CN109721868A

CN109721868A - The manufacturing method of thermoplastic resin extrusion foaming plate

Info

Publication number: CN109721868A
Application number: CN201811284906.5A
Authority: CN
Inventors: 关谷俊介; 桥爪祥辉; 友利格
Original assignee: JSP Corp
Current assignee: JSP Corp
Priority date: 2017-10-31
Filing date: 2018-10-31
Publication date: 2019-05-07
Anticipated expiration: 2038-10-31
Also published as: JP6898829B2; JP2019081855A; KR102671095B1; CN109721868B; KR20190049531A

Abstract

Problem of the present invention is that providing the manufacturing method that can steadily manufacture the thermoplastic resin extrusion foaming plate of the long-term excellent in heat insulating performance compared with previous extrusion foaming plate.In the manufacturing method of thermoplastic resin extrusion foaming plate of the invention, foaminess resin fusant is subjected to extrusion foaming, the fusant is obtained from being kneaded thermoplastic resin and physical blowing agent, in this manufacturing method, thermoplastic resin includes polystyrene resin (a), specific PET series resin (b), with polystyrene resin (c1) and specific PET series resin (c2) are kneaded obtained from hybrid resin (c), polystyrene resin (a), PET series resin (b) and hybrid resin (c) are cooperated with special ratios, total use level relative to polystyrene resin (a) and polystyrene resin (c1), PET series resin (b) and polyethylene terephthalate The use level of ester system resin (c2) is in particular range.

Description

The manufacturing method of thermoplastic resin extrusion foaming plate

Technical field

The present invention relates to the manufacturing methods of thermoplastic resin extrusion foaming plate, specifically, are related to be suitable as building Build the manufacturing method of the thermoplastic resin extrusion foaming plate of the heat-barrier material on wall, floor, roof of object etc..

Background technique

Thermoplastic resin extrusion foaming plate (hereinafter also referred to extrusion foaming using polystyrene resin as substrate resin Plate) there is excellent thermal insulation and mechanical strength, therefore the object for being shaped to plate is widely used as heat-barrier material etc..It is such to squeeze Foamed board usually passes through following manner and manufactures out: in an extruder by after polystyrene resin heating melting, to gained fusant Middle indentation physical blowing agent is simultaneously kneaded and obtains foaminess melting mixing object, by gained foaminess melting mixing object by additional setting Mold etc. in extruder front end carries out extrusion foaming in area of low pressure, and figuration is plate, to manufacture.

In the manufacture of such extrusion foaming plate, as physical blowing agent, (hereinafter also referred to using hydrocarbon, HF hydrocarbon HFO).These foaming agents remain in bubble, contribute to the raising of the thermal insulation of extrusion foaming plate.On the other hand, foaming agent from Slow loss comes out in extrusion foaming plate, therefore there are problems that the thermal conductivity of extrusion foaming plate slowly rises.To prevent the hydrocarbon The technology of the loss of equal physical blowing agents as a purpose is disclosed in patent document 1.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2016-94532 bulletin.

Summary of the invention

Subject to be solved by the invention

It is disclosed in patent document 1 in the manufacturing method of extrusion foaming plate, polystyrene is used as thermoplastic resin Thus the hybrid resin of resin and specific PET series resin is effectively prevented foaming agent and sends out from extrusion Loss in plate is steeped, the extrusion foaming plate that can maintain excellent thermal insulation throughout long-time has been obtained.

But in recent years, foamed board is gradually required to further increase long-term thermal insulation.Problem of the present invention is that mentioning For can steadily manufacture the thermoplastic resin extrusion foaming plate of the long-term excellent in heat insulating performance compared with previous extrusion foaming plate Manufacturing method.

The means used to solve the problem

According to the present invention, the manufacturing method of thermoplastic resin extrusion foaming plate as shown below is provided.

[1] manufacturing method of thermoplastic resin extrusion foaming plate, which is characterized in that carry out foaminess resin fusant Extrusion foaming, the foaminess resin fusant are the extrusions obtained from being kneaded thermoplastic resin and physical blowing agent Foamed board is 20 ~ 50kg/m with a thickness of 10 ~ 150mm, apparent density³, in the manufacturing method,

The thermoplastic resin includes: polystyrene resin (a)；Fusing heat based on JIS K7122-1987 is lower than 5J/g The PET series resin (b) of (including 0)；With hybrid resin (c), the hybrid resin (c) is by polyphenyl 50 ~ 95 weight % of vinylite (c1) and based on JIS K7122-1987 fusing heat be lower than 5J/g poly terephthalic acid Obtained from glycol ester system resin (c2) 5 ~ 50 weight % is kneaded, wherein aforementioned polystyrene system resin (c1) and poly- pair aforementioned Ethylene terephthalate system resin (c2) adds up to 100 weight %；

Relative to 100 parts by weight of total use level of aforementioned polystyrene system's resin (a) and aforementioned polystyrene system resin (c1), The total of aforementioned PET series resin (b) and aforementioned PET series resin (c2) is matched Resultant is 10 ~ 100 parts by weight.

[2] manufacturing method of the thermoplastic resin extrusion foaming plate according to aforementioned 1, which is characterized in that aforementioned poly- pair The use level of ethylene terephthalate system's resin (b) is matched relative to aforementioned PET series resin (c2's) The ratio between resultant is 0.5 ~ 4.

[3] manufacturing method of the thermoplastic resin extrusion foaming plate according to aforementioned 1 or 2, which is characterized in that aforementioned 200 DEG C, shear velocity 100s of polystyrene resin (a)^-1Under conditions of melt viscosity (η a) be 500 ~ 2500Pas, 200 DEG C, shear velocity 100s of aforementioned PET series resin (b)^-1Under conditions of melt viscosity (η b) The ratio between melt viscosity (η a) relative to polystyrene resin (a) (η b/ η a) is 0.4 ~ 2.

[4] manufacturing method of the thermoplastic resin extrusion foaming plate according to aforementioned 3, which is characterized in that aforementioned mixing 200 DEG C, shear velocity 100s of resin (c)^-1Under conditions of melt viscosity (η c) relative to aforementioned polystyrene system's resin (a) The ratio between melt viscosity (η a) (η c/ η a) be 0.2 ~ 1.

[5] manufacturing method of the thermoplastic resin extrusion foaming plate according to aforementioned 1 or 2, which is characterized in that aforementioned Hybrid resin (c) is derived from the clast of polystyrene serial resin extruded foamed board and/or the recycling raw material of crushed material, described poly- Phenylethylene resin series extrusion foaming plate includes that the fusing heat based on JIS K7122-1987 is poly- to benzene lower than 5J/g (including 0) Naphthalate system resin.

[6] manufacturing method of the thermoplastic resin extrusion foaming plate according to aforementioned 1 or 2, which is characterized in that will before It states hybrid resin (c) and is processed as pellet.

Invention effect

The manufacturing method of thermoplastic resin extrusion foaming plate according to the present invention can steadily manufacture extrusion foaming plate, simultaneously The extrusion foaming thermal insulation board of long-term excellent in heat insulating performance can be manufactured.

Detailed description of the invention

Fig. 1 is the cross-section photograph of the pellet of hybrid resin (c) used in embodiment 1 (C-1).

Fig. 2 is the cross-section photograph of the pellet of hybrid resin (c) used in embodiment 7 (C-5).

Fig. 3 is the cross-section photograph of the pellet of hybrid resin (c) used in embodiment 9 (C-7).

Fig. 4 is the cross-section photograph (section MD of the bubble chamber film of extrusion foaming plate obtained in embodiment 1；5000 times).

Fig. 5 is the cross-section photograph (section TD of the bubble chamber film of extrusion foaming plate obtained in embodiment 1；5000 times).

Fig. 6 is the cross-section photograph (section MD of the bubble chamber film of extrusion foaming plate obtained in embodiment 1；20000 times).

Fig. 7 is the cross-section photograph (section TD of the bubble chamber film of extrusion foaming plate obtained in embodiment 1；20000 times).

Fig. 8 is the cross-section photograph (section MD of the bubble chamber film of extrusion foaming plate obtained in comparative example 1；5000 times).

Fig. 9 is the cross-section photograph (section TD of the bubble chamber film of extrusion foaming plate obtained in comparative example 1；5000 times).

Figure 10 is the cross-section photograph (section MD of the bubble chamber film of extrusion foaming plate obtained in comparative example 1；20000 times).

Figure 11 is the cross-section photograph (section TD of the bubble chamber film of extrusion foaming plate obtained in comparative example 1；20000 times).

Specific embodiment

Hereinafter, the manufacturing method for thermoplastic resin extrusion foaming plate of the invention is described in detail.

In the manufacturing method of thermoplastic resin extrusion foaming plate (hereinafter also referred to as extrusion foaming plate) of the invention, it will contain There is the foaminess resin fusant of specific thermoplastic resin and physical blowing agent to pass through the additional mould for being set to outlet of extruder Have and carry out extrusion foaming, figuration is plate, thus manufactures extrusion foaming plate.

Thermoplastic resin used in the present invention includes polystyrene resin (a), specific poly terephthalic acid second two Alcohol ester system's resin (b) (hereinafter also referred to as PET series resin (b)) and specific hybrid resin (c). Further, hybrid resin (c) is by polystyrene resin (c1) and specific PET series resin (c2) (hereinafter also referred to as PET series resin (c2)) mixing obtains.

Here, polystyrene resin (a) and polystyrene resin (c1) are polystyrene resin.In addition, poly- Ethylene glycol terephthalate system's resin (b) and PET series resin (c2), which refer to, to be had as dicarboxylic acids The terephthalic acid (TPA) ingredient units of ingredient units and glycol component unit as diol component unit are as main component list The polyester based resin of member.Resin (b) and resin (c2) are also collectively referred to as PET series resin (I).

Then, it is illustrated for use as the polystyrene resin of polystyrene resin (a).

As polystyrene resin (a), it can be cited for example that with polystyrene (GPPS), using styrene as mainly at Copolymer in cinnamic acrylic ester, the styrene-methacrylate copolymer, Styrene-acrylic copolymer, benzene second divided Alkene-methacrylic acid copolymer, styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene- Styrol copolymer, acrylonitrile-styrene acrylate copolymer, styrene-methylstyrene copolymer, styrene-diformazan Base styrol copolymer, styrene-ethyl styrol copolymer, styrene-diethyl copolymer, polystyrene and poly- The hybrid resin etc. of phenylate.In addition, they may be used alone or in combination two or more.It should be noted that aforementioned polystyrene Styrene content content in copolymer is preferably 50 moles of % or more, particularly preferably 80 moles of % or more.

