CN110003582A - Heat resistance styrene resin composite, molded product, extrusion sheet and food packaging container - Google Patents
Heat resistance styrene resin composite, molded product, extrusion sheet and food packaging container Download PDFInfo
- Publication number
- CN110003582A CN110003582A CN201811540540.3A CN201811540540A CN110003582A CN 110003582 A CN110003582 A CN 110003582A CN 201811540540 A CN201811540540 A CN 201811540540A CN 110003582 A CN110003582 A CN 110003582A
- Authority
- CN
- China
- Prior art keywords
- heat resistance
- copolymer
- mass
- resin
- resin composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/08—Copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2471/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Wrappers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention provides the heat resistance styrene resin composite of the balancing good of heat resistance and intensity, mouldability, and the molded product, non-foamed sheet material and foam sheet especially suitable for micro-wave oven food containers formed using the heat resistance styrene resin composite.The heat resistance styrene resin composite contains styrene-(methyl) acrylic copolymer (A), Polyphony Ether resin (B) and MBS resin (C), and the nuclear phase of MBS resin (C) is butadiene-based rubber, shell phase is using methyl methacrylate monomer and styrenic monomers as the copolymer of principal component.
Description
Technical field
The present invention relates to the heat resistance styrene resin composites of the balancing good of heat resistance and intensity, mouldability；Make
Molded product, non-foamed sheet material and the foam sheet formed with the heat resistance styrene resin composite.
Background technique
Styrene-(methyl) acrylic acid series copolymer excellent heat resistance compared with general polystyrene, thus it is extensive
For the packaging materials such as food containers, the foamed board of the heat-insulating material purposes of house, LCD TV light diffusing sheet etc. raw material.
In packaging material field, styrene-(methyl) acrylic acid series copolymer is mostly used for the food packaging for heating such as micro-wave ovens
Container, but in recent years, convenience store etc. is to shorten heating time to improve business efficiency, and HIGH-POWERED MICROWAVES furnace is popularized, thus is wanted
It asks than previous higher heat resistance.In addition, in order to save resource, also in the lightness for seeking molded product, in addition, from content
From the viewpoint of the increased container enlargement of object, design, the resin that the mechanical strengths such as brittleness, mouldability are improved is by the phase
To.
Styrene-(methyl) acrylic acid series copolymer has the shortcomings that more crisp compared with general polystyrene, therefore mentions
Method of the rubber mass ingredient as reinforcing material is gone out to add in styrene-(methyl) acrylic acid series copolymer.Such as patent
Document 1 discloses addition impact resistance polystyrene (HIPS), methyl methacrylate-butadiene-styrene copolymer resins
(MBS) foam sheet made of rubber mass ingredient, patent document 2 are disclosed by styrene-t copolymer resins and benzene
The phenylethylene resin series foam sheet that ethylene-butylene copolymer resins are constituted.
In addition, patent document 3 discloses polyphenylene oxide and aromatic series and alkenyl-as the method for taking into account heat resistance and toughness
The copolymer resins of acrylic monomer and the blending resin of polystyrene, patent document 4 pass through the benzene that will have specific composition
Ethylene-methacrylic acid copolymer merges the specific weight average molecular weight of setting with polyphenylene oxide group to attempt to improve heat resistance, intensity
And mouldability.
[existing technical literature]
[patent document]
Patent document 1: Japanese Unexamined Patent Publication 2-58548 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2000-136257 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2012-140549 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2014-205761 bulletin
Summary of the invention
[subject to be solved by the invention]
However, the prior art that above-mentioned document is recorded is still to be improved in the following aspects.
The first, in the technology of Patent Documents 1 to 2, in order to improve the mechanical strengths such as brittleness, need to add more rubber mass at
Point, thus there are problems that heat resistance reduction.In addition, being difficult to maintain to bear significantly to become in the post forming of extrusion sheet
The melting tension of shape, so the molding such as to crack, ooze out bad for molded product.
The second, in the technology of patent document 3~4, although heat resistance and mouldability are improved compared with prior art, brittleness
Improvement and insufficient, especially for deep drawn container, complicated shape container, in Product transport or and lid, particularly for foodstuff containers
Material may crack when chimeric, it is therefore desirable to further improve.
Present invention is made in view of the above circumstances, and the purpose is to realize that above-mentioned heat resistance and intensity, the balance of mouldability are excellent
Different project.
The inventors of the present invention have made intensive studies in view of the above problems, as a result, it has been found that passing through combination styrene-(methyl) third
The MBS resin of olefin(e) acid copolymer, polyphenylene oxide and specific structure can be obtained with the heat resistance that cannot achieve in the prior art, by force
It spends, the heat resistance styrene resin composite of the balance of mouldability, and by using the heat resistance phenylethylene resin series group
Object is closed, the non-foamed sheet material and foam sheet of the balancing good of heat resistance, intensity, mouldability can be obtained, so as to complete this hair
It is bright.
[technological means for solving project]
I.e. the present invention is as shown in following (1)~(10).
(1) a kind of heat resistance styrene resin composite contains styrene-(methyl) acrylic copolymer (A), polyphenylene oxide
It is resin (B) and MBS resin (C), the nuclear phase of MBS resin (C) is butadiene-based rubber, and shell phase is with methyl methacrylate
The copolymer of monomer and styrenic monomers as principal component.
(2) the heat resistance styrene resin composite as described in above-mentioned (1), wherein by above-mentioned copolymer (A), above-mentioned polyphenyl
When the total amount of ether system resin (B) and above-mentioned MBS resin (C) is set as 100 mass %, the content of above-mentioned copolymer (A) is 50~
98.9 mass %, the content of above-mentioned Polyphony Ether resin (B) are 1~30 mass %, the content of above-mentioned MBS resin (C) is 0.1~
20 mass %.
