WO2015046259A1 - Résine de polypropylène modifié, mousse de résine, conteneur fabriqué à partir de résine moussante, et procédé de production de résine de polypropylène modifié - Google Patents

Résine de polypropylène modifié, mousse de résine, conteneur fabriqué à partir de résine moussante, et procédé de production de résine de polypropylène modifié Download PDF

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Publication number
WO2015046259A1
WO2015046259A1 PCT/JP2014/075307 JP2014075307W WO2015046259A1 WO 2015046259 A1 WO2015046259 A1 WO 2015046259A1 JP 2014075307 W JP2014075307 W JP 2014075307W WO 2015046259 A1 WO2015046259 A1 WO 2015046259A1
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Prior art keywords
polypropylene resin
resin
mass
parts
modified polypropylene
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PCT/JP2014/075307
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English (en)
Japanese (ja)
Inventor
洵史 山下
祥介 川守田
英司 福山
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積水化成品工業株式会社
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Priority to JP2015539269A priority Critical patent/JP6568798B2/ja
Publication of WO2015046259A1 publication Critical patent/WO2015046259A1/fr

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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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms

Definitions

  • the present invention relates to a modified polypropylene resin obtained by modifying a polypropylene resin, a method for producing a modified polypropylene resin by modifying a polypropylene resin to produce a modified polypropylene resin, and the modified polypropylene resin.
  • the present invention relates to a resin foam and a container made of foamed resin.
  • polypropylene resins have been used as raw materials for various molded articles because of their excellent mechanical properties and chemical resistance.
  • a molded product made of polypropylene resin is generally produced by extrusion molding, blow molding, foam molding, or the like. Since a polypropylene resin generally has crystallinity, the viscosity and melt tension at the time of melting are low. For this reason, a molded product made of polypropylene resin may not have a desired property even if the conditions are set with high accuracy at the time of production.
  • a resin foam sheet made of polypropylene resin is generally formed by extruding and foaming a polypropylene resin. During this extrusion foaming, bubbles are easily broken due to insufficient tension of the cell membrane, and a dense foam state is obtained. It may not be.
  • the resin foam sheet may be insufficient in strength or poor in appearance when a large number of coarse bubbles in which the bubble film is broken and a plurality of bubbles are connected exist.
  • the resin foam sheet is used as a raw material sheet for producing foamed resin containers such as food trays by thermoforming. However, if the resin foam sheet is not in a dense foamed state, it has excellent strength and appearance. There is a risk of making it difficult to form the container.
  • Patent Document 1 discloses that a modified polypropylene resin is obtained by modifying a crystalline polypropylene resin using an organic peroxide and a crosslinking aid.
  • a modified polypropylene resin of Patent Document 1 at least one of diacrylate and triacrylate is used as the crosslinking aid.
  • Patent Document 2 discloses that a polyolefin-based modified resin is prepared using an organic peroxide, a radical scavenger, and a (meth) acrylate monomer.
  • the modified resins disclosed in Patent Documents 1 and 2 are considered to exhibit a higher melt tension than the resin before the modification.
  • the modified resins disclosed in Patent Documents 1 and 2 do not exhibit sufficiently high melt tension. For this reason, it is difficult to make a resin foam sheet made of polypropylene resin into a dense foam state by extrusion foaming or the like.
  • it is not restricted to the case where it uses as a forming material of a resin foam sheet that a high melt tension is calculated
  • a resin composition containing a polypropylene resin, an organic peroxide, and an acrylic polyfunctional monomer is reacted to bond the acrylic polyfunctional monomer to the polypropylene resin.
  • a modified polypropylene resin which is contained in an amount of 0.2 parts by mass or less and the acrylic polyfunctional monomer is contained in an amount of 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polypropylene resin. To do.
  • the present invention is a resin foam formed from the above-mentioned modified polypropylene resin, has a density of 0.025 g / cm 3 or more and 0.5 g / cm 3 or less, and 30% or less.
  • the present invention relates to a modified polypropylene resin in which a resin composition containing a polypropylene resin, an organic peroxide, and an acrylic polyfunctional monomer is melt-kneaded and the acrylic polyfunctional monomer is bonded to the polypropylene resin.
  • the organic peroxide is contained in an amount of 0.0005 parts by mass or more and 0.2 parts by mass or less with respect to 100 parts by mass of the polypropylene resin, and the acrylic resin is produced.
  • a method for producing a modified polypropylene resin is provided.
  • a modified polypropylene resin having a high melt tension can be obtained, a dense foamed resin foam can be obtained, and a resin foam having a good appearance can be obtained.
  • the modified polypropylene resin according to the present embodiment is obtained by reacting a resin composition containing (A) a polypropylene resin, (B) an organic peroxide, and (C) an acrylic polyfunctional monomer, to form the acrylic polyfunctional resin.
  • a functional monomer is bonded to the polypropylene resin, and the acrylic polyfunctional monomer is bonded to the polypropylene resin by a radical generated by an organic peroxide.
