WO2000061368A1

WO2000061368A1 - Composite material comprising polystyrene resin foam layer and thermoplastic resin layer

Info

Publication number: WO2000061368A1
Application number: PCT/JP1999/005996
Authority: WO
Inventors: Akira Iwamoto; Manabu Sato; Kenichi Takase; Toru Kino; Takasi Muroi; Yoshiaki Momose
Original assignee: Jsp Corporation
Priority date: 1999-04-09
Filing date: 1999-10-28
Publication date: 2000-10-19
Also published as: TW473430B; AU6367199A

Abstract

A composite material comprising a polystyrene resin foam layer, an alloy layer on at least one side of the polystyrene resin foam layer and a thermoplastic resin layer on the alloy layer, wherein the thermoplastic resin layer comprises a resin selected from a polyolefin resin and a polyester resin, the alloy layer comprises a mixture of a polystyrene resin with a thermoplastic resin selected from a polyolefin resin and a polyester resin, with the proviso that the thermoplastic resin in the alloy layer is a polyolefin resin when the thermoplastic resin layer consists substantially of a polyolefin resin, and the thermoplastic resin in the alloy layer is a polyester resin when the thermoplastic resin layer consists substantially of a polyester resin, and wherein the adhesion strength between the polystyrene resin foam layer and the thermoplastic resin layer is 980 mN/25mm or more.

Description

Specification

Composite materials with polystyrene resin foam layer and thermoplastic resin layer

The present invention relates to a composite material, and more particularly to a sheet or plate-like composite material having a polystyrene resin foam layer and a thermoplastic resin layer.

Background art

Expanded polystyrene sheets are widely used as materials for thermoforming various containers such as trays, bowls, and cups. However, foamed polystyrene sheets have poor oil and solvent resistance. Moreover, its heat resistance is relatively low, and when the container is heated in a microwave oven, it tends to be deformed.

In order to improve the disadvantages of these foamed polystyrene sheets, multilayer sheets in which a resin film of polyethylene, polypropylene, polyester, etc. is provided on one or both sides of a foamed polystyrene sheet have been studied. the _c Utility Model 5 9 1 7 6 2 8 discloses that have, polystyrene resin 4 0-6 0 by weight. /. A composite sheet is shown in which a polyolefin resin film is bonded to a foamed polystyrene sheet using a molten mixture of 60 to 40% by weight of a polyolefin resin as an adhesive. The adhesive strength of this composite sheet is as low as 294 mNZcm or less, and there is a problem that the polyolefin resin film peels off at the time of molding bowls and cups.

Japanese Utility Model Publication No. 62-209-69 discloses that foamed polystyrene is used as an adhesive with a mixture of polybutadiene, polyisoprene, styrene-butadiene copolymer, or a mixture of thermoplastic rubber and polyethylene. A composite sheet is shown in which a polyolefin resin film is adhered to a sheet. However, in order to obtain high adhesive strength, it is necessary to use a large amount of thermoplastic rubber, which is more than three times more expensive than polystyrene, polyethylene, etc. There is a problem above. In addition, when, for example, polypropylene is used as the polyolefin resin film, the adhesive strength cannot be sufficiently satisfied. Japanese Utility Model Publication No. 62-137384 proposes that urethane or an ethylene / vinyl acetate copolymer is used as an adhesive, but it is effective to use a used laminate effectively. It has problems that it cannot be recycled, the laminate has low heat resistance, and the ethylene // vinyl acetate copolymer has a strong odor. On the other hand, in recent years, there has been a strong demand for recycling plastic containers, and this also applies to multilayer films formed by laminating resin films of the above-mentioned polyethylene, polypropylene, polyester, etc. on expanded polystyrene sheets. The method of recycling this multilayer film is to separate it into layers, to recover each resin, to melt the multilayer film, and then to recover each resin by fractional distillation, and to multilayer film. There is a method of melting and recovering as a resin mixture. The former two methods are not advantageous in terms of cost. The third method requires that the mixture be free of substances that would interfere with the purpose of reuse.

The present invention has been made in view of the above-mentioned problems of the prior art, and is a composite material including a polystyrene resin foam layer and a thermoplastic resin layer, wherein the adhesive strength of both layers is a composite material such as a bowl. It is an object of the present invention to provide a composite material that is high enough to withstand the formation of a deep container, has high oil resistance, is inexpensive, and can be recycled.

Disclosure of the invention

According to the present invention, there are provided a polystyrene resin foam layer, an alloy layer provided on at least one of both surfaces of the polystyrene resin foam layer, and a thermoplastic resin layer provided on the aperture layer. A composite material,

The thermoplastic resin layer is selected from a polyolefin resin and a polyester resin. Made of plastic

The alloy layer is composed of a mixture of a polystyrene resin and a thermoplastic resin selected from a polyolefin resin and a polyester resin. However, when the thermoplastic resin layer is composed of a polyolefin resin, the resin heat of the alloy layer is reduced. The plastic resin is a polyolefin resin, and when the thermoplastic resin layer is made of a polyester resin, the resin thermoplastic resin of the alloy layer is a polyester resin; and

A composite material having an adhesive strength between the polystyrene resin foam layer and the thermoplastic resin layer of 98 OmN / 25 mm or more is provided.

The present invention will now be described in detail with reference to the drawings. In the figure, FIG. 1 is a diagram showing a graph of crystallization time measurement.

Polystyrene resin foam layer

The polystyrene resin used for the polystyrene resin foam layer in the present invention includes a homopolymer and a copolymer of styrene. The styrene monomer unit contained in the copolymer is at least 25% by weight or more, preferably 50% by weight or more.

Examples of the polystyrene resin include polystyrene, rubber-modified polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene-acrylonitrile copolymer, and styrene-acrylic acid copolymer. Polymer, styrene-methacrylic acid copolymer, styrene-methyl methacrylate copolymer, styrene-methyl methacrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl acrylate Examples thereof include a copolymer, a styrene-maleic anhydride copolymer, a polystyrene-polyphenylene ether copolymer, and a mixture of polystyrene and polyphenylene ether.

For the purpose of improving brittleness, etc. of these resins, styrene-conjugated ,

Polypropylene resin or its hydrogenated product is blended. Polyolefin resin such as polypropylene resin or high-density polyethylene is blended at a ratio of 20% by weight or less in consideration of mixing of recycled resin. be able to. The heat resistance of the composite material of the present invention can be improved by using a polystyrene resin having a vicat softening point of 110 ° C. or higher. In the present specification, the vicat softening point of the resin refers to a value determined by JIS K7206 (test load is Α method, heating rate of heat transfer medium is 50 ° CZ).

The melt viscosity of polystyrene resin is the melt viscosity under the conditions of 190 ° C and a shear rate of 100 sec- ¹ . It is more than 20 Pa and less than 10 Pa, less than OOOPa. 0 0-5, OOOP a 's. If the melt viscosity is less than 20 Pa · s, the molten resin extruded from the die at the time of foam molding may sag, making molding difficult. On the other hand, if it exceeds 10, OOOP a 's, the extrusion pressure will increase and extrusion molding will be difficult, and there is a possibility that high quality foams cannot be molded.

Polystyrene density of the resin foam layer is usually 0. 0 3 5~ 0. 7 g Z cm 3, preferably 0. 0 5~ 0. 5 g Z cm 3, particularly those for thermoforming 0. 0 7~ 0. 5 g / cm ³ things Shi preferred Rere. When the density is less than ^{0. 0 3 5 g / cm 3} , or insufficient strength of the molded article obtained by molding a composite material, a hole in the molded article results in lack of elongation when heated vacuum forming May occur. On the other hand, if its density is greater than 0.7 g Z cm ^3, it is economically disadvantageous. In addition, the heat insulation of the molded article such as a container is deteriorated. For example, when hot water is poured, the container cannot be held by hand.

The thickness of the polystyrene resin foam layer is usually 0.5 to 10 mm, preferably 0.7 to 5 mm, especially 0.7 to 4 mm for thermoforming. Is preferred. If the thickness of the foam layer is less than 0.5 mm, the wall thickness of the molded product obtained by vacuum forming or the like becomes insufficient, and the strength and the heat insulating property tend to be inferior. On the other hand, if the thickness is more than 10 mm, uneven heating inside and outside of the sheet is likely to occur during heating vacuum forming, and precise temperature control is required.

Further, the open cell ratio (A STM D 285, Procedure C) of the foam layer is preferably 40% or less. The open cell ratio of the foam layer affects the secondary foaming property at the time of thermoforming and the quality (physical properties such as strength) of the obtained secondary molded product.

The polystyrene resin foam layer can be obtained by any known method using a foaming agent such as an organic foaming agent, an inorganic foaming agent, or a decomposable foaming agent. Examples of the organic blowing agent include propane, n-butane, i-butane, a mixture of n-butane and i-butane, aliphatic hydrocarbons such as pentane and hexane, and cyclic compounds such as cyclobutane and cyclopentane. Aliphatic hydrocarbons, trichlorofluoromethane, dichlorodifluoromethane, 1, 1—difluoroethane, 1,1—diphneololol 1—chloroethane, 1,1,1,2, -tetranoleoloethane, methyl chloride, ethyl chloride And halogenated hydrocarbons such as methylene chloride, and mixtures thereof. Examples of the inorganic foaming agent include a gas such as nitrogen and carbon dioxide and water. Further, examples of the decomposable blowing agent include azodicarbonamide, dinitrosopentamethylentramine, azobisisobutyronitrile, sodium bicarbonate and the like. These foaming agents can be appropriately mixed and used. Among them, it is preferable to use a material that does not contain hydrogen hydride and has little effect on the environment such as destruction of the ozone layer. The amount of the foaming agent used is not particularly limited, but is generally in the range of 0.01 to 0.1 mol per 100 g of the resin. a

You.

In the polystyrene resin foam layer, various additives which are usually added to the polystyrene resin as needed, for example, a nucleating agent, an antioxidant, a heat stabilizer, so long as the object of the present invention is not significantly impaired. , An antistatic agent, a conductivity-imparting agent, a weathering agent, an ultraviolet absorber, a coloring agent, a flame retardant, an inorganic filler and the like can be added.