Among these polystyrene resins, preferably polystyrene, styrene-methacrylate copolymer, benzene second Alkene-acrylate copolymer, Styrene-acrylic copolymer, Styrene-methyl Acrylic Acid Copolymer, phenylethylene-maleic anhydride Copolymer.

200 DEG C of polystyrene resin (a) preferable temperature, shear velocity 100s used in the present invention^-1Under conditions of Melt viscosity (η a) is 1500 ~ 3000Pas.Melt viscosity (η a) is more preferably 1600Pas or more, is more preferably 1700Pas or more.In addition, melt viscosity (η a) be more preferably 2500Pas or less, further preferably 2300Pas with Under, particularly preferably 2000Pas or less.If the melt viscosity (η a) of polystyrene resin (a) be aforementioned range in, Polystyrene resin (a), PET series resin (b) and hybrid resin (c) mix well, and manufacture is squeezed Extrusion molding when foamed board improves out.

Further, the melting tension used in the present invention at preferably 200 DEG C of polystyrene resin (a) be 30cN with On.If the melting tension is to maintain to fit for forming polystyrene resin phase in walls in aforementioned range The melt viscosity of conjunction, while bubble is difficult to rupture in extrusion foaming, therefore can obtain that apparent density is low and excellent in heat insulating performance Extrusion foaming plate.From the point of view, aforementioned melt tension is preferably 35cN or more, further preferably 40cN or more. It should be noted that the upper limit of melting tension above-mentioned is about 100cN, preferably 60cN.The melting tension (MT) is according to ASTM D1238 measurement.The melting tension (MT) made キャピログラ Off 1D can be made for example, by (strain) Toyo Seiki and Measurement.

As the polystyrene with aforementioned specific melting tension, it can be cited for example that by using with branched structure Macromonomer polymerize obtained from imported the polystyrene resin etc. of special branched structure in the molecule.Make For the polystyrene resin, DIC corporation HP780 etc. can be enumerated.

Then, for the aforementioned PET series resin as the ingredient for constituting aforementioned thermoplastic resin (b) it is illustrated.

PET series resin (b) is measuring with resin fusing based on JIS K7122-1987 Associated fusing heat (Q) (hereinafter also referred to as fusing heat (Q)) is lower than the polyethylene terephthalate of 5J/g (including 0) Ester system resin.It should be noted that the fusing heat (Q) of PET series resin (b) also referred to as melts heat (Qb), the fusing heat (Q) of aftermentioned PET series resin (c2) also referred to as melts heat (Qc).

Here, the PET series resin (b) in the present invention, which refers to, to be had as dicarboxylic acid component's list First terephthalic acid (TPA) ingredient units and the glycol component unit as diol component unit are as the poly- of main component unit Ester system resin.It should be noted that it can be used in order to control the crystallinity of the PET series resin (b) His ingredient units.

As other dicarboxylic acid components of the PET series resin (b), can be used dicarboxylic acids or Its ester-forming derivatives.As ester-forming derivatives, it can be cited for example that the esters such as Arrcostab that carbon atom number is 1 ~ 4 or so are derivative Acid carboxylic acid halides such as the salt such as object, di-ammonium salts, diacid chloride etc..As the dicarboxylic acids in the PET series resin (b) Ingredient units can enumerate M-phthalic acid, 2,6-naphthalenedicarboxylic acid, phthalic acid, 4,4'- biphenyl dicarboxylic acid, 3,4'- biphenyl The aromatic dicarboxylic acids such as dioctyl phthalate, 1,4- naphthalenedicarboxylic acid, 1,5- naphthalenedicarboxylic acid, 2,5- naphthalenedicarboxylic acid, 2,7- naphthalenedicarboxylic acid or its acid Aliphatic dicarboxylic acids such as the derivatives such as acid anhydride or oxalic acid, succinic acid, adipic acid, decanedioic acid, dodecanedioic acid or derivatives thereof or The alicyclic dicarboxylic acids such as 1,4 cyclohexanedicarboxylic acid, 1,3- cyclohexane cyclohexanedimethanodibasic, decahydro naphthalenedicarboxylic acid, tetrahydro naphthalenedicarboxylic acid.This A little dicarboxylic acid components can be used alone, two or more also can be used.

As other diol components of the PET series resin (b), fatty family two can be used Pure and mild aromatics system glycol (including dihydric phenol) or its ester-forming derivatives.Specifically, propylene glycol, trimethylene two can be enumerated The aliphatic diols such as alcohol, diethylene glycol, 1,4- butanediol, neopentyl glycol, 1,4 cyclohexane dimethanol, 1,3- hexamethylene diformazan The aromatic diols such as ester ring types glycol, the bisphenol-As such as alcohol, 1,6- cyclohexanediol；Or bis- (the 1,1- dimethyl -2- hydroxyethyls) 2 of 3,9-, Tetra- oxaspiro of 4,8,10- [5.5] hendecane (hereinafter referred to as spiral shell glycol), (1,1- dimethyl -2- hydroxyethyl) -5- ethyl -5- Hydroxymethyl -1,3- dioxanes (hereinafter referred to as dioxanes glycol) etc. has the glycol of cyclic ether skeleton.These diol components can To be used alone, two or more also can be used.

As PET series resin (b), it is aforementioned among, as other diol component units, preferably Contain the diol component unit with cyclic ether skeleton.The total amount of these diol components with cyclic ether skeleton is preferably two It is 10 moles of % or more in alcohol component, more preferably in diol component is 15 ~ 60 moles of %, further preferably 20 ~ 50 moles of %.

In addition, PET series resin (b) further preferably with cyclic acetal skeleton glycol at Sub-unit is as other diol component units.As the diol component unit with cyclic acetal skeleton, preferably spiral shell glycol Or dioxanes glycol.

In addition, as other diol component units, further preferably comprising being selected from cyclohexanedimethanol ingredient units, neopentyl glycol One or more of ingredient units.It should be noted that the content of the ester ring types diol component unit such as cyclohexanedimethanol is preferably two It is 25 ~ 40 moles of % in alcohol component.

The crystalline degree of PET series resin (b) can be adjusted by following methods: as Dicarboxylic acid component and use M-phthalic acid other than terephthalic acid (TPA) etc. and change rubbing for these dicarboxylic acid component's units The method of your ratio；The cyclohexanedimethanol other than ethylene glycol, spiral shell glycol etc. are used as diol component and change these The method etc. of the molar ratio of diol component unit.

PET series resin (b) can be for example, by a small amount of by benzoic acid, Benzoylbenzene first The monofunctional compounds such as acid, methoxy poly (ethylene glycol) and the ingredient units derived block molecular end.In addition, can also On a small quantity comprising being spread out by polyfunctional compounds such as Pyromellitic Acid, trimellitic acid, trimesic acid, glycerine, pentaerythrites The ingredient units born.

It should be noted that the crystallization degree of PET series resin (b) is high, aforementioned fusing heat (Qb) mistake Gao Shi, before thermoplastic resin is cooled to blowing temperature in extruder, the crystallization of PET series resin Change has begun, it is difficult to obtain the extrusion foaming plate of target.Here, fusing heat is poly- to benzene two lower than 5J/g (including 0) Formic acid glycol ester system resin refers to the PET series resin of amorphism or low-crystalline.From the viewpoint It sets out, the fusing heat (Qb) of PET series resin (b) is preferably shorter than 2J/g (including 0), is more preferably Lower than 1J/g (including 0).

The fusing heat (Q) based on JIS K7122-1987 in this specification is measured using hot flow type differential scanning calorimetry Device (hereinafter referred to as DSC device), after test film is heated to 300 DEG C with 10 DEG C/min of heating speed, with 10 DEG C/min Cooling velocity be cooled to 30 DEG C and carry out the status adjustment of test film, thereafter by test film with 10 DEG C/min of heating speed 300 DEG C are heated to, DSC curve is thus obtained, is measured based on gained DSC curve.

In the present invention, 200 DEG C of the temperature of aforementioned PET series resin (b), shear velocity 100s^-1's Under the conditions of melt viscosity (η b) be preferably 1500 ~ 4000Pas.Melt viscosity is the polyethylene terephthalate of the range In ester system's resin (b), polystyrene resin (a), hybrid resin (c) mix well, are able to easily form and are constituting gas The poly terephthalic acid of the gas barrier excellent effect of striated is oriented in the thermoplastic resin of vacuolar membrane along bubble chamber film direction Glycol ester system resin phase.If the melt viscosity (η b) is excessively high, PET series resin (b) is possible to It is separated into island or is formed blocky.On the other hand, if the melt viscosity is too low, it is likely that cause mold in extruder Interior pressure reduction, or be difficult to form thermal insulation board.Therefore, the lower limit of the melt viscosity (η b) be more preferably 1700Pas, into One step is preferably 1800Pas.The upper limit of the melt viscosity (η b) is more preferably 2500Pas, is more preferably 2300Pa·s。

Then, it is illustrated for hybrid resin (c) used in the present invention.

Hybrid resin (c) is by polystyrene resin (c1) and the aforementioned fusing heat based on JIS K7122-1987 Hybrid resin obtained from PET series resin (c2) lower than 5J/g (including 0) is kneaded.

As polystyrene resin (c1), it can be used as polystyrene resin (a) above-mentioned and illustrate poly- Phenylethylene resin series.

PET series resin (c2) refers to the terephthalic acid (TPA) as dicarboxylic acid component's unit Ingredient units, polyester based resin of the glycol component unit as main component unit as diol component unit.It should say It is bright, other compositions unit also can be used.

For example, it is preferable to contain the diol component unit conduct with the cyclic acetals skeleton such as spiral shell glycol or dioxanes glycol The PET series resin (c2) of diol component unit other than ethylene glycol.It should be noted that from following again It is preferably single by dicarboxylic acid component identical with aforementioned PET series resin (b) from the perspective of ring The polyester based resin that first and identical diol component unit is formed.

