JPH05177777A - Multilayered sheet having low temperature high speed moldability and molded container - Google Patents

Abstract

PURPOSE:To provide a molding sheet excellent in moldability such as deep drawn properties or low temp. high speed moldability, having a high rigidity and moldable by various molding methods. CONSTITUTION:In a multilayered sheet consisting of two or more thermoplastic resin layers, the tensile modulus of elasticity of the resin forming at least one layer is 50-300 kg/mm<2> and the thickness of the surface layer is 2-50% and VSP of the resin forming the surface layer and the resin adjacent thereto is 0.8-2 and ORS of all layers of the sheet is below 2 kg/cm<2>.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a high rigidity, which has improved moldability, especially low-temperature and high-speed moldability and deep-drawability, and is mainly vacuum molding, pressure molding, plug molding, bending molding or a combination thereof. The present invention relates to a thermoplastic resin multi-layer sheet used for various types of packaging containers such as foods molded by, and various other cases.

[0002]

2. Description of the Related Art Conventionally, as a plastic sheet which has been secondarily molded by a pressure molding method, a vacuum molding method, a plug assist molding method or a combination thereof, a hard vinyl chloride ( PVC) sheet,
High impact polystyrene (HIPS) sheets, expanded polystyrene sheets (PSP), polypropylene sheets, stretched polystyrene sheets and the like are generally known. Among them, PVC sheets and polystyrene stretched sheets are used in fields where transparency is required. The stretched polystyrene sheet has excellent transparency and rigidity,
Since it is a stretched sheet as compared with a PVC sheet, it is difficult to form. For example, a stretched polystyrene sheet is inferior in deep drawability, requires heating at a relatively high temperature for a long time, and is generally difficult to form by a method other than the hot plate contact pressure air forming method. Furthermore, it is weaker in strength than a PVC sheet.

On the other hand, PVC sheets (generally 5 to 5% plasticizer)
(Including about 20% by weight) has excellent formability and is capable of deep drawing, and in addition to the hot plate contact pressure forming, various methods such as radiant heating type pressure forming, vacuum forming, plug assist forming, etc. It can be molded by the method. However, rigid PVC
In addition to the sanitary and quality problems of plasticizers, the sheet has a problem of pollution due to chlorine gas generated during combustion.
There is a demand for a sheet that replaces the VC sheet.

In order to solve the above problems, for example, a method has been proposed in which a polyolefin resin is laminated on a stretched polystyrene sheet to improve deep drawability and mold reproducibility. For example, JP-A-49-18976 discloses that
A composite sheet obtained by dry laminating a general-purpose polystyrene (GPPS) stretched sheet with a non-stretched polypropylene sheet via an adhesive, and in JP-A-55-114458, a GPPS layer is formed by a coextrusion method, a dry lamination method or the like. There is described a composite stretched sheet obtained by laminating a polyolefin layer such as low-density polyethylene or polypropylene via an adhesive layer and then stretching. However, in these methods, there is a limit to the improvement of moldability due to the stretched sheet, and the transparency and rigidity are poor because the olefin resin is disposed on the surface layer.

In addition, Japanese Patent Publication No. 51-5862 discloses that
There is a description of a non-stretchable sheet for molding, which is composed of a composition containing a small amount of hardened oil of animal or food oil in a styrene-butadiene block copolymer (SBBC) containing 60 to 90% by weight of styrene hydrocarbon. Although this product can be deep-drawn, it is liable to be clouded and its transparency is insufficient. Also, S
Since it is a single sheet of BBC, it has inferior rigidity and inferior oil resistance to the stretched polystyrene sheet.

Further, Japanese Patent Publication No. 3-67016 discloses that
In a stretched sheet made of a composition of polystyrene and SBBC, a method for solving the moldability (deep drawability) of the stretched styrene resin sheet by controlling the heat shrinkage stress and the butadiene concentration is described. However, this tends to reduce the strength of the sheet and tends to have poor productivity because the stretching conditions are limited.

Further, JP-A No. 2-120044, JP-A No. 2-185438, and JP-A No. 3-99846 disclose a styrene resin having an improved molding cycle, deep drawing property, molding condition range and the like. Multilayer stretched sheets have been proposed, and although these sheets have improved moldability as compared with polystyrene stretched sheets, it is hard to say that they meet the level of PVC sheets. Furthermore, the above-mentioned problem that the molding method is limited has not been sufficiently solved.

[0008] Recently, an amorphous polyester sheet has been attracting attention as a sheet made of a new clean material to replace the PVC sheet. This is made from a resin obtained by copolymerizing an acid component or an alcohol component constituting the polyester to make it amorphous, or a sheet whose extruded product is rapidly cooled to suppress its crystallinity.

However, this is generally poor in workability,
In particular, for a sheet whose crystallinity is suppressed by quenching, crystallization may progress in some cases during heating during secondary molding, and it is difficult to control the conditions thereof. Also,
Since these have a low softening point, heat resistance is insufficient, deformation and blocking are likely to occur, and rigidity is inferior compared to styrene resin stretched sheets and PVC sheets, so it is necessary to make thick sheets and molded products. Since the resin itself is expensive, it leads to cost increase. in this way,
With the current technology, it is difficult to obtain a transparent transparent sheet which has few hygiene and environmental problems and is excellent in moldability (deep drawability, low-temperature high-speed moldability) and has rigidity.

[0010]

Under the above circumstances, the present invention is capable of forming by various methods such as vacuum forming, pressure forming, plug forming, bending forming method, or a combination thereof, and at a low temperature and a high speed. The purpose of the present invention is to provide a high-rigidity multilayer sheet excellent in moldability and deep drawability.

[0011]

In order to achieve the above-mentioned object, in the present invention; in a multilayer sheet comprising two or more layers of thermoplastic resin having at least one surface layer and at least another adjacent layer, (a) ) The elastic modulus of the thermoplastic resin (A) forming the surface layer is 50 to 300 kg / mm ² ,
(B) The ratio (Va / Vb) of the Vicat softening point (Va ° C.) of the resin (A) and the Vicat softening point (Vb ° C.) of the thermoplastic resin (B) constituting the other layer adjacent thereto is 0. .8-
(C) the surface layer has a thickness ratio of 2 to 50% with respect to all layers, and (d) the sheet has a heat shrinkage stress of less than 2.0 kg / cm ² . A multi-layered sheet, which is characterized by being present, is adopted.

The present invention will be described in detail below. In the present invention, specifically, a thermoplastic resin (A) (hereinafter referred to as a layer) forming at least one surface layer and a thermoplastic resin (B) (hereinafter referred to as b) constituting another layer adjacent to the layer. Examples of the resin used for the layer) include styrene resins, acrylic resins, polyester resins, polyphenylene ether resins, polycarbonate resins, polyolefin resins and copolymers thereof. Further, copolymers of these thermoplastic resins with a styrene-based monomer, butadiene, or a monomer having a conjugated diene structure such as isoprene, a resin obtained by hydrogenating a double bond derived from the conjugated diene, or the like. Resins modified with carbonyl group-containing monomers (hereinafter, these are collectively referred to as S
BBC) or the like may be mixed. These resins are 1
The same kind or different kinds of resins may be freely combined and used.

The layers a and b of the present invention are multilayer sheets obtained by laminating any one selected from these resin groups so as to satisfy the conditions such as the Vicat softening point, the tensile modulus of elasticity, and the heat shrinkage stress described later. I wish I had it.