Thermoplastic resin layer

The thermoplastic resin used for the thermoplastic resin layer laminated on the polystyrene resin foam layer includes a polyolefin resin or a polyester resin. The thickness of the thermoplastic resin layer is generally 0.1 to 1 mm, preferably 0.15 to 0.8 mm, more preferably 0.015 to 0.35 mm, and the polystyrene The ratio to the thickness of the resin foam layer is generally 3 to 50%, preferably 5 to 40%. If the thickness of the thermoplastic resin layer is smaller than the above-mentioned range, the sheet is likely to have through holes and breakage during secondary molding, which is not preferable. On the other hand, if the thickness is too large, the foaming layer may be melted if the composite material is molded with the best heating time for the thermoplastic resin layer as well as the cost.

It is preferable to use a high-density polyethylene-polypropylene resin as the thermoplastic resin layer in terms of heat resistance and appearance. When high-density polyethylene is used, the surface of the composite material has a matte appearance. On the other hand, when a polypropylene resin is used, a composite material having excellent surface gloss can be obtained. It is preferable to use a polyester resin for the thermoplastic resin layer from the viewpoints of fragrance retention and gas barrier properties.

In the thermoplastic resin layer, various additives such as antioxidants, heat stabilizers, antistatic agents, conductivity-imparting agents, nucleating agents, weathering agents, UV inhibitors, „

Coloring agents, flame retardants, inorganic fillers and the like can be added as appropriate. Particle size I n n! In the thermoplastic resin layer Add 1 to 100 nm of kaolin, myriki, silica, tanolek, creis, zinc methacrylate, highly saturated nitrile rubber, liquid crystal polymer, etc. in an amount of 3 to 10% by weight based on the resin. It can be finely dispersed to form a so-called nanocomposite. As a result, the tensile strength, tensile modulus, bending strength, bending modulus, gas permeability, transparency, flame retardancy, heat stability, and the like are improved. If necessary, a compatibilizer can be added for dispersion.

Although not very desirable in terms of recyclability, in addition to the thermoplastic resin layer laminated on the polystyrene resin foam layer, a film-like polyamide resin, vinylidene chloride, saponified ethylene vinyl acetate copolymer, and It can also be laminated with the foam as a composite material by combining with other functional materials such as lumidium foil.

In addition, one or two additional thermoplastic resin layers directly bonded to the thermoplastic resin layer formed of polyolefin resin or polyester resin should be provided as the outermost layer of the composite material. Can be.

Next, the polyolefin resin and the polyester resin forming the thermoplastic resin layer will be described in detail.

Polyolefin resin

The polyolefin resin includes homopolymers, copolymers (random copolymers, block copolymers, and the like) of olefins, and blends. In the present invention, particularly, from the viewpoint of heat resistance, those having a vicat softening point of 112 ° C or more, and those having a softening point of 120 ° C or more (the upper limit of the softening point is particularly limited) However, it is about 160 ° C.), but it is particularly preferable to use high-density polyethylene or polypropylene resin. _Q

The propylene resin includes homopolymers, copolymers and blends of propylene.

In the propylene copolymer, the copolymer component includes ethylene, butylene and other monoolefins, and the α-olefin has 12 or less, preferably 8 or less carbon atoms. The content of the copolymer components, ethylene, butylene and other monoolefins, is 20% by weight or less for block copolymers and 8% by weight or less for random copolymers. Preferably.

In the blend body of a propylene resin, the resin for the blend includes a homopolymer of ethylene, a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms, and a carbon number of And the homopolymers of "one-olefin" having 4 to 6 are exemplified.

In a preferred embodiment of the present invention, the polyolefin resin for forming the thermoplastic resin layer has (i) a melting point of 150. A mixture of a polypropylene resin having a melting point of not more than C (hereinafter, also referred to as a low melting point polypropylene resin) and a polyethylene resin having a melting point of not less than 130 ° C (hereinafter, also referred to as a high melting point polyethylene resin); A polypropylene resin exceeding C (hereinafter also referred to as a high-melting-point polypropylene resin), and (iii) a resin having a melting point of 130 and a main component of the above-mentioned polyethylene resin are used. In this case, the “main component” means that the resin or mixed resin (i) to (iii) is about 80% by weight of the thermoplastic resin layer. /. Within the range not impairing the object and effect of the present invention, for example, 70 parts by weight or less of a polystyrene resin of 100 parts by weight or less of the resin (i) to (iii) or a mixed resin, It means that other polymers such as nylon resin, polyester resin, rubber and the like may be further included.

The low-melting polypropylene resin includes a copolymer of propylene and the like. g

You. In the propylene copolymer, the copolymer component includes ethylene, butylene, and other α-olefins, and the ct-olefin has a carbon number of 12 or less, preferably 8 or less. The content of the copolymer components, ethylene, butylene, and other α-olefins, is 8% in the case of a random copolymer. / ₀ or less is preferable. Further, in consideration of the mold releasability of the molded product, the melting point of the low melting point polypropylene resin is preferably at least 138 ° C. A particularly preferred melting point range of the low melting point polypropylene resin is 140 to 150 ° C.

The high melting point polypropylene resin includes propylene homopolymers and copolymers. As the high melting point polypropylene resin, various conventionally known ones can be used. The upper limit of the melting point is usually about 165 ° C. Its preferred melting point range is 158 to 164 ° C.

The high-melting-point polyethylene resin includes a copolymer of ethylene and α-olefin having 3 to 12 carbon atoms, and examples thereof include conventionally known various materials such as high-density polyethylene. The upper limit of the melting point is usually 140 ° C. Its preferred melting point range is 132-138 ° C.

In the case of the mixed resin (i), the amount of the low melting point polypropylene resin is preferably less than 100% by weight, more preferably 70% by weight, based on the total weight of the low melting point polypropylene resin and the high melting point polyethylene resin. On the other hand, the amount of the high melting point polyethylene resin is preferably 0% by weight. / ₀ more than 85 weight. /. The content is more preferably 30 to 70% by weight.

By using the mixed resin (i) or the high-melting-point polyethylene resin (iii), a multilayer sheet having not only oil resistance but also heat resistance and good impact resistance at low temperatures can be obtained.

In the case of the polyolefin resin (ii), not only oil resistance but also In particular, a multilayer sheet having good heat resistance can be obtained.

In consideration of the moldability, it is preferable that the polyolefin resin constituting the thermoplastic resin layer has the above-mentioned composition (i) to (iiii) and has a high crystallization rate. In particular, the semi-crystallization time of the polyolefin resin at 100 ° C. is 30 seconds or less, preferably 2 to 28 seconds. If the time exceeds 30 seconds, the moldability will deteriorate.

The half-crystallization time referred to in this specification was previously set at 300 ° C using a crystallization rate measuring device (MK-801 type manufactured by Meto Co., Ltd. (former Kotaki Shoji Co., Ltd.)) The heated resin sample can be put into a crystallization bath set at 100 ° C. for measurement. The measurement sample should be in the form of a film. In this case, the thickness of the finolem shall be 0.1 ± 0.2 mm, and the dimensions of the film shall be 15 x 15 mm square. This is sandwiched between power microscope glasses and used as a measurement sample. For the light source lamp, the support value is 3 V.

The crystallization rate measuring device manufactured by Metron Co., Ltd. is a device for determining the degree of crystallinity from the relationship between the crystallization of a sample and the birefringence of light, and the half-crystallization time referred to in this specification is defined as It is determined from the obtained time-birefringence light quantity curve (I) shown in FIG. That is, the amount of light due to birefringence in the sample increases with time, and finally becomes constant (value Λ) after time point a. The half-crystallization time is the time c in the curve (I) that gives the amount of light B equal to ΛΖ2. In FIG. 1, (II) represents a change in the bath temperature when the crystallization bath temperature is set to a temperature D (100 ° C. in the case of the present invention).

Polyester resin

As the thermoplastic resin layer, a polyester resin can be used in addition to the polyolefin resin described above. Polyester resin is dicarboxylic acid II

Method of polycondensing component and diol component: It is produced by transesterification of polyester homopolymer and Z or polyester copolymer. As the polyester resin, an aromatic polyester resin having a half-crystallization time at 100 ° C. of 30 minutes or more is preferably used. The aromatic polyester resin is composed of a dicarboxylic acid component and a diol component, at least one of which is aromatic. As the dicarboxylic acid component of the aromatic polyester resin, dicarboxylic acid or an ester-forming derivative thereof can be used. Examples of the ester-forming derivatives include ester derivatives such as dimethyl ester and getyl ester, salts such as diammonium salts, and acid halides such as dichloride.

The dicarboxylic acid component units in the polymer include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, phthalic acid, 4,4'-diphenyl carboxylic acid, and 3,4'-diphenyl Aromatic dicarboxylic acids such as dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and esters thereof A component unit derived from a forming derivative or a component unit derived from an aliphatic dicarboxylic acid such as oxalic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid or an ester-forming derivative thereof; or Alicyclic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, decalindicarboxylic acid, and tetralindicarboxylic acid Include Bonn acid or a component unit derived from an ester-forming derivative thereof, these one or two or more Ru are contained in the polymer.

As the diol component of the aromatic polyester resin used in the present invention, aliphatic and aromatic diols (including divalent phenol) can be used. As the diol component unit in the polymer, there are aliphatic diols such as ethylene glycol, cyclohexanedimethanol, propylene glycol, trimethylene daryl, diethylene glycol, and 1,4-butanediol, or esters thereof. Alicyclic diols such as 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,6-cyclohexanediol, etc., or their ester formation And a component unit derived from an aromatic diol such as bisfuninol A or an ester-forming derivative thereof.

In addition, the above aromatic polyester resin may have its molecular end sealed with a component unit derived from a monofunctional compound such as a small amount of benzoic acid, benzoyl benzoic acid, methoxypolyethylene glycol, or the like. Les ,. Also, it may contain a small amount of a component unit derived from a polyfunctional compound such as pyromellitic acid, trimellitic acid, trimesic acid, glycerin, and pentaerythritol.

The half-crystallization time of the aromatic polyester resin can be adjusted by using two or more dicarboxylic acid components such as terephthalic acid and isophthalic acid to change the molar ratio of the dicarboxylic acid component units. It can be adjusted by using two or more kinds of diol components such as ethylene glycol and cyclohexanedimethanol and changing the molar ratio of the diol component units.

As the aromatic polyester resin having a half-crystallization time of 30 minutes or more, an aromatic polyester copolymer having a half-crystallization time of 30 minutes or more is preferable. Particularly preferred examples are 75 to 40 mol. / ₀ ethylenic glycol and 25-60 mol ⁰ /. Diol component consisting of cyclohexanedimethanol And a dicarboxylic acid component composed of terephthalic acid.