  • the organic peroxide is contained in an amount of 0.0005 parts by mass or more and 0.2 parts by mass or less with respect to 100 parts by mass of the polypropylene resin, and A resin composition containing an acrylic polyfunctional monomer in an amount of 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polypropylene resin is melt-kneaded and has a melt tension (MS of 10 cN or more at 230 ° C.) )have.
  • “Modified polypropylene resin in which acrylic polyfunctional monomer is bonded to polypropylene resin” means only those in which acrylic polyfunctional monomer is bonded to all polypropylene resins. is not.
  • modified polypropylene resin in which an acrylic polyfunctional monomer is bonded to a polypropylene resin means that the acrylic polyfunctional monomer is only bonded to the polypropylene resin. Absent. That is, the case where there is an acrylic polyfunctional monomer that is not bonded to the polypropylene resin or a homopolymer formed by the monomer is also within the intended range of the modified polypropylene resin of the present invention.
  • the modified polypropylene resin according to this embodiment has a high melt tension (MS), it is suitable for forming a resin foam having a good appearance and excellent strength. Even if the modified polypropylene resin according to the present embodiment is foamed at a high foaming ratio, it is difficult to cause foam breakage inside, and a resin foam having a good appearance can be obtained. Moreover, the modified polypropylene resin according to the present embodiment has an advantage that a resin foam sheet having a dense foamed state can be easily obtained when the foam is extruded and foamed into a sheet shape.
  • the modified polypropylene resin according to the present embodiment is better as the melt tension (MS) is higher in that it is less likely to cause foam breakage when foamed.
  • the modified polypropylene resin is preferably melt tension at 230 °C (MS 230) is greater than or equal to 11 cN, and more preferably the melt tension (MS 230) is greater than or equal to 15 cN.
  • the modified polypropylene resin preferably has a melt tension (MS 250 ) at 250 ° C. of 10 cN or more.
  • melt tension (MS) becomes a low value, so that measurement temperature is high normally, when melt tension (MS250) in 250 degreeC is 10 cN or more, melt tension (MS230) in 230 degreeC is also 10 cN or more. It can be judged that.
  • the melt tension (MS 230 ) at 230 ° C. of the modified polypropylene resin according to this embodiment is usually 30 cN or less.
  • the resin composition used for obtaining the modified polypropylene resin according to this embodiment preferably contains “(D) radical scavenger”, and “(E) other than components (A) to (D)”. Ingredients "may be included.
  • a polypropylene resin is a polymer obtained by polymerizing a propylene monomer.
  • one or more of a homopolymer of propylene monomer and a copolymer of polymerization components mainly composed of propylene monomer can be contained in the resin composition as (A) polypropylene resin.
  • the content of propylene monomer is preferably 50% by mass or more, and the content of propylene monomer is more preferably 80% by mass or more.
  • the content of is particularly preferably 90% by mass or more.
  • the copolymerization may be random copolymerization or block copolymerization.
  • the component other than the propylene monomer is preferably one or more of an ethylene monomer and an ⁇ -olefin monomer having 4 to 8 carbon atoms.
  • polypropylene resins include propylene homopolymers, propylene random polymers, and propylene block polymers.
  • the polypropylene resin is preferably a homopolymer of a propylene monomer, and is preferably a propylene homopolymer.
  • the polypropylene resin preferably has a melt mass flow rate (MFR) of 0.2 g / 10 min or more.
  • MFR melt mass flow rate
  • the melt mass flow rate (MFR) of the (A) polypropylene resin is more preferably 0.3 g / 10 min or more, and particularly preferably 0.5 g / 10 min or more.
  • the melt mass flow rate (MFR) is preferably 15 g / 10 minutes or less, more preferably 10 g / 10 minutes or less, and particularly preferably 5 g / 10 minutes or less.
  • said MFR of (A) polypropylene-type resin is measured on the conditions of the test temperature of 230 degreeC, and the load of 21.18N based on B method of JISK7210: 1999.
  • (B) Organic peroxide An organic peroxide having a one-minute half-life temperature of 150 ° C. or higher and 280 ° C. or lower is used.
  • the one minute half-life temperature of the organic peroxide is preferably 160 ° C. or higher, and more preferably over 170 ° C.
  • the 1 minute half-life temperature of the organic peroxide is preferably 270 ° C. or lower, and more preferably 260 ° C. or lower.
  • As for an organic peroxide only 1 type may be used and 2 or more types may be used together.
  • the 1-minute half-life temperature of the organic peroxide can be confirmed by the following method described in “NOF Corporation Organic Peroxide (10th edition)”.
  • the thermal decomposition is carried out at several temperatures, the half-life (t 1/2 ) at each temperature is measured, and the relationship between ln (t 1/2 ) and (1 / T) is plotted Then, the temperature at which the half-life is 1 minute can be obtained from the obtained straight line.