Specifically, the styrene resin and its copolymer are at least one styrene selected from α-alkyl-substituted styrene such as styrene and α-methylstyrene, nuclear alkyl-substituted styrene, nuclear halogen-substituted styrene and the like. A polymer comprising a styrene-based monomer, and at least one of the styrene-based monomers (in the case of two or more, the total amount thereof),
Binary, ternary or quaternary of 50% by weight or more, preferably 60% by weight, more preferably 70% by weight or more of these monomers and at least one other monomer copolymerizable with the monomer (described later). The above copolymer, or impact-resistant polystyrene (HIPS: transparent one) obtained by graft-polymerizing a small amount (15% by weight or less) of a rubber component, or at least one monomer and butadiene described above. , A block copolymer with a conjugated diene such as isoprene. These polymers may be used alone or in combination of two or more depending on the purpose.

Specifically, as the monomer copolymerizable with the styrene-based monomer, acrylic acid and its esters (eg, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acryl) are used. Alcohol group of alcohol component such as acid pentyl has C _{1 to} C ₁₂
), Methacrylic acid and its esters (for example, those having the same alcohol components as above, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate), fumar Α, β- such as acid, maleic acid, itaconic acid
Unsaturated dicarboxylic acids and their monoesters, diesters, anhydrides and imidized products thereof (for example, maleic anhydride, maleimide, etc.), acrylonitrile, or acrylic acid and methacrylic acid (or their esters adjacent to each other in the molecule) ) And other monomer units, which are secondarily derived by an intramolecular dehydration (or dealcoholization) reaction, and a conjugated diene having a conjugated double bond such as an imidized product thereof, butadiene, and isoprene. And so on.

Of these, preferably acrylic acid,
Or methacrylic acid and the number of carbon atoms of these alkyl groups is C
It is an ester with a _{1 to} C ₁₂ alcohol component, more preferably an ester with a C _{2 to} C ₁₂ alcohol, and even more preferably an ester with a C _{3 to} C ₈ alcohol.
These monomer components may be used alone or in combination of two or more, and when the carbon number of the alcohol is C _1, a ternary or higher alkoxide component with another C ₂ or more alcohol component is used. Polymers are preferred.

The copolymerization form of these monomers and the styrene-based monomer is not particularly limited, but is a random copolymer or a random copolymer of the styrene-based monomer and the copolymerizable monomer. A block copolymer consisting of a polymer block and a styrene polymer homoblock, or another random copolymer block, or a copolymer of a block mainly composed of a styrene monomer and the copolymerizable block, or a copolymer. Copolymers containing a linear, branched, or cyclic hydrocarbon such as C _{4 to} C ₂₂ alkyl group, cycloalkyl group, etc. in a part (in the molecule or at least one of terminal groups) of the polymer Is preferred.

Among these, the block copolymer comprising a styrene-based monomer-the random copolymer block of the copolymerizable monomer and a styrene-based polymer homoblock is compatible with other styrene-based resins. Can be increased and may be particularly preferable. Further, C ₄ to C is added to 1 part of the above copolymer.
_When other components such as the above-mentioned hydrocarbon component of ₂₂ are included, the strength of the resin is improved, which may be preferable. These hydrocarbon components are added with the residue of the polymerization catalyst, the residue of the chain transfer agent, and the olefin monomer during the polymerization. It can be introduced by a technique such as (adding hydrogen later if necessary). As the residue of the polymerization catalyst, for example, at least one of monofunctional catalysts such as well-known catalysts such as peroxides and bifunctional, trifunctional, trifunctional, tetrafunctional, and higher functional catalysts is arbitrarily selected.

Examples of polyfunctional catalysts include those having a tetrafunctional ketal structure having a cyclohexane ring.
Further, a chain transfer agent may be added, and examples thereof include n-butyl mercaptan, n-octyl mercaptan, and n-dodecyl mercaptan.

The copolymer may be copolymerized with a conjugated diene as a third component or a further component, and known rubbers may be grafted or homogenized by adding it before or after the polymerization. , Incorporating matrix, or so-called salami structuring, etc.,
Alternatively, it may be a marble-like multi-layered granular material polymerized or copolymerized in layers, and it may be more preferable to add these high-impact formulations, and the copolymer or the composition thereof is also included. Among these, the average particle diameter of the multilayer granular material is preferably in the range of 0.05 to 10 μm. In addition, the salami structured one also has this range of small particle size and large particle size.

Further, in order to improve the strength of the sheet, it is particularly preferable to use a block copolymer containing the above-mentioned conjugated diene,
70% styrene resin with transparent high impact formulation
A composition with the styrene-based polymer is blended in an amount of not more than 50% by weight, more preferably not more than 50% by weight, still more preferably not more than 30% by weight.

Next, the acrylic resin and its copolymer used in the present invention means methacrylic acid, methacrylic acid ester (eg, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid). Butyl, pentyl methacrylic acid, and other alkyl groups having C _{1 to} C ₁₅ , preferably C _{1 to} C ₈ alcohol components), acrylic acid, acrylic acid esters (for example, the above-mentioned methacrylic acid esters) Similarly, an alkyl group having a carbon number of C _{1 to} C ₁₅ , preferably a C _{1 to} C ₈ alcohol component), a monomer selected from acrylonitrile and the like, and (meth) acrylic acid (ester) adjacent in the molecule. ), Cyclized anhydrides formed by dealcoholization reaction between them, and further reacted with amines, ammonia, etc. Polymer comprising at least one selected from imidized substance occurring in a, and one of these monomers
50% by weight or more, preferably 6 or more in total
It is a copolymer containing 0% by weight, more preferably 70% by weight or more.

Further, like the above-mentioned styrene resin, a copolymer with a conjugated diene, a resin added with a high impact formulation,
At least 1 each mainly composed of a block copolymer containing a random part and a homo part, a copolymer containing an alkyl group, and a (meth) acrylic acid ester and a styrene- (meth) acrylic acid ester copolymer as in the case of the styrene resin. It also includes a marble resin in which seed resins are arranged in layers. These may be used alone or in combination of two or more. Examples of the monomer copolymerizable with these monomers include the above-mentioned styrene-based monomers, mono- or dicarboxylic acids such as fumaric acid and maleic acid, anhydrides thereof, and further imidized compounds. The copolymerization method of these copolymerizable monomers and acrylic monomers is not particularly limited as in the above-mentioned styrene resin.

Further, in a terpolymer of 3 or more composed of other components such as a styrene-based monomer, an acrylic-based monomer and butadiene, each of the styrene-based monomer and the acrylic-based monomer is contained. The amount is less than 50% by weight, and even if it does not correspond to any of the above-mentioned styrene resin and acrylic resin, the copolymerization in which the total amount of these styrene resin and acrylic monomer is 50% by weight or more. Resins are intended to be included within the scope of this invention.

As an example of this, for example, 40% by weight of styrene, 30% by weight of methyl methacrylate, 30% of butadiene
Examples thereof include, but are not limited to, a copolymer composed of 45% by weight, a copolymer composed of 45% by weight of styrene, 45% by weight of methyl methacrylate, and a copolymer of 15% by weight of maleic anhydride.

As the polyester resin, for example, at least one dicarboxylic acid component such as terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid and adipic acid, and ethylene glycol, alkylene glycols, cycloalkyl glycols, etc. It is a copolymer containing at least one glycol component or oxyacid as a copolymerization component, and generally polyethylene terephthalate, polybutylene terephthalate, polynaphthalene terephthalate, etc. are known, but in the present invention, an acid component or / Further, a polyester obtained by copolymerizing a glycol component with a glycol component to reduce the crystallization speed, or a polyester having a reduced crystallinity or being amorphized is more preferable.

Particularly preferred is a copolymer containing terephthalic acid as a main component as an acid component and ethylene glycol and cyclohexanedimethanol as main components as a glycol component. It may also include a copolymer of an aliphatic polyether such as polytetramethylene glycol. These may be used alone or in a blend of two or more.