In the present invention, the film-like aromatic polyester resin may be a polyolefin resin such as a polystyrene resin, a polypropylene resin, or a polyethylene resin, a nylon resin, or a high-molecular-weight resin as long as the object of the present invention is not impaired. Resins such as impact polystyrene, styrene-containing thermoplastic elastomers, etc., elastomers and rubbers are approximately 40% by weight. /. It may be contained in the following proportions.

The thickness of the polyester resin is preferably from 0.01 to 0.5 mm, particularly preferably from 0.03 to 0.2 mm. If it is less than 0.01 mm, it is stretched and further thinned during thermoforming, so that breakage and pinholes are liable to occur, and the solvent resistance of the composite material is liable to decrease, and it is difficult to obtain sufficient oil resistance. If it exceeds 0.5 mm, it will be difficult to adhere to the polystyrene resin foam, resulting in high cost. Also, from the viewpoint of the recyclability of the composite material, the amount of the laminated polyester resin is 50% by weight of the composite material. /. Hereinafter, the content is preferably 25% by weight or less.

The adhesive strength between the polystyrene resin foam layer and the thermoplastic resin layer of the composite material of the present invention is 980 mNZ25 mm or more, particularly preferably 2451 mN / 25 mm or more, and more preferably 3677 mN. It has a large value of 25 mm or more. <The upper limit of the adhesive strength is usually about 122 58 mN / 25 mm. A composite material having such a large interlayer adhesive strength is provided for the first time by the present invention.

The interlayer adhesive strength of the composite material of the present invention having a large value as described above means that the phase structure index PI value between the polystyrene resin foam layer and the thermoplastic resin layer is 0.5 to: 1.5, Preferably 0.6 to: 1.4, more preferably 0.6. This is due to having an alloy layer in the range of 7 to 1.3. The following is a description of the error layer.

Alloy layer

The alloy layer is mainly composed of a mixed resin of a polystyrene resin and a thermoplastic resin, and the weight ratio of the polystyrene resin to the thermoplastic resin is 95: 5 to 30:70, and 90:10 to 40:40. : 60, particularly preferably 85: 15 to 55: 45. The total amount of the polystyrene resin and the thermoplastic resin is 50% by weight or more based on the alloy layer. As the thermoplastic resin used for the alloy layer, the same resin as the thermoplastic resin used for the thermoplastic resin layer laminated on the alloy layer, or the same kind of thermoplastic resin that can be heat-fused is used. Is preferably used.

If the amount of polystyrene resin in the mixed resin of the alloy layer exceeds 95: 5, the adhesive strength between the alloy layer and the polystyrene foam layer can be satisfied, but the adhesive strength between the alloy layer and the thermoplastic resin layer can be improved. May be insufficient in adhesive strength. On the other hand, when the amount of the polystyrene resin is lower than 30:70, the adhesive strength between the alloy layer and the thermoplastic resin layer can be satisfied, but the adhesive strength between the polystyrene resin foam layer and the alloy layer can be improved. The strength may be insufficient.

The thickness of the alloy layer is in the range of 15 to 200 m, and the adhesive strength tends to increase as the thickness increases, and is preferably 20 to 150 / j m. The thickness of the alloy layer is 3 to 50%, preferably 5 to 40% of the thickness of the polystyrene resin foam layer. If the thickness of the alloy layer is less than 3%, the adhesion becomes insufficient, while if it exceeds 50%, the foam layer is heated when the alloy layer is laminated on the foam layer, and as a result, the foam The open cell ratio of the layer tends to be high, and also causes cost increase.

When polyester resin is used as the thermoplastic resin of the alloy layer, the melting point _ig

Is preferably 105 ° C. or more and 200 ° C. or less, since a composite having high heat resistance can be obtained.

The melting point in the present specification is determined from a melting peak of a DSC curve obtained by a heat flux differential scanning calorimetry performed in accordance with JIS K7112. Details are as follows. Approximately 5 mg of a film having a thickness of 0.5 mm or less is used as a test piece. Immediately after the temperature is raised to 0 ° C higher, the temperature is lowered to 40 ° C in a cooling rate of 10 ° CZ, and then immediately at a heating rate of 10 ° C / min. The melting point is defined as the peak temperature of the melting peak of the DSC curve (when two or more melting peaks are present, the melting peak area is larger) when the temperature is raised to about 30 ° C higher. In this specification, a differential scanning calorimeter, Shimadzu Heat Flux Differential Scanning Calorimeter DSC-50 manufactured by Shimadzu Corporation is used, and the nitrogen gas inflow rate is set to 20 m 1 / min. Then, the melting point obtained by performing the above measurement was adopted.

If necessary, additives such as a compatibilizer, an adhesive, an elastic component, a viscosity modifier and the like can be added to the alloy layer in an amount of less than 50% by weight based on the alloy layer.

The alloy layer preferably contains a compatibilizer. As the compatibilizing agent, any one can be used as long as it can compatibilize the polystyrene resin and the thermoplastic resin of the alloy layer, and various conventionally known ones can be used. In particular, the use of a styrene-containing thermoplastic elastomer not only improves the adhesion between the polystyrene foam layer and the thermoplastic resin layer, but also improves the impact strength and brittleness of the composite material. Is preferred. When the thermoplastic resin of the alloy layer is a polyester resin, the styrene-containing thermoplastic elastomer is made of polystyrene. It functions as a viscosity regulator for lowering the viscosity of the mixed resin of the polyester resin and the polyester resin, thereby improving the kneading property of the polystyrene resin and the polyester resin.

Examples of the styrene-containing thermoplastic elastomer include styrene-ethylene-butylene-styrene-block copolymer (SEBS), styrene-ethylene-propylene-styrene-block copolymer (SEPS), and styrene-butadiene. Styrene block copolymer (SBS) or styrene-isoprene-styrene block copolymer (SIS). Styrene content of the styrene-containing thermoplastic Heras Tomah one This is preferably 1 0-6 0 weight ^_0/0. SBS or SIS has a polystyrene crystal phase as a hard segment, and has a structure in which polybutadiene or polyisoprene is block copolymerized as a soft segment. On the other hand, SEBS and SEPS are obtained by highly hydrogenating polybutadiene and polyisoprene contained in SBS and SIS to saturate the double bonds in the main chain. These styrene-containing thermoplastic elastomers such as SEBS, SEPS, SBS, and SIS are described in detail in “Plastic Age”, pp. 101-106. (June 1985) Have been. The addition of the compatibilizer increases the adhesive strength between the polystyrene resin foam layer and the thermoplastic resin layer, and further increases the impact strength and brittleness of the composite material when the compatibilizer of the styrene-containing thermoplastic elastomer is used. Is improved.

The compatibilizer is generally added in an amount of from 0: to 30 parts by weight, preferably from 0.5 to 10 parts by weight, per 100 parts by weight of the total amount of the polystyrene resin and the thermoplastic resin in the alloy layer. You. In the case of a styrene-containing thermoplastic elastomer, the content is preferably 2 to 10 parts by weight. The addition of this compatibilizer increases the adhesive strength between the polystyrene resin foam layer and the thermoplastic resin layer, Impact strength and brittleness are improved. When the thermoplastic resin of the alloy layer is a polyester resin, the styrene-containing thermoplastic elastomer is preferably used in an amount of 0.3 to 100 parts by weight of the total amount of the polystyrene resin and the polyester resin in the alloy layer. 20 parts by weight, more preferably 0.5 to 15 parts by weight, is added. As described above, the styrene-containing thermoplastic elastomer acts as a compatibilizer, an elasticity-imparting agent, and a viscosity modifier, and is preferably added to the alloy layer.

An elastic component can be added to the alloy layer for the purpose of improving brittleness. As the elastic component, a random copolymer, a block copolymer, a graft copolymer, or a mixture of these copolymers composed of a styrene component such as styrene or α-methylstyrene and a butadiene or isoprene-based gen component is used. Compounds. The elastic component is preferably added in an amount of 2 to 50 parts by weight, more preferably 5 to 30 parts by weight, per 100 parts by weight of the total of the polystyrene resin and the thermoplastic resin in the alloy layer. Parts by weight.

The elastic component containing the above-mentioned styrene-containing thermoplastic elastomer is used in the polystyrene resin foam layer in order to improve its brittleness, and is used in an amount of 0.5 to 30 parts by weight per 100 parts by weight of the polystyrene resin. Parts, preferably 1 to 20 parts by weight, can be added.

An adhesive such as an ethylene-vinyl acetate copolymer can be added to the alloy layer. The ethylene / butyl acetate copolymer is preferably used in an amount of not more than 25 parts by weight per 100 parts by weight of the mixed resin of the polystyrene resin and the thermoplastic resin, from the viewpoint of economy and reduction of odor.

As mentioned earlier, the alloy layer has a phase structure index ΡI value in the range of 0.5 to 1.5. The phase structure index Ρ Ι value indicates the mixed state of the polystyrene resin and the thermoplastic resin of the alloy layer, and is defined by the following equation (1). PI value = (7; Λ · Φl¾ZB · A) Equation (1) In the above equation (1), φ. Is the volume fraction of the polystyrene resin phase in the alloy layer, and 7A is 190 ° C, melt viscosity of polystyrene resin at shear rate 100 sec · ', Φ _Β is volume fraction of thermoplastic resin phase in alloy layer, heat at 77 ± 190 ° C shear rate 100 sec ¹ It is the melt viscosity of the plastic resin.

When the PI value of the alloy layer is smaller than 0.5, the thermoplastic resin in the alloy layer is covered with the polystyrene resin and is hardly exposed on the bonding surface, and the bonding strength between the foam layer and the alloy layer is satisfactory. However, the adhesive strength between the alloy layer and the thermoplastic resin layer is insufficient, and delamination occurs when the composite material is molded into a molded article such as a bowl or the like obtained by thermoforming. on the other hand becomes easier _c, the PI value comes to more than 1.5, polystyrene down resin Aroi layer is not easily exposed to the covered adhesive surface to the thermoplastic resin, the adhesion between the thermoplastic resins layer and Aroi layer Although the strength is satisfactory, the adhesive strength between the alloy layer and the foam layer is insufficient, and delamination tends to occur when the composite material is formed into a molded article such as a container. The PI value is preferably in the range of 0.6 to 1.4, particularly 0.7 to 1.3, because of the excellent adhesive strength between the foam layer and the thermoplastic resin layer.