It should be noted that in PET series resin (c2), PET series resin (c2) crystallization degree is also high, when fusing heat (Qc) is excessively high, is cooled to thermoplastic resin in extruder when squeezing out When blowing temperature, the crystallization of PET series resin is had begun, it is difficult to obtain the extrusion foaming of target Plate.From the point of view, the fusing heat (Qc) of PET series resin (c2) be preferably shorter than 2J/g ( Including 0), more preferably less than 1J/g (also include 0).

Hybrid resin (c) includes 50 ~ 95 weight % of aforementioned polystyrene system resin (c1) and aforementioned poly terephthalic acid second Diol ester system resin (c2) 5 ~ 50 weight % (wherein, the polystyrene resin (c1) and PET series Resin (c2) adds up to 100 weight %).If the content of PET series resin (c2) is very few, it is difficult to Obtain the desired gas barrier effect for thermoplastic resin extrusion foaming plate, it is possible to can not be by physical blowing agent from gas Loss in from bubble to atmosphere is suppressed to desired degree.On the other hand, if PET series resin (c2) content is excessive, then when manufacturing aftermentioned hybrid resin (c), PET series resin (c2) can not be It is fully dispersed in polystyrene resin (c1), as a result, desired phase structure can not be obtained in bubble chamber film sometimes.From institute It states viewpoint to set out, the lower limit of the content of PET series resin (c2) is preferably 10 weight %, more preferably 15 Weight %.The upper limit of the content is preferably 40 weight %, more preferably 35 weight %.Wherein, aforementioned polystyrene system resin (c1) and Aforementioned PET series resin (c2) adds up to 100 weight %.

In the present invention, 200 DEG C of the temperature of hybrid resin (c), shear velocity 100s^-1Under conditions of melt viscosity (η c) it is excellent It is selected as 400 ~ 2000Pas.If the melt viscosity of hybrid resin (c) is the range, polystyrene resin (a), poly- pair Ethylene terephthalate system's resin (b) mixes well, is able to easily form in the polystyrene tree for constituting bubble chamber film The PET series resin of the gas barrier excellent effect of striated is oriented in rouge along bubble chamber film direction Phase.From foregoing viewpoint, the lower limit of the melt viscosity (η c) of hybrid resin (c) be more preferably 500Pas, further preferably For 550Pas, particularly preferably 600Pas.The upper limit of the melt viscosity (η c) be more preferably 1500Pas, further it is excellent It is selected as 1200Pas, particularly preferably 1000Pas.

In order to meet the range of viscosities of aforementioned hybrid resin (c), 200 DEG C of the temperature of polystyrene resin (c1), shearing Speed 100s^-1Under conditions of melt viscosity (η c1) be preferably 1000 ~ 2000Pas.In addition, similarly, poly terephthalic acid 200 DEG C of the temperature of glycol ester system resin (c2), shear velocity 100s^-1Under conditions of melt viscosity (η c2) be preferably 1000 ~ 4000Pa·s。

In the present invention, as described above, polystyrene resin (a), PET series resin are used (b) and obtained from being kneaded polystyrene resin (c1) with PET series resin (c2) it mixes Resin (c).Only polystyrene resin (a) and PET series resin (b) are kneaded with previous as a result, And extrusion foaming plate obtained from extrusion foaming is compared, can manufacture can be maintained low shape for thermal conductivity throughout the longer time The extrusion foaming plate of state.Its reason can consider as follows.

Hybrid resin (c) can be by by polystyrene resin (c1) and poly- terephthaldehyde with barrier properties for gases Sour glycol ester system resin (c2) mixing obtains.The cross-section photograph of the hybrid resin (c) obtained in this way is shown in Fig. 1 ~3.By Fig. 1 ~ 3 it is found that in hybrid resin (c), PET series resin (c2) is in hybrid resin (c) Fine dispersion.

Together by the hybrid resin (c) and polystyrene resin (a) and PET series resin (b) Supply is heated, melts, is kneaded to extruder and extrusion foaming, thus by PET series resin (b) The PET series resin (I) constituted with PET series resin (c2) is in bubble chamber film Fine dispersion, and the PET series resin easy to form for being formed as striated along bubble chamber film direction (I) phase.As a result, being easy to play barrier properties for gases, it is believed that obtain the foamed board of long-term excellent in heat insulating performance.

By the heating of polystyrene resin (a), PET series resin (b) and hybrid resin (c), melt Melt, be kneaded and the cross-section photograph of the bubble chamber film of extrusion foaming plate obtained from extrusion foaming is shown in Fig. 4.As shown in Figure 4, it is formed poly- Ethylene glycol terephthalate system resin (I) is separated into the phase structure of striated along bubble chamber film direction.

As shown in Figure 4, in the bubble chamber film cross-section photograph for squeezing out thermal insulation board, if forming the length along bubble chamber film Direction confirms the pattern of a large amount of striated phases formed by PET series resin (I), then effectively prevents Only after extrusion foaming in bubble remaining physical blowing agent loss into atmosphere.The low physical blowing agent of thermal conductivity as a result, It is remained in bubble throughout for a long time, while oxygen, nitrogen from atmosphere being inhibited to flow into the bubble of extrusion foaming plate.It is tied Fruit is, it is believed that the thermal conductivity of extrusion foaming plate can be remained to low state throughout the longer time.

It should be noted that in the following description, squeeze out confirmed in the bubble chamber film cross-section photograph of thermal insulation board by poly- to benzene two The striated that formic acid glycol ester system resin (I) is formed mutually is also referred to as " striated phase ".

Then, it is illustrated for the manufacturing method of hybrid resin (c).

As the manufacturing method of hybrid resin (c), following methods can be enumerated: by aforementioned polystyrene system resin (c1), PET series resin (c2) and the additive cooperated as needed supply together to the supply unit of extruder, And the method being kneaded in an extruder；(2) by polystyrene resin (c1) and PET series resin (c2) method being kneaded by kneader etc. such as.

In addition, the manufacturing method as hybrid resin (c), squeezing of generating when the manufacture using extrusion foaming plate can be enumerated Out the clast of foamed board, the extrusion foaming plate containing PET series resin (c2) cut, is crushed, The method of crushed material obtained from crushing etc..

It should be noted that the clast of extrusion foaming plate is to carry out in the manufacturing step of extrusion foaming plate by extrusion foaming And figuration is that the foaming body of plate is cut and obtains generating when the operation of the extrusion foaming plate of target size.In addition, squeezing The crushed material of foamed board is in the manufacturing step of extrusion foaming plate, by being made to extrusion foaming plate, by extrusion foaming plate out Foaming plate generated when target size etc. crush to generation.Using polystyrene resin (a) and poly- pair Ethylene terephthalate system's resin (b) and/or PET series resin (c2) and manufacture extrusion foaming plate When, the clast and/or crushed material and recycled resin obtained from being kneaded them that extrusion foaming plate can be used are as mixed Resin (c).

Particularly, by temporarily being heated in extruder, melting, be kneaded the clast of extrusion foaming plate obtained from the step of And/or crushed material；By making the recirculation step of the clast and/or crushed material of the extrusion foaming plate by heating, melting, mixing Obtained from recycled resin etc. be originated from the clast of extrusion foaming plate and/or the recycling raw material of crushed material, there are compound trees The tendency that the melt viscosity for the PET series resin (c2) for including in rouge reduces.Concomitantly, polyphenyl PET series resin (c2) in vinylite is easy more imperceptibly to disperse.Therefore, it is followed aforementioned again When ring raw material is used as hybrid resin (c), PET series resin (c2) more imperceptibly disperses, and sends out squeezing out It is easy to stretch when bubble.It therefore, the use of aforementioned recycling raw material is particularly preferred extrusion foaming plate as hybrid resin (c) Manufacturing method.

It should be noted that in preceding method, it is convenient as the processing of the manufacture raw material of extrusion foaming plate from hybrid resin (c) Viewpoint is set out, and partical is preferably processed to.

Then, for polystyrene resin (a), PET series resin (b) and hybrid resin (c) Mixing ratio, the use level of PET series resin (c2) in hybrid resin (c) and aforementioned thermoplastic Property resin in PET series resin (I) (i.e. PET series resin (b) and poly- pair The total of ethylene terephthalate system resin (c2)) use level be illustrated.

In the present invention, polystyrene resin (a), the PET series resin of thermoplastic resin are constituted It (b) is preferably 10 ~ 80 weight % of polystyrene resin (a), poly terephthalic acid second two with the mixing ratio of hybrid resin (c) 5 ~ 40 weight % of alcohol ester system's resin (b), 10 ~ 70 weight % of hybrid resin (c).Wherein, polystyrene resin (a), poly- to benzene two The mixing ratio of formic acid glycol ester system's resin (b) and hybrid resin (c) adds up to 100 weight %.If polystyrene tree The mixing ratio of rouge (a) is too low, it is likely that can not steadily manufacture extrusion foaming plate has if the mixing ratio is excessively high Possibly desired gas barrier effect can not be shown.If the mixing ratio of PET series resin (b) It is too low, it is likely that desired gas barrier effect can not to be shown, if the mixing ratio is excessively high, it is likely that can not stablize Ground manufactures extrusion foaming plate.If the mixing ratio of hybrid resin (c) is too low, poly- pair can not be made in polystyrene resin Ethylene terephthalate system resin (I) fine dispersion and the phase structure for forming long-term excellent in heat insulating performance, it is possible to can not show Desired long-term thermal insulation out, further, it is possible that being difficult to be stably formed extrusion foaming plate.On the other hand, if the match ratio Example is excessively high, it is likely that can not steadily manufacture extrusion foaming plate.

From the point of view, aforementioned cooperation ratio is preferably 20 ~ 70 weight % of polystyrene resin (a), gathers to benzene two 7 ~ 20 weight % of formic acid glycol ester system's resin (b), 15 ~ 65 weight % of hybrid resin (c), more preferably polystyrene resin (a) 30 ~ 65 weight %, 8 ~ 18 weight % of PET series resin (b), 25 ~ 60 weight % of hybrid resin (c), into One step be preferably 35 ~ 60 weight % of polystyrene resin (a), 9 ~ 16 weight % of PET series resin (b), 30 ~ 55 weight % of hybrid resin (c).Wherein, polystyrene resin (a), PET series resin (b) and Hybrid resin (c) adds up to 100 weight %.