Further, polyphenylene ether resin (P
PE) means a resin having a repeating structure of 1,4-phenylene ether as a main skeleton, and specific examples thereof include poly (2,6-dimethyl-1,4-phenylene) ether and poly (2-methyl-). Known resins such as 6-ethyl-1,4-phenylene) ether and poly (2,6-diethyl-1,4phenylene) ether are mentioned, and poly (2,6-dimethyl-1,4-phenyl) is particularly preferable. PPE having a main structure of phenylene) ether. Also, for example,
A known other phenylene ether unit such as a 2- (dialkylaminomethyl) -6-methylphenylene ether unit or a 2- (N-alkyl-N-phenylaminomethyl-6-methylphenylene ether) unit may be included as a partial structure. It does not matter, and it may be a copolymer partially containing tri-substituted phenol such as 2,3,6-trimethylphenol. In some cases it may be preferable to knit the molecular ends and add a stabilizing formulation.

This stabilizing formulation is described, for example, in JP-A-1-
The methods described in JP-A-172451, JP-A-2-276823 and the like can be mentioned. In addition, PPE to which a known stabilizing formulation having the above skeleton as a main skeleton is added may be used. This may be used as one main component or as a blend of two or more main components. These PPE are generally used by blending with the above-mentioned styrene polymer, styrene-modified polypropylene and the like, and are preferable from the viewpoint of improving fluidity and moldability. In addition, there is an advantage that any heat resistance can be imparted by blending.

The polycarbonate resin is a resin synthesized from an aromatic dihydroxy compound by a known method such as transesterification, phosgene reaction, solvent method and the like. As the aromatic dihydroxy compound, 2.2- (4,4-bishydroxyphenyl) propane (biphenol A) is preferably used as the aromatic dihydroxy compound. Further, a copolymer of a hydroxy compound and diols, dibasic acids, diamines and the like may be used. These may be used alone or in a blend of two or more.

As the polyolefin resin, polyethylene, polypropylene, poly-1-butene, poly-4-
Methyl-1-pentene and the like and known copolymers thereof and the like can be mentioned, but polypropylene resin is particularly preferable. The polypropylene resin is a polypropylene homopolymer, a random or block copolymer of propylene and ethylene or a C _{4 to} C ₂₀ α-olefin, or an unsaturated carboxylic acid, maleic anhydride, styrene, or the like, Examples include modified resins.

In the present invention, in the a layer and the adjacent b layer, the above-mentioned resins can be used alone or in an arbitrary combination of two or more kinds within the conditions described later. Also,
The sheets a and b may be formed by using the same resin having different molecular weights, different copolymerization composition ratios, and different blending composition ratios. When two or more kinds of resins are mixed in the same layer and used, it is general and preferable to select the resins so that the transparency is not deteriorated. However, depending on requirements, an opaque sheet or a pearl luster A sheet (for example, a blend of styrene-based resins and acrylic-based resins) can be prepared by combining the resins, and this case is also within the scope of the present invention. Further, in the case of a sheet requiring transparency, considering the film forming property and the recycling property of scrap generated at the time of secondary molding, it is preferable to use a combination of the resins of the layers a and b so as not to deteriorate the transparency.

The layers a, b constituting the low-temperature high-speed moldable multilayer sheet of the present invention, the recovery layer described later, etc. are transparent as the second component or more components as long as the characteristics of the present invention are not impaired. High impact rubber component, SBB mentioned above
C, hydrogenated products thereof, or known modified resins having a styrene-based component content of less than 50% by weight, various compatibilizing agents (for example, styrene-methyl methacrylate, polybutylene terephthalate-styrene, and (modified) polyolefin). -Graft or block copolymers such as styrene) or various publicly known modifiers, petroleum resin (hydrogen-containing additive), modified resin such as polyamide (former), silicone resin, crosslinked granular silicone resin, etc. And known lubricants, antistatic agents, heat stabilizers, antioxidants, antifogging agents, plasticizers, mineral oils, oligomers, fatty acid esters, etc.
A known additive (the latter) such as a colorant may be added if necessary.

These additives may be added in a mixture, and the former modifier is preferably less than 50% by weight, more preferably 30% by weight or less with respect to the resin constituting each of the layers a and b. , And more preferably 10% by weight or less. The latter additive is preferably 15% by weight or less, more preferably 10% by weight or less, further preferably 5% by weight or less.

Of these, the preferred resins for the a phase are: From the viewpoint of imparting moldability, styrene resins and compositions thereof. 2. From the viewpoint of imparting oil resistance, styrene-acrylonitrile-based copolymers, styrene- (meth) acrylic acid ester-based copolymers, acrylic resins, polycarbonate-based resins, polyester-based resins, polypropylene and the like, and compositions thereof. 3. From the viewpoint of imparting heat resistance, heat-resistant styrene-based resins such as styrene- (meth) acrylic acid-based copolymers, styrene-maleic anhydride copolymers, PPE-based resins and their polystyrenes, and other resins , (Meth) acrylic acid ester-based- (meth) acrylic acid- (styrene-based) copolymer, (meth) acrylic acid ester-based-
Heat-resistant acrylic resins such as maleic anhydride, polycarbonate resins, poly-4-methyl-1-pentene, polypropylene and the like, and compositions thereof. 4. From the viewpoint of imparting a high elastic modulus, styrene resin, acrylic resin, PP
E-based resins and their compositions. And so on.

From the viewpoint of imparting moldability, preferable resins constituting the layer b are styrene resins and their compositions, acrylic resins containing styrene monomers, and the like.

Among these, as an example of a preferable combination of resins, a styrene resin and an SBBC composition are used for the a layer, and a styrene resin and S different from the a layer are used for the b layer.
Combination of composition with BBBC; or combination of styrenic resins such as similar combination of a layer and b layer made of SBBC; or polycarbonate or polyester for a layer, SBBC or SBBC for b layer
And a composition of a styrene-based resin; an amorphous copolyester for the layer a, and a styrene- (meth) acrylic acid ester (alcohol is C _{2 to} C ₁₂ ) -based copolymer for the layer b; A blend of PPE and styrene-based resin in the layer a, a combination of styrene-based resin in the layer b as a main component; styrene-acrylonitrile copolymer in the layer a, styrene- (meth) acrylic acid ester in the layer b (alcohol is C ₂ -C ₁₂₎ based copolymer combination of polymers; a layer of acrylic resin, styrene located on the b - mainly acrylic resin or styrene resin such as an acrylic copolymer or more conjugated diene copolymerized resin However, the combinations are not limited to these.

In the present invention, the Vicat softening of the resin constituting the layer a (A; Vicat softening point Va ° C.) and the resin constituting the layer b adjacent thereto (B: Vicat softening point Vb ° C.) It is important to select so that the ratio (Va / Vb) of points (according to ASTM D-1525, load 1 Kg, temperature rising rate 2 ° C./min., Hereinafter referred to as VSP) is 0.8 to 2. ..

If this ratio is less than 0.8, the a layer is overheated under the heating conditions required for the secondary molding, and the surface is roughened, which is not preferable. In particular, in the case of hot plate contact thermoforming, the sheet is apt to adhere to the surface of the hot plate, resulting in defective molded articles and fouling of the hot plate. Also, in the case of a sheet of three layers or more,
Even if a high VSP resin having high heat resistance is used as the inner layer b layer resin, it is not very effective in improving the practical heat resistance of the molded product, and from the viewpoint of imparting heat resistance, the high VSP resin is used as the surface layer. It is more effective to use.