The composite material of the present invention can be manufactured by a conventionally known method. As a typical method, an alloy layer and a thermoplastic resin layer are sequentially supplied to a previously produced foam layer by an extruder and adhered thereto; the previously produced foam layer and the thermoplastic resin layer are bonded together. There are a method of bonding with an alloy layer supplied from an extruder, and a method of simultaneously forming an alloy layer and a thermoplastic resin layer on a foam layer by coextrusion. Among them, the composite material (multi-layer sheet) obtained by the multi-layer co-extrusion method has a thimble process and can be reduced in cost compared to other methods. It is preferable because the adhesion strength between the body layer and the alloy layer and between the alloy layer and the thermoplastic resin layer is increased.

The polystyrene resin, the thermoplastic resin, the compatibilizer, and the like used in the alloy layer may be dry-blended in a pellet form and then directly introduced into the inlet of an extruder, or may be melt-kneaded in advance.

The composite of the present invention has a structure in which a thermoplastic resin layer is provided on at least one surface via an alloy layer. When only one surface has a thermoplastic resin layer, the other surface can be a polystyrene resin layer alloy layer. Since the polystyrene resin layer is excellent in printability and glossiness, it can be appropriately printed. The alloy layer is also excellent in printability and glossiness, so that printing can be performed appropriately. Further, since two alloy layers can be simultaneously laminated on both sides of the foam layer by the co-extrusion method using the same extruder, the productivity is excellent.

For example, a composite material in which a polystyrene resin layer such as high impact polystyrene (HIPS) is laminated on the first surface of a polystyrene resin foam and a thermoplastic resin is laminated on the second surface via an alloy layer, A composite material obtained by laminating a thermoplastic resin on the second surface of a polystyrene resin foam through an alloy layer by extrusion or the like is obtained, and then a high-impact polystyrene melt is produced using a T-die. Of the polystyrene resin foam layer, alloy layer, thermoplastic resin layer and polystyrene resin layer by coextrusion lamination, etc.

In the alloy layer, various additives which are usually added to the polystyrene resin and the thermoplastic resin as necessary, for example, a nucleating agent, an antioxidant, and a heat-stable agent, within a range not significantly impairing the object of the present invention. Agents, antistatic agents, conductivity-imparting agents, weathering agents, ultraviolet absorbers, coloring agents, flame retardants, inorganic fillers, etc. go

be able to.

The composite material of the present invention is formed by laminating a polystyrene resin foam layer and a thermoplastic resin layer with extremely high adhesive strength, and is excellent in oil resistance and thermoformability. Since no special adhesive is used, it can be manufactured at low cost and is suitable for recycling. That is, the melted composite material can be reused as an alloy layer of the composite material.

Further, by forming the thermoplastic resin layer with a polypropylene resin having a vicat softening point of 112 ° C. or higher, a composite material having excellent heat resistance can be obtained.

By forming the thermoplastic resin layer with a polyester resin having a half-crystallization time of 30 minutes or more, a composite material having excellent recyclability, thermoformability, and heat sealability can be obtained. In particular, since the polyester resin layer is excellent in oil resistance, fragrance retention, gas barrier properties, and adhesion to other wrap films, this composite material is particularly effective as a material for molding containers and the like.

The following examples further illustrate the invention.

Example:! ~ 19, Comparative example:! ~ 3

Sheet composites having the configurations shown in Tables 1, 2, 5, and 6 were produced. Tables 1, 2, 5, and 6 also show the density (gZ cm ³ ) of this composite, the thickness of the composite ( _mm ), and the type of composite material used in its manufacture. Indicated. Furthermore, Table 1, Table 2, Table 5 and Table 6, oil resistance of the composite material, the adhesive strength (mNZ25 mm) and continuous cell ratio of the foam layer of polyolefin resin layer (2 'or sigma ²⁾ (% ) showed that.

Table 1, Table 2, in the composite material shown in Table 5 and Table 6, Poriorefui down resin (Z ¹⁾ represents the surface layer, Poriorefui emission resin layer (Z ²⁾ shows the back surface layer. In the adhesive strength, Z indicates the adhesive strength between the polyolefin resin layer (Z ¹ ) forming the surface layer and the foam layer (X), and Z ² ZX Indicates the adhesive strength between the polyolefin resin layer (Z) forming the backside layer and the foam layer (X).

The specific contents of the types of composite materials shown in Tables 1, 2, 5, and 6 are as follows. The resin temperature shown in Table 1, Table 2, Table 5 and Table 6 is the resin temperature when extruded from the die (die) of the extruder.

(After lami)

Two extruders with a diameter of 65 mm and a diameter of 9 Omm were used as extruders, and a cylindrical gap of 84 mm in diameter and 0.5 mm in thickness was used as a die. What had it was used.

Using a 65 mm diameter extruder, heat and knead a specified amount of resin and additives from the raw material inlet to 100 parts by weight of resin in the amounts shown in Table 3 or Table 4, and bring the temperature to about 200 ° C. Press the foaming agent and amount shown in Table 3 or Table 4 into the adjusted resin mixture, and then supply it to an extruder with a diameter of 9 ° mm and adjust the resin temperature to Table 1 or 2 The resin was extruded from the die.

The extruded cylindrical resin was cut open along the cooled cylinder having a diameter of 200 mm in the drawing and extrusion direction to obtain a polystyrene resin foam sheet, and the foam sheet was wound up.

A polyolefin resin film having a thickness shown in Table 1 or Table 2 was laminated on the obtained foamed sheet via an alloy layer shown in Table 3 or Table 4 to obtain a composite material. The alloy layer was extruded with a 5 Omm diameter extruder from the raw material inlet through a prescribed amount of resin shown in Table 3 or Table 4 and, if necessary, an amount of phase shown in Table 3 or Table 4 per 100 parts by weight of alloy. The solubilizer was heated and kneaded, and was extruded and supplied from a T-die having a width of 600 mm at 200 ° C.

(Co-extrusion)

Two extruders with a diameter of 65 mm and a diameter of 9 Omm as extruders for foam layers An extruder with a diameter of 50 mm was used as the extruder for the polyolefin resin layer, and an extruder with a diameter of 40 mm was used as the extruder for the alloy layer. The one with a cylindrical slit with a diameter of 84 mm and a thickness of 0.5 mm was used.

The foam layer was heated and kneaded with a prescribed amount of resin and additives from the raw material inlet using a 65 mm diameter extruder in the amounts shown in Table 3, Table 4, Table 7, or Table 8 per 100 parts by weight of resin. Then, the blowing agent and the amount shown in Table 3, Table 4, Table 7 or Table 8 are injected into the resin mixture adjusted to about 200 ° C., and then fed to an extruder having a diameter of 9 O mm. The resin temperature was adjusted as shown in Table 1, Table 2, Table 5, and Table 6. On the other hand, the polyolefin resin layer is supplied from an extruder with a diameter of 50 mm, and the alloy layer is supplied from an extruder with a diameter of 40 mm to one or both sides of the melt for forming a polystyrene resin foam layer, as required. The melt was mixed with the melt for forming a foam layer inside the die and coextruded. The alloy layer was added with a compatibilizer in an amount shown in Table 3, Table 4, Table 7, or Table 8 per 100 parts by weight of the alloy of the polystyrene resin and the polyolefin resin as required.

The composite material was wound up by pulling the extruded cylindrical resin along a cooled cylinder having a diameter of 200 mm.

Table 3, Table 4, the foam layer of the composite material shown in Table 7 or Table 8 (X), Aroi layer (Υ ', Υ ²⁾ and Poriorefui emission resin layer (Ζ', ζ ²⁾ the specific contents of It will be shown. In the table, the amount (weight / ₀ ) of the PS resin or the glass resin in the alloy layer is a value based on the total weight of 100% by weight of the PS resin and the glass resin. In Examples 14 and 17, in the alloy layer, 25 parts by weight of a resin (to be described later) was added as an elastic component to 100 parts by weight of the mixed resin of the PS resin and the Ρ〇 resin. did. Also in Example 19, the resin 後述 described later as an elastic component in the alloy layer was added to 100 parts by weight of the mixed resin of the PS resin and the Ο resin. And 25 parts by weight.

The specific contents of the PS resin (polystyrene resin) indicated by reference numerals for the foam layer (X) are as described below. The talc blended with the PS resin is Highfila # 12 manufactured by Matsumura Sangyo Co., Ltd. Further, in the foaming agents indicated by the symbols, B represents a butane mixture composed of 70 wt% of n-butane and 30 wt% of iso-butane, n-p represents n-pentane, and CF 40 S represents "Hydrocerol CF 40 S" (chemical blowing agent) manufactured by Dainichi Seika Co., Ltd. is shown.

Regarding the alloy layer (Υγ ² ) The specific contents of the resin (polyolefin resin) and the compatibilizer are as described below.

The alloy composition of the alloy layer (γ ¹ ) and the alloy layer (γ ² ) are the same. The specific contents of the Ρ ο resin (符号 ζ ² ) indicated by reference numerals for the Ρ Ρ layer (polyolefin layer) are as shown below.

The composition of the 成分 layer (ζ ¹ ) and the Ο layer (ζ_) is the same.

Tables 1, 2, 5, 6, 11, 12, 13 for the above composite materials and Table 1, 2, 5, 6, 9, 11, 11, 12, 13 Is as follows.

(Oil resistance)

To the center of a 25 mm X 4 O mm sheet, add 0.025 ml of rice cooked rice seasoning oil (Fresh Kuchiichi Nore White, Kuchiichi Ring Co., Ltd.) and spread evenly. The mixture was heated at ° C for 5 minutes and the change before and after was examined.

〇 · · · No change

X · · · Erosion on sheet surface

(Adhesive strength)

Between the polystyrene resin foam layer (X) and the polyolefin resin layer (Z) The bond strength between the specimens was determined by cutting a 25 mm wide test piece from the composite material and measuring it in a 90 ° peel test at a peel rate of 300 mm / min in accordance with JISZ 0237. (MNZ 25 mm) was taken as the adhesive strength.