(3) the heat resistance styrene resin composite as described in above-mentioned (1) or (2), wherein will contain in above-mentioned copolymer (A)
When some styrenic monomer units and (methyl) acrylic monomer units total is set as 100 mass %, styrenic monomers
The content of unit is 80~99 mass %, and the content of (methyl) acrylic monomer units is 1~20 mass %.
(4) the heat resistance styrene resin composite as described in any one of above-mentioned (1)~(3), wherein above-mentioned copolymer
(A) weight average molecular weight (Mw) is 100,000~400,000.
(5) the heat resistance styrene resin composite as described in any one of above-mentioned (1)~(4), vicat softening temperature are
108 DEG C or more.
(6) a kind of molded product, be by heat resistance styrene resin composite described in any one of above-mentioned (1)~(5) at
Made of type.
(7) a kind of non-foamed sheet material, by heat resistance styrene resin composite described in any one of above-mentioned (1)~(5)
It is molded with.
(8) a kind of foam sheet is by heat resistance styrene resin composite described in any one of above-mentioned (1)~(5)
It is molded with.
(9) a kind of food packaging container, being will be made of non-foamed sheet forming described in above-mentioned (7).
(10) a kind of food packaging container, being will be made of duct foam sheet molding described in above-mentioned (8).
[invention effect]
The balancing good of the heat resistance of heat resistance styrene resin composite of the invention and intensity, mouldability, therefore
Be especially applicable for micro-wave oven food containers, when carrying out the various shapes processing such as deep drawn, can be obtained crackle generate it is few
Food containers.
Specific embodiment
The present invention described further below.
<heat resistance styrene resin composite>
Heat resistance styrene resin composite of the invention contains: styrene-(methyl) acrylic copolymer (A)；Polyphenylene oxide
It is resin (B)；And MBS resin (C), the nuclear phase of MBS resin (C) they are butadiene-based rubber, shell phase is with methyl methacrylate
The copolymer of ester monomer and styrenic monomers as principal component.
Heat resistance styrene resin composite of the invention by above-mentioned copolymer (A), above-mentioned Polyphony Ether resin (B) with
When the total amount of above-mentioned MBS resin (C) is set as 100 mass %, the content of preferably above-mentioned copolymer (A) is 50~98.9 matter
% is measured, the content of above-mentioned Polyphony Ether resin (B) is 1~30 mass %, and the content of above-mentioned MBS resin (C) is 0.1~20 matter
Measure %.When the content of above-mentioned Polyphony Ether resin (B) is less than 1 mass %, the improvement of brittleness and heat resistance is insufficient sometimes, above-mentioned
When the content of Polyphony Ether resin (B) is greater than 30 mass %, heat resistance is reduced, thus not preferred.In addition, above-mentioned MBS resin (C)
Content less than 0.1 mass % when, brittleness, the improvement of mouldability are small, and the content of above-mentioned MBS resin (C) is greater than 20 matter
When measuring %, mobility can be reduced excessively, therefore molding processibility reduces.
The melt flows that heat resistance styrene resin composite of the invention measures under conditions of 200 DEG C, 49N load
Rate (MFR) is preferably 0.1~10g/10 points, more preferably 0.2~5.0g/10 points, particularly preferably 0.3~2.0g/10 points.
Productivity if melt flow rate (MFR) (MFR) is less than 0.1g/10 points when extrusion molding is deteriorated, sometimes if more than 10g/10 points
Mechanical strength reduces.
The vicat softening temperature of heat resistance styrene resin composite of the invention is preferably 108 DEG C or more, more preferably
It is 110 DEG C or more, particularly preferably 112 DEG C or more.If vicat softening temperature is lower than 108 DEG C, sometimes by heat resistance styrene
The heat resistance for the molded product that based resin composition obtains is insufficient.
The melting tension (MT) that heat resistance styrene resin composite of the invention is measured at 200 DEG C be preferably 10gf with
On, more preferably 15gf or more, particularly preferably 20gf or more.If melting tension is less than 10gf, the improvement of mouldability
It is small.
<styrene-(methyl) acrylic copolymer (A)>
In styrene-(methyl) acrylic copolymer (A) of the invention, it is with styrenic monomers and (methyl) acrylic monomers
These essential components and the other vinyl monomers that can be copolymerized with them can be copolymerized by essential component as needed.
As styrenic monomers, the substituted benzenes second such as p-methylstyrene between styrene, α-methylstyrene, neighbour can be enumerated
Alkene can be a kind in these monomers or mixture of more than two kinds, optimization styrene.
As (methyl) acrylic monomers, acrylic acid, methacrylic acid can be enumerated, can be their mixture, wherein
Consider from ease of manufacturing, preferably methacrylic acid.
As the above-mentioned vinyl monomer that can be copolymerized with styrenic monomers and (methyl) acrylic monomers, such as can lift
Methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid fourth out
The acrylic monomers such as ester；The vinyl cyanides base system monomer such as acrylonitrile, methacrylonitrile；N- methylmaleimido, N- ethyl
Maleimide, N- butyl maleimide, N- octyl maleimide, N- isopropylmaleimide, N- phenyl Malaysia acyl
The maleimides amine system monomer such as imines, N- N-cyclohexylmaleimide；The unsaturation carboxylic such as maleic anhydride, itaconic anhydride, citraconic anhydride
Sour glycosides can be used 1 in them kind or be two kinds or more.
As the polymerization of styrene-(methyl) acrylic copolymer (A) of the invention, can enumerate mass polymerization,
Styrene polymerization method well known to solution polymerization process, suspension polymerization etc..In addition, as solvent, such as benzene, toluene, second can be used
The alkyl benzenes such as benzene, dimethylbenzene；The ketones such as acetone, methyl ethyl ketone；Aliphatic hydrocarbons such as hexane, hexamethylene etc..As reactor design, fit
The continuous polymerization mode being preferably formed by combining using type reactor, plug flow reactor, ring-like reactor will be thoroughly mixed.