Relative to 100 parts by weight of total use level of aforementioned polystyrene system's resin (a) and polystyrene resin (c1), The total use level of aforementioned PET series resin (b) and PET series resin (c2) (i.e. the use level of PET series resin (I)) is 10 ~ 100 parts by weight.If the use level is very few, It is possible that desired gas barrier effect can not be shown, if the use level is excessive, it is likely that can not steadily manufacture crowded Foamed board out.From the point of view, the lower limit of the use level is preferably 15 parts by weight, is more preferably 20 parts by weight, is further Preferably 25 parts by weight.In addition, the upper limit of the use level is preferably 80 parts by weight, is more preferably 70 parts by weight, is further preferred For 60 parts by weight, particularly preferably 50 parts by weight.

Relative to 100 parts by weight of aforementioned polystyrene system's resin (a), aforementioned PET series resin (b) use level is preferably 10 ~ 40 parts by weight.By being set as the use level, it is good can more stably to manufacture barrier properties for gases Extrusion foaming plate.From the point of view, the lower limit of the use level is preferably 15 parts by weight, more preferably 20 parts by weight.This Outside, the upper limit of the use level is preferably 37 parts by weight, more preferably 35 parts by weight.

Further, the use level of aforementioned PET series resin (b) is relative to aforementioned poly- terephthaldehyde The ratio between the use level of sour glycol ester system resin (c2) (b/c2) is preferably 0.5 ~ 4.The ratio between the use level be more preferably 0.7 with Upper, further preferably 1.0 or more, especially preferred more than 1.0.In addition, the upper limit of the ratio between the use level be more preferably 3.5, into One step is preferably 3.0, particularly preferably 2.0.

By the way that the ratio between aforementioned cooperation amount (b/c2) is set as in aforementioned range, PET series resin (I) dispersity improves, while PET series resin (I) is moderately stretched, therefore can be further Improve the barrier properties for gases of extrusion foaming plate.In addition, the use level of PET series resin (b) is more than poly- pair When the use level of ethylene terephthalate system resin (c2), the barrier properties for gases of extrusion foaming plate can be further increased, because This is more preferably.Its reason is still uncertain, it is believed that gathering by the way that there are PET series resin (c2) Ethylene glycol terephthalate system's resin (b) is easy moderately to be stretched in polystyrene resin, easy to form largely to include The striated phase of the PET series resin (I) of PET series resin (b).

Then, for polystyrene resin (a), PET series resin (b) and hybrid resin (c) The relationship of melt viscosity be illustrated.In the present invention, the melt viscosity of aforementioned PET series resin (b) The ratio between the melt viscosity (η a) of (η b) relative to aforementioned polystyrene system's resin (a) (η b/ η a) is preferably 0.4 ~ 2.Than (η b/ η a) Lower limit be more preferably 0.6.In addition, its upper limit is more preferably 1.5.If this is than within the scope of this, polystyrene resin (a) it is mixed well with PET series resin (b), in the bubble chamber film cross-section photograph for squeezing out thermal insulation board, Striated phase easy to form from PET series resin (b).

Further, in the present invention, the melt viscosity (η c) of aforementioned hybrid resin (c) is relative to aforementioned polystyrene system resin (a) the ratio between melt viscosity (η a) (η c/ η a) is preferably 0.2 ~ 1.0.25 is more preferably than the lower limit of (η c/ η a), further excellent It is selected as 0.3.The upper limit than (η c/ η a) is more preferably 0.9, further preferably 0.6.

If this is than within the scope of this, polystyrene resin (a), PET series resin (b) It is mixed well with hybrid resin (c).Particularly, the PET series resin (c2) in hybrid resin (c) Disperse well in polystyrene resin, while PET series resin (b) and poly terephthalic acid Glycol ester system resin (c2) is easy to be stretched, easy to form poly- to benzene two in the bubble chamber film cross-section photograph for squeezing out thermal insulation board The striated phase of formic acid glycol ester system resin (I).

Polystyrene resin (a), poly terephthalic acid second in the present invention, by using melt viscosity for aforementioned range Diol ester system's resin (b) and hybrid resin (c), are capable of forming the poly terephthalic acid that can show These gases barriering effect Glycol ester system resin (I) is mutually in polystyrene resin with pattern existing for striated phase.As the pattern, preferably exist It confirms to form multiple PET series resins (I) in the bubble chamber film cross-section photograph of gained extrusion foaming plate Striated phase phase structure, more preferable formation co-cable transmission, in the co-cable transmission, the PET series The continuity of resin (I) phase improves to which PET series resin (I) is mutually same as polystyrene resin Ground forms continuous phase.When PET series resin (I) forms such pattern, it is effectively prevented and is squeezing out hair After bubble in bubble remaining physical blowing agent loss into atmosphere.As a result, it is possible to think the low physical blowing of thermal conductivity Agent remains in bubble throughout for a long time, while oxygen, nitrogen from atmosphere being inhibited to flow into the bubble of extrusion foaming plate, by The thermal conductivity of extrusion foaming plate can be remained low state throughout long-time by this.

It,, can be according to expectation in aforementioned thermoplastic resin in the range of not hindering the purpose of the present invention in the present invention Purpose mix in addition to aforementioned polystyrene system's resin (a), PET series resin (b), polystyrene Other compositions except resin (c1) and PET series resin (c2).As other compositions, can enumerate Such as PET series resin, polyolefin resin, polystyrene other than resin (b), resin (c2) Elastomer etc..It should be noted that the upper limit of its use level is generally in terms of 100 weight % by constituting the thermoplastic resin of extrusion foaming plate, Preferably 30 weight %, further preferably 20 weight %, particularly preferably 10 weight %.

Then, it is illustrated for physical blowing agent used in the present invention.

As physical blowing agent, organic physical blowing agents and/or inorganic physical blowing agent can be used.As organic physics Foaming agent can enumerate the saturated hydrocarbons that carbon atom number is 3 ~ 5, the aliphatic alcohol that carbon atom number is 1 ~ 5, HF hydrocarbon (HFO), ether Class, alkyl chloride class.In addition, water, carbon dioxide, nitrogen etc. can be enumerated as inorganic physical blowing agent.These foaming agents can be with Individually or mix two or more use.

The saturated hydrocarbons for being 3 ~ 5 as aforementioned carbon atom number, can enumerate propane, normal butane, iso-butane, pentane, isoamyl Alkane, pentamethylene, neopentane etc..

As aforementioned HF hydrocarbon (HFO), anti-form-1 can be enumerated, 3,3,3- tetrafluoropropenes (trans- HFO-1234ze), Cis- -1,3,3,3- tetrafluoropropene (cis- HFO-1234ze), 1,1,1,2- tetrafluoropropene (HFO-1234yf), 2,3,3,3- tetra- The chlorine fluoro unsaturated hydrocarbons such as the chloro- 3,3,3- trifluoro propene of the fluoro such as fluoropropene unsaturated hydrocarbons, 1-.In the method for the present invention, hair is squeezed out Bubble plate contains at least one kind of in 1,3,3,3- tetrafluoropropene, 2,3,3,3- tetrafluoropropene, the chloro- 3,3,3- trifluoro propene of 1- Long-term thermal insulation is realized, so it is preferred that.

The aliphatic alcohol for being 1 ~ 5 as aforementioned carbon atom number, it can be cited for example that methylol (methanol), ethyl alcohol (second Alcohol), normal propyl alcohol, isopropanol, butanol, sec-butyl alcohol (isobutanol), the tert-butyl alcohol, aryl alcohol, crotonyl alcohol, propargyl alcohol, n-amyl alcohol, secondary penta Alcohol, isoamyl alcohol, tert-pentyl alcohol, neopentyl alcohol, 3- amylalcohol, 2-methyl-1-butene alcohol, 3- methyl -2- butanol etc..Among these, ethyl alcohol pair Environment, the safety of human body are excellent, so it is preferred that.

As aforementioned ethers, dimethyl ether, Anaesthetie Ether, ethyl-methyl ether, di-n-butyl ether, diisopropyl can be enumerated Ether etc..

As aforesaid alkyl chlorine class, methyl chloride, ethyl chloride etc. can be enumerated.

The total use level of the average thermoplastic resin 1kg of physical blowing agent is fitted according to desired being associated with for apparent density Work as selection, apparent density is 20 ~ 50kg/m in order to obtain³Extrusion foaming plate, preferably about 0.5 ~ 3 mole, more preferably 0.6 ~ 2.5 mole.

In the present invention, among physical blowing agent above-mentioned, preferably carbon atom number be 3 ~ 5 saturated hydrocarbons, HF hydrocarbon (HFO), the physical blowing agent (α) that the aliphatic alcohol and water that carbon atom number is 1 ~ 5 combines, mixing ratio are preferably carbon original 20 ~ 60 moles of mole % of %, HFO3 ~ 50 of the saturated hydrocarbons that subnumber is 3 ~ 5, aliphatic alcohol 3 ~ 40 moles of %, water 5 that carbon atom number is 1 ~ 5 (wherein, HFO, the aliphatic alcohol that carbon atom number is 1 ~ 5, carbon atom number are 3 ~ 5 saturated hydrocarbons and the match ratio of water to ~ 50 moles of % The total amount of example is 100 moles of %).

In physical blowing agent (α), if the mixing ratio of aforementioned saturated hydrocarbons is that can reduce apparent close in aforementioned range Degree squeezes out stability without reducing.In addition, it is excellent can be also readily derived long-term thermal insulation even if not adding a large amount of fire retardant Different extrusion foaming plate.In addition, the saturated hydrocarbons is high to the solubility of polystyrene resin, therefore it can be improved extrusion stability, It is slow to the gas penetration speed of polystyrene resin simultaneously, therefore can protect the thermal conductivity of extrusion foaming plate throughout the long period It is low for holding.From the point of view, the mixing ratio of saturated hydrocarbons is preferably 25 ~ 60 moles of %, more preferably 30 ~ 50 moles of %.

The use level of the average thermoplastic resin 1kg of aforementioned saturated hydrocarbons is preferably 0.1 ~ 3 mole, more preferably 0.2 ~ 2.5 Mole, further preferably 0.3 ~ 2 mole.If it is stable extrusion foaming within the scope of this, is able to carry out, it is easy to get the phase The extrusion foaming plate of the apparent density of prestige.

Aforementioned HF hydrocarbon be consumption ozone latent energy value be zero, global warming potential is very small and caused by environment Bear small foaming agent.Further, the thermal conductivity with gaseous state is low, is difficult to aptitude to burn, therefore by satisfying with aforementioned It is applied in combination with hydrocarbon, the usage amount of saturated hydrocarbons can be reduced, the additive amount of fire retardant can be reduced.