If the above VSP ratio exceeds 2,
Since the b layer having a low VSP is overheated during the heating in the secondary molding, the viscosity difference between the a and b layers becomes large, and as a result, the flow behavior of each layer at the time of molding is different and a molded product with a large uneven thickness is formed. However, in some cases, the b layer may foam, which is not preferable. In particular, when a radiant heating type molding machine is used, the slack of the sheet generated at the time of heating increases, and the uneven thickness tends to increase.

In particular, in order to obtain a secondary molded product having less uneven thickness and good appearance, the VSP ratio is preferably 0.9 to 1.7, more preferably 1.01 to 1.5. It is good, and more preferably 1.05 to 1.5. Further, in the low-temperature high-speed moldable multilayer sheet of the present invention, the tensile modulus of the thermoplastic resin (A) constituting the a layer (using an injection molding machine, a test piece was prepared in accordance with JIS K-6871, JIS K- 271 elastic modulus is measured according to 6871)
Should be 50 to 300 Kg / mm ² . When the tensile elastic modulus is less than 50 kg / mm ² , the rigidity of the sheet and the secondary molded product is too low, and as a result, it is necessary to form a thick sheet or molded product, which is not preferable. Also, 300 Kg /
If it exceeds mm ² , it is not preferable because the secondary molded product does not have flexibility and is easily scratched.

To balance these characteristics,
The tensile elastic modulus is preferably 70 to 280 Kg / mm ² , more preferably 80 to 270, further preferably 1
It is better to set it to 00 to 270 Kg / mm ² . In addition, it is preferable that the tensile elastic modulus of the layer a is higher than that of the adjacent layer b in order to maintain the rigidity of the secondary molded sheet.

In the present invention, the heat shrinkage stress of all the layers of the sheet (ORS, maximum peak stress value at each temperature measured according to ASTM D-1504, and silicone oil used as a heating medium) is the same as that of the present invention. 2 Kg / cm ² for the purpose of imparting low temperature high speed molding and deep drawability
It must be: In addition, the ORS is 1.7 Kg for stable molding under a wide range of conditions and methods.
/ Cm ² or less, more preferably 1.
6 Kg / cm ² or less, more preferably 0.01 to 1.5
It is Kg / cm ² .

The ORS value of the sheet before forming is not more than the upper limit value, and of course, even if the sheet before forming is more than the upper limit value, the sheet is heated and formed under the conditions for forming the sheet. A sheet in which the ORS value of the sheet whose orientation is relaxed by heating immediately before is within the above range is also within the range of the present invention. The reason is that the ORS value that affects the deep drawability and the low-temperature high-speed formability, which are the main objects of the present invention, is not the value of the sheet before forming, but the value after being relaxed by heating immediately before forming. .. The ORS value of the above-mentioned sheet just before molding is obtained from the flange portion of the molded product or the heated skeleton after molding. Alternatively, the sheet may be obtained by simply heating the sheet with a molding machine under the same conditions as when molding, and then cooling the sheet. Further, it is necessary that at least one direction of the sheet has the above value.

The low-temperature high-speed moldable multilayer sheet of the present invention has at least one surface layer made of the thermoplastic resin (A) and a multilayer made of the adjacent thermoplastic resin (B), and other layers such as ethylene acetic acid. Vinyl-based copolymers, known adhesive resin layers mainly for adhesion between respective layers mainly composed of various elastomers, ethylene-vinyl alcohol resin, barrier resin layers mainly composed of polyvinylidene chloride and the like, recovered resin layers, A third or more additional layer selected from the above thermoplastic resins may be optionally added.

The term "adjacent to another layer adjacent to at least one surface layer" as used in the present invention means at least one surface layer (a layer) and a layer next to it, but at least one layer may be present if necessary. Adjacent to one surface layer (a layer), a known adhesive resin layer mainly for the purpose of adhesion may be present in an amount of 10% or less, preferably 5% or less, and more preferably 3% or less with respect to all layers. , The layer adjacent to each other via the adhesive resin layer is defined as another adjacent layer (layer b).

To illustrate the layer structure of the low-temperature high-speed formability other layer sheet of the present invention, at least one surface layer made of the thermoplastic resin (A) is A, and another adjacent layer made of the thermoplastic resin (B) is B, Let G be the adhesive layer added as necessary, R be the recovery resin layer, and C be the other additional layer; A / B, A / B /
A, A / G / B, A / (B + R) / A, A / B / C, A
/ B / R / A, A / B / A / B, A / B / A / B / A,
A / B / R / C / B, A / B / R / B / A, A / G / B
/ G / A, A / B / C / B / A, A / B / R / C / R /
Examples include B / A and A / B / A / R / A / B / A. The present invention is not limited to these, and may be arbitrarily configured within a range that does not impair the characteristics of the present invention, but the thickness ratio of at least one surface layer (a layer) made of the thermoplastic resin (A) (three or more layers). In the case of the sheet, when both the front and back surface layers are composed of the thermoplastic resin (A), the total thickness thereof is important to be 2 to 50% with respect to all layers.

If the thickness of the layer a is less than 2%, the effects of the surface layer (improvement of moldability, oil resistance, heat resistance, rigidity, etc.) cannot be obtained, and if it exceeds 50%, the effect of modification by the surface layer. Not only is not improved, but also the moldability is deteriorated, especially the high-speed moldability is deteriorated, which is not preferable. When high formability is required, the thickness of the a layer is preferably 4 to 40%,
More preferably, it should be 10 to 35%. Also,
In a sheet having three or more layers, when the recovered resin satisfies the condition of the thermoplastic resin (B), the recovered resin layer may be the b layer.

Of these, a particularly preferred layer structure is 3
In the two-layer sheet, both front and back layers are composed of a thermoplastic resin (A), and the inner layer is composed of a thermoplastic resin (B) or a blend of the resin and a recovered resin of the sheet; The surface layer is made of the thermoplastic resin (A), the central layer is made of the recovered resin of the sheet, and the layer sandwiched between these is made of the thermoplastic resin (B). In some cases, a two-layer sheet in which the front and back surface layers are made of different resins may be preferable depending on the application and required performance.

There are no particular restrictions on the method for producing the low-temperature, high-speed formable multilayer sheet of the present invention, and in the conventional method for producing a multilayer sheet, the multilayer sheet is melt-extruded and cast by coextrusion to obtain a multilayer. A method of forming a sheet, a method of melt-extruding a sheet and laminating it with another sheet while being in a high temperature state to form a multilayer sheet, or a single-layer sheet made of each of the thermoplastic resins (A) and (B) described above. A method of laminating via heat or an adhesive can be adopted.

In the present invention, the sheet is not usually stretched, but a sheet stretched by a known method so as to be within the above-mentioned ORS range may be used if necessary. Further, what is called flow orientation may be applied at high temperature. In this case, the draw ratio is generally 1.05 to 40, preferably 1.1 to 30, more preferably 1.5 to 25, and further preferably 2.0 to 20. The draw ratio is a value obtained by dividing the die slit clearance by the sheet thickness.

The overall thickness of the low-temperature, high-speed moldable multilayer sheet of the present invention is not particularly limited, but it is generally preferably 0.05 to 2.0 mm, more preferably, for molding food packaging containers and the like. The range is 0.09 to 1.5 mm, and more preferably 0.1 to 0.8 mm.

The low-temperature high-speed moldable multilayer sheet of the present invention is one of the known surface treatments (for example, antifogging treatment, releasing treatment, antistatic treatment, corona treatment, etc.) performed on polystyrene-based stretched sheets and the like. Or a combination of two or more)
May be performed on both sides or one side of the sheet. In many cases, it is preferable that these surface treatments are carried out for a molded sheet for food packaging.