  • organic peroxide of this embodiment is not specifically limited, For example, a hydroperoxide compound, a dialkyl peroxide compound, a peroxyketal compound, an alkyl perester compound, a percarbonate compound, a ketone peroxide compound And diacyl peroxide compounds.
  • hydroperoxide compound examples include 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide.
  • dialkyl peroxide compound examples include dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane, 1,3-bis (t-butylperoxyisopropyl)- Benzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3, and tris (t-butylperoxy) triazine Etc.
  • Examples of the peroxyketal compound include 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-t-butylperoxycyclohexane, 2,2-di ( t-butylperoxy) -butane, 4,4-di-t-butylperoxyvaleric acid-n-butyl ester, and 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane Etc.
  • Examples of the alkyl perester compound include t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate, and the like.
  • Examples of the percarbonate compound include t-butyl peroxyisopropyl carbonate.
  • the organic peroxide (B) in the present embodiment is preferably a dialkyl peroxide compound, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane, or More preferably, it is any of 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3.
  • the content of the (B) organic peroxide with respect to 100 parts by mass of the (A) polypropylene resin is 0.0005 parts by mass or more and 0.2 parts by mass or less.
  • the modified polypropylene resin of this embodiment if the content of (B) organic peroxide is too small, the reactivity of the resin composition becomes low, so that high melt tension may not be exhibited.
  • the modified polypropylene resin of this embodiment if the content of the organic peroxide (B) is excessive, a decomposition reaction of the polypropylene resin is likely to occur at the time of melt kneading, so that high melt tension may not be exhibited. .
  • the resin composition does not control the reaction conditions during melt-kneading with high accuracy.
  • a modified polypropylene resin having excellent melt tension can be produced.
  • the content of (B) the organic peroxide to (A) 100 parts by mass of the polypropylene resin is: The amount is preferably 0.005 parts by mass or more, and more preferably 0.1 parts by mass or less.
  • the (C) acrylic polyfunctional monomer is a component that chemically bonds to the (A) polypropylene resin to form a branched structure and act as a crosslinking agent.
  • the (C) acrylic polyfunctional monomer contained in the resin composition of the present embodiment may be one type or two or more types.
  • the (C) acrylic polyfunctional monomer of this embodiment is preferably a monomer having a plurality of (meth) acryloyl groups, and is preferably a monomer having a plurality of acryloyl groups.
  • the term “(meth) acryloyl group” refers to an acryloyl group or a methacryloyl group.
  • the acrylic polyfunctional monomer may be a bifunctional or higher acrylic monomer, may be a bifunctional acrylic monomer, may be a trifunctional acrylic monomer, or may be a tetrafunctional acrylic. It may be a system monomer.
  • bifunctional acrylic monomer examples include alkanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include neopentyl glycol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, ethylene glycol adduct di (meth) acrylate of bisphenol A, and propylene glycol adduct di (meth) acrylate of bisphenol A. .
  • trifunctional acrylic monomer examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane ethylene oxide-added tri (meth) acrylate, glycerin propylene oxide-added tri (meth) acrylate, and Examples include tri (meth) acryloyloxyethyl phosphate.
  • tetrafunctional acrylic monomer examples include pentaerythritol tetra (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate.
  • the (C) acrylic polyfunctional monomer may be a bifunctional acrylic monomer.
  • Alkanediol di (meth) acrylate is more preferable, and alkanediol diacrylate is particularly preferable.
  • Content of (C) acrylic polyfunctional monomer in the said resin composition is 0.5 mass part or more and 20 mass parts or less with respect to 100 mass parts of (A) polypropylene resin. If the content of the (C) acrylic polyfunctional monomer is too small, the modified polypropylene-based resin may not exhibit sufficient melt tension without sufficiently forming a branched or crosslinked structure in melt-kneading. If the content of the (C) acrylic polyfunctional monomer is excessive, the modified polypropylene resin tends to become unreacted in part of the (C) acrylic polyfunctional monomer during melt kneading. There is a risk of having.
  • the resin composition does not control the reaction conditions during melt-kneading with high accuracy.
  • a modified polypropylene resin having excellent melt tension can be produced.
  • the content of the (C) acrylic polyfunctional monomer with respect to 100 parts by mass of the (A) polypropylene resin is preferably 0.8 parts by mass or more, and preferably 9 parts by mass or less.
  • the resin composition has a content of (C) acrylic polyfunctional monomer exceeding 1.5 parts by mass with respect to 100 parts by mass of (A) polypropylene resin. Particularly preferred is 1.6 parts by mass or more.
  • the mass ratio between the content of (C) the acrylic polyfunctional monomer and the content of (B) the organic peroxide is not particularly limited, but the mass ratio ((C) Low content of acrylic polyfunctional monomer / (B) content of organic peroxide) means that during reaction by melt kneading, (B) the polypropylene resin is attacked by radicals generated by organic peroxide. This means that the abundance of the acrylic polyfunctional monomer is small relative to the number formed.