In physical blowing agent (α), if the mixing ratio of HFO is that not will cause gained extrusion foaming in aforementioned range Independent air bubble rate, the apparent density of plate reduce or foamed state is deteriorated, and HFO can be largely remained in bubble, therefore obtain The extrusion foaming plate of long-term excellent in heat insulating performance.From the point of view, the mixing ratio of HFO be preferably 5 ~ 40 moles of %, more preferably For 10 ~ 30 moles of %.

The use level of the average thermoplastic resin 1kg of aforementioned HFO is preferably 0.05 ~ 0.5 mole/kg.If the use level Within the scope of this, then to remain a effective amount of HFO in the extrusion foaming plate after extrusion foaming, being formed has squeezing for long-term thermal insulation Foamed board out.From the point of view, the use level of HFO be more preferably 0.1 ~ 0.4 mole/kg, further preferably 0.15 ~ 0.3 mole/kg.

In physical blowing agent (α), if the mixing ratio for the aliphatic alcohol that aforementioned carbon atom number is 1 ~ 5 is aforementioned range It is interior, then the excellent aforementioned poly terephthalic acid second two of barrier properties for gases can be formed while obtaining desired apparent density Alcohol ester system resin (I) phase.

The aliphatic alcohol that the carbon atom number is 1 ~ 5, which has, specifically improves PET series resin (b), the characteristic of the plasticity of PET series resin (c2).Pass through the effect, relative reduction thermoplastic resin In PET series resin (b), PET series resin (c2) is relative to polyphenyl second The viscosity of olefine resin, thus, it is possible to be readily formed by PET series resin (b), poly terephthalic acid second The striated phase for the PET series resin (I) that diol ester system resin (c2) is constituted.From the point of view, The mixing ratio for the aliphatic alcohol that carbon atom number is 1 ~ 5 is more preferably 5 ~ 30 moles of %, further preferably 8 ~ 20 moles of %.

The use level for the aliphatic alcohol that aforementioned carbon atom number is 1 ~ 5 thermoplastic resin 1kg that is averaged is preferably 0.05 ~ 0.3 to rub That, more preferably 0.07 ~ 0.28 mole, further preferably 0.08 ~ 0.25 mole, particularly preferably 0.10 ~ 0.23 mole.

In physical blowing agent (α), fat that the use level (γ) of aforementioned HF hydrocarbon is 1 ~ 5 relative to aforementioned carbon atom number The molar ratio (γ/β) of the use level (β) of race's alcohol is preferably 0.3 ~ 4.If the molar ratio is that can obtain in the range Extrusion foaming plate with excellent long-term thermal insulation.

From the point of view, which is more preferably 0.5 ~ 3.5, further preferably 1 ~ 2.

It should be noted that use hydrocarbon, HFO as in the extrusion foaming plate of foaming agent, these foaming agents and the fluorine used in the past Leon class is compared, relatively fast to the penetration speed of polystyrene resin, therefore after extrusion foaming, compared with premature expansion agent from hair Thus there is the tendency that the long-term thermal insulation of extrusion foaming plate is easily reduced in loss in foam.On the other hand, through the invention Obtained from extrusion foaming plate, by using PET series resin (c2) in polystyrene resin With hybrid resin (c) existing for microdispersed state, in the bubble chamber film cross-section photograph of gained extrusion foaming plate, it is easy to form The pattern of a large amount of striated phases formed by PET series resin (I) is confirmed in bubble chamber film.Its result Be, through the invention obtained from extrusion foaming plate, be effectively prevented physical blowing agent, particularly the loss of HFO, also prevent Air is flowed into from atmosphere into bubble, and the superior foaming compared with previous extrusion foaming plate of long-term thermal insulation is consequently formed Plate.

In physical blowing agent (α), by the way that water and saturated hydrocarbons, HFO and aliphatic alcohol to be used together, institute is further improved The expansion ratio for obtaining extrusion foaming plate, can reduce apparent density.The mixing ratio of water be preferably 5 ~ 50 moles of % (wherein, HFO, The total amount of the mixing ratio of aforementioned aliphatic alcohol, aforementioned saturated hydrocarbons and water is 100 moles of %).But even if not using water, Also extrusion foaming plate can be manufactured.

If the mixing ratio of water is to be easy while obtaining desired apparent density within the scope of this, prevent from squeezing out The deterioration of the bubble shape of foamed board can be readily derived the extrusion foaming plate of long-term excellent in heat insulating performance.Go out from the viewpoint Hair, the mixing ratio are 10 ~ 40 moles of %, more preferably 15 ~ 35 moles of %.

Then, it is added for fire retardant, flame retardant used in the present invention, thermal insulation modifier, bladder regulator etc. Agent is illustrated.

Thermoplastic resin extrusion foaming plate obtained from through the invention is mainly used as thermal insulation board for building, therefore preferably full Record in " measuring method A " specified in sufficient JIS A9511 (2006R) 5131 with extruded polystyrene foam insulation board Flammability standard as object.Meet the thermoplastic resin extrusion foaming plate of the standard and exists except through adjusting aforementioned saturated hydrocarbons Except content in extrusion foaming plate, it can also be realized by adding fire retardant.

As the fire retardant that can cooperate in thermoplastic resin extrusion foaming plate of the invention, it is preferable to use bromine system is fire-retardant Agent.As bromide fire retardant, brominated bisphenol flame retardant, bromination isocyanuric acid ester flame retardant or brominated fourth two can be enumerated Alkene-styrol copolymer flame retardant etc..

Brominated bisphenol flame retardant refers to the bromide of bisphenol-A, Bisphenol F, bisphenol S or their derivative, can enumerate Tetrabromobisphenol A-bis- (the bromo- 2- methyl-propyl ethers of 2,3- bis-), tetrabromobisphenol A-bis- (2,3- dibromopropyl ethers) etc..

Bromination isocyanuric acid ester flame retardant refers to the bromide of isocyanuric acid or isocyanuric acid derivative, can enumerate different Cyanurate list (2,3- dibromopropyl) ester etc..

As brominated butadiene-styrol copolymer, block copolymer, random copolymer or grafting can be directly used altogether The known substance such as polymers can enumerate polystyrene-brominated polybutadiene copolymer etc..Specifically, can enumerate The commercially available products such as the FR122P of Emerald3000, ICL-IP company of Chemtura company.

Total use level of bromide fire retardant is suitably determined according to desired anti-flammability, meets JIS A9511 in order to obtain The polystyrene serial resin extruded foaming body of the flammability standard for the extruded polystyrene foam insulation board that (2006R) is recorded, phase 1 ~ 10 parts by weight, more preferably 2 ~ 8 parts by weight are preferably cooperated for 100 parts by weight of thermoplastic resin.If total use level is Within the scope of this, then fire retardant will not hinder foaminess, obtain the extrusion foaming body of good surface state.

It should be noted that foregoing flame retardants may include in addition to brominated bisphenol flame retardant, bromination isocyanuric acid ester system are fire-retardant Other fire retardants except agent and brominated butadiene-styrol copolymer flame retardant.The additive amount of other fire retardants relative to The additive amount of fire retardant is totally preferably 20 weight % or less, more preferably 10 weight % or less.

As the method that foregoing flame retardants cooperate into thermoplastic resin, can use the fire retardant of regulated proportion and heat Plastic resin is supplied together to the method for flowing the supply unit of setting on extruder and being kneaded in an extruder.Except this it It outside, can also be using the side for supplying fire retardant into molten thermoplastic resin from the fire retardant supply unit being arranged on the way in extruder Method.It should be noted that when fire retardant is supplied to extruder by fire retardant and thermoplastic resin can be constituted using to extruder supply The method of substance obtained from the polystyrene resin of rouge etc. is dry-mixed；Make flame retardant masterbatch, fire retardant melting mixing object, simultaneously It is supplied together with thermoplastic resin to the method for extruder.Particularly, from the viewpoint of dispersibility, it is preferred to use production is fire-retardant Masterbatch is simultaneously supplied to the method for extruder.

It, can be by hindered phenolic stabilizer, phosphorus system stabilizer and the amine system stabilizer that is obstructed in extrusion foaming plate of the invention Equal stabilizers are added in thermoplastic resin.These stabilizers capture the halogen that the bromide fire retardant in processing is decomposed and generated Free radical, halide ion, thus, it is possible to inhibit the molecular weight of polystyrene resin to reduce, colour.

It further, can be by 2,3- dimethyl -2,3- diphenyl butane, 2,3- diethyl -2,3- bis- as flame retardant The hexichol such as the diphenyl alkanes such as phenyl butane, 2,4- diphenyl -4-methyl-1-pentene, 2,4- diphenyl -4- ethyl -1- amylene The polyalkylbenzene such as base alkene, poly- 1,4- diisopropyl benzene, triphenyl phosphate, tricresyl phosphate base two (2,6- xylyl) ester, three Antimony oxide, antimony pentoxide, ammonium sulfate, zinc stannate, cyanurate, isocyanuric acid, triallyl isocyanurate, melamine cyanogen urea Nitrogenous cyclic compound, silicone compound, the oxidations such as acid esters, melamine, melam (melam), melem (melem) Phosphorus series compounds such as the inorganic compounds such as boron, zinc borate, zinc sulphide, red phosphorus system, ammonium polyphosphate, phosphonitrile, hypophosphites etc. are matched Together in thermoplastic resin.These compounds may be used alone or in combination two or more.

In extrusion foaming plate of the invention, thermal insulation is cooperated to improve in the aforementioned thermoplastic resin of Xiang Zuowei substrate resin Agent, so as to further increase thermal insulation.As thermal insulation modifier, the oxidation of the metal such as titanium oxide may be exemplified out Micropowder, infrared ray masking pigment, hydrotalcite of the metals such as object, aluminium, ceramics, carbon black, graphite etc. etc..They can be used a kind Or two or more.The additive amount of the thermal insulation modifier is relative to 100 parts by weight of thermoplastic resin preferably in about 0.5 ~ 10 weight It is used in the range of part, further preferably uses 1 ~ 8 parts by weight.

In addition, can suitably cooperate bladder regulator, pigment, dyestuff etc. as needed in substrate resin in the present invention The various additive such as colorant, heat stabilizer, filler.