As one example, various silicones (including oils, emulsions, and latexes) are used as a mold release treatment agent, an antifogging agent known as an antifogging treatment agent, for example, glycerin with an acid-aliphatic agent. -Based ester, sorbitan-based ester, sucrose-based ester, polyoxyethylene-based ester, etc., alkyl alkylolamine, alkyl
Examples include alkylol amide. A molding container comprising the low temperature and high speed moldable multilayer sheet of the present invention can be obtained by molding the sheet by a known method. There is no particular limitation on the molding method, and for example, a commonly used method such as vacuum forming, pressure forming, plug assist forming, bending forming or a combination thereof of a sheet heated by means such as hot plate contact heating or radiant heating is used. You can go in.

[0055]

The present invention will be described in detail below with reference to examples, but the invention is not limited thereto.

The evaluation method is as follows. Tensile modulus of surface layer resin: JIS by injection molding machine
A test piece was prepared in accordance with K-6871, and JISK-
Measures 2% elastic modulus according to 6871 (unit: kg / m
m ² ). rigidity:

Opening diameter 80 mm, bottom diameter 70 mm,
A cup-shaped container having a depth of 28 mm is molded by a hot plate pressure molding machine (heating time 2 seconds, molding pressure 2 kg / cm ² , molding temperature adjusted so that R at corner is 3.0 ± 0.5 mm), Compression rate of 5 randomly selected 5 molded products
The resistance force when compressed by 5 mm at mm / min was measured and evaluated from the average (kg) according to the following criteria (thickness: 0.25 m
m sheet). ◎: Resistance is 2 kg or more ○: Resistance is 1.5 kg or more and less than 2 kg ... Pass level △: Resistance is 1 kg or more and less than 1.5 kg ×: Resistance is less than 1 kg

Vicat Softening Point: ASTM D-15
25 measurement (load 1 kg, heating rate 2 ° C / min),
The composition was measured after melting and kneading. Moldability: -I: Hot plate heating type pneumatic forming property: A test sheet was evaluated using a hot plate heating type pneumatic forming machine under the following conditions under a mold.

-I-1: molding temperature range (0.25 mm
Sheet) of the hot plate temperature of the molding machine VSP-20 to + 50 ° C. of the highest VSP resin in each layer forming the hot plate temperature sheet of the molding machine, heating time 2.5 seconds, molding time 1.8 seconds, molding pressure 4.0k
120 × 85 mm square, depth 25 under conditions of g / cm ² m
mm containers were molded.

The molded products for 20 shots were visually inspected, and the temperature at which 5% or more of the molded products became defective due to excessive heating (transfer of hot plate, dirt, etc.) was A ° C., and conversely due to insufficient heating. The temperature at which mold reproducibility began to occur in 5% or more of the molded products was defined as B ° C., the molding temperature range was determined from (A−B) ° C., and the following criteria were evaluated. The wider the molding temperature range,
Generally, low temperature molding is possible. ⊚: 25 ° C. or higher ○: 15 ° C. or higher and lower than 25 ° C .... Pass level Δ: 10 ° C. or higher and lower than 15 ° C. ×: Less than 10 ° C.

-I-2: High-speed moldability (evaluated with a sheet of 0.25 mm) The hot plate temperature of the molding machine was set to VSP of the resin of each layer forming the sheet or VSP of the highest VSP resin in the composition + 30 ° C (by excessive heating). When a defect occurs, the temperature is set to A ° C evaluated in the above molding temperature range), and the heating time is 0.4 to 5 seconds, the molding time is 2.2 seconds, and the molding pressure is 4.5 kg / cm ² , It is composed of a 105 × 105 mm square body with a depth of 30 mm and a lid with a depth of 20 mm. A hood pack having a fitting portion on the entire surface of the flange portion was formed.

Molded articles for 20 shots were visually inspected, and 5% or more of the molded articles had poor mold reproducibility due to insufficient heating,
The heating time at which fitting failure began to occur was set as the lower limit of the molding time and used as a guide for high-speed moldability. The shorter the heating time, the better the high-speed moldability.

-I-3: Deep drawing formability (0.40 mm
The sheet temperature of the molding machine was evaluated in the above-mentioned molding temperature range as the hot plate temperature of the molding machine.
100 ° m opening diameter under the conditions of -5 ° C, heating time 3.5 seconds, molding time 2.0 seconds, molding pressure 5.0 kg / cm ^2.
A cylindrical cup having a m and a depth of 40 to 100 mm was formed. No cracking, whitening, tearing, etc. occurred, and the average of the ratio of the minimum thickness of five molded products randomly taken out of the molded product for 20 shots of life to the sheet thickness before molding was 0.1 or more. The following criteria were used to evaluate the maximum drawing depth that gives a molded product.

⊚: Maximum drawing depth of 75 mm or more ○: Maximum drawing depth of 60 mm or more and less than 75 mm ... Pass level Δ: Maximum drawing depth of 50 mm or more and less than 60 mm ×: Maximum post-mortemization of less than 50 mm

-II: Radiant heating type vacuum forming property A test sheet was evaluated by performing a forming test using a radiant heating type vacuum forming machine with plug assist under the following conditions and a die.

-II-I: High speed moldability (0.25 mm
The sheet temperature of the molding machine is set to VSP + 150 ° C., which is the maximum VSP resin in the resin or composition of each layer forming the sheet, the heating time is 2 to 14 seconds, the vacuum pressure is 700 mmHg, and the size is 150 × 100 mm square. A container having a depth of 45 mm was molded. 5 randomly selected from 20 shot molding containers
The pieces were taken out, the thickness distribution of the molded container was measured, and the heating time (second) at which the thinnest part of the wall of the molded product gave a molded product having a thickness of 20% or more of the sheet before molding was used as a measure of high-speed moldability. ..

-II-2: Deep drawing formability (0.4 mm
The sheet temperature of the molding machine is set to VSP of the highest VSP resin in each layer forming the sheet or the composition of the sheet, and the heating time is set to 3 to 8 seconds (molding under optimum conditions)
Then, the vacuum pressure is 720 mmHg, the opening diameter is 75 mm,
A cup having a bottom surface diameter of 50 mm and a depth of 75 mm was molded. The thickness distribution of the molded product excluding 1/3 part of the upper part of the cup was measured, and evaluated according to the following criteria from the ratio of the minimum thickness part to the thickness of the sheet.

⊚: Thickness ratio is 15% or more. ◯: Thickness ratio is 10% or more and less than 15%. Δ: Thickness ratio is 5% or more and less than 10%. X: Thickness ratio is less than 5%. Is.

○ GPPS: General-purpose polystyrene (Mw =
250,000, VSP = 106 ° C., tensile elastic modulus = 230 kg /
mm ² ). SBA1: Styrene-butyl acrylate copolymer (15% by weight of butyl acrylate random copolymer, V
SP = 77 ° C., tensile elastic modulus = 210 kg / mm ² )

SBA2: styrene-butyl acrylate copolymer (butyl acrylate 10% by weight, styrene-
A copolymer composed of a butyl acrylate copolymer block and a styrene block, containing 0.03% by weight of a C ₁₂ alkyl component derived from n-dodecylmercaptan in a part of the styrin block, VSP = 90 ° C., tensile elastic modulus = 215 kg /
mm ² ). SBA3: styrene-methyl methacrylate-butyl acrylate-graft rubber copolymer (45% by weight of styrene, 32% by weight of methyl methacrylate, 11% by weight of butyl acrylate, 12% by weight of graft rubber, VSP = 8)
1 ° C., tensile elastic modulus = 125 kg / mm ² ).

SBBC: Styrene-butadiene block copolymer (27 wt% butadiene S-B-S block copolymer, VSP = 86 ° C., tensile elastic modulus = 110)
kg / mm ² ). SIBC: Styrene-isoprene block copolymer (30% by weight of isoprene, S-I-S-I type block copolymer, VSP = 81 ° C, tensile elastic modulus = 100 kg / m)
m ² ).