In this specification, the adhesive strength may be measured as described above.If it is not possible to cut out a test piece with a width of 25 mm, cut out a test piece as wide as possible and perform the above measurement on the cut out test piece. The obtained value (mN) is multiplied by (width of 25Z test piece (mm)) to obtain the adhesive strength (mNZ25 mm).

Hereinafter, the thickness of the composite, the basis weight of the composite, the density of the composite, and the density of the polystyrene resin foam in the table are as follows.

(Composite material thickness)

The thickness of the composite material was measured at any 20 points on the vertical cross section in the thickness direction, and the average value was adopted. The thickness was measured using a micrograph and converted to an enlargement magnification to determine each thickness.

(Composite material weight)

A test piece having a length of 20 cm (length) × 20 cm (width) × composite material was cut out from the composite material, and the weight of the test piece (g) was measured. m ² ) was calculated.

(Composite material density)

A test piece similar to the basis weight measurement of the composite material was prepared, the test piece weight (g) was measured, and the test piece volume (cm) obtained by measuring 20 cm (length) × 20 cm (width) × the thickness (cm) of the composite material It was determined by dividing the test piece weight (g) by ³ ).

(Density of polystyrene resin foam layer)

From the basis weight of the composite material (g Zm ^2), poly ester resin, Aroi layer and the basis weight of each polystyrene resin (g Zm ²⁾ (calculator than each of the density and thickness ), The basis weight (gZm ² ) of only the foam layer, which is obtained by subtracting, is converted to the basis weight (gZcm ² ), and the basis weight (gZcm ² ) is converted to the thickness (gZcm ² ) of the foam layer only. cm).

The specific contents of the resin indicated by reference numerals in Tables 7 and 8 are as follows.

(1) Resin Λ

"HH32" (made by Idemitsu Petrochemical Co., Ltd.) (general-purpose polystyrene (GPPS), melt viscosity 204 Pa, density 1.05 g Z cm ")

(2) Resin B

"HH30J" manufactured by Idemitsu Petrochemical Co., Ltd. (GPPS, melt viscosity 1 230 Pas, density 1.05 g Zcm)

(3) Resin C

Asahi Kasei Co., Ltd., “Stylon 6 7 9” (GPPS, melt viscosity 8330 Pa · S, density 1.05 g / cm)

(4) Resin D

Made of A-And-Am-styrene, “G9001” (styrene-methacrylic acid copolymer, melt viscosity 280 Pas, density 1.05 g Zcm ³ , Softening point 1 110 ° C or higher)

(5) Resin H

Nippon Polyolefin Co., Ltd., “ΡΜ761Λ” (Propylene-ethylene block copolymer, melt viscosity 660 Pa · S, melting point 163.4 ° C, density 0.

S g / cm ³ Bika' preparative softening point 1 2 0 ° C or more, half-crystallization time (1 0 0 ° C) 7 seconds)

(6) Resin I

"MK2111" (Propylene-ethylene bronze) manufactured by Nippon Polyolefin Block copolymer, melt viscosity 800 Pa, S melting point 16 3 ° C, density 0.9 g Z cm ³ , Vicat softening point 120 ° C or more, semi-crystallization time (10 0 0. C) 10 seconds or less)

(7) Resin J

“E250G” manufactured by Idemitsu Petrochemical Co., Ltd. (Propylene-ethylene block copolymer, melt viscosity 1570 Pa · S, melting point 163 ° C, density ◦ .9 g Z cm ³ , Vicat softening point of 120 ° C or more, half-crystallization time (100 ° C) of 10 seconds or less

(8) Resin K

Nippon Polyolefin Co., Ltd., "KB 1 7 5 A" (high-density polyethylene, melt viscosity 1 9 1 0 P a · S , melting point 1 3 4 ° C, density ^{0. 9 5 7 g Z cm 3} , bi Chikara' DOO Softening point of more than 120 ° C, half-crystallization time (100 ° C) of less than 10 seconds)

(9) Resin V

Asahi Kasei Co., Ltd., “Tuftec HI041” (hydrogenated styrene-butadiene styrene block copolymer, melt viscosity 290 Pa S ', density 0.9

/:

g κ cm)

(10) Resin W

Nippon Oil & Fats Co., Ltd., “Modiper A 3100” (styrene graft polypropylene, melt viscosity 360 Pas, density 0.94 g / cm ³ )

(1 1) Resin M

“F8188” (Propylene-ethylene random copolymer melt viscosity 630 Pa'S (190 ° C), melting point 145.7 C, density 0.9, manufactured by Chisso Corporation) g / cm ³ , Vicat softening point above 120 ° C, half-crystallization time (100 ° C) 25 seconds)

(1 2) Resin N M

Manufactured by Idemitsu Petrochemical Co., Ltd., "3 1 0 E" (high-density polyethylene ethylene, melt viscosity 1 6 5 0 P a 'S , density ^{0. 9 6 5 g Z cm 3} , melting point 1 3 6.C, Vika Tsu DOO Softening point 130 ° C, half-crystallization time (100 ° C) 10 seconds or less)

(13) Resin O

“520 MB” (manufactured by Idemitsu Petrochemical Co., Ltd.) (high-density polyethylene, melt viscosity: 1900 Pas, density: 964 gZc nT, melting point: 133 ° C, vicat softening point: 1 2 8 ° C, half-crystallization time (100 ° C) 10 seconds or less

(1 4) Resin P

Idemitsu Petrochemical Co., Ltd., “J5051HP” (Propylene-ethylene block copolymer, melt viscosity 260 Pas, melting point 16 ° C, density 0.9 gZ cm ³ , Vicat softening point 15 1 ° C, half-crystallization time (100 ° C) 10 seconds or less)

(15) Resin Q

Manufactured by Idemitsu Petrochemical Co., Ltd., "2 1 0 JZ" (high-density polyethylene, melt viscosity 8 2 0 P a 'S, mp 1 3 5. 6.C, density 0. 9 6 8 _§ Roh. 111 ^3, Vika Tsu Softening point 1 229 ° C, half-crystallization time (100 ° C) 5 seconds

(16) Resin R

Nippon Polyolefin Co., Ltd. “PM731M” (Propylene-ethylene random copolymer, melt viscosity 610 Pa ■ S, melting point 149.4 ° C, density 0.9 g / cm \ Softening point of more than 120 ° C, half-crystallization time (100 ° C) for 17 seconds

(17) Resin X

Asahi Kasei Co., Ltd., “Tuftec L512” (hydrogenated styrene-butadiene styrene block copolymer, melt viscosity 290 Pa · S, density 0.91 g

/ cm )

(18) Resin Y Asahi Kasei Co., Ltd., “Toughbrene 125” (styrene butadiene styrene block copolymer, melt viscosity 11210 Pa · S, density 0.95 g / cm ³ ) (19) Resin Z

"K Resin KR05" manufactured by Philips (styrene butadiene styrene block copolymer, melt viscosity 1150 Pa'S, density 1. OlgZ

3 ヽ

cm )

The melt viscosities given for the present invention have been measured as follows.

(Melting viscosity of resin)

The melt viscosity under the conditions of shear rate 100 sec ¹ was measured using a nozzle with a nozzle diameter (D) of 1.0 mm and L / D = 10 (L is the nozzle length (mm)). The measurement was carried out at 0 ° C. with Reobis 2100 manufactured by Thiast. The above formula (1) was used to calculate the PI value of the alloy layer. When adding a compatibilizer, calculate without the compatibilizer. A calculation example in the case of the embodiment is shown below.

Use resin ：

HH32 (PS resin) (Melt viscosity 2400 Pa, S, density 1.05 g

/ cm )

F 8 1 8 8 (PO resin) (Melt viscosity 6300 Pa · S)

210 JZ (PO resin) (Melting viscosity 82 0 Pa · S)

First, determine the melt viscosity of the PO component. For this purpose, 2 1 0 JZ (density ^{0. 9 6 8 g / cm:} i) the determined volume ratio of the probe trend between F 8 1 8 8 (density ^{0. 9 g Z c m '3} ). Since the blend ratio in this case is 10:10 (weight ratio), the volume ratio is 48.2: 51.8.

Viscosity of PP component = 10 " However,

a = [{1 og (viscosity of F8188: 660 X10) X51.8 +

1 og (viscosity of 210 JZ: 82 0 X 10) X 48 .2} / 100] Therefore, the viscosity of the P〇 component is 731 Pa'S.

Volume fraction of P〇 component:

[{(10 / 0.96.8) + (10 / 0.9)} / {(10 / 0.968) + (10 / 0.9) + (6Zl.0 5)}] X 1 0 0-2 7

Volume fraction of PS:

[(60, 1.05) / {(10 / 0.96 8) + (10 / 0.9) +

(6 0/1 .0 5)}) X 100 = 7 3

So the ΡI value is

Ρ I = (viscosity of P S component: 2 0 4 0 X Ρ 体 volume fraction of Ρ component: 2 7) /

(Viscosity of Ο component: 7 3 1 X P S component volume fraction: 7 3) = 1.0 3

Examples 20 to 23, Comparative Examples 4 to 6

A composite having the configuration shown in Table 9 was produced. Table 9 shows the density (g Z cm ³ ), the thickness of the composite (mm), and the adhesive strength (mNZ 25 mm) of the polyolefin resin layer (Z 1 or Z 2). Table 9 also shows the moldability, mold release and heat resistance of the composite.

Formability 〇 good

Δ Polyolefin resin layer has uneven stretching. Releasability 〇 Good

Δ Mold may stick to the mold during mold release Heat resistance なし No deformation of container

X with deformation In the composite materials shown in Table 9, the polyolefin resin (Z1) indicates the surface layer, and the polyolefin resin layer (Z2) indicates the back layer.

The specific contents of the manufacturing method of the composite material shown in Table 9 are as follows.

Two extruders with a diameter of 65 mm and 9 Omm as extruders for the foam layer, an extruder with a diameter of 5 Omm as the extruder for the polyolefin resin layer, and an alloy layer Each extruder used had a diameter of 4 O mm, and the die used was a die having a diameter of 84 mm and a thickness of 0.5 mm and having a cylindrical slit.