As aforementioned bladder regulator, such as talcum, kaolin, mica, silica, calcium carbonate, sulfuric acid can be used The inorganic material powders such as barium, titanium oxide, aluminium oxide, clay, bentonite, diatomite, azo-2-carboxylic acid's diamides etc. are known Chemical foaming agent etc..Wherein, it is suitably for not hindering anti-flammability and is easily adjusted the talcum of bubble diameter.The addition of bladder regulator Amount is different according to type, target bubble diameter of bladder regulator etc., relative to 100 parts by weight of thermoplastic resin, preferably About 0.01 ~ 8 parts by weight, further preferably 0.01 ~ 5 parts by weight, particularly preferably 0.05 ~ 3 parts by weight.

Bladder regulator uses preferably in the form of masterbatch from the viewpoint of dispersibility.The masterbatch of bladder regulator When talcum is for example used as bladder regulator by preparation, preferably reach 20 ~ 80 weight %'s relative to the content of substrate resin with talcum Prepared by mode, more preferably prepare in such a way that the content reaches 30 ~ 70 weight %.

Hereinafter, the various physical property of thermoplastic resin extrusion foaming plate obtained from being directed to through the invention are retouched in detail It states.

In extrusion foaming plate obtained from through the invention, the thermoplastic resin of its bubble chamber film is constituted by polystyrene tree Rouge and PET series resin are constituted, and the PET series resin, which has, is used as dicarboxyl The terephthalic acid (TPA) ingredient units of sour component unit and glycol component unit as diol component unit are as main component Unit.Further, according to the present invention, it is suppressed that by PET series resin (b) and poly terephthalic acid second The PET series resin (I) that diol ester system resin (c2) is constituted mutually is separated into island and/or bulk, can PET series resin (I) is set mutually to be stretched as striated along bubble chamber film and disperse, therefore can be in polyphenyl The PET series resin that can show gas barrier effect is formed in the bubble chamber film section of vinyl (I) phase.PET series resin (I) is mutually in the bubble chamber film cross-section photograph of extrusion foaming plate, with multiple The form of line shape phase and be identified.It should be noted that PET series resin (b) and poly terephthalic acid second two Alcohol ester system resin (c2) is difficult to differentiate between after melting mixing, with PET series resin in extrusion foaming plate (I) form of phase and be observed.

It should be noted that in this specification, the poly terephthalic acid of the striated confirmed in the cross-section photograph of bubble chamber film Glycol ester system resin (I) mutually refers in cross-section photograph, in the direction (length direction and gas of bubble chamber film along bubble chamber film The vertical direction of the thickness direction of vacuolar membrane) on the linear or band-like shape there are PET series resin (I) Cheng Xiang.

Aforementioned PET series resin (I) mutually inhibit air intrusion bubble chamber film in, be able to suppress with Physical blowing agent loss headed by HF hydrocarbon is into atmosphere.Therefore, it is able to suppress the rising of the thermal conductivity of extrusion foaming plate, time And thermal conductivity is suppressed to for a long time low.Further, specific by being formed obtained from through the invention in extrusion foaming plate PET series resin (I) phase, effectively inhibit air flow into bubble in.

The apparent density of extrusion foaming plate obtained from through the invention is 20 ~ 50kg/m³.When apparent density is too small, system It makes extrusion foaming plate itself to become difficult, and forms the insufficient extrusion foaming plate of mechanical strength depending on the application.Another party Face, when apparent density is excessive, it is difficult to sufficient thermal insulation is played, it is furthermore also not preferred from the viewpoint of light weight.From institute It states viewpoint to set out, the lower limit of the apparent density is preferably 25kg/m³, the upper limit is preferably 45kg/m³。

The extrusion foaming plate with a thickness of 10 ~ 150mm.When thickness is excessively thin, wanted in the case where being especially used as heat-barrier material The thermal insulation asked is possible to become inadequate.On the other hand, different according to the size of extruder, but when thickness is blocked up, foaming Extrusion molding is possible to become difficult.The lower limit of the thickness is more preferably 15mm, and the upper limit is more preferably 120mm.

The thickness direction mean air bubble diameter of extrusion foaming plate is preferably 0.05 ~ 2mm.Its lower limit is more preferably 0.06mm. Its upper limit is more preferably 0.7mm, further preferably 0.3mm.By making the mean air bubble diameter of thickness direction be in aforementioned model In enclosing, it can be cooperateed with the composition of aforementioned apparent density range and infrared ray is inhibited to penetrate, it is superior to be easy to get thermal insulation Extrusion foaming plate.

The measuring method of mean air bubble diameter in this specification is as described below.

It is first in the measurement of the mean air bubble diameter (DTav), the mean air bubble diameter (DWav) of width direction of thickness direction First at 3 positions of total near the central portion of the width direction vertical cross-section of extrusion foaming plate and two ends, with photo In the small number of chambers reach 200 to 500 or so modes, adjust enlargement ratio in the range of 50 times to 200 times or so and obtain To enlarged photograph.Then, on each photo, the image processing software NS2K- of Na ノシステ system Co. Ltd. system is used Pro measures the expense thunder diameter of expense the thunder diameter and width direction of the thickness direction of each bubble.Thereafter, by dividing these values Not carry out arithmetic average, the mean air bubble diameter (DTav) of thickness direction, the mean air bubble diameter of width direction can be found out (DWav)。

The mean air bubble diameter (DLav) for squeezing out direction measures as described below.Firstly, by the width of extrusion foaming plate At the position that direction is halved, extrusion foaming plate is cut along extrusion direction and obtains squeezing out direction vertical cross-section, with Machine obtains the microscope enlarged photograph at 3 positions for squeezing out direction vertical cross-section.Then, on each photo, Na is used The image processing software NS2K-pro of ノシステ system Co. Ltd. system measures the expense thunder diameter in the extrusion direction of each bubble. Then, by the way that these values are carried out arithmetic average respectively, the mean air bubble diameter (DLav) for squeezing out direction can be found out.

In addition, the mean air bubble diameter DH of the horizontal direction of extrusion foaming plate is set as the arithmetic mean of instantaneous value of DWav and DLav.

In extrusion foaming plate obtained from through the invention, bubble deformation rate is preferably 0.7 ~ 2.0.Bubble deformation rate refers to By the value (DT/DH) that the DT found out using aforementioned measuring method is divided by DH to be calculated, the bubble deformation rate is smaller compared with 1, Then bubble is flat (horizontally long shape), bigger compared with 1, then elongate shape.When bubble deformation rate is too small, bubble is flat It is flat, therefore compressive strength is likely to decrease, in addition, flat bubble will restore strong to spherical tendency, therefore extrusion foaming plate Dimensional stability be also possible to reduce.When bubble deformation rate is excessive, number of bubbles tails off in a thickness direction, therefore because of bubble shape Thermal insulation improvement effect becomes smaller caused by shape.From such a viewpoint, the lower limit of the bubble deformation rate is more preferably 0.8. Its upper limit is preferably 1.5, more preferably 1.2.By being in bubble deformation rate in aforementioned range, formation mechanical strength, And the thermoplastic resin extrusion foaming plate with higher thermal insulation.

The independent air bubble rate of extrusion foaming plate obtained from through the invention is preferably 85% or more, more preferably 90% with Upper, further preferably 92% or more, particularly preferably 93% or more.Independent air bubble rate is higher, then the physical blowing agents such as HFO can be with It is stopped in bubble longlyer, high heat-proof quality can be maintained throughout long-time.Independent air bubble rate S (%) is according to ASTM- The process C of D2856-70, using air comparison expression densimeter (such as Toshiba's ベッ Network マ Application (strain) make, air comparison expression specific gravity Meter, model: 930 types) and measure.

Further, through the invention obtained from thermoplastic resin extrusion foaming plate expectation meet JIS A9511 (2006R) The standard of thermal conductivity specified in 4.2.

Further, through the invention obtained from extrusion foaming plate manufacture after thermal conductivity after 1 day be preferably 0.0270W/ (mK) below, more preferably 0.0260W/ (mK) below, further preferably 0.0250W/ (mK) below. If the thermal conductivity is to form excellent in heat insulating performance within the scope of this and be suitable for the extrusion foaming plate of building materials purposes.Further, should Extrusion foaming plate is in terms of long-term thermal insulation is also excellent, for the thermal conductivity after manufacture after 100 days, preferably also 0.0265W/ (mK) below, further preferably 0.0260W/ (mK) below.Extrusion foaming obtained from through the invention In plate, aforementioned polystyrene system's resin (a), polyethylene terephthalate are used with special ratios as thermoplastic resin It is resin (b) and hybrid resin (c) to extrusion foaming, therefore is formed in bubble chamber film and play the aforementioned of gas barrier effect PET series resin (I) phase of pattern.Therefore, aforementioned HFO is effectively prevented from extrusion foaming plate Loss and air flow into bubble, even if passing through 100 days after fabrication, thermal conductivity is also maintained low.

Embodiment

Hereinafter, illustrating the present invention by embodiment and comparative example.But the present invention is not limited to these embodiments.

Polystyrene resin used in embodiment and comparative example is shown in as follows.

As polystyrene resin (a), polystyrene resin (c1), under use is cooperated with weight ratio shown in hereafter Polystyrene 1 (PS1), polystyrene 2 (PS2) shown in text, resin 1, resin 2 obtained from polystyrene 3 (PS3).

Polystyrene resin

Resin 1: polystyrene 1

Resin 2: the polystyrene that polystyrene 1 and polystyrene 2 are obtained by mixing with the weight ratio of 26:40

It should be noted that resin 2 to be carried out to melt viscosity (200 DEG C, 100s of pellet obtained from melting mixing at 200 DEG C^-1) For 1000Pas.

Resin 3: polystyrene 3

(1) polystyrene 1 (PS1): DIC corporation class name HP780, and melt viscosity (200 DEG C of temperature, shear velocity 100s^-1) =1946Pas melts tension (200 DEG C)=45cN

(2) polystyrene 2 (PS2): PS ジャパ Application corporation class name 679, melt viscosity (200 DEG C of temperature, shear velocity 100s^-1)=673Pas melts tension (200 DEG C)=3cN

(3) polystyrene 3 (PS3): DIC corporation class name HP600ANJ, and melt viscosity (200 DEG C of temperature, shear velocity 100s^-1)=1424Pas melts tension (200 DEG C)=18cN.