HIPS: high impact polystyrene (8 wt% butadiene graft copolymer, VSP = 103
° C, tensile modulus = 160 kg / mm ² ). Hydrogenated SBBC: Hydrogenated double bond derived from butadiene of styrene-butadiene block copolymer (55% by weight of butadiene).

○ TPS: styrene-based elastomer (styrene-butadiene block copolymer, butadiene 65
Wt% S-B-S type block copolymer). ○ AS: styrene-acrylonitrile copolymer (25% by weight of acrylonitrile, VSP = 108 ° C., tensile elastic modulus = 215 kg / mm ² ).

MS: Styrene-methyl methacrylate copolymer (30% by weight of methyl methacrylate, VSP = 1
07 ° C., tensile elastic modulus = 200 kg / mm ² ). SMAA: Styrene-methacrylic acid copolymer (methacrylic acid 9% by weight, VSP = 127 ° C., tensile elastic modulus = 2
25 kg / mm ² ).

PMMA: polymethylmethacrylate (VSP = 108 ° C., tensile modulus = 230 kg / m
m ² ). ASMAA: methyl methacrylate-α-methylstyrene-methacrylic acid- (methacrylic acid (methyl) intramolecular condensation compound) (composition ratio is 85: 8: 2: 5% by weight in order), VSP = 135 ° C, tensile elastic modulus = 250kg / m
m ² ).

Acrylic rubber: a marble-like resin composed of three layers and having an average particle size of 0.15 μm, the innermost layer being PMMA,
The central layer is SBA (BA: 80% by weight), and the outermost layer is PMM
A. ○ PC: Polycarbonate (straight polymer composed of biphenol A, VSP = 152 ° C., tensile elastic modulus =
170 kg / mm ² ).

PET: terephthalic acid as an acid component, ethylene glycol as a glycol component: 70
Mol%, 1,4-cyclohexanedimethanol: 30 mol%, and used for polycondensation copolymerization (V
SP = 82 ° C., tensile modulus = 160 kg / mm ² , melting point = not observed by DSC method). PPE: the one disclosed in JP-A-2-276823, which is modified with 12% by weight of poly (2,6-dimethyl-1,4-phenylene) ether (polystyrene),
VSP = 212 ° C., tensile modulus = 225 kg / m
m ² ).

○ PP: polypropylene copolymer (a random copolymer containing 8% by weight of ethylene, modified with 13% by weight of an alicyclic saturated hydrocarbon resin, VSP = 15)
2 ° C., tensile elastic modulus = 90 kg / mm ² ). O Modified PP: polystyrene graft polypropylene copolymer (34% by weight styrene graft copolymer, VS
P = 112 ° C., tensile elastic modulus = 115 kg / mm ² ).

EVA: ethylene-vinyl acetate copolymer (20% by weight of vinyl acetate). ○ Terpene resin Yasuhara Chemical Co., Ltd. product name "Clearon M-115". Modified SBBC: A resin obtained by hydrogenating a double bond derived from butadiene of a styrene-butadiene block copolymer (35% by weight of styrene) and modified with 3% by weight of maleic anhydride.

(Example 1, Comparative Example 1) The screw diameter was
The 3-layer T-die was attached to a co-extruder of 50 mm (inner layer) and 30 mm (surface layer), and Table 1 was attached to each extruder.
Each layer resin shown in was supplied. When two or more kinds of resins were supplied, pellets obtained by dry-blending at a ratio shown in Table 1 and melt-kneading with a vent type twin-screw extruder having a screw diameter of 30 mm were used. The resin extruded from the T-die (slit clearance: 2 mm) was rapidly cooled with a casting roll, and the 0.25 mm and 0.
A 4 mm 3 layer sheet was wound up. Further, the single-layer sheet of Comparative Example 1 was formed in the same manner by attaching a single-layer T-die to a 65 mm extruder. The evaluation results of the rigidity and formability of this sheet are shown in Tables 1 to 3.

[0081]

[Table 1]

[0082]

[Table 2]

[0083]

[Table 3]

Tables 1-2 are examples of 3-layer sheets. From Tables 1 and 2, it can be seen that various thermoplastic resins can be used in the low temperature high speed moldable multilayer sheet of the present invention. The ORS of this sheet is 0.7 to 1.5 in the vertical direction.
kg / cm ^2, the transverse direction within the scope of the present invention and 0 kg / cm ^2, both of which are good moldability. In addition, in all sheets, the Haze measured according to ASTM D-1003 was 10% or less, and the transparency was good (in particular, the sheets of Experiment Nos. 1, 2, 3, 5, 8, 9 were H
Excellent transparency with AZE of 2% or less). In addition, the experiment No.
The sheet molded products of 2, 3, 5, 8, 9 can be easily wrapped with a commercially available polyvinyl chloride wrap, and these sheets are particularly excellent in oil resistance.
Even if it was left for 0 days, it was not deteriorated by being cracked by the plasticizer contained in the wrap (occurrence of cracks, whitening, decrease in strength, etc.).

Table 3 is a comparative example, and the experiment No. 10 and 1
In No. 2, the VSP ratio is out of the range of the present invention. Experiment No. The sheet of No. 10 has a VSP of the surface layer (a layer) resin which is too lower than that of the inner layer (b layer). Therefore, when molded by the hot plate heating type pressure molding method, the a layer surface is rough and a good molded product cannot be obtained. Further, in order to suppress the surface roughness, when molded at a low temperature, a good molded product cannot be obtained due to whitening, breakage and the like. Further, when the radiant heating type vacuum forming method is used, long-time heating is required and deep drawability is poor.
Experiment No. The sheet No. 12 is an example in which the VSP ratio of the a layer and the b layer is too large. In this case, the viscosity of the b layer resin becomes too low when heated by a molding machine, and a good molded product is obtained by any molding method. I couldn't do that. Experiment No. 11
The sheet a is an example in which the layer a is too thick. In this case, the deep drawing formability is deteriorated, and long heating is required for forming.
In addition, the experiment No. Similar results are obtained in the case of a single layer sheet such as No. 13. From these, it is understood that the VSP ratio of each layer and the thickness ratio of the a layer are important in order to exert the effects of the present invention.

(Example 2) Each layer resin shown in Table 4 was supplied to an extruder in the same manner as in Example 1 and extruded from a T-die. After cooling the extruded resin, it is reheated by a heating roll (roll temperature: Experiment Nos. 14 and 15 is 105 ° C., Experiment No.
No. 16 is 123 ° C., Experiment No. 16 17 is 126 ° C.), and after stretching 1.4 times in the machine direction depending on the speed ratio of the roll, tenter (tenter temperature: Experiment Nos. 14 and 15 is 118 ° C., experiment N
o. No. 16 is 134 ° C., Experiment No. 17 was stretched 1.8 times in the transverse direction at 136 ° C.). The ORS of these sheets are 3.1 / 3.2, 1.8 / 2.0, 2.2 / 2.4,
It was 2.6 / 2.8 (length / width, unit kg / cm ² ). The ORS of the sheet after heating under the respective molding conditions of these sheets is 1.4 to 1.9, 0.8 to 1.4, and 1.
0 to 1.6, 1.2 to 1.7 (depending on molding conditions)
Met. Table 4 shows the evaluation results of the rigidity and formability of this sheet.
Shown in.

(Comparative Example 2) A film was formed in the same manner as in Example 2 except that the stretching ratio was 2.5 times in the longitudinal direction and 3.3 times in the lateral direction. The ORS of these sheets is 5 to 6 kg / cm ² , and the ORS of the sheets after heating under each molding condition is 2.7 to 4.1.
It was kg / cm ² . Table 5 shows the evaluation results of the rigidity and formability of this sheet.