The foam layer was heated and kneaded with a prescribed amount of resin and additives from the raw material input port in an extruder with a diameter of 65 mm in the amount shown in Table 10 per 100 parts by weight of resin, and was heated to about 200 ° C. The mixed foaming agent of 30% by weight of isobutane and 70% by weight of normal butane was press-fitted into the extruder shown in Table 10 with respect to the resin mixture adjusted to the above, and then the blowing agent-containing molten resin was mixed with a diameter of 9%. The feed was to a 0 mm extruder. On the other hand, the polyolefin resin layer is supplied from an extruder with a diameter of 50 mm, and the alloy layer is supplied from an extruder with a diameter of 4 Omm to one or both sides of the molten resin for forming a polystyrene resin foam layer, as required. In section 內, it was combined with the molten resin for foam layer formation and co-extruded. Note that the compatibilizer was added to the alloy layer as needed in the amount shown in Table 10.

The extruded cylindrical resin was taken out along a cooled cylinder (mandrel) having a diameter of 200 mm, and then the composite material was wound into a roll. Table 10 shows the specific contents of the foam layer (X), the alloy layer (Y), and the polyolefin resin layer (Zl, Z2) constituting the composite material.

The specific contents of the PS resin (polystyrene resin) indicated by reference numerals for the foam layer (X) are as described above. The talc blended with the PS resin is Matsumura Sangyo's High Filler # 12. The specific contents of the PO resin (polyolefin resin) and the compatibilizer with respect to the alloy layer (Y) are as described above.

The specific contents of the P O resin indicated by reference numerals with respect to the P O layer (polyolefin layer) (Z 1, Z 2) are as described above.

The composition of the P O layer (Z 1) and that of the P〇 layer (Z 2) are the same. In Tables 9 and 10, the specific contents of the resin indicated by the reference numerals are the same as those described above, and the others are as follows.

(1) Resin F

"ET203" (Propylene-ethylene random copolymer, melt viscosity 7500 Pa · s (190 ° C), melting point 138.5 ° C, vicat softening, manufactured by Chisso Corporation) Point 1 19 ° C, density 0.9 g Z cm ³ , half-crystallization time (100 ° C) 53 seconds)

(2) Resin G

“F1188” (polypropylene homopolymer, melt viscosity 6.50 Pa · s (190 ° C), melting point 160.3 ° C, Vicat softening point 1 5 1 ° C, density 0.9 g Z cm ³ , half-crystallization time (100 ° C) 6 seconds)

(3) Resin L

Idemitsu Petrochemical Co., Ltd., "F-714NP" (Propylene-ethylene random copolymer, melt viscosity 65500 Pa's (190 ° C), melting point 154.6.C , Vicat softening point above 120 ° C, Density 0.9 g Z cm ³ , Semi-crystallization time 11 sec)

Regarding the moldability and mold release properties shown in Table 9, the composite materials obtained in Examples and Comparative Examples were stored in a single-shot molding machine (PL AVA C-FE36 HP type manufactured by Sanwa Kogyo Co., Ltd.). With a partitioning rib that divides it into six equal parts, a rectangular shape with a length of 210 mm, a width of 55 mm, and a depth of 50 mm Was attached and vacuum forming was performed for evaluation. In this molding test, all of the 40 dials of the voltage regulator of the upper heater were set to 30 and all of the 6 dials of the lower heater were set to 40. I went.

Regarding the heat resistance shown in Table 9, the composite materials obtained in Examples and Comparative Examples were molded into a rectangular container of 210 mm in length and 150 mm in width and 50 mm in depth. 300 ml of hot water at 0 ° C was added, and the mixture was heated in a 500 W microwave oven for 1 minute, and then checked for deformation.

Example 2 4

A composite having the configuration summarized in Table 11 was made.

Two extruders having a diameter of 65 mm and a diameter of 9 Omm were used in tandem type as extruders for producing a foam layer. In this case, an extruder with a diameter of 50 mm was used as the extruder for the polyester resin layer, an extruder with a diameter of 40 mm was used for the production of the alloy layer, and a die with a diameter of 84 mm was used. mm and a cylindrical slit with a gap of 0.5 mm were used.

Polystyrene resin for foam layer production from the raw material inlet of an extruder with a diameter of 65 mm Λ 98.6 parts by weight and hydrocerol CF 4 OS as a cell regulator (manufactured by Dainichi Seika Kogyo Co., Ltd.) ) Was added, and the mixture was heated and kneaded in an extruder, and 1.1 parts by weight of a foaming agent A was injected into the resin kneaded material adjusted to about 200 ° C., and then It was fed to a 90 mm diameter extruder and adjusted to a resin temperature of 167 ° C. On the other hand, the polyester resin B laminated on the foam layer is extruded by adjusting the resin temperature to 215 ° C with a 50 mm diameter extruder, and the resin constituting the alloy layer is a polystyrene resin F 6 0% by weight and polyester resin G40 0% ⁰ /. The mixture was extruded from a 40 mm diameter extruder while adjusting the resin temperature to 150 ° C. Then, the resin constituting the alloy layer and the polyester resin were supplied from the foam sheet side in such a manner as to be laminated in this order, and were combined with the foamable resin inside the die and co-extruded.

The extruded cylindrical foamed resin was taken out along a cooled cylinder having a diameter of 200 mm, and then cut open to obtain a composite material, which was wound up.

In this composite material, the thickness of the foam layer is 1.4 mm, the thickness of the alloy layer is 0.04 mm, and the thickness of the film-like polyester resin is 0.05 mm. A polystyrene resin L with a resin temperature of 260 ° C was extruded from a 65 mm diameter extruder equipped with a 700 mm wide T die on the obtained sheet, and extruded and laminated to perform one side. Then, a composite material in which a 0.15 mm-thick film-like polystyrene resin was laminated and adhered, and a film-like polyester resin was laminated and adhered to one surface of the other side via an alloy layer was obtained.

Polystyrene resin F is trade name Styrone H8601, manufactured by A & M Styrene Co., Ltd. and has a melt viscosity of 98 Pas and a vicat softening point of 9 6 ° C, the density is ^{1. 0 5 g / cm 3} .

Polyester resin G is a product name: Biono Ire # 1903, manufactured by Showa High Polymer Co., Ltd., with a melt viscosity of 62 Pas, a melting point of 114 ° C, and a density of 1 . a 2 6 g Z cm ^3.

Polystyrene resin L is trade name RQ301, manufactured by Denki Kagaku Kogyo Co., Ltd., its melt viscosity is 650 Pas, its vicat softening point is 97 ° C, and its density is 1. is a 0 5 g Z cm ^3.

The polyester resin B is polyester PETG 6763 from Eastman Chemical Japan Co., Ltd., has a half-crystallization time of 60 minutes or more (100 ° C), and has a melt viscosity of 210 ° C. Polymerization using P aS, density 1.26 g Z cm ³ _n ,

34

As a product (modified ethylene-vinyl acetate copolymer), melcene MX 28, melt viscosity 2770 Pa · S, density 0.94 g / cm ³ , melting point 117 ° C, east Soichi Co., Ltd. was used.

As the blowing agent ブ, a butane mixture consisting of 70% by weight of n-butane and 30% by weight of iso-butane was used.

Comparative Example 7

Composites having the configurations summarized in Table 12 were prepared.

A composite material was obtained in the same manner as in the example except that polyester resin P was used instead of polyester resin B as the polyester resin. The polyester resin P, manufactured by Nippon Unipet Co., Ltd., has a melt viscosity of RT 543, a half-crystallization time of less than 30 minutes (100 ° C), and unmelted at 190 ° C. unmeasurable, the density 1. 2 6 g / cm ^3.

Comparative Example 8

Composites having the configurations summarized in Table 12 were prepared.

Polyester resin P was used in place of polyester resin B as the polyester resin, and the composite material was extruded in the same manner as in the example except that the extruder was extruded at a resin temperature of 270 ° C from a 50 mm diameter extruder. Obtained.

Next, the physical properties of each of the composite materials obtained in the above Examples and Comparative Examples were measured, and their extrusion foaming properties were evaluated. Further, their moldability and heat resistance were evaluated as follows. The results are shown in Table 11 or Table 12.

(Formability)

The composite material obtained in each of the examples and comparative examples was formed using a single-shot molding machine (PL AVAC-FE36HP type manufactured by Sanwa Kogyo Co., Ltd.) with an opening shape of 150 mm in diameter and a bottom diameter of 1 2. Attach a container mold of 0 mm, depth of 60 mm or 30 mm with a frustoconical shape. Vacuum forming was performed. In this molding test, all 40 dial scales for the upper heater and the voltage regulator were set to 30 and all six dial scales for the lower heater and the voltage regulator were set to 40. I went. The moldability (thermoformability) was evaluated based on the appearance of the obtained molded body.

◎: Good mold reproducibility and appearance at draw ratio of 09

〇: Good mold reproducibility and appearance at a draw ratio of 0 4 (depth: 6 O mm)

Mold reproducibility and Z or appearance are poor at an aperture ratio of 09

△: Good mold reproducibility and appearance at a draw ratio of 0 2 (depth: 3 O mm)

Mold reproducibility and Z or appearance are poor at an aperture ratio of 04

For the above-described drawing ratio of 0.9, a frustoconical container molding die having an opening of 95 mm in diameter, a bottom diameter of 70 mm, and a depth of 105 mm was used. As a result of the test, all of the composite materials of the examples had a low open cell ratio, and were able to obtain a deep drawn molded body having good mold reproducibility in heating and vacuum forming. Also, the adhesive strength was strong.

On the other hand, in the case of the composite material of the comparative example, a deep drawn product having good mold reproducibility could not be obtained in the heating vacuum forming. In Comparative Example 8, the open cell ratio was high even when a multilayer foam sheet was obtained. In addition, as shown in Comparative Examples 7 and 8, a composite material in which a polyester resin laminated on a foam layer in the form of a film via an alloy layer as a polyester resin having a half-crystallization time of less than 30 minutes was subjected to heating vacuum. Under the molding conditions of the polystyrene resin foam during molding, the polyester part did not stretch sufficiently, and the surface of the molded body was shiny. (Heat-resistant)

Pour boiling water into a molded body with a draw ratio of 0.4 obtained in the thermoforming test at a depth of 50 mm for 5 seconds, then leave it open for 4 minutes without lid, and then discard hot water The appearance inside the container was observed.

〇: No change

△: Peeling of polyester resin layer on sheet surface

Example 2 5

Create a composite material in which a polyolefin resin layer, an adhesive layer (1), a polyester resin layer, an alloy layer (2), a polystyrene resin foam layer, an alloy layer (3), and a polyolefin resin layer are laminated in this order. did.

