JPH06104353B2 - Laminate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a laminate having excellent heat resistance and heat insulating properties. More specifically, the present invention relates to a laminate excellent in heat resistance and heat insulating material, which is applied as a heat insulating material, a cushioning material, a packaging material, a packing material, a levitation material, an electrical insulating material, a structural material and the like.

[Conventional technology]

The spread of microwave ovens and the accompanying spread of cooked foods in recent years is truly remarkable. Conventionally, paper, ceramics, and plastics have been used as materials for microwave oven containers, and polypropylene resins have been mainly used as plastics.

This is because foods in this field are mainly foods prepared by softly cooking dry foods with steam of water, and therefore, heat resistance of 130 ° C. is sufficient, and polypropylene resin can be sufficiently applied. However, the variety of cooked foods has increased in recent years, and foods that are rich in meat, oil, vegetables and the like have been demanded as microwave foods. Therefore, it is required to withstand temperatures of 140 ° C or higher, be oil resistant, and have heat resistance.

Therefore, a resin material that can withstand such a wide temperature range is demanded. A resin material that can sufficiently withstand this temperature range is a so-called engineering plastic material such as crystalline polyester resin (material whose heat resistance is improved by crystallizing polyester resin), polyetherimide, and aromatic polyester liquid crystal polymer. Only known.

Although these engineering plastics are high in price and suitable for the processing technology and the materials themselves, not all are suitable as food containers, and these are not heat insulating containers for warm food. There is a problem with the lack.

[Problems to be solved by the invention]

As described above, not only can it be used for the above-mentioned applications, but it does not deform even if an oily food is heated to a temperature of 130 ° C. or higher, that is, it has excellent heat resistance, and is a plastic with good heat insulation. No material has been proposed.

From these facts, the present invention is to eliminate these drawbacks (problems), that is, to obtain a laminate as an inexpensive plastic material having excellent heat resistance and heat insulating properties.

[Means and Actions for Solving Problems]

According to the invention, these problems consist of (A) a resin layer consisting essentially of a thermoplastic polyester resin and (B) a foam layer formed by foaming an ethylene polymer mixture 1.1 to 60 times. The ethylene-based polymer mixture is (1) at least ethylene and at least one selected from the group consisting of α, β-unsaturated monocarboxylic acids, α, β-unsaturated dicarboxylic acids, their anhydrides and half esters. A copolymer (I) comprising a monomer having a polar group, and (2) a copolymer comprising at least ethylene and an ethylenically unsaturated monomer having at least one polar group selected from the group consisting of a hydroxyl group or an epoxy group. It is composed of the polymer (II), and the mixing ratio of the copolymer (I) in the total amount of the copolymer (I) and the copolymer (II) is 1 to 99% by weight.
However, the ratio of the total amount of carboxyl groups and carboxylic acid anhydride groups in the copolymer (I) to the total amount of hydroxyl groups and glycidyl groups in the copolymer (II) is a molar ratio.
0.2: 1 to 5: 1, the copolymerization ratio of ethylene in each of these copolymers is 30 to 99.5% by weight, and the copolymerization ratio of the monomer having a polar group is 0.1.
It can be solved by a laminate, characterized in that it is ~ 70% by weight. Hereinafter, the present invention will be specifically described.

(A) Thermoplastic Polyester Resin The thermoplastic polyester resin used in the present invention is a polyester having a structural unit represented by the following formula [(I) formula] as a main repeating unit, and all repeating units are of the (I) formula. It is composed of a structural unit represented by.

Typical examples of the thermoplastic polyester resin include:
Polyethylene terephthalate, polyethylene-2,6-naphthalene-dicarboxylate, polybutylene terephthalate and more than 50% of the total number of repeating units,
And ethylene terephthalate, butylene terephthalate or ethylene-2,6-naphthalene dicarboxylate, the rest being other components modified polyethylene terephthalate modified polybutylene terephthalate and modified polyethylene-2,6-naphthalene dicarboxylate. To be

These modified polyesters preferably contain other components in an amount of 20% or less of all repeating units.

These thermoplastic polyester resins preferably have an intrinsic viscosity (orthochlorophenol, 35 ° C.) of 0.4 or more, particularly 0.5 or more.

Further, it is desirable to add a known nucleating agent such as polyolefin to