[0088]

[Table 4]

[0089]

[Table 5]

The experiment No. of Table 4 14 to 17 are examples of the present invention, and all have good moldability. Experiment N
o. Sheets 14, 16, and 17 have ORS of 2k before forming
It exceeds g / cm ² , but is 2 kg / cm ² or less when heated by a molding machine. Even in such a case, the moldability is good, the strength of the sheet is improved by a slight stretching, the amount of SBBC added to the reinforcement can be reduced, and the rigidity of the molded product can be increased (for example, Experiment No. The rigidity of the molded product of No. 1 was 2.2 kg, while the experiment N
o. That of 16 is 2.8 kg). On the other hand, the experiment No. Nos. 18 to 21 are examples of sheets having ORS of 2 kg / cm ² or more even after being heated by a molding machine, and it can be seen that the deep drawing formability and the radiation heating type vacuum formability are inferior.

(Example 3) The screw diameter was 50 mm.
(Center layer), 40φ mm (intermediate layer), 40 φmm (surface layer) co-extruder was equipped with a 5-layer T-die, the same as in Example 1 except that each layer resin shown in Table 4 was supplied to each extruder. A film was formed. Each of the ORSs has a vertical length of 0.6 to 1.
7, the width was 0 to 0.3 (kg / cm ² ). The evaluation results of the rigidity and formability of this sheet are shown in Tables 6-8.

[0092]

[Table 6]

[0093]

[Table 7]

[0094]

[Table 8]

Experiment No. The recovered resins constituting the central layers 22 and 25 were three-layered sheets each consisting of a layer and b layer formed by the method of Example 1, pulverized, pelletized through an extruder and reused. It is a thing. Tables 6-8
Is an example of a five-layer sheet, and Experiment No. In 22 to 25, the intermediate resin layer corresponds to the b layer. In addition, the experiment No. 26-2
No. 9 is an example in which an adhesive layer is included between the a layer (surface layer) and the b layer (center layer). In each case, good moldability is exhibited, and the experiment No. The sheets Nos. 21 to 27 have good transparency (Haze 10% or less, particularly Experiment Nos. 22, 25, 2).
7 indicates excellent transparency with a HAZE of 2% or less). The sheet of Experiment No. 29 is opaque,
It shows pearl luster.

(Example 4) Experiment No. 1 of Example 1 1,
After corona-treating the sheet surfaces of Nos. 2, 16 and 22, a 4% aqueous solution of a 1: 1: 2 mixture of sugar ester, polyvinyl alcohol and three components of silicon emulsion was prepared by the method described in JP-B-63-62538. 0.3 g / m ^{2 was} applied on each side of the sheet. This sheet was molded into a mold whose high-speed moldability was evaluated by a hot plate heating type pressure molding machine and then filled with rice at about 60 ° C. and observed for 30 minutes, but no clouding due to water droplets occurred in the molding container. Also, frozen croquette was placed on the sheets of Experiment Nos. 4, 5, and 24 that had been subjected to the same surface treatment and heated in a microwave oven for 5 minutes, but the molded container did not fog and the molded product did not deform. It was

(Example 5) Screw diameter is 50 mm
(B layer), 30φmm (a layer), 30φmm co-extruder with a three-layer T-die attached, a layer of 30φmm extruder mixed composition of ASMAA and acrylic rubber 8: 2 (melt kneaded in advance. ) To a 50φ mm extruder with SBA-2
A 55:45 mixture of CB and SBBC (melted and kneaded in advance) was supplied to another 30T mm extruder of 1T-die with EVA as an adhesive layer, and the thickness ratio of a layer / adhesive layer / b layer was 2
A 0.08 mm sheet of 8/2/70 was formed in the same manner as in Example 1. This sheet was heat-laminated on both sides of a low-expansion polystyrene sheet by a known method, and then a laminated sheet (SBA + SBBC mixture layer) was formed into a bowl. Ramen, soup, sesame oil, and water were added to the bowl and wrapped, and then heated in a microwave oven for 3 minutes, but the molded product was not deformed.

INDUSTRIAL APPLICABILITY The low-temperature, high-speed multilayer sheet of the present invention is excellent in rigidity, imparts high-speed moldability in a secondary molded product by pressure molding, vacuum molding, etc., and improves deep drawability. Further, scraps generated during sheet film formation, secondary molding, etc. can be reused and are environmentally friendly. For example, they can be widely used as sheets for molding food packaging containers and other article packaging containers, and their industrial use. Great value.

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[Procedure amendment]

[Submission date] March 24, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction content]

Further, polyphenylene ether resin (P
PE) means a resin having a repeating structure of 1,4-phenylene ether as a main skeleton, and specific examples thereof include poly (2,6-dimethyl-1,4-phenylene) ether and poly (2-methyl-). Known resins such as 6-ethyl-1,4-phenylene) ether and poly (2,6-diethyl-1,4phenylene) ether are mentioned, and poly (2,6-dimethyl-1,4-phenyl) is particularly preferable. PPE having a main structure of phenylene) ether. Also, for example,
A known other phenylene ether unit such as a 2- (dialkylaminomethyl) -6-methylphenylene ether unit or a 2- (N-alkyl-N-phenylaminomethyl-6-methylphenylene ether) unit may be included as a partial structure. It does not matter, and it may be a copolymer partially containing tri-substituted phenol such as 2,3,6-trimethylphenol. In some cases, it may be preferable to modify the molecular ends and add a stabilizing formulation.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

This stabilizing formulation is described, for example, in JP-A-1-
The methods described in JP-A-172451, JP-A-2-276823 and the like can be mentioned. In addition, PPE to which a known stabilizing formulation having the above skeleton as a main skeleton is added may be used. This may be a blend of two or more may be used in combination. These PPE are generally used by blending with the above-mentioned styrene polymer, styrene-modified polypropylene and the like, and are preferable from the viewpoint of improving fluidity and moldability. In addition, there is an advantage that any heat resistance can be imparted by blending.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

[Correction content]

These may be used as a mixture, and the addition amount
Is preferably less than 50% by weight, more preferably 30% by weight or less, still more preferably 10% by weight or less with respect to the resin constituting each of the layers a and b. The latter additive is preferably 15% by weight or less, more preferably 10% by weight or less, further preferably 5% by weight or less.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

Of these, the preferred resins for the a phase are: From the viewpoint of imparting moldability, styrene resins and compositions thereof. 2. From the viewpoint of imparting oil resistance, styrene-acrylonitrile-based copolymers, styrene- (meth) acrylic acid ester-based copolymers, acrylic resins, polycarbonate-based resins, polyester-based resins, polypropylene and the like, and compositions thereof. 3. From the viewpoint of imparting heat resistance, heat-resistant styrene-based resins such as styrene- (meth) acrylic acid-based copolymers, styrene-maleic anhydride copolymers, PPE-based resins and their polystyrenes, and other resins Composition, (meth) acrylic acid ester-based- (meth) acrylic acid- (styrene-based) copolymer, (meth) acrylic acid ester-based-
A heat resistant acrylic resin such as maleic anhydride, a polycarbonate resin, poly-4-methyl-1-pentene, polypropylene and the like, and compositions thereof. 4. From the viewpoint of imparting a high elastic modulus, a styrene resin,
Acrylic resin, PPE resin and the like, and compositions thereof. And so on.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction content]

[0036] Also preferred the b layer as the resin that make up the from the viewpoint of imparting formability, styrene resin and its composition and, an acrylic resin containing a styrene monomer.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0053

[Correction method] Change

[Correction content]