In styrene-(methyl) acrylic copolymer (A) of the invention, by styrenic monomer unit and (methyl) propylene
When the total amount of acid monomer units is set as 100 mass %, the content of optimization styrene system monomeric unit is 80~99 mass %,
The content of (methyl) acrylic monomer units is 1~20 mass %, and the content of more preferable styrenic monomer unit is 85~98
Quality %, the content of (methyl) acrylic monomer units are 2~15 mass %.If the content of (methyl) acrylic monomer units is small
In 1 mass %, then the heat resistance of the molded product obtained by serial heat-resistant styrene resin composites is insufficient, if (methyl) acrylic acid
The content of monomeric unit is greater than 20 mass %, then serial heat-resistant styrene resin composites or the non-foamed obtained by the composition
The mouldability reduction of sheet material, foam sheet.The content of (methyl) acrylic monomer units can pass through the material liquid in polymerization process
(methyl) concentration of acrylic acid adjust.
The weight average molecular weight (Mw) of styrene-(methyl) acrylic copolymer (A) of the invention is preferably 100,000~400,000,
More preferably 12~350,000, particularly preferably 150,000~300,000.Intensity is insufficient if Mw is less than 100,000, if Mw is greater than 400,000
Mobility reduces.The Mw of styrene-(methyl) acrylic copolymer can by reaction temperature in polymerization process, the residence time,
Type and amount of the solvent used when the type and additive amount of polymerization initiator, the type of chain-transferring agent and additive amount, polymerization etc.
To adjust.
<Polyphony Ether resin (B)>
Polyphony Ether resin (B) of the invention is under the action of oxidative coupling catalyst, with oxygen or oxygen-containing gas Pyrogentisinic Acidization
Close the homopolymer or copolymer indicated made of at least one kind of carry out oxidation polymerization in object, by the repetitive unit of formula (1).In addition,
They can be a kind, be also possible to the mixture of two or more resin.
[changing 1]
(in formula, R1、R2、R3、R4Respectively hydrogen atom, halogen atom, alkyl, substituted hydrocarbon radical, 1 therein necessarily hydrogen it is former
Son.In addition, n is repetitive unit.)
As the concrete example of oxybenzene compound, phenol can be enumerated；O-, m-, paracresol；2,6-, 2,5-, 2,4- or 3,5- bis-
Methylphenol；2- methyl -6- phenylphenol；2,6-diphenylphenol；2,6- diethyl phenols；2- methyl -6- ethyl -phenol；2,
3,5-, 2,3,6- or 2,4,6- pseudocuminols；3 methy 6 tert butyl phenol；Thymol, 2- methyl -6- allyl benzene
Phenol etc., wherein preferably 2,6- xylenol, 2,6-diphenylphenol, 3- methyl-t-butyl phenol and 2,3,6- trimethylbenzenes
Phenol.
Oxidative coupling catalyst used in polymerization as Polyphony Ether resin (B) of the invention, is not particularly limited,
It can be used at least one kind of (referring to U.S. Patent No. 4042056, U.S. Patent No. in the heavy metal compounds such as copper, manganese, cobalt
No. 3306874, No. 3306875 bulletins of U.S. Patent No. etc.).
The molecular weight of Polyphony Ether resin (B) of the invention is not particularly limited, preferred characteristics viscosity be 0.30dl/g with
The Polyphony Ether resin of upper (in 25 DEG C of temperature, solvent chloroform).If being less than 0.30dl/g, sometimes bad mechanical strength.In addition, excellent
Selecting inherent viscosity is 0.30~0.60dl/g.
<MBS resin (C)>
MBS resin (C) of the invention is that nuclear phase is butadiene-based rubber, and shell phase is with methyl methacrylate monomer and styrene
It is copolymer of the monomer as principal component, i.e., the so-called methyl methacrylate-butadiene-styrene with core-shell structure is total
Polymers.
As the butadiene-based rubber for constituting above-mentioned nuclear phase, polybutadiene, SBR styrene butadiene rubbers, propylene can be enumerated
Nitrile-butadiene copolymer rubber, butadiene-acrylic acid copolymer rubber, preferably polybutadiene, styrene-butadiene copolymer.
In addition, above-mentioned shell phase is will to connect using methyl methacrylate monomer and styrene monomer as the copolymer of principal component
Branch is formed in above-mentioned butadiene-based rubber, the total and copolymer of grafting of methacrylic acid monomer and styrene monomer
The ratio of total monomer units is preferably 90 mass % or more, more preferably 92 mass % or more, particularly preferably 94 mass % with
On.As the monomeric unit other than methyl methacrylate monomer and styrene monomer, (methyl) acrylic acid second can be enumerated
(methyl) acrylate such as ester, (methyl) butyl acrylate, from the viewpoint of mobility improvement, preferred butyl acrylate.
The round equivalent particle size of the weight of MBS resin (C) of the invention preferably dispersed particle is 10~1000nm, more preferably 30
~500nm, particularly preferably 50~300nm.If the round equivalent particle size of weight is less than 10nm, brittleness improvement is small, if more than
1000nm, then mouldability, rigidity reduce.The round equivalent particle size of weight can acquire in the following way: be seen with transmission electron microscope
Photo is examined, binary conversion treatment is carried out using the image analysis software " A is as monarch " of engineering company, Asahi Chemical Industry, finds out and disperse with gained
The identical diameter of a circle of the area of particle (circle equivalent particle size: Di), it is round equivalent particle size (Dv) to find out weight according to the following formula.