  • the high mass ratio ((C) / (B)) means that a large amount of an acrylic polyfunctional monomer is present with respect to the number of attacks of the polypropylene resin by radicals.
  • the resin composition has a specific mass ratio ((C) / (B)) in order to make it easy to produce a modified polypropylene resin having a high melt tension and hardly causing odor problems. It is preferable to be within the range. That is, the mass ratio ((C) / (B)) is preferably 50 or more, more preferably 100 or more. Further, the mass ratio ((C) / (B)) is preferably 1000 or less, more preferably 200 or less, and particularly preferably 150 or less.
  • the resin composition preferably includes (D) a radical scavenger.
  • D) Use of the radical scavenger is effective for increasing the melt tension of the modified polypropylene resin. That is, the D) radical scavenger is effective in obtaining a resin foam having a good appearance using a modified polypropylene resin.
  • the radical scavenger is capable of reacting with alkyl radical species.
  • the radical scavenger can be bonded to the acrylic monomer after being bonded to the alkyl radical.
  • a radical scavenger only 1 type may be used and 2 or more types may be used together.
  • radical scavenger examples include quinone compounds (quinones), naphthoquinone compounds (naphthoquinones), phenothiazine compounds (phenothiazines), and the like.
  • Examples of the quinone compound include p-benzoquinone, p-naphthoquinone, 2-t-butyl-p-benzoquinone, and 2,5-diphenyl-p-benzoquinone.
  • Examples of the naphthoquinone compound include 1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, vitamin K, and the like.
  • Examples of the phenothiazine compound include phenothiazine, bis- ( ⁇ -methylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, and bis- ( ⁇ -dimethylbenzyl) phenothiazine.
  • the content of the (D) radical scavenger with respect to 100 parts by mass of (A) polypropylene resin is preferably 0.005 parts by mass or more, more preferably 0.05 parts by mass or more. Further, the content of the (D) radical scavenger with respect to 100 parts by mass of (A) polypropylene resin is preferably 1 part by mass or less.
  • the content of the radical scavenger is not less than the lower limit and not more than the upper limit, the melt tension of the modified polypropylene resin is effectively increased, and the appearance of the foam is further improved.
  • (E) other components to be contained in the resin composition include (E1) acrylic monofunctional monomers and various (E2) additives.
  • the resin composition preferably includes (E) an acrylic monofunctional monomer.
  • the modified polypropylene resin is more suitable for the formation of a resin foam having a good appearance, because the melt tension excellent in the use of the (E) acrylic monofunctional monomer is easily exhibited.
  • Acrylic monofunctional monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2 ethylhexyl (meth) acrylate, isoamyl (meth) acrylate, lauryl (meth) acrylate, stearyl ( And (meth) acrylate, isostearyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate and the like.
  • the content of the (E) acrylic monofunctional monomer with respect to 100 parts by mass of the (A) polypropylene resin is preferably 1 part by mass or more, more preferably 3 parts by mass or more. Moreover, it is preferable that content of (E) acrylic monofunctional monomer is 15 mass parts or less with respect to 100 mass parts of (A) polypropylene resin.
  • the (E2) additive may be contained in the resin composition before being melt kneaded or at the time of melt kneading. Further, the (E2) additive may be added after melt-kneading and contained in the modified polypropylene resin. (E2) As for an additive, only 1 type may be used and 2 or more types may be used together.
  • the additive is appropriately used according to various purposes and is not particularly limited.
  • Specific examples of additives include a weather resistance stabilizer, an antistatic agent, an antioxidant, a light stabilizer, a crystal nucleating agent, a pigment, a lubricant, a slippery property or an antiblocking property.
  • Surfactants, inorganic fillers, and dispersibility improvers that improve the dispersibility of inorganic fillers. Examples of the dispersibility improver include higher fatty acids, higher fatty acid esters, and higher fatty acid amides.
  • Method for producing modified polypropylene resin In the method for producing a modified polypropylene resin, (A) 100 parts by mass of a polypropylene resin, (B) 0.0005 parts by mass or more and 0.2 parts by mass or less of an organic peroxide, and (C) an acrylic polyfunctional monomer. A resin composition containing 0.5 parts by mass or more and 20 parts by mass or less is melt-kneaded to obtain a modified polypropylene resin. At the time of melt kneading the resin composition, the resin composition is heated to bring the resin composition into a molten state. The resin composition reacts by heating during melt kneading.
  • the organic peroxide generates a radical by the heating, and the radical attacks the hydrogen bonded to the tertiary carbon of the polypropylene resin to form an alkoxy radical.
  • ⁇ -cleavage occurs and molecular cleavage of the polypropylene resin occurs, but in this embodiment, an acrylic polyfunctional monomer is bonded to the site to form a branched structure (crosslinked structure).