As PET series resin (b), PET series resin (c2), use SPET1, SPET2, PETG1 shown below.

SPET1: gas chemical company, Mitsubishi class name S3002, melt viscosity (200 DEG C of temperature, shear velocity 100s^-1)= 3500Pas melts tension (200 DEG C)=3cN, melts heat=0J/g

SPET2: gas chemical company, Mitsubishi class name S3012, melt viscosity (200 DEG C of temperature, shear velocity 100s^-1)= 2000Pas melts tension (200 DEG C)=3cN, melts heat=0J/g

PETG1: heat by extruder Dui イーストマ Application ケミカ Le corporation class name GN001 and heat modification PET series resin, melt viscosity (200 DEG C of temperature, shear velocity 100s^-1)=1800Pas, fusing Heat=0J/g.

Bladder regulator

Use using talcum of the polystyrene resin as basic resin and containing 60 weight % (loose village's industry (strain) system, trade name: Ha イ Off ィラー #12) talc masterbatch MB6S.

Fire retardant

Use mixes bis- (the bromo- 2- methyl-propyl ether of 2,3- bis-) (the first industrial pharmaceutical systems of (i) tetrabromobisphenol-A-with weight ratio 3:2 ) and the fire retardant of (ii) tetrabromobisphenol-A-bis- (2,3- dibromopropyl ether) (the first industrial pharmaceutical SR720) SR130.

Graphite

It is made using レジノカラー industrial (strain), trade name: SBF-T-6526.

Titanium oxide

It is made using ビッ Network ス (strain) is expanded day, trade name: PS-ET2813.

Physical blowing agent

Following (1) ~ (4) are used as physical blowing agent.

(1) saturated hydrocarbons that carbon atom number is 3 ~ 5: iso-butane (referred to as " i-Bu ")

(2) HFO: trans-1,3,3,3-tetrafluoropropene (HFO-1234ze)

(3) aliphatic alcohol that carbon atom number is 1 ~ 5: ethyl alcohol

(4) water.

The manufacture of hybrid resin (c)

(1) resin granular material " C-1 " " C-2 " " C-3 " " C-4 "

By the poly terephthalic acid of type shown in type shown in table 1, the polystyrene resin (c1) of proportion, table 1, proportion Type shown in glycol ester system resin (c2) and table 1, the graphite of proportion, titanium oxide, fire retardant, bladder regulator supply to Aftermentioned extruder, further supplies each physical blowing agent by physical blowing agent supply mouth, and heating melting, is kneaded, squeezes out hair Bubble, manufactures polystyrene serial resin extruded foamed board.It should be noted that the extrusion of condition and aftermentioned embodiment 1 when squeezing out is sent out The manufacturing condition for steeping plate is identical.After the extrusion foaming plate is crushed, supply to extruder, heating, is kneaded melting, shown in table 1 Heating melting at a temperature of be extruded as twist material shape.It cuts, the strand material water cooling of extrusion to obtain hybrid resin with granulator (c) resin granular material " C-1 " " C-2 " " C-3 " " C-4 ".

[table 1]

。

(2) resin granular material " C-5 " " C-6 " " C-7 "

By type shown in table 1, proportion polystyrene resin (c1) and table 1 shown in type, proportion poly- terephthaldehyde To extruder, heating, is kneaded melting for sour glycol ester system resin (c2) supply, and the heating melting shown in table 1 at a temperature of squeezes out Shape is expected to twist.It by the strand material water cooling of extrusion, is cut with granulator, to obtain resin granular material " C-5 ".Then, by resin granular material " C-5 " to extruder, heating, is kneaded melting for supply (for the second time) again, and the heating melting shown in table 1 at a temperature of is extruded as Twist material shape.It by the strand material water cooling of extrusion, is cut with granulator, to obtain resin granular material " C-6 ".Then, by resin granular material " C- 6 " to extruder, heating, is kneaded melting for (third time) supply again, and the heating melting shown in table 1 at a temperature of is extruded as twisting material Shape.It by the strand material water cooling of extrusion, is cut with granulator, to obtain resin granular material " C-7 ".

Device

Prepare manufacturing device, wherein the 2nd extruder of the 1st extruder of internal diameter 65mm and internal diameter 90mm are connected in series, foaming Agent inlet is set near the terminal of the 1st extruder, and having width direction section is rectangle (gap 1mm × width The flat-die of resin outlet (die lip) 115mm) is connect with the outlet of the 2nd extruder, further in the resin outlet of the flat-die Additional setting size enlargement apparatus (guider), the size enlargement apparatus (guider) are provided with by upper and lower a pair by polytetrafluoroethylene (PTFE) tree The plate that rouge is formed.It should be noted that on the guider, by the thickness direction along foamed board with the gap configured in parallel of 25mm A pair of polyflon plate up and down forms the access for being divided into 25mm between the upper and lower.

Embodiment 1 ~ 9, comparative example 1 ~ 3

In a manner of reaching each use level shown in table 2, resin, fire retardant, bladder regulator, graphite, titanium oxide are supplied To extremely aforementioned 1st extruder.Then, they are heated to 220 DEG C, melting is kneaded and resin melt is made, and Cong 1 is squeezed The blowing agent injection port that the front end of machine is nearby arranged out, will match the physical blowing agent of composition shown in table shown in table 2 Ratio supply to fusant, melting mixing, producing foamed resin melt.The foaminess resin fusant is then shifted To the 2nd extruder and the 3rd extruder, the temperature that resin temperature is adjusted to such suitable foaming shown in table (is stated in table For extrusion resin temperature；The blowing temperature is the foaminess resin melting measured at the position at the joint portion of extruder and mold The temperature of object) after, it is squeezed out from die lip into guider with the spray volume of 70kg/hr, in foaming while the access for passing through guider, Thus molding (figuration) is plate.The thermoplastic resin extrusion foaming plate of thickness 28mm is obtained as a result,.Gained extrusion foaming plate Physical property, evaluation are shown in table 2.

[table 2]

。

In embodiment 1, using including poly- terephthaldehyde shown in 43 weight % of polystyrene resin, table 2 shown in table 2 The thermoplastic resin of hybrid resin (c) " C-1 " shown in sour 13 weight % of glycol ester system's resin (b) and table 1 is sent out as physics Iso-butane, HFO, ethyl alcohol, water are used in mixed way by infusion with proportion shown in table 2.Electron microscopic is passed through to gained extrusion foaming plate When mirror shoots cross-section photograph, in the section of bubble chamber film, as shown in Figure 4, polyethylene terephthalate can be confirmed Ester system resin (I) forms multiple striated phases in polystyrene resin, and further polystyrene resin is with poly- to benzene two Formic acid glycol ester system resin (I) forms co-cable transmission.

By the value of the thermal conductivity of table 2 it is found that the thermal conductivity of gained extrusion foaming plate changes with time small, long-term thermal insulation It is excellent.

In embodiment 2, substitute hybrid resin (c) " C-1 ", using hybrid resin (c) " C-2 ", in addition to this with embodiment 1 Get similarly extrusion foaming plate.As shown in Table 2, the thermal conductivity of gained extrusion foaming plate changes with time small, long-term heat-insulated Property is excellent.

In embodiment 3, substitute hybrid resin (c) " C-1 ", using hybrid resin (c) " C-3 ", in addition to this with embodiment 1 Get similarly extrusion foaming plate.As shown in Table 2, the thermal conductivity of gained extrusion foaming plate changes with time small, long-term heat-insulated Property is excellent.

Embodiment 4 is change polystyrene resin (a), PET series resin (b), hybrid resin (c) example of mixing ratio.Since the mixing ratio of hybrid resin (c) is few, lead to PET series tree The formation effect of rouge (I) phase is small, and the thermal conductivity after manufacture after 1 day and after 100 days becomes larger compared with Example 1.

Embodiment 5 is change polystyrene resin (a), PET series resin (b), hybrid resin (c) example of mixing ratio.Since the mixing ratio of hybrid resin (c) is more, lead to the heat after manufactured after 1 day and after 100 days Conductance becomes larger compared with Example 1.

Embodiment 6 is the example that PET-G is used as PET series resin (b).It knows to make In the case where with PET-G, compared with the comparative example 3 of unused hybrid resin (c), thermal conductivity change with time it is also small, for a long time Thermal insulation also improves.

On the other hand, in comparative example 1, as shown in Table 2, use and contain polystyrene resin " resin 2 " 77 weights Measure % and 23 weight % of PET series resin (b) but the thermoplastic resin of unmated hybrid resin (c), system Make extrusion foaming plate.Using only the PET series resin (b) as pure raw material without the use of compound tree When rouge (c), the dispersity of PET series resin (I) deteriorates, and polyethylene terephthalate It is that resin (I) is difficult to be stretched, there are the tendencies that the fringe-like structures of PET series resin (I) tail off (Fig. 8 ~ 11).In addition, the difference of the thermal conductivity behind after manufacture 1 day and after 100 days and embodiment are compared, it is known that the extrusion of comparative example Changing over time for the thermal conductivity of foamed board is big.

Comparative example 2 is the example that hybrid resin (c) " C-1 " is not used for embodiment 1.Use unmated mixing When the thermoplastic resin of resin (c), it is difficult to steadily manufacture good extrusion foaming plate.

Comparative example 3 is to use PET-G as PET series resin (b) and do not use compound tree The example of rouge (c).With the comparison of embodiment 6 it is found that thermal conductivity changes with time greatly, long-term thermal insulation is reduced.

Embodiment 7 is the recycling raw material (recycled resin) of foamed board to be substituted as hybrid resin (c) and use will be pure The example of hybrid resin (c) " C-5 " obtained from raw material method as shown in table 1 is heated, melted, is kneaded.It carries out 1 time In the cross-section photograph of hybrid resin (c) " C-5 " pellet of heating melting processing, as shown in Figure 2, poly terephthalic acid second two Alcohol ester system resin (c2) micro disperse in polystyrene resin, and form striated phase.Therefore, thermal conductivity is at any time Variation it is small, long-term thermal insulation is most excellent.

Embodiment 8,9 is for embodiment 7 using increasing hybrid resin obtained from the number of heat treatment (c) example of " C-6 " " C-7 ".At this point, the cross-section photograph of hybrid resin (c) pellet is as shown in Figure 3, although passing through heating It handles and micro disperse, but since striated mutually gradually interrupts, long-term thermal insulation reduces compared with Example 7.Therefore, it is known that Heat treatment number when manufacturing recycled resin is preferred less.

Each physical property in table measures as follows.

(melt viscosity)

Made キャピログラ Off 1D is made in the measurement of melt viscosity using Toyo Co., Ltd.'s essence mechanism, 200 DEG C of temperature, Shear velocity 100s^-1Under conditions of carry out.Specifically, first prepare barrel diameter 9.55mm, length 350mm machine barrel and The aperture of nozzle diameter 1.0mm, length 10.0mm.Then, the set temperature of machine barrel and aperture is set as 200 DEG C, heat will be passed through Wind circulating drying machine compared with glass transition temperature low 10 DEG C at a temperature of carried out abundant drying resin be added should In machine barrel, melt viscosity is measured after placing 4 minutes, using the value obtained herein as melt viscosity (Pas).It should be noted that It is measured in such a way that the resin squeezed out in measurement from aperture twists and is not mixed into bubble as far as possible in material.

It should be noted that measurement PET series resin (b), PET series resin (c2) when, before the assay, 12 hours dry resins are expended in 80 DEG C of vacuum drying oven.

(apparent density)

The measurement of apparent density is carried out according to JIS K7222:1999.

(independent air bubble rate)

In this specification, for the independent air bubble rate of extrusion foaming plate, measured by the process C of aforementioned ASTM-D2856-70 each The independent air bubble rate of sample is found out their measured value in the form of arithmetic mean of instantaneous value (5 points or more) by following formula (1).From 3 positions of total near two ends of central portion and width direction of extrusion foaming plate cut out cutting sample, by each cutting Sample is as measurement sample, for each measurement Specimen Determination independent air bubble rate, using the arithmetic of the independent air bubble rate at 3 positions Average value.It should be noted that cutting sample be set as being cut into vertical 25mm × horizontal 25mm × thickness 20mm from extrusion foaming plate it is big Sample that is small and not having extrusion foaming plate epidermis.

S(%)=(Vx-W/ρ)×100/(VA-W/ρ) (1)

Wherein, Vx: pass through the true volume (cm for the cutting sample that the aforementioned measurement using air comparison expression densimeter is found out³) (bubble for being equivalent to the independent air bubble part in the volume and cutting sample for constituting the resin of cutting sample of extrusion foaming plate is total The sum of volume)

VA: the apparent volume (cm for the cutting sample that the outside dimension of the cutting sample as used in measurement calculates³)

W: cutting sample total weight (g) used in measurement

ρ: the density (g/cm of the substrate resin of extrusion foaming plate is constituted³)。

(mean air bubble diameter of thickness direction)

For the mean air bubble diameter (DTav) of thickness direction, measured by preceding method.Firstly, obtaining the width of extrusion foaming body The enlarged photograph that the enlargement ratio of the central portion and three positions of total near two ends of spending direction vertical cross-section is 50 times. On each photo, using the image processing software NS2K-pro of Na ノシステ system Co. Ltd. system, each bubble is measured These values are carried out arithmetic average respectively, thus find out thickness by the bubble diameter of thickness direction and the bubble diameter of width direction The mean air bubble diameter (DTav) in direction.In addition, by the bubble diameter of the width direction found out by preceding method divided by thickness Thus the bubble diameter in direction calculates the bubble deformation rate of foamed board.

(direction MD of the bubble chamber film of extrusion foaming plate and the section of the direction TD cross-section photograph, hybrid resin (c) pellet are shone Piece)

Firstly, by being embedded in epoxy resin from the center portion of extrusion foaming plate with the foaming body that size appropriate is cut out.Packet After burying, cut out from foaming body with glass cutter perpendicular to the face (section MD) of thickness direction or perpendicular to the face for squeezing out direction (section TD) is sliced with diamond tool from the ultrathin of foaming body that section cuts out about 0.1 μm of thickness.In the slice that will be cut out (sample) be placed in Cu it is online in the state of, be put into togerther in culture dish, seal at room temperature, cruelly with 2%OsO4 aqueous solution number ml It is exposed in OsO4 steam, dye within 30 minutes.Then, by sample with mix immediately before use NaClO aqueous solution number ml and The solution that the RuCl3 crystal of 1 spoon of small spoon amount is obtained by mixing is added in culture dish together, seals at room temperature, is exposed to and is produced In raw RuO4 steam, dye within 30 minutes.Using transmission electron microscope, the ultrathin type of the foaming body through dyeing is shot Slice.In the electron micrograph of shooting, white portion is polystyrene resin, and black portions are poly terephthalic acid Glycol ester system resin (I).It should be noted that transmiting electricity using Jeol Ltd.'s system as transmission electron microscope Sub- microscope " JEM-1010 ".

In addition, the center portion of hybrid resin (c) pellet is cut out with size appropriate, it is embedded in epoxy resin.Packet After burying, in a manner of identical with extrusion foaming body, the face (MD section) parallel with the extrusion direction of hybrid resin (c) pellet is shot Cross-section photograph (5000 times of multiplying power).

[shooting condition]

Transmission electron microscope: Jeol Ltd.'s transmission electron microscope " JEM-1010 "

Acceleration voltage: 100kV

Dyeing: ruthenium tetroxide

Multiplying power: 5000 times, 20000 times.

(the phase state of PET series resin (I))

Using the cross-section photograph of the bubble chamber film of aforementioned extrusion foaming plate, PET series resin is visually observed (I) pattern is evaluated according to following benchmark.

◎: in bubble chamber film section, PET series resin (I) forms multiple striated phases, poly- terephthaldehyde Sour glycol ester system resin (I) is stretched well.

Zero: in bubble chamber film section, PET series resin (I) forms multiple striated phases, but poly- pair of part Ethylene terephthalate system resin (I) is not sufficiently tensile, there is thick phase.

×: in bubble chamber film section, PET series resin (I) forms massive phase.

(thermal conductivity, the difference of thermal conductivity)

After extrusion foaming plate after immediately manufacturing is saved 1 day, further preservation 100 days under 23 DEG C, the atmosphere of humidity 50%, Thermal conductivity is measured by the following method, is thus found out after the thermal conductivity and manufacture after the manufacture of extrusion foaming plate after 1 day 100 days Thermal conductivity afterwards.

From extrusion foaming plate, cutting out vertical 200mm × horizontal 200mm × thickness 10mm extrusion foaming plate, there is no epidermises Test film, for the test film, plate heat-flow meter method (2 pieces of sides of heat-flow meter for being recorded based on JIS A1412-2 (1999) Formula, 38 DEG C of high temperature side, 8 DEG C of low temperature side, 23 DEG C of mean temperature), measure thermal conductivity.

In addition, the thermal conductivity behind after manufacture 100 days is subtracted thermal conductivity after 1 day after manufacture, thus find out thermal conductivity it Difference.

(manufacture stability)

The evaluation of the foamed state of extrusion foaming plate is carried out according to following benchmark.

◎: extrusion foaming status pole is good, does not find bumps in foaming plate surface

Zero: extrusion foaming is in good condition, there are bumps in a part in foaming plate surface

×: largely there are bumps in foaming plate surface in extrusion foaming state difference.

(flammability)

Carry out 5131 measuring method A's according to JIS A9511 (2006R) 5131 for gained extrusion foaming plate Burning test.Measurement cuts out 5 test films to an extrusion foaming plate and carries out, and " all test film Flames are within 3 seconds Hour, without remaining dust, and be not above knock limit line and burn " the case where be evaluated as zero, in addition to this case where comment Valence be ×.

Claims

1. the manufacturing method of thermoplastic resin extrusion foaming plate, which is characterized in that foaminess resin fusant is carried out extrusion hair Bubble, the foaminess resin fusant are the extrusion foaming plates obtained from being kneaded thermoplastic resin and physical blowing agent With a thickness of 10 ~ 150mm, apparent density be 20 ~ 50kg/m³, in the manufacturing method,

The thermoplastic resin includes:

Polystyrene resin (a),

Fusing heat based on JIS K7122-1987 is lower than the PET series resin of 5J/g (including 0) (b) and

Hybrid resin (c), the hybrid resin (c) are by 50 ~ 95 weight % of polystyrene resin (c1) and based on JIS PET series resin (c2) 5 ~ 50 weight % of the fusing heat of K7122-1987 lower than 5J/g is kneaded and obtains It arrives, wherein the polystyrene resin (c1) adds up to PET series resin (c2's) 100 weight %；

Relative to 100 parts by weight of total use level of the polystyrene resin (a) and the polystyrene resin (c1), The total of the PET series resin (b) and the PET series resin (c2) is matched Resultant is 10 ~ 100 parts by weight.

2. the manufacturing method of thermoplastic resin extrusion foaming plate according to claim 1, which is characterized in that described poly- to benzene Cooperation of the use level of naphthalate system's resin (b) relative to the PET series resin (c2) The ratio between amount is 0.5 ~ 4.

3. the manufacturing method of thermoplastic resin extrusion foaming plate according to claim 1 or 2, which is characterized in that described poly- 200 DEG C, shear velocity 100s of phenylethylene resin series (a)^-1Under conditions of melt viscosity (η a) be 500 ~ 2500Pas, institute State 200 DEG C, shear velocity 100s of PET series resin (b)^-1Under conditions of melt viscosity (η b) phase The ratio between melt viscosity (η a) for polystyrene resin (a) (η b/ η a) is 0.4 ~ 2.

4. the manufacturing method of thermoplastic resin extrusion foaming plate according to claim 3, which is characterized in that the compound tree 200 DEG C, shear velocity 100s of rouge (c)^-1Under conditions of melt viscosity (η c) relative to the polystyrene resin (a) The ratio between melt viscosity (η a) (η c/ η a) is 0.2 ~ 1.

5. the manufacturing method of thermoplastic resin extrusion foaming plate according to claim 1 or 2, which is characterized in that described mixed Resin (c) is derived from the clast of polystyrene serial resin extruded foamed board and/or the recycling raw material of crushed material, the polyphenyl Vinylite extrusion foaming plate includes that the fusing heat based on JIS K7122-1987 is poly- to benzene two lower than 5J/g (including 0) Formic acid glycol ester system resin.

6. the manufacturing method of thermoplastic resin extrusion foaming plate according to claim 1 or 2, which is characterized in that will be described Hybrid resin (c) is processed as pellet.