[number 1]
<manufacturing method of heat resistance styrene resin composite>
As the manufacturing method of heat resistance styrene resin composite of the invention, can enumerate above-mentioned styrene-(methyl)
Acrylic copolymer (A), above-mentioned Polyphony Ether resin (B) and above-mentioned MBS resin (C) are blended together, carry out melting extrusion
Method；In advance by styrene-(methyl) acrylic copolymer (A) and above-mentioned Polyphony Ether resin (B) melting extrusion, then to crowded
Above-mentioned MBS resin (C) is mixed in product out, again the method for melting extrusion；In advance by styrene-(methyl) acrylic copolymer
(A) with above-mentioned Polyphony Ether resin (B) melting extrusion, the mother for containing above-mentioned MBS resin (C) is then mixed into extrusion product
Grain, the again method etc. of melting extrusion.
Within the scope of the effect of the invention, it can be combined as needed to heat resistance phenylethylene resin series of the invention
Cooperate other thermoplastic resins, rubber reinforcement material in object.
As the concrete example of thermoplastic resin, polystyrene, impact resistance polystyrene (HIPS), syndiotaxy can be enumerated
Polystyrene, acrylonitritrile-styrene resin, acrylonitrile-butadiene-styrene copolymer, methacrylic acid-methacrylic acid
Methyl esters-styrol copolymer, methacrylic acid Block チ Le-styrol copolymer, maleic anhydride-styrene copolymers, Malaysia acyl
The polystyrene resins such as imines-styrol copolymer, α-methylstyrene-styrol copolymer；Polypropylene, propylene-alpha-olefin
The polyolefin-based resins such as copolymer；The aliphatic polyester such as poly (l-lactic acid), poly- D-ALPHA-Hydroxypropionic acid, poly- D, Pfansteihl system resin etc., these can
It is applied in combination using a kind, or by two or more.
As the concrete example of rubber reinforcement material, can enumerate natural rubber, polybutadiene, polyisoprene, polyisobutene,
Polychlorobutadiene, polysulfide rubber, thiokol, acrylic rubber, polyurethane rubber, organic silicon rubber, epichlorohydrin rubber, benzene second
Alkene-butadiene block copolymer, styrene-butadiene-styrene, styrene-isoprene block copolymer, benzene second
Alkene-isoprene-styrene block copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-butadiene-benzene
Ethylene block copolymer, hydrogenated styrene isoprene block copolymer, hydrogenated styrene isoprene-styrene block are total
The vinyl benzene rubbers such as polymers and ethylene propylene rubber, ethylene propylene diene rubber, straight-chain low density polyethylene based elastomers
Etc. olefin-baseds rubber, these can be used a kind or two or more be applied in combination.
Following additive: phosphorus system, benzene can be added in heat resistance styrene resin composite of the invention as needed
The lubricants such as the higher fatty acids such as the antioxidants such as phenol system, amine system, stearic acid and its salt, ethylene bis-stearamide；Liquid Paraffin,
The plasticizer such as polyethylene wax, microwax；Talcum, inorganic filler, ultraviolet absorbing agent, antistatic agent, fire retardant, colorant, face
Material, deodorant, antifoggant etc..
<manufacturing method of non-foamed sheet material, foam sheet>
Heat resistance styrene resin composite of the invention can be used extrusion forming, extrusion forming, ejection formation, project it is hollow
The method of forming well known to molding, blow molding, special-shaped extrusion molding etc. is processed into various molded products.Alternatively, it is also possible to various hairs
It is expanded moldings that bubble forming technique, which is combined into type, or uses T-shaped mould piece extruder, biaxial stretch-formed processing unit (plant), inflation
Processing unit (plant) is processed into sheet material or film.
As the manufacturing method of non-foamed sheet material of the invention, can enumerate melting resin is molding from T-shaped mould extrusion
Method；Rolling-molding method, film blowing etc., it is preferable to use T-shaped mould from the aspect of productivity and film thickness precision.In addition,
Sheet material can be single layer, only can also use heat resistance phenylethylene resin series of the invention in the outermost layer of multi-layer sheet or internal layer
Composition.As the manufacturing method of multi-layer sheet, the coetrusion using feed block mould or branch manifold mould can be enumerated；In advance individually
Superficial layer, then the method with substrate sheet heat lamination is made.
The thickness of non-foamed sheet material of the invention is not particularly limited, generally 0.05~10mm, preferably 0.2~1mm,
Further preferably 0.3~0.8mm.If sheet thickness is less than 0.05mm, the rigidity and intensity of sheet material are insufficient sometimes.Separately
Outside, if more than 10mm, then not preferred in terms of light weight.
As the manufacturing method of foam sheet of the invention, well known extrusion foaming sheet manufacturing method can be used.Specifically
For, the following methods can be used: 2 single axle extruding machines or biaxial extruder arranged in series will be foamed with First extruder
Resin temperature is adjusted to 120 DEG C~180 DEG C by cooling with second extruder by agent melting mixing together with foaming nucleation agent
Afterwards, atmosphere is emitted by circular mode and carries out decompression foaming.
As foaming agent, the aliphatic hydrocarbons such as propane, normal butane, iso-butane, pentane, hexane can be used；Cyclobutane, pentamethylene etc.
Ring type aliphatic hydrocarbon；The halogen such as trichlorofluoromethane, dicholorodifluoromethane, 1,1- Difluoroethane, the fluoro- chloride of 1,1- bis-, methylene chloride
For physical blowing agents such as hydrocarbon.In addition, it is possible to use azodicarbonamide, dinitrosopentamethylene tetramine, azodiisobutyronitrile,
The decomposition-type foaming agents such as sodium bicarbonate, citric acid；The inorganic gas such as carbon dioxide, nitrogen or water.These foaming agents can properly mix
It uses, it is industrial mostly using butane, it is excellent from the viewpoint of foaming extrusion, the post forming of foam sheet, foaming agent
Choosing uses the mixed butanes being made of iso-butane and normal butane.Butane is slow to the penetration speed of polystyrene resin, therefore
About 1~3 mass % is usually retained in foaming extrusion foam sheet.The residual quantity will affect second time of foaming thickness when post forming
Degree, hot formability, therefore pass through during certain maturation is set with appropriate adjustment.