  • the acrylic polyfunctional monomer was obtained after mixing the (A) polypropylene resin and the (B) organic peroxide from the viewpoint of making the addition effect remarkable. It is preferable to add to the mixture. However, (A) polypropylene resin, (B) organic peroxide, and (C) acrylic polyfunctional monomer may be mixed together.
  • the (D) radical scavenger may be added before the (C) acrylic polyfunctional monomer is added, or may be added after the (C) acrylic polyfunctional monomer is added, and together with other components. May be mixed.
  • the acrylic monofunctional monomer may be added before adding (C) the acrylic polyfunctional monomer, or may be added after adding (C) the acrylic polyfunctional monomer, and other components. And may be mixed together.
  • the half-life temperature of 1 minute of the organic peroxide is T1 (° C.)
  • T1 half-life temperature of 1 minute of the organic peroxide
  • the resin composition is melt-kneaded at a temperature of (T1 + 15) ° C. or lower, the polypropylene resin is effectively modified because decomposition of the polypropylene resin is difficult to proceed.
  • the temperature at the time of melt-kneading the resin composition is T1 (° C.) or less. It is preferable.
  • the temperature at the time of melt-kneading is preferably (T1-15) ° C. or higher, particularly preferably (T1-15) ° C. or higher and (T1 + 15) ° C. or lower.
  • the temperature at which the resin composition is melt-kneaded is set so that the melting point of the polypropylene resin is Tm ( (Tm + 15) ° C. or higher, and preferably 270 ° C. or lower.
  • the temperature is preferably 180 ° C. or higher.
  • melt kneading of the resin composition can be carried out using general equipment such as a kneader, a Banbury mixer, an extruder.
  • the temperature of the resin composition at the time of melt-kneading can usually be grasped by a temperature measuring device attached to these devices.
  • a temperature measuring device attached to these devices.
  • the cylinder is usually divided into 4 to 8 zones so that the temperature can be individually set, and the set temperature and measured temperature of each zone can be grasped on the operation panel. . Therefore, the temperature of the resin composition in the melt-kneading can be generally grasped from the actually measured value of the cylinder temperature shown on the operation panel.
  • the temperature of the resin composition may be higher than the temperature measurement point at a location other than the temperature measurement point due to shear heat generation. That is, in melt kneading by an extruder, the actual temperature of the resin composition may be higher than the actual measurement value shown on the operation panel.
  • the error between the actual temperature of the resin composition and the actually measured value is usually about 10 ° C. at most. Therefore, for example, if it is necessary to adjust the temperature of the resin composition at the time of melt-kneading to Tx ° C. or lower, the temperature of the actual resin composition is set to Tx ° C. by setting the temperature of the device to (Tx ⁇ 10) ° C. or lower. Can be prevented.
  • melt-kneading the resin composition it is preferable to use an extruder. It is preferable to supply the resin composition to an extruder and cause a crosslinking reaction in the extruder to extrude the modified polypropylene resin from the extruder while forming the modified polypropylene resin.
  • a modified polypropylene resin is efficiently obtained by continuously supplying the resin composition to an extruder and continuously extruding the modified polypropylene resin from the extruder.
  • the extruder examples include a single screw extruder and a twin screw extruder.
  • the said extruder can be used for manufacture of a modified polypropylene resin as a single or a tandem-type extruder connected in plural.
  • a twin screw extruder is preferable from the viewpoint of further increasing dispersibility and reactivity of other components with respect to the polypropylene resin as the base resin.
  • the modified polypropylene resin according to this embodiment can be suitably used to obtain a resin foam.
  • a resin foam having a good appearance can be obtained.
  • the resin foam is preferably a resin foam sheet formed by extrusion foaming into a sheet shape, or a product obtained by thermoforming the resin foam sheet. Examples of the thermoforming include vacuum forming, pressure forming, vacuum / pressure forming, match mold forming, and press forming.
  • a container is preferable.
  • the foamed resin container thus produced is preferably used as various packaging containers because it is not only lightweight and high in strength, but also easily mass-produced.
  • the foamed resin container is preferably used for food packaging because it is excellent in heat insulation and the like.
  • the surface of the resin foam of the present embodiment may be laminated with a non-woven fabric, metal foil, decorative paper, printing film, etc. depending on the application within the range that does not interfere with the object of the invention.
  • the resin foam is obtained by foaming the modified polypropylene resin, for example, by foaming the modified polypropylene resin using a foaming agent.
  • the foaming agent is not particularly limited.
  • the foaming agent may be a chemical foaming agent or a physical foaming agent.
  • the foaming agent is preferably a readily volatile foaming agent.
  • the boiling point of the foaming agent is preferably equal to or lower than the softening temperature of the modified polypropylene resin.
  • the blowing agent include hydrocarbons such as propane, n-butane, i-butane, n-pentane, i-pentane, and cyclopentane, halides thereof, carbon dioxide gas, and nitrogen.
  • the said foaming agent only 1 type may be used and 2 or more types may be used together.
  • the density of the resin foam is preferably 0.025 g / cm 3 or more, more preferably 0.09 g / cm 3 or more.
  • the density of the resin foam is preferably 0.5 g / cm 3 or less, more preferably 0.25 g / cm 3 or less.
  • the density of the resin foam is not less than the lower limit, the rigidity and heat resistance of the resin foam are increased.
  • the density is not more than the upper limit, the heat insulating property of the resin foam is increased.
  • the density of the resin foam is lowered by foaming at a high foaming ratio, the appearance of the resin foam tends to deteriorate.
  • the modified polypropylene resin according to the present invention a resin foam having a good appearance can be obtained even if the density of the resin foam is lowered by foaming at a high foaming ratio.
  • the density of the resin foam is measured by the method described in JIS K7222: 1999 “Measurement of foamed plastic and rubber-apparent density”, and specifically by the following method.
  • Apparent density (g / cm 3 ) mass of foam (g) / volume of foam (cm 3 )
  • “DIGIMATIC” CD-15 type manufactured by Mitutoyo Corporation can be used.
  • the open cell ratio of the resin foam is preferably 30% or less, more preferably 20% or less.
  • the open cell ratio means the proportion of open cells in the cell structure of the resin foam.
  • a bubble in which a cell (unit of bubble structure) is continuous with an adjacent cell is referred to as an open cell, and a bubble in which each cell is completely independent is referred to as a closed cell.
  • the open cell ratio of the resin foam is measured by the following method. That is, a plurality of sheet-like samples having a length of 25 mm and a width of 25 mm are cut out from the resin foam, and the cut samples are overlapped so that there is no gap to obtain a measurement sample having a thickness of 25 mm. Is measured to 1/100 mm using “Digimatic Caliper” manufactured by Mitutoyo Corporation, and the apparent volume (cm 3 ) is obtained. Next, the volume (cm 3 ) of the sample for measurement is obtained by the 1-1 / 2-1 atmospheric pressure method using an air comparison type hydrometer 1000 type (manufactured by Tokyo Science).
  • the open cell ratio (%) is calculated from these obtained values and the following formula, and the average value of 5 tests is obtained.
  • the measurement is carried out in a JIS K7100-1999 symbol 23/50, second grade environment after conditioning for 16 hours in a JIS K7100-1999 symbol 23/50, second grade environment.
  • the air-comparing hydrometer corrects with a standard sphere (large 28.9 cc, small 8.5 cc).
  • Open cell ratio (%) 100 x (apparent volume-volume measured with an air comparison hydrometer) / apparent volume
  • NFR 5-Dimethyl-2,5-di (t-butylperoxy) -hexyne-3
  • NOF Corporation“ Perhexine 25B ” 1 minute half-
  • the resin composition was melt-kneaded in a twin-screw extruder under conditions of a resin temperature of 200 ° C. and a rotation speed of 85 rpm, and the resin composition was reacted to form a modified polypropylene resin.
  • This melt-kneading was carried out by a twin-screw extruder whose temperature was set so that the temperature became higher as the cylinder went downstream.
  • the resin temperature is a value measured by a thermocouple disposed at the center portion in the radial direction of the breaker plate interposed between the extruder and a die attached to the tip of the extruder.
  • an organic peroxide having a 1-minute half-life temperature of 194 ° C. is used, so that the temperature of the resin composition does not become 15 ° C. higher than the 1-minute half-life temperature due to shearing heat generation.
  • the resin temperature was set to 200 ° C., and the resin composition was melt-kneaded.
  • the modified polypropylene resin was extruded in a strand form at a discharge rate of 5 kg / h from a die having a diameter of 4 mm, a land of 5 mm, and a number of holes of 2 attached to the tip of the extruder.
  • the extruded strand-shaped modified polypropylene resin was cooled by passing through a cooling water tank having a length of 2 m containing 30 ° C. water.
  • the cooled strand-shaped modified polypropylene resin was cut with a pelletizer to obtain pellets.
  • melt kneading was further performed.
  • the kneaded material melt-kneaded by the first extruder is transferred to a second extruder having a diameter of 65 mm, and the temperature of the melt-kneaded material is transferred from the first extruder while continuing the melt kneading by the second extruder.
  • the temperature was lower than the temperature at the time of extrusion, and extrusion foaming was performed from a cylindrical die having a diameter of 60 mm at a discharge rate of 30 kg / hour to obtain a cylindrical foam.
  • the obtained cylindrical foam is cooled by blowing air with an air ring larger than its diameter on a mandrel having a diameter of 170 which is cooled with water of about 20 ° C. An incision was made at one point on the circumference with a cutter to obtain a long belt-shaped resin foam sheet.
  • Example 2 A modified polypropylene resin pellet and a resin foam were obtained in the same manner as in Example 1 except that the resin temperature was changed from 200 ° C to 185 ° C.
  • a modified polypropylene resin pellet and a resin foam were obtained in the same manner as in Example 1 except that 0.015 parts by mass of p-benzoquinone (manufactured by Wako Pure Chemical Industries, Ltd.) was further supplied.
