを含む材料を反応させることにより得られる反応物であり、
前記シリコーン樹脂縮重合体粒子が、下記式(1)で表される構造単位を有しかつシロキサンである第1の有機珪素化合物と、下記式(2)で表される第2の有機珪素化合物と、下記式(3A)又は下記式(3B)で表される第3の有機珪素化合物とを含む混合材料を反応させることにより得られたシリコーン樹脂縮重合体粒子である、シリコーン樹脂縮重合体粒子とポリ塩化ビニルとの反応物。
CH2=CR3-(CH2)p-SiR4q(OR5)3-q ・・・式(2)
前記式(2)中、R3は水素原子又はメチル基を表し、R4及びR5はそれぞれ水素原子又は炭素数1~3のアルキル基を表し、pは0~3の整数を表し、qは0~2の整数を表す。
R6-Si(OR7)3 ・・・式(3A)
前記式(3A)中、R6及びR7はそれぞれ炭素数1~3のアルキル基を表す。
Si(OR8)4 ・・・式(3B)
前記式(3B)中、R8は炭素数1~3のアルキル基を表す。 - 前記シリコーン樹脂縮重合体粒子が、前記式(1)で表される構造単位を有しかつシロキサンである第1の有機珪素化合物100重量部と、前記式(2)で表される第2の有機珪素化合物3重量部以上、7重量部以下と、前記式(3A)又は前記式(3B)で表される第3の有機珪素化合物2重量部以上、10重量部以下とを含む混合物を反応させることにより得られたシリコーン樹脂縮重合粒子である、請求項1に記載のシリコーン樹脂縮重合体粒子とポリ塩化ビニルとの反応物。
- 前記シリコーン樹脂縮重合体粒子が、前記式(1)で表される構造単位を有しかつシロキサンである第1の有機珪素化合物と、前記式(2)で表される第2の有機珪素化合物と、前記式(3A)又は前記式(3B)で表される第3の有機珪素化合物と、下記式(4A)、下記式(4B)又は下記式(4C)で表される第4の有機珪素化合物とを含む混合材料を反応させることにより得られたシリコーン樹脂縮重合体粒子である、請求項1に記載のシリコーン樹脂縮重合体粒子とポリ塩化ビニルとの反応物。
- 前記シリコーン樹脂縮重合体粒子が、前記式(1)で表される構造単位を有しかつシロキサンである第1の有機珪素化合物100重量部と、前記式(2)で表される第2の有機珪素化合物0.5重量部以上、10重量部以下と、前記式(3A)又は前記式(3B)で表される第3の有機珪素化合物0.5重量部以上、10重量部以下と、前記式(4A)、前記式(4B)又は前記式(4C)で表される第4の有機珪素化合物0.25重量部以上、10重量部以下とを含む混合材料を反応させることにより得られたシリコーン樹脂縮重合体粒子である、請求項3に記載のシリコーン樹脂縮重合体粒子とポリ塩化ビニルとの反応物。
- 前記反応物は、前記シリコーン樹脂縮重合体粒子と前記塩化ビニルモノマーとの合計100重量%中、前記シリコーン樹脂縮重合体粒子の含有量が2重量%以上、95重量%以下であり、かつ前記塩化ビニルモノマーの含有量が5重量%以上、98重量%以下である材料を反応させることにより得られる、請求項1~4のいずれか1項に記載のシリコーン樹脂縮重合体粒子とポリ塩化ビニルとの反応物。
- 前記反応物は、前記シリコーン樹脂縮重合体粒子と前記塩化ビニルモノマーとの合計100重量%中、前記シリコーン樹脂縮重合体粒子の含有量が2重量%以上、20重量%以下であり、かつ前記塩化ビニルモノマーの含有量が80重量%以上、98重量%以下である材料を反応させることにより得られる、請求項1又は2に記載のシリコーン樹脂縮重合体粒子とポリ塩化ビニルとの反応物。
- 前記反応物は、前記シリコーン樹脂縮重合体粒子と前記塩化ビニルモノマーとの合計100重量%中、前記シリコーン樹脂縮重合体粒子の含有量が20重量%以上、95重量%以下であり、かつ前記塩化ビニルモノマーの含有量が5重量%以上、80重量%以下である材料を反応させることにより得られる、請求項3又は4に記載のシリコーン樹脂縮重合体粒子とポリ塩化ビニルとの反応物。
- 前記式(2)で表される第2の有機珪素化合物が、ビニルトリエトキシシラン又はビニルトリメトキシシランである、請求項1~7のいずれか1項に記載のシリコーン樹脂縮重合体粒子とポリ塩化ビニルとの反応物。
- 前記反応物が、前記シリコーン樹脂縮重合体粒子と前記塩化ビニルモノマーとを含む材料を反応させた後、溶剤を用いて洗浄することにより得られている、請求項1~8のいずれか1項に記載のシリコーン樹脂縮重合体粒子とポリ塩化ビニルとの反応物。
- 請求項9に記載のシリコーン樹脂縮重合体粒子とポリ塩化ビニルとの反応物の製造方法であって、
前記シリコーン樹脂縮重合体粒子と前記塩化ビニルモノマーとを含む材料を反応させた後、溶剤を用いて洗浄することに前記反応物を得る、シリコーン樹脂縮重合体粒子とポリ塩化ビニルとの反応物の製造方法。 - 請求項1~9のいずれか1項に記載のシリコーン樹脂縮重合体粒子とポリ塩化ビニルとの反応物と、塩化ビニル樹脂又は塩素化塩化ビニル樹脂とを含有する、塩化ビニル樹脂組成物。
- 前記シリコーン樹脂縮重合体粒子とポリ塩化ビニルとの反応物の含有量と、前記塩化ビニル樹脂及び前記塩素化塩化ビニル樹脂の合計の含有量とが重量比で、2.0:98.0~60.0:40.0である、請求項11に記載の塩化ビニル樹脂組成物。
- 前記シリコーン樹脂縮重合体粒子に由来する粒子の含有量が、1.6重量%以上、51重量%以下である、請求項11又は12に記載の塩化ビニル樹脂組成物。
- 前記塩素化塩化ビニル樹脂を含有し、
塩素含有率が56.5重量%以上、65.5重量%以下である、請求項11~13のいずれか1項に記載の塩化ビニル樹脂組成物。 - 請求項1~9のいずれか1項に記載のシリコーン樹脂縮重合体粒子とポリ塩化ビニルとの反応物を用いた塩化ビニル樹脂組成物の製造方法であって、
前記シリコーン樹脂縮重合体粒子と前記塩化ビニルモノマーとを含む材料を反応させることにより得られる前記反応物を用いて、
前記反応物と前記塩化ビニル樹脂又は前記塩素化塩化ビニル樹脂とを配合して、前記反応物と前記塩化ビニル樹脂又は前記塩素化塩化ビニル樹脂とを含有する塩化ビニル樹脂組成物を得る工程を備える、塩化ビニル樹脂組成物の製造方法。 - 前記反応物と前記塩素化塩化ビニル樹脂とを配合して、前記反応物と前記塩素化塩化ビニル樹脂とを含有し、かつ塩素含有率が56.5重量%以上、65.5重量%以下である塩化ビニル樹脂組成物を得る、請求項15に記載の塩化ビニル樹脂組成物の製造方法。
- 前記シリコーン樹脂縮重合体粒子と前記塩化ビニルモノマーとを含む材料を反応させて、前記反応物を得る工程をさらに備える、請求項15又は16に記載の塩化ビニル樹脂組成物の製造方法。
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US14/422,296 US9382368B2 (en) | 2012-08-17 | 2012-08-17 | Reactant of silicon resin polycondensate particles and polyvinyl chloride, method for manufacturing said reactant, vinyl chloride resin composition, and method for manufacturing vinyl chloride resin composition |
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EP12891353.0A EP2886568B1 (en) | 2012-08-17 | 2012-08-17 | Reactant of silicon resin polycondensate particles and polyvinyl chloride, method for manufacturing said reactant, vinyl chloride resin composition, and method for manufacturing vinyl chloride resin composition |
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