As foaming nucleation agent, the inorganic material powders such as talcum, calcium carbonate, clay can be enumerated, these can be used alone, or
Can be used as mixture come using.Wherein, from reduce bubble diameter effect it is good and cheap from the aspect of, most preferably slide
Stone.The adding method of foaming nucleation agent is not particularly limited, and can make an addition to the supply hole for the machine of directly extruding, can also be with resin
It adds together.Alternatively, it is also possible to prepare with the homopolymer of styrene or styrene-methylmethacrylate copolymer etc. as substrate
Master batch, supplied using the master batch.The additive amount of foaming nucleation agent is usually 0.1~5 mass %.Alternatively, it is also possible to
Cooperate the metal salt of higher fatty acids, higher fatty acids in the master batch in advance.Alternatively, it is also possible to contain ethylene bis-stearamide etc.
Lubriation material；It is the adhesive agents such as atoleine, organic silicone oil, other surfactants, antistatic agent, antioxidant, plasticizer, resistance to
Wait agent, pigment etc..
The thickness of foam sheet of the invention is generally 0.1~100mm, preferably 0.5~4mm, more preferably 1~3mm.
If the thickness of foam sheet is less than 0.1mm, vessel strength, thermal insulation after post forming are reduced.If the thickness of foam sheet
Greater than 100mm, then the temperature that sheet material is easy to happen when post forming is uneven, and mouldability is deteriorated sometimes.
The density of foam sheet of the invention is generally 5~500kg/m3, preferably 50~400kg/m3, more preferably 60
~300kg/m3.If the density of foam sheet is less than 5kg/m3, then the vessel strength after post forming reduces.If foam sheet
Density is greater than 500kg/m3, then without preferred from the viewpoint of lightweight, thermal insulation.Density D (kg/m3) can be by foam sheet
Weight per square meter S (g/m2) and sheet thickness T (mm) calculated according to D=S/T.
In addition, superficial layer, the density ratio thickness of the superficial layer can be arranged at the sheet material table back side in foam sheet of the invention
The central portion in direction is low, referred to as surface layer.By the way that surface layer is arranged, sheet strength can be improved, exquisite appearance can also be made.Surface layer can lead to
It crosses and air-cooled adjust is carried out to foam sheet surface immediately after circular mode taking-up.
Foam sheet of the invention can by its one or both sides laminating thermoplastic resin sheet or film come improve mouldability,
The characteristics such as intensity, rigidity, oil resistivity.As above-mentioned composition piece or the thermoplastic resin of film, polystyrene, high impact polystyrene
Equal polystyrene resins, polypropylene-based resin, polyester based resin, high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density
Polyethylene, vinyl-vinyl acetate copolymer etc..The thickness of piece or film is not particularly limited, preferably 0.01mm~0.3mm.
Vacuum forming, compressed air molding, matched-mold forming, reversed can be used in non-foamed sheet material of the invention or foam sheet
Drawing and forming, air slip forming, ridge put up shape, plunger ridge frame (Plug-and-ridge) molding, plug assist forming, reversed
Plunger stretches thermoforming process well known to assistant formation etc., is processed into pallet, convenient container, bowl container, cup, box with cover etc.
The container of various shape, size.
Even if by container obtained from non-foamed sheet material of the invention or duct foam sheet molding in the state that food is housed
Carry out microwave stove heating cook will not generation container deformation, burn swollen, therefore be applicable to micro-wave oven food containers.
[embodiment]
Embodiment exemplified below illustrates the present invention, but the present invention is not limited to these embodiments.
<manufacture of Styrene-methyl Acrylic Acid Copolymer (A)>
(1) manufacture of Styrene-methyl Acrylic Acid Copolymer S-1
Following 1st~the 3 reactors are connected and constitute polymerization process.
1st reactor: volume 39L's is thoroughly mixed type reactor with stirring blade
2nd reactor: volume 39L's is thoroughly mixed type reactor with stirring blade
3rd reactor: the plug flow reactor with static mixer of volume 16L
The condition of each reactor is as follows.
1st reactor: 120 DEG C of [reaction temperature]
2nd reactor: 128 DEG C of [reaction temperature]
3rd reactor: [reaction temperature] is adjusted to the temperature gradient on flow direction with 125~130 DEG C
Material liquid preparation is as follows.
Monomer relative to 97 mass % of styrene, 2.7 mass % of methacrylic acid constitutes 100 mass parts, mixes ethylbenzene
10 mass parts, as the 2 of polymerization initiator, 2 bis- 0.025 mass parts of (4,4- t-butyl peroxy cyclohexyl) propane, raw material is made
Liquid.
Material liquid is continuously supplied in the feed speed of 12.0kg/hr and is set as 120 DEG C of the 1st reactor and gathers
It closes, the 2nd reactor that then continuous investment is set as 128 DEG C is polymerize.The polymerisation conversion of 2nd reactor exit is
65%.Then, the 3rd reactor of the temperature gradient with 125~130 DEG C is adjusted to the polymerization is continued until polymerisation conversion reaches
70%.
Polymer fluid is imported by two sections of vacuum volatilization slots with preheater in series, by unreacted styrene and ethylbenzene point
From rear, cutting granulation after squeezing out and cool down in rope form.It should be noted that the temperature of first segment preheater is set as 200 DEG C, vacuum is de-
The pressure for waving slot is set as 66.7kPa, and the temperature of second segment preheater is set as 240 DEG C, and the pressure of vacuum volatilization slot is 0.9kPa.
The characteristic of gained Styrene-methyl Acrylic Acid Copolymer S-1 is shown in table 1.
(2) manufacture of Styrene-methyl Acrylic Acid Copolymer S-2
Change the temperature condition of the 1st~3 reactor as follows using following material liquid, it is in addition to this identical as the manufacture of S-1.By its
Characteristic is shown in table 1.