  • Example 4 A modified polypropylene resin pellet and a resin foam were obtained in the same manner as in Example 1 except that the amount of 1,6-hexanediol diacrylate was changed from 3 parts by mass to 1.6 parts by mass.
  • Example 5 A modified polypropylene resin pellet and a resin foam were obtained in the same manner as in Example 1 except that the amount of 1,6-hexanediol diacrylate was changed from 3 parts by mass to 1.5 parts by mass.
  • Example 7 The organic peroxide was converted from 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3 (“NO-HAKU“ PERHEXIN 25B ”, 1 minute half-life temperature T1: 194 ° C.) to 2 , 5-dimethyl-2,5-di (t-butylperoxy) -hexane (“Perhexa 25B” manufactured by NOF Corporation, 1 minute half-life temperature T1: 180 ° C.), and the resin temperature is 200 ° C.
  • the pellets of the modified polypropylene resin and the resin foam were obtained in the same manner as in Example 1 except that the temperature was changed from 180 to 180 ° C.
  • Example 8 The amount of 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3 was changed from 0.03 parts by weight to 0.1 parts by weight, and 1,6-hexanediol diacrylate 3 parts by mass (“A-HD-N” manufactured by Shin-Nakamura Chemical Co., Ltd.) was changed to 5 parts by mass of trimethylolpropane triacrylate (“A-TMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.), polypropylene resin ( E111G) 100 parts by mass and 0.1 parts by mass of organic peroxide (Perhexine 25B) were stirred and mixed in a ribbon blender, except that 0.05 parts by mass of p-benzoquinone as a radical scavenger was supplied. In the same manner as in Example 1, pellets of a modified polypropylene resin and a resin foam were obtained.
  • Example 9 Except that the amount of 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3 was changed from 0.03 parts by mass to 0.005 parts by mass, the same as Example 1 was performed. Then, pellets of a modified polypropylene resin and a resin foam were obtained.
  • Example 10 A modified polypropylene resin pellet and a resin foam were obtained in the same manner as in Example 9 except that the polypropylene resin was changed from E111G to E200GP and the resin temperature was changed from 200 ° C to 195 ° C. .
  • Example 11 Example except that the polypropylene resin was changed from E111G to E200GP, the organic peroxide was changed from perhexine 25B to perhexa 25B, and the resin temperature in the extruder was changed from 200 ° C. to 180 ° C. In the same manner as in Example 9, pellets of a modified polypropylene resin and a resin foam were obtained.
  • the pellets and foams of the modified polypropylene resin were obtained in the same manner as in Example 9 except that the temperature was changed to 195 ° C.
  • Example 9 except that the polypropylene resin was changed from E111G to J105G, the organic peroxide was changed from perhexine 25B to perhexa 25B, and the resin temperature was changed from 200 ° C. to 180 ° C. Thus, pellets of a modified polypropylene resin and a resin foam were obtained.
  • Example 14 Other than changing the blending amount of A-HD-N from 3 parts by weight to 2.1 parts by weight, further using 0.9 parts by weight of A-TMPT, and changing the resin temperature from 200 ° C. to 195 ° C. In the same manner as in Example 9, pellets of a modified polypropylene resin and a resin foam were obtained.
  • Example 15 Other than changing the blending amount of A-HD-N from 3 parts by weight to 1.5 parts by weight, further using 1.5 parts by weight of A-TMPT, and changing the resin temperature from 200 ° C. to 195 ° C. In the same manner as in Example 9, pellets of a modified polypropylene resin and a resin foam were obtained.
  • Example 16 Other than changing the blending amount of A-HD-N from 3 parts by weight to 0.9 parts by weight, further using A-TMPT 2.1 parts by weight, and changing the resin temperature from 200 ° C. to 195 ° C. In the same manner as in Example 9, pellets of a modified polypropylene resin and a resin foam were obtained.
  • Example 17 The polypropylene resin was changed from E111G to E200GP, and 1,6-hexanediol diacrylate (“A-HD-N” manufactured by Shin-Nakamura Chemical Co., Ltd.) from the middle of the twin screw extruder using a liquid injection pump In the same manner as in Example 9, except that 3 parts by mass of isostearyl acrylate (“ISTA” manufactured by Osaka Organic Chemical Industry Co., Ltd.), which is an acrylic monofunctional monomer, was supplied together when 3 parts by mass was supplied. Of high quality polypropylene resin and foam.
  • ISA isostearyl acrylate
  • Example 18 The polypropylene resin was changed from E111G to E200GP, and 1,6-hexanediol diacrylate (“A-HD-N” manufactured by Shin-Nakamura Chemical Co., Ltd.) from the middle of the twin screw extruder using a liquid injection pump In the same manner as in Example 9, except that 10 parts by mass of isostearyl acrylate (“ISTA” manufactured by Osaka Organic Chemical Industry Co., Ltd.), which is an acrylic monofunctional monomer, was supplied together when 3 parts by mass was supplied. Quality polypropylene resin pellets and resin foam were obtained.