As extruders for producing a polystyrene-based resin foam layer, two extruders having a diameter of 90 mm and a diameter of 120 mm were connected in tandem.

For the alloy layers (2) and (3), an extruder with a diameter of 65 mm was used. Adhesion layer between polyester resin layer and polyolefin resin layer in _c- composite using extruder with diameter of 45 mm as extruder for polyester resin layer (1) Extruder with diameter of 65 mm for production Was used.

As a _c- base using an extruder with a diameter of 65 mm for the production of a polyolefin resin layer, a cylinder with a diameter of 135 mm and a gap of 0.3 mm was used. .

Polystyrene resin for foam layer production from the raw material inlet of an extruder with a diameter of 90 mm Λ 98.6 parts by weight and hydrocerol CF 40 S as a cell regulator (Dainichi Seika Kogyo Co., Ltd.) 0.3 parts by weight), heated and kneaded in the extruder, and 1.1 parts by weight of the foaming agent A was injected into the resin mixture adjusted to about 200 ° C. The resin was fed to a 20 mm extruder, and the resin temperature was adjusted to 165 ° C. The blowing agent Λ is n-butane 70% by weight, is ό I

A butane mixture consisting of 30% by weight of o-butane was used.

The resin constituting the alloy layers (2) and (3) on both sides of the polystyrene resin foam layer is resin 50% by weight as a polyester resin and resin 50% by weight as a polystyrene resin. 100 parts by weight of the mixture was added with 10 parts by weight of compatibilizer T, and these were added to an extruder having a diameter of 65 mm from an extruder.

The resin temperature was adjusted to 0 ° C.

The resin constituting the polyester resin laminated on the polystyrene resin foam layer via the alloy layer (2) is resin S, which is extruded at a resin temperature of 200 ° C from an extruder with a diameter of 45 mm. Was adjusted.

As the adhesive layer (1) mainly composed of a mixture of a polyester resin and a polyolefin resin, the polyester resin contains 70% by weight of the resin S. /. As the polyolefin resin, 3% by weight of resin M was used. This was adjusted to a resin temperature of 170 ° C. by an extruder having a diameter of 65 mm.

The resin constituting the two outermost polyolefin resin layers of the composite material was resin M, which was adjusted to a resin temperature of 185 ° C by an extruder having a diameter of 65 mm.

The respective resins are merged inside the die and co-extruded to form a polyolefin resin layer, an adhesive layer (1), a polyester resin layer, an alloy layer (2), a polystyrene resin foam layer, an alloy layer (3), and a polyolefin resin. The cylindrical foamed resin laminated in the order of the layers was taken out along a cooled cylinder having a diameter of 335 mm, and then cut open to obtain a composite material, which was wound up. Table 13 shows properties of the obtained composite material.

Example 26

The resin constituting the polyolefin resin layer is resin H (propylene-ethylene block copolymer), and the adhesive layer (1), alloy layer (2), and (3) are yellow. A composite material was obtained in the same manner as in Example 25, except that 4.2 parts by weight of EPS-E40518 manufactured by Pigment Polycarbon Industry Co., Ltd. was added to 100 parts by weight of the mixed resin.

Example 2 7

The adhesive layer (1), the alloy layers (2) and (3) were mixed with black pigment SBF-T-1683 (carbon black) manufactured by Resinoka Ichi Kogyo Co., Ltd. A composite material was obtained in the same manner as in Example 25 except that 2 parts by weight was added. Example 2 8

The resin constituting the polyolefin resin layer is resin E (high-density polyethylene), and the foaming agent A is 0 for the resin kneaded material adjusted to about 200 ° C as the polystyrene resin foam layer. A composite material was obtained in the same manner as in Example 25, except that 0.7 parts by weight was pressed and the density of the polystyrene foam layer was 0.35 g Z cm ³ and the thickness was 0.55 mm.

Example 2 9

A composite material was obtained in the same manner as in Example 28 except that resin N (high-density polyethylene) was used as the resin constituting the polyolefin resin layer and resin D was used as the polystyrene resin foam layer.

In Examples 25 to 29, the open cell ratio was 8 to 20%.

The symbols of the components shown in Examples 25 to 29 are the same as those described above, and the others are as follows.

Polyolefin resin E

Higashisoichi Ltd. "two boron Hard 4 0 0 0" (high-density polyethylene, melting point 1 3 5 ° C, density ^{0. 9 6 4 g / cm 3} , melt viscosity 6 3 0 P a ■ s ( 190 ° C) Vicat softening point 130 ° C)

Polyester resin S "PESTAG PETG 6763 J" (melt viscosity 2100 Pas, density 1.26 g / c semi-crystallization time 60 minutes or more) manufactured by Yeastman Chemical Japan Co., Ltd.

Compatibilizer T

Asahi Kasei Kogyo Co., Ltd. “Tuftec H1141” (hydrogenated styrene butadiene styrene block copolymer, density 0.91 g / cm ³ )

Table 1 Example Example Example Example Example Example Example Example Example 1 2 3 4 5 6 7 8

PO layer (Z ¹ ) U. υ. Υο υ. Υο υ. 0 n uoc υ. Uo U. UO layer (Y ¹ ) U. υ. Υο η υ. Υ. Υ. N u. Π Π Constitution

Foam layer (X) 1 q 1 1 R · Q o

(Thickness: mm)

Layer (Y ² ) η

υ. υο υ. υο υ. i υ. U. u.

PO layer (Z ² ) 1 0.05 0.05 0.05 0.1 0.05 1 Composite density (gZ cm ³ ) 0.18 0.25 0.31 0.28 0.31 0.27 0.2 0.8 Composite thickness (mm) 1.98 2.1 1.8 2.0 1.9 2.2 2.55 2.5 Type of manufacturing method Co-extrusion Co-extrusion Co-extrusion Co-extrusion Co-extrusion Co-extrusion Laminated resin temperature (° C) 175 179 178 178 178 173 190 175 Oil resistance 〇〇〇〇〇 O 〇〇

Z '/ X adhesive strength

3185 5882 4902 6372 4412 7107 5392 4902 (mN / 2 5 mm)

Z ² ZX adhesive strength

3430 2695 4657 2940 4902 4412 (mN / 2 5 mm)

Open cell ratio of foam layer (%) 16 13 18 15 16 12 20 15

Table 2

Table 3 Example Example Example Example Example Example Example Example Example Example

Q rr

丄 4 o

O b o

PS resin type A A B B B B D A Type of additive and talc talc talc talc talc talc talc Foam layer None

1 1 1 1.o 1 1 丄

Type of blowing agent and B B B n -p B B B CF40S amount (% by weight) 1.0 1.4 l. Υ 1.1 I.0 I, u on. B

Type of P S resin A A B C B B D A and amount (% by weight) 7Λ

0 00 00 7 7Q

/ 0 / Π U O

ΡΟType of resin H H H I I K J H and amount (% by weight) 22 25 30 45 35 55 30 22 Alloy layer

Types of compatibilizer

None V5 V5 V5 W3 V4 V5 None and quantity (parts by weight)

Ρ I value 1.02 1.20 0.93 0.99 0.97 0.86 0.89 1.02 Finolem layer Type of resin JHHHIKIJ

Table 4 Comparative examples Comparative examples Comparative examples

1 Δ 3

P S resin type A A B Additive type and talc Talc Talc Foam layer

Amount (parts by weight) 1 1 1 Type of blowing agent and B B B amount (% by weight) 1.6 1.6 1.0

Type of P S resin A A B and amount (% by weight) 85 50 55

PO resin type H H H and amount (% by weight) 15 50 45 Alloy layer

Compatibilizer type V V None

5 5

PI value 0.64 3.61 1.78 Film layer PO resin type JHK

Table 5 Example Example Example Example Example Example

丄丄丄 Ζ 1 l * o}

PO layer (Z ¹ ) 0.03 0.04 0.04 0.03 0.035 Alloy layer (γ ¹ ) 0.06 0.05 0.05 0.04 0.05 Composition of composite material

Foam layer (X) 0.63 2.4 2.0 0.9 0.63

(Thickness: mm)

Alloy layer (Y ² ) 0.06 0.05 0.05 0.04 0.05

PO layer (Z ² ) 0.03 0.04 0.04 0.03 0.035 Composite density (gZc m ³ ) 0.45 0.16 0.17 0.31 0.48 Composite thickness ( _mm ) 0.78 2.6 2.2 1.05 0.8 Manufacturing method Co-extrusion Co-extrusion Co-extrusion Co-extrusion Co-extrusion Resin temperature (° C) 165 160 174 178 182 Oil resistance 〇〇〇〇〇

Z ¹ X adhesive strength

6985 8090 5270 5147 5147 (mN / 2 5 mm)

Z ² / X adhesive strength

6617 7600 5147 5637 5270 (mN / 2 5 mm)

Open cell ratio of foam layer (%) 15 16 14 12 18

Table 6 Normally 51 cases 芙 K6 cases 夹 ffi cases Actual Sfe cases

14 15 16 17 18 19

PO layer (Z ¹ ) 0.03 0.03 0.03 0.03 0.03 0.03 Alloy layer (Y ¹ ) 0.04 0.04 0.06 0.06 0.06 0.04 Composition of composite material

Foam layer (X) 0.9 0.9 0.54 0.54 0.54 1.1

(Thickness: mm)

Alloy layer (Y ² ) 0.04 0.04 0.06 0.06 0.06 0.04

PO layer (Z ² ) 0.03 0.03 0.03 0.03 0.03 0.03 Composite density (/ cm ³ ) W. Jn υ. C: u.u Composite thickness ( _mm ) 1 05 1.05 0 7 0 7 0 7 1_ 25 Type of manufacturing method Coextrusion Coextrusion Coextrusion Coextrusion Coextrusion Coextrusion Resin temperature (V) 165 165 168 167 166 160 160 Oil resistance 160 〇〇〇〇 ζ ζν / χAdhesive strength

6617 6127 5147 7352 6985 3430

(mN / 25 mm)

z x adhesive strength

5025 5637 5882 6862 5882 4902 (raN / 25 mm)

Open cell ratio of foam layer (%) 15 18 13 14 17 12

Table 7 Example Example Example Example Example Example

9 10 11 12 13 p Class of S resin AADD n Foam ja Additive type and talc talc talc talc talc amount (parts by weight) 1.0 0.8 0.8 1.0 1.2 Type of blowing agent and BBBBB amount (% by weight) 0.9 1.6 1.65 1.0 0.8