<material liquid>
Monomer relative to 94.8 mass % of styrene, 5.2 mass % of methacrylic acid constitutes 100 mass parts, mixes ethylbenzene 10
Mass parts, as the 2 of polymerization initiator, 2 bis- 0.025 mass parts of (4,4- t-butyl peroxy cyclohexyl) propane, material liquid is made.
<condition>
1st reactor: 120 DEG C of [reaction temperature]
2nd reactor: 125 DEG C of [reaction temperature]
3rd reactor: [reaction temperature] is adjusted to the temperature gradient on flow direction with 125~130 DEG C
(3) manufacture of Styrene-methyl Acrylic Acid Copolymer S-3
Change the temperature condition of the 1st~3 reactor as follows using following material liquid, it is in addition to this identical as the manufacture of S-1.By its
Characteristic is shown in table 1.
<material liquid>
Monomer relative to 93 mass % of styrene, 7 mass % of methacrylic acid constitutes 100 mass parts and mixes 10 mass of ethylbenzene
Part, as the 2 of polymerization initiator, 2 bis- 0.02 mass parts of (4,4- t-butyl peroxy cyclohexyl) propane, material liquid is made.
<condition>
1st reactor: 128 DEG C of [reaction temperature]
2nd reactor: 138 DEG C of [reaction temperature]
3rd reactor: [reaction temperature] is adjusted to the temperature gradient on flow direction with 125~138 DEG C
[table 1]
<Examples 1 to 9, comparative example 1~3>
By using the above method manufacture Styrene-methyl Acrylic Acid Copolymer (A) (S-1~3) and Polyphony Ether resin (B),
MBS resin (C), high impact polystyrene (D) are mixed in the Henschel blender of quality % ratio shown in table 2, with being set as
(Kobe Steel is made for 230~260 DEG C of biaxial extruder；KTX30 α) melting mixing.Solid physical property is shown in table 2.
It should be noted that using following substance as polyphenylene oxide (B), MBS resin (C), high impact polystyrene (D).
<polyphenylene oxide (B)>
Trade name: " IUPIACE PX100L " Mitsubishi Engineering-Plastics corporation
Inherent viscosity 0.41g/dl
<MBS resin (C)>
MBS-1 trade name: " KANE ACE M-511 " KANEKA corporation
The round equivalent particle size 170nm of weight
MBS-2 trade name: " KANE ACE B-564 " KANEKA corporation
The round equivalent particle size 70nm of weight
MBS-3 trade name: " METABLEN C-201A " Mitsubishi Chemical Ind's system
The round equivalent particle size 80nm of weight
MBS-4 trade name: " METABLEN C-223A " Mitsubishi Chemical Ind's system
The round equivalent particle size 150nm of weight
<high impact polystyrene (D)>
Trade name: " ToyoStyrol H848 " Japan styrene corporation
1.9 μm of rubber constituent 10.0%, rubber size
Then, above-mentioned resin combination is supplied to the sheet extruder of screw diameter 40mm.The temperature in resin melting area
Be set as 200~240 DEG C, from T-shaped mould (clothes hanger pattern) with discharge rate 10kg/h melting extrusion after, with the calendering for being set as 80 DEG C
Roller, contact roll press, obtain the non-foamed sheet material of width 40mm, thickness 0.4mm.The characteristic of gained non-foamed sheet material is shown in table
2。
In addition, above-mentioned resin combination to be supplied in the serial type extruder of screw diameter 40mm φ and 50mm φ, manufacture
Foam sheet.Firstly, uniformly mixing relative to 100 mass parts of resin made of above-mentioned melting mixing by styrene-methyl propylene
2.3 mass parts of talcum master batch of sour 60 mass % of methyl terpolymer and 40 mass % of talcum composition, obtained mixture is supplied
To the extruder of screw diameter 40mm φ.Then, by as the butane of foaming agent from extruder front end relative to 100 matter of resin
It measures the ratio that part is 1.7 mass parts to be pressed into, carries out dissolving mixing.Barrel temperature at this time is 230~270 DEG C, resin temperature is
235~250 DEG C, pressure be 12~18MPa.
Thereafter, the extruder for being transferred to screw diameter 50mm φ by being set as 230 DEG C of connecting tube, by being adjusted to barrel temperature
160~200 DEG C, 160~170 DEG C of resin temperature, 15~17MPa of pressure, die gap 0.6mm, bore 40mm circular mode with
Discharge rate 10kg/hr squeeze out, make an addition to diameter 152mm through cooling cylinder and taking-up, cut with cutter for 1 point in the lower part of circumference
It opens and obtains foam sheet.Gained foam sheet with a thickness of 1.7mm, density 150kg/m3.Its characteristic is shown in table 2.
It should be noted that carrying out each physical property, performance evaluation by the following method.
(1) methacrylic acid content in Styrene-methyl Acrylic Acid Copolymer
Copolymer 0.5g is weighed at room temperature uses hydroxide after being dissolved in the mixed solution of toluene/ethanol=8/2 (volume ratio)
Potassium 1mol/ ethanol solution carries out acid-base titration and detects terminal, calculates methacrylic acid by the usage amount of potassium hydroxide-ethanol solution
The content of quality criteria.It should be noted that being surveyed using potential difference automatic detection device (capital of a country Electronics Industry Company system, AT-510)
It is fixed.
(2) molecular weight
Weight average molecular weight (Mw), Z-average molecular weight (Mz), number-average molecular weight (Mn) press following item using gel permeation chromatography (GPC)
Part measurement.
GPC machine: Waters corporation Alliance System 2695
Column: Tosoh corporation TSKgel-GMHXL (ID) × 300mm (L)
Mobile phase: tetrahydrofuran 0.35ml/min
Sample solution concentration: 0.2 mass %
Injection rate: 50 μ L
Temperature: 40 DEG C
Detector: differential refractometer Waters corporation Alliance System 2414
The molecular weight that each elution time is calculated by the elution curve of monodisperse polystyrene, the molecule as polystyrene conversion
Amount calculates.