  • ISA isostearyl acrylate
  • Example 2 Comparative Example 2 Except that the blending amount of 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3 was changed from 0.03 parts by mass to 0.3 parts by mass, the same as Example 1 was performed. As a result, pellets of the modified polypropylene resin were obtained. Using the resulting modified polypropylene resin pellets, an attempt was made to produce a resin foam in the same manner as in Example 1. However, when the modified polypropylene resin of Comparative Example 2 was used, a resin foam could not be obtained.
  • Example 3 A modified polypropylene resin was obtained in the same manner as in Example 1 except that 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3 was not used. Using the resulting modified polypropylene resin pellets, a resin foam was obtained in the same manner as in Example 1.
  • the initial speed at the beginning of winding is 3.94388 mm / s
  • the acceleration is 12 mm / s 2
  • the winding speed is gradually increased
  • the winding speed when the tension observed by the tension detection pulley is suddenly reduced is the breaking speed. It was.
  • the maximum tension until this breaking speed was observed was measured as melt tension.
  • Density of resin foam The density of the obtained resin foam was measured. In general, it is preferable that the density of the resin foam is “A”.
  • Open cell ratio of foam The open cell ratio of the obtained foam was measured.
  • the resin foam preferably has an open cell ratio of “A”.
  • Example 3 The appearance of the foam of Example 3 was the same as that of Examples 1 to 2, 4, and 6 to 16, although it had a high expansion ratio. From this, it can be seen that according to the present invention, a modified polypropylene-based resin advantageous in obtaining a resin foam having extremely high melt tension and good appearance can be obtained.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

Le but de la présente invention est de fournir une résine de polypropylène modifié qui présente une très grande tension à l'état fondu et permet la production d'une mousse ayant un excellent aspect. L'invention concerne une résine de polypropylène modifié dans laquelle un monomère polyfonctionnel acrylique est lié à une résine de polypropylène.
PCT/JP2014/075307 2013-09-27 2014-09-24 Résine de polypropylène modifié, mousse de résine, conteneur fabriqué à partir de résine moussante, et procédé de production de résine de polypropylène modifié WO2015046259A1 (fr)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2020194172A1 (fr) * 2019-03-26 2020-10-01 積水化成品工業株式会社 Feuille expansée de résine d'acide polylactique, article moulé en résine et procédé de production de feuille expansée de résine d'acide polylactique

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JP2002137305A (ja) * 2000-10-31 2002-05-14 Grand Polymer Co Ltd 自動車用成形天井材およびその製造方法
JP2006316241A (ja) * 2004-10-18 2006-11-24 Sekisui Chem Co Ltd ポリオレフィン系樹脂組成物及びポリオレフィン系樹脂発泡体の製造方法
JP2008222811A (ja) * 2007-03-12 2008-09-25 Japan Polypropylene Corp 改質ポリプロピレン系樹脂の製造法
WO2012049690A1 (fr) * 2010-10-14 2012-04-19 Reliance Industries Ltd. Procédé de préparation de polymères de propylène à forte résistance à l'état fondu

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CN101376683B (zh) * 2008-10-07 2011-09-21 中国科学院长春应用化学研究所 一种高熔体强度聚丙烯的制备方法
JP5368148B2 (ja) * 2009-04-07 2013-12-18 株式会社カネカ 射出発泡成形用ポリプロピレン系樹脂組成物及び該樹脂組成物からなる射出発泡成形体

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JP2002137305A (ja) * 2000-10-31 2002-05-14 Grand Polymer Co Ltd 自動車用成形天井材およびその製造方法
JP2006316241A (ja) * 2004-10-18 2006-11-24 Sekisui Chem Co Ltd ポリオレフィン系樹脂組成物及びポリオレフィン系樹脂発泡体の製造方法
JP2008222811A (ja) * 2007-03-12 2008-09-25 Japan Polypropylene Corp 改質ポリプロピレン系樹脂の製造法
WO2012049690A1 (fr) * 2010-10-14 2012-04-19 Reliance Industries Ltd. Procédé de préparation de polymères de propylène à forte résistance à l'état fondu

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020194172A1 (fr) * 2019-03-26 2020-10-01 積水化成品工業株式会社 Feuille expansée de résine d'acide polylactique, article moulé en résine et procédé de production de feuille expansée de résine d'acide polylactique
JP2020158608A (ja) * 2019-03-26 2020-10-01 積水化成品工業株式会社 ポリ乳酸樹脂発泡シート、樹脂成形品、および、ポリ乳酸樹脂発泡シートの製造方法
JP7246223B2 (ja) 2019-03-26 2023-03-27 積水化成品工業株式会社 ポリ乳酸樹脂発泡シート、樹脂成形品、および、ポリ乳酸樹脂発泡シートの製造方法

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