Type of PS resin A A D D D and amount (% by weight) 75 75 75 75 70

ΡΟType of resin H M N N O and amount (% by weight) 25 25 25 25 30 Alloy layer

Type of compatibilizer V V V XX and amount (parts by weight) 5 5 5 5 5

Ρ I value 1.20 1.26 0.62 0.62 0.54 Finolem layer ΡΟ Resin type HMNN 0

Table 8 Example Example Example Example Example Example Example

14 15 16 17 18 19

Type of PS resin A A A A A A A Type and amount of additive Talc Talc Talc Talc Talc CF40S Foam layer

(Parts by weight) 1.0 1.0 0.8 0.8 0.8 0.2 Type and amount of blowing agent B B B B B B (% by weight) 1.0 1.0 0.8 0.8 0.8 1.8

Type of PS resin and A A A A A A Amount (% by weight) 75 75 75 75 75 75

PO resin type and M Q Q M R H amount (% by weight) 25 25 25 25 25 25 Alloy layer

Type of compatibilizer and amount of Y V V Y V X (parts by weight) 25 5 5 25 10 6.25

PI value 1.26 0.90 0.90 1.26 1.30 1.20 Film layer PO resin type MQQMRH

Table 9 Example Comparative Example

20 21 22 23 4 5 6

M / Q M / Q Μ / Η

Type (weight ratio) L ヮ G Η F

= -7 / 3 = 3/7

PO layer

At 1 00

11 5 5 6 7 8 53 Semi-crystallization time (sec)

PO layer (Z 1) 0.03 0.03 0.03 0.03 0.03 0.03 0.03 Composite material Alloy layer (Y) 0.04 0.04 0.04 0.04 0.04 0.04 0.04

Foam layer (X) 1.12 1.12 1.12 1.12 0.82 1.12 1.12 (Thickness:

mm; Alloy layer (Y) 0.04 0.04 0.04 0.04 0.04 0.04 0.04

PO layer (Z 2) 0.03 0.03 0.03 0.03 0.03 0.03 0.03 Composite density (gZcm ³ ) 0.25 0.25 0.25 0.25 0.29 0.25 0.25 Composite thickness ( _mm ) 1.26 1.26 1.26 1.26 0.96 1.26 1.26 Rapid continuity (%) 17 17 16 19 20 17 17 Adhesive strength X / Z 1 4412 7600 7845 6372 5392 5392 4167 (mN / 25mm) X / Z 2 3922 5147 6127 4657 4167 4657 3800 Moldability 〇〇〇 Δ Δ Δ Δ Release property 〇〇〇〇〇〇 Δ Heat resistance 〇〇〇〇〇 Ο 〇

Table 1 o Actual method δ example Comparative example

20 21 22 23 4 5 6 types M / Q M / Q M / ll

PO layer G H F

(Weight ratio) = 5/5 = 7/3 = 3/7

P S resin type H

Ηοϋ H O HbU H60 H60 and quantity (% by weight) 71.25

PO resin type A10 A14 G G

Adhesive layer JN ϋ t ϋ and amount (% by weight) CIO C6 23.75 23.75 Type of compatibilizer

K20 K20 K20 then 5 K20 L5 K20 and quantity (% by weight)

P S Type of fat H H H H H H H H Type of additive

Foam layer Talc 1 Talc 1 Talc 1 Tanolek 1 Talc 1 Tanolek 1 Tanolek 1 and amount (parts by weight)

Amount of blowing agent

1.25 1.25 1.25 1.25 1.25 1.25 1.25 (% by weight)

P I value 1.22 1.03 1.14 1.22 1.20 1.22 1.06

•

Item Example 24 Polyester resin layer thickness (mm)

Thickness of alloy layer (mm) 0.04 Polystyrene tree Ji thickness (mm) 1.4 Density of foam layer (gcm ³ )

Polystyrene resin layer Thickness (mm; (J. み Thickness (mm)) 1.64 Basis weight (gZm ² ) 551 Density (gZcm ³ ) 0.34 Open cell ratio (%) 16 Properties of composite material Adhesive strength

5025 (mN / 25 mm)

Oil resistance 〇 Formability ◎ Heat resistance 〇

PI value 0.88

Table 12 Comparative Example Item

7 8 Polyester resin layer thickness (mm) 0.05 0.05 Alloy layer thickness (mm) 0.03 0.04 Polystyrene resin thickness (mm) 1.9 1.4 Foam layer density (gcm ³ ) 0.105 0.21 Polystyrene resin layer thickness, mm ) 0.15 Thickness (mm) 1.98 1.64 Basis weight (gZm ² ) 292 551 Density (gZcm ³ ) 0.15 0.34 Open cell ratio (%) 22 74 Properties of composite materials Adhesive strength

8825 5637 (mN / 25 mm)

Oil resistance 〇〇 Formability △ △ Heat resistance Unmeasurable Unmeasurable

PI value

68

52

Table 13 Example Example Example Example Example Example Item 07

Polyolefin thickness

22.5 22.5 22.5 22.2 22.2

Thickness

Adhesive layer (1) 28.8 28.8 28.8 17.6 17.6

(m no

Polyester thickness

31.5 31.5 31.5 19 19 Resin layer

Thickness

Alloy layer (2) 97 97 97 34.5 34.5

810 810 810 400 400 Polystyrene

Resin body layer

0.21 0.21 0.21 0.35 0.35

(g / cm ³ )

Thickness

Alloy layer (3) 97 97 97 34.5 34.5

(μm)

Polyolefin thickness

13.5 13.5 13.5 22.2 22.2 Resin layer (μm)

Thickness

1.1 1.1 1.1 0.55 0.55 (mm)

Basis weight

340 340 340 280 280 (g m ² )

Composite properties Density

0.61 0.61 0.61 0.68 0.68 (g m ³ )

Oil resistance 〇〇〇〇〇 Moldability 〇〇〇〇〇 Heat resistance 〇〇〇〇〇

Ρ I value 0.80 0.80 0.80 0.80 0.80 Adhesive strength (mN / 25mm)

Polyester resin layer / 4902 5392 5147 5270 5147 Polystyrene resin foam layer

Claims

The scope of the claims

1. A composite material comprising a polystyrene resin foam layer, an alloy layer provided on at least one of both surfaces of the polystyrene resin foam layer, and a thermoplastic resin layer provided on the alloy layer,

The thermoplastic resin layer is made of a resin selected from a polyolefin resin and a polyester resin,

The alloy layer is composed of a mixture of a polystyrene resin and a thermoplastic resin selected from a polyolefin resin and a polyester resin. However, when the thermoplastic resin layer is composed of a polyolefin resin, the thermoplastic resin of the alloy layer is a polyolefin resin. When the thermoplastic resin layer is made of a polyester resin, the thermoplastic resin of the opening layer is a polyester resin; and

A composite material having an adhesive strength between the polystyrene resin foam layer and the thermoplastic resin layer of at least 980 mN / 25 mm.

2. The composite material according to claim 1, wherein the alloy layer has a phase structure index P I of 0.5 to 1.5, wherein P I is defined by the following formula.

P I = ". \ B / 1 B 'Φ. \)

Wherein, phi., The volume fraction of the polystyrene resin of the Aroi layer, 7? _Lambda 1

9 0 ° C, time melt viscosity of the polystyrene resin at a shear rate of 1 0 0 sec, φ _B is the volume fraction of the thermoplastic resin of the Aroi layer, _beta is 1 9 0 ° C shear rate of 1 0 0 sec ¹ is the melt viscosity of the thermoplastic resin.

3. The composite material according to claim 1, wherein the alloy layer has a phase structure index P I of 0.7 to 1.3.

4. The alloy layer includes a compatibilizing agent for increasing the compatibility between the polystyrene resin and the thermoplastic resin of the alloy layer. The composite material according to any one of claims 1 to 3, wherein the composite material comprises 0.1 to 30 parts by weight per 100 parts by weight of the total of the lent resin and the thermoplastic resin.

5. The composite according to any one of claims 1 to 4, wherein a weight ratio of the polystyrene resin to the thermoplastic resin in the alloy layer is in a range of 95: 5 to 30:70.

6. The composite material according to claim 4, wherein the compatibilizer is a styrene-containing thermoplastic elastomer.

7. The elastomer is styrene-butadiene-styrene block copolymer, styrene-isof. 7. The composite according to claim 6, wherein the composite is selected from a styrene-block copolymer, a styrene-ethylene-butylene-styrene block copolymer, and a styrene-ethylene-propylene-styrene block copolymer. Wood.

8. The composite material according to any one of claims 1 to 7, wherein the thickness of the opening layer is 15 to 200 m.

9. The composite material according to any one of claims 1 to 8, wherein the alloy layer is obtained by co-extrusion with the polystyrene resin foam layer.

10. The composite material according to any one of claims 1 to 9, wherein the thermoplastic resin layer is made of a polyolefin resin having a vicat softening point of 112 ° C or higher.

11. The composite material according to any one of claims 1 to 9, wherein the thermoplastic resin layer is made of an aromatic polyester resin having a half-crystallization time at 100 ° C of 30 minutes or more.

12. The aromatic polyester resin contains an aromatic carboxylic acid component unit and a diol component unit, the aromatic carboxylic acid component unit contains a terephthalic acid component unit, and the diol component unit contains ethylene glycol. Claim 1 1 comprising the component unit and the cyclohexanedimethanol component unit 00

The composite material according to the item.

1 3. A mixture of (a) a polypropylene resin having a melting point of at most 150 C and a (b) polyethylene resin having a melting point of at least 130 C and having a melting point different from that of the resin (a). from it, the amount of the resin _(a) is 1 ◦ less than 0 wt% total weight of 5 0 wt% or more of the resin _(a) and (b), the amount of the resin (b) is a resin (a) The semi-crystallization time at 100 ° C. of the mixture is not more than 50% by weight and not more than 0% by weight and not more than 50% by weight of the total weight of (b). The composite according to any one of the above.

14. The composite material according to any one of claims 1 to 10, wherein the thermoplastic resin layer is made of a polypropylene resin having a melting point of more than 150 ° C.

1 5. The composite material according to any one of claims 1 to 10, wherein the thermoplastic resin layer is made of a polyethylene resin having a melting point of 130 ° C or more.