Physical property is evaluated by the following method.
(3) melt flow rate (MFR)
It is found out under conditions of 200 DEG C, 49N load based on JIS K7210.
(4) vicat softening temperature
Test film is made using Jet forming machine, is found out under conditions of 50N load based on JIS K7206.
(5) deflection under load temperature
Test film is made using Jet forming machine, is found out under conditions of 1.8MPa stress based on JIS K7191.
(6) tension (MT) is melted
Using CAPIROGRAPH 1B type (Toyo Seiki corporation), in 200 DEG C, barrel diameter 9.55mm of bucket temperature, capillary pipe length: L
Extrusion resin under conditions of extruded velocity 10mm/ minutes, will carry in=10mm, capillary diameter: D=1mm (L/D=10), bucket
The rope form resin flowed out from capillary at 60cm, is fixed on coiler, will wind linear speed below the die head by the setting of lotus determination part
Degree gradually raised speed from 4m/ minutes, measured the load until rope extrudate is broken.When improving convoluting speed stable load in
Certain value, therefore average value is found out as melting tension value (MT) to the range of stable load.
The characteristic of non-foamed sheet material, foam sheet, molded product is evaluated by the following method.
(7) sheet material impact strength
It is measured using film shock machine BU-302 (TESTER SANGYO corporation) with impacting spherical surface R12.7mm.It is non-
Foam sheet, the surface of foam sheet, the back side respectively carry out 20 measurements, impact using the resultful average value of institute as sheet material strong
Degree.
(8) mouldability
Foam sheet is thermoformed into the cup-shaped receptacle of bore φ 100mm, depth 100mm using single-shot formula molding machine.It will heating
Constant temperature is 280 DEG C, changes heating time as unit of 0.5 second, confirms the heating time of not generation container aperture, exudation,
The situation that plastic time width is 10 seconds or more is evaluated as ◎；8~10 seconds the case where, are evaluated as zero；5~8 seconds the case where
It is evaluated as △；5 seconds or less situations are evaluated as × to evaluate deep drawn mouldability.
(9) vessel strength (rupture)
To the container obtained under conditions of above-mentioned plastic, small desk testing machine Ez-test (company, Shimadzu Seisakusho Ltd. is used
System；Model: Ez-SX), in the state of the both ends in the direction entrance TD with 2 plate holding vessels, with the speed of 500m/mm
Compress one end, will be displaced 30mm when there is a situation where rupture to be evaluated as ◎ completely；Only foaming cross-sectional internal is ruptured
Situation is evaluated as zero；By foaming section surface layer, there is a situation where rupture to be evaluated as △；It will be whole from foaming section surface layer to inside
There is a situation where rupture be evaluated as × to evaluate vessel strength.
(10) heat distortion of resistance to micro-wave oven
Surface shape is observed with microwave stove heating 70 seconds of power output 1500W to the container obtained under conditions of above-mentioned plastic
State absolutely not generation container will deform or be evaluated as ◎ the case where protuberance；It will be observed that container part slight deformation or protuberance
The case where be evaluated as zero；It will be observed that there is a situation where severely deformed or protuberances to be evaluated as △ for container；By container shapes collapse or
There is a situation where aperture is evaluated as × to evaluate heat resistance.
[table 2]
The heat resistance styrene resin composite of embodiment and the resin group without MBS resin (C) of comparative example 1~2
Close object, comparative example 3 the resin combination without Polyphony Ether resin (B) compare, the intensity of non-foamed sheet material and foam sheet,
Mouldability increases substantially.
[industrial availability]
The balancing good of the heat resistance of heat resistance styrene resin composite of the invention and intensity, mouldability, therefore
It can be processed into the various shapes such as deep drawn container using extrusion sheet made of the heat resistance styrene resin composite, it can be wide
It is general to be used for multiple use.Rupture can be obtained by being especially used for when micro-wave oven food containers occurs few food containers, therefore produces
Rupture when product transport, when chimeric with lid, particularly for foodstuff containers material is reduced, and food abandonment loss reduces.
Claims (10)
1. a kind of heat resistance styrene resin composite contains styrene-(methyl) acrylic copolymer (A), polyphenylene oxide
It is resin (B) and MBS resin (C), the nuclear phase of the MBS resin (C) is butadiene-based rubber, shell phase is with methacrylic acid
The copolymer of methylmethacrylate monomer and styrenic monomers as principal component.
2. heat resistance styrene resin composite according to claim 1, wherein by the copolymer (A), described poly-
When the total amount of phenylate system resin (B) and the MBS resin (C) is set as 100 mass %, the content of the copolymer (A) is
The content of 50~98.9 mass %, the Polyphony Ether resin (B) are 1~30 mass %, and the content of the MBS resin (C) is
0.1~20 mass %.
3. heat resistance styrene resin composite according to claim 1 or 2, wherein will contain in the copolymer (A)
Total amount when being set as 100 mass % of some styrenic monomer units, (methyl) acrylic monomer units, styrenic monomers
The content of unit is 80~99 mass %, and the content of (methyl) acrylic monomer units is 1~20 mass %.
4. heat resistance styrene resin composite according to claim 1 or 2, wherein the weight of the copolymer (A) is equal
Molecular weight (Mw) is 100,000~400,000.
5. heat resistance styrene resin composite according to claim 1 or 2, vicat softening temperature be 108 DEG C with
On.
6. a kind of molded product is to form heat resistance styrene resin composite according to any one of claims 1 to 5
Made of.
7. a kind of non-foamed sheet material is by heat resistance styrene resin composite according to any one of claims 1 to 5
It is molded with.
8. a kind of foam sheet, be by heat resistance styrene resin composite according to any one of claims 1 to 5 at
Made of type.
9. a kind of food packaging container, being will be made of non-foamed sheet forming as claimed in claim 7.