[0053] Also, low-temperature high-speed moldability multilayer sheet of the present invention, known surface treatment taking place in the polystyrenic stretched sheets (e.g., anti-fogging and releasing treatment, antistatic treatment, 1 corona treatment or the like Species or a combination of two or more species)
May be performed on both sides or one side of the sheet. In many cases, it is preferable that these surface treatments are carried out for a molded sheet for food packaging.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0061

[Correction method] Change

[Correction content]

-I-2: High-speed moldability (evaluated with a sheet of 0.25 mm) The hot plate temperature of the molding machine was set to VSP of the resin of each layer forming the sheet or VSP of the highest VSP resin in the composition + 30 ° C (by excessive heating). When a defect occurs, the temperature is set to A ° C evaluated in the above molding temperature range), and the heating time is 0.4 to 5 seconds, the molding time is 2.2 seconds, and the molding pressure is 4.5 kg / cm ² , A hood pack having a fitting portion on the entire surface of the flange portion was formed by a 105 × 105 mm square main body having a depth of 30 mm and a lid having a depth of 20 mm.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0063

[Correction method] Change

[Correction content]

-I-3: Deep drawing formability (0.40 mm
The sheet temperature of the molding machine was evaluated in the above-mentioned molding temperature range as the hot plate temperature of the molding machine.
100 ° m opening diameter under the conditions of -5 ° C, heating time 3.5 seconds, molding time 2.0 seconds, molding pressure 5.0 kg / cm ^2.
A cylindrical cup having a m and a depth of 40 to 100 mm was formed. No cracking, whitening, or tearing occurred, and the average ratio of the minimum thickness of five molded products randomly picked from the molded products of 20 shots to the sheet thickness before molding was 0.1 or more. The following criteria were used to evaluate the maximum drawing depth that gives a molded product.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Name of item to be corrected] 0066

[Correction method] Change

[Correction content]

-II-I: High speed moldability (0.25 mm
The sheet temperature of the molding machine is set to VSP + 150 ° C., which is the maximum VSP resin in the resin or composition of each layer forming the sheet, the heating time is 2 to 14 seconds, the vacuum pressure is 700 mmHg, and the size is 150 × 100 mm square. A container having a depth of 45 mm was molded. 5 randomly selected from 20 shot molding containers
Take out the individual pieces, measure the thickness distribution of the molded container, and use the shortest heating time (second) as a measure of high-speed moldability to give a molded product in which the thinnest part of the molded product wall is 20% or more of the thickness of the sheet before molding. did.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0076

[Correction method] Change

[Correction content]

Acrylic rubber: a marble-like resin composed of three layers and having an average particle size of 0.15 μm, the innermost layer being PMMA,
The middle layer is SBA (BA: 80% by weight) and the outermost layer is PMM
A. ○ PC: Polycarbonate (straight polymer composed of biphenol A, VSP = 152 ° C., tensile elastic modulus =
170 kg / mm ² ).

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0077

[Correction method] Change

[Correction content]

PET: terephthalic acid as an acid component, ethylene glycol as a glycol component: 70
Mol%, 1,4-cyclohexanedimethanol: 30 mol%, and used for polycondensation copolymerization (V
SP = 82 ° C., tensile modulus = 160 kg / mm ² , melting point = not observed by DSC method). PPE: poly (2,6-dimethyl-1,4-phenylene) ether (shown in JP-A-2-276823 )
Modified with 12% by weight polystyrene
Made , VSP = 212 ° C, tensile elastic modulus = 225kg
/ Mm ² ).

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0079

[Correction method] Change

[Correction content]

EVA: ethylene-vinyl acetate copolymer (20% by weight of vinyl acetate). ○ terpene resin: Ya scan Hara Chemical Company under the trade name "Clearon M-115". Modified SBBC: A resin obtained by hydrogenating a double bond derived from butadiene of a styrene-butadiene block copolymer (35% by weight of styrene) and modified with 3% by weight of maleic anhydride.

[Procedure Amendment 13]

[Document name to be amended] Statement

[Name of item to be corrected] 0081

[Correction method] Change

[Correction content]

[0081]

[Table 1]

[Procedure Amendment 14]

[Document name to be amended] Statement

[Correction target item name] 0095

[Correction method] Change

[Correction content]

Experiment No. The recovered resins constituting the central layers 22 and 25 were three-layered sheets each consisting of a layer and b layer formed by the method of Example 1, pulverized, pelletized through an extruder and reused. It is a thing. Tables 6-8
Is an example of a five-layer sheet, and Experiment No. In 22 to 25, the intermediate resin layer corresponds to the b layer. In addition, the experiment No. 26-2
No. 9 is an example in which an adhesive layer is included between the a layer (surface layer) and the b layer (center layer). In each case, good moldability is exhibited, and the experiment No. The sheets Nos. 22 to 28 have good transparency (Haze 10% or less, especially Experiment Nos. 22, 25, 2).
7 indicates excellent transparency with a HAZE of 2% or less). The sheet of Experiment No. 29 is opaque,
It shows pearl luster.

[Procedure Amendment 15]

[Document name to be amended] Statement

[Correction target item name] 0096

[Correction method] Change

[Correction content]

(Example 4) Experiment Nos. 1 to 3 of Examples 1 to 3 were used.
After corona treatment of the sheet surface of 1, 2, 16, 22
According to the method described in JP-B-63-62538, a 4% aqueous solution of a 1: 1: 2 mixture of sugar ester, polyvinyl alcohol and three components of silicon emulsion was applied on both sides of the sheet at 0.3 g / m ² . This sheet was molded into a mold whose high-speed moldability was evaluated by a hot plate heating type pressure molding machine and then filled with rice at about 60 ° C. and observed for 30 minutes, but no clouding due to water droplets occurred in the molding container. In addition, the frozen croquette was put into the sheets of Experiment Nos. 4, 5, and 24 that had been subjected to the same surface treatment and heated in a microwave oven for 5 minutes.
The molded container was not fogged and the molded product was not deformed.

[Procedure 16]

[Document name to be amended] Statement

[Correction target item name] 0097

[Correction method] Change

[Correction content]

(Example 5) Screw diameter is 50 mm
(B layer), 30φmm (a layer), 30φmm co-extruder with a three-layer T-die attached, a layer of 30φmm extruder mixed composition of ASMAA and acrylic rubber 8: 2 (melt kneaded in advance. ) To a 50φ mm extruder with SBA-2
A mixture of 55:45 of SBBC the (previously melt-kneaded) to supply the EVA as an adhesive layer on the other one 30φmm extruders, a layer / adhesive layer / b layer thickness ratio is 28/2
A / 70 0.08 mm sheet was formed in the same manner as in Example 1. After thermally laminating this sheet on both sides of the low-expansion polystyrene sheet by a known method, (the laminating surface is
SBA + SBBC mixture layer) A bowl was molded. Ramen, soup, sesame oil, and water were added to the bowl and wrapped, and then heated in a microwave oven for 3 minutes, but the molded product was not deformed.

Claims (1)

[Claims] 1. A multi-layer sheet comprising two or more layers of a thermoplastic resin having at least one surface layer and at least another adjacent layer, wherein (a) the elastic modulus of the thermoplastic resin (A) forming the surface layer. Is 50 to 300 kg / mm ² , and (b) the Vicat softening point (Va ° C.) of the resin (A) and the Vicat softening point (Vb ° C.) of the thermoplastic resin (B) constituting the other layer adjacent to the resin (A) are The ratio (Va / Vb) is 0.8 to
(C) the thickness ratio of the surface layer is 2 to 50% with respect to all layers, and (d) the heat shrinkage stress of the sheet is less than 2.0 kg / cm ² . A multi-layered sheet characterized by being present.