10. a kind of food packaging container, being will be made of duct foam sheet molding according to any one of claims 8.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017243650A JP2019108506A (en) | 2017-12-20 | 2017-12-20 | Heat-resistant styrene resin composition, molded article, extruded sheet, and food packaging container |
| JP2017-243650 | 2017-12-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110003582A true CN110003582A (en) | 2019-07-12 |
Family
ID=67165147
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811540540.3A Pending CN110003582A (en) | 2017-12-20 | 2018-12-17 | Heat resistance styrene resin composite, molded product, extrusion sheet and food packaging container |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2019108506A (en) |
| CN (1) | CN110003582A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116041869A (en) * | 2022-12-21 | 2023-05-02 | 大连理工大学 | Low-dielectric polyphenyl ether modified polystyrene material and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022004508A1 (en) * | 2020-06-30 | 2022-01-06 | 東洋スチレン株式会社 | Styrene-based resin composition and molded article thereof |
| KR20230135058A (en) * | 2021-01-22 | 2023-09-22 | 이데미쓰 고산 가부시키가이샤 | Styrene-based resin composition |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000272061A (en) * | 1999-03-25 | 2000-10-03 | Denki Kagaku Kogyo Kk | Stylene resin heat resistant foam laminate sheet and manufacture thereof |
| CN1487976A (en) * | 2001-11-22 | 2004-04-07 | ������������ʽ���� | Flame-retardant resin composition |
| WO2005056268A1 (en) * | 2003-12-12 | 2005-06-23 | Basf Aktiengesellschaft | Expandable styrole polymer granulates |
| CN103987780A (en) * | 2011-12-20 | 2014-08-13 | 东洋苯乙烯股份有限公司 | Styrene-based optical resin composition, molded product, and light guide plate |
| JP2014205761A (en) * | 2013-04-12 | 2014-10-30 | 東洋スチレン株式会社 | Heat resistant resin foam sheet and container |
-
2017
- 2017-12-20 JP JP2017243650A patent/JP2019108506A/en active Pending
-
2018
- 2018-12-17 CN CN201811540540.3A patent/CN110003582A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000272061A (en) * | 1999-03-25 | 2000-10-03 | Denki Kagaku Kogyo Kk | Stylene resin heat resistant foam laminate sheet and manufacture thereof |
| CN1487976A (en) * | 2001-11-22 | 2004-04-07 | ������������ʽ���� | Flame-retardant resin composition |
| WO2005056268A1 (en) * | 2003-12-12 | 2005-06-23 | Basf Aktiengesellschaft | Expandable styrole polymer granulates |
| CN103987780A (en) * | 2011-12-20 | 2014-08-13 | 东洋苯乙烯股份有限公司 | Styrene-based optical resin composition, molded product, and light guide plate |
| JP2014205761A (en) * | 2013-04-12 | 2014-10-30 | 東洋スチレン株式会社 | Heat resistant resin foam sheet and container |
Non-Patent Citations (1)
| Title |
|---|
| 汪多仁: "《绿色化工助剂》", 31 January 2006, 科学技术文献出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116041869A (en) * | 2022-12-21 | 2023-05-02 | 大连理工大学 | Low-dielectric polyphenyl ether modified polystyrene material and preparation method thereof |
| CN116041869B (en) * | 2022-12-21 | 2024-05-17 | 大连理工大学 | Low-dielectric polyphenyl ether modified polystyrene material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2019108506A (en) | 2019-07-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6271147B2 (en) | Heat-resistant resin foam sheet and container | |
| CN110003582A (en) | Heat resistance styrene resin composite, molded product, extrusion sheet and food packaging container | |
| JP5717451B2 (en) | Heat resistant resin composition and foamed molded body | |
| JP2013100427A (en) | Highly branched styrenic resin composition for foaming | |
| JP6353638B2 (en) | Heat-resistant resin non-foamed sheet and container | |
| JP3271753B2 (en) | Polystyrene resin and foamed molded article thereof | |
| CN101790562A (en) | Polystyrene compositions and methods of making and using same | |
| JP2009029871A (en) | Styrenic resin composition and method for producing foamed sheet | |
| JP6203973B1 (en) | Heat-resistant styrene resin composition, foam sheet, and food container | |
| JP6457898B2 (en) | Styrenic resin for molding, molded product, and manufacturing method of molded product | |
| JP2015071678A (en) | Heat-resistant resin composition, and foam molding of the same | |
| JP6302629B2 (en) | Styrene- (meth) acrylic acid copolymer composition | |
| JP7100996B2 (en) | Heat-resistant styrene resin compositions, articles, foam sheets, and food packaging containers | |
| JP6580409B2 (en) | Styrenic resin composition and foam molded article | |
| JP6827728B2 (en) | High-strength modified polyphenylene ether-based resin extruded foam sheet for deep drawing, deep-drawing high-strength molded product manufacturing method, deep-drawing high-strength modified polyphenylene ether-based resin extruded foam sheet and deep-drawing high-strength foam molded product | |
| JP2931162B2 (en) | Method for producing polystyrene resin | |
| JP7084771B2 (en) | Heat-resistant styrene resin composition, molded article, foam sheet, and container for food packaging | |
| JP5234723B2 (en) | Method for producing styrene resin foam sheet | |
| JP2008144025A (en) | Method for producing styrene-based resin foam sheet | |
| JP6861014B2 (en) | Heat-resistant styrene resin composition, molded product, extruded sheet, and container for food packaging | |
| CN107057183A (en) | Composition, inner container of icebox and preparation method thereof, refrigerator | |
| JP6580416B2 (en) | Styrenic resin | |
| JP2019156881A (en) | Heat-resistant styrene-based resin composition, formed product, foam sheet, and food packaging container | |
| JP2018002995A (en) | Styrenic resin composition | |
| JP6279383B2 (en) | Polystyrene resin composition for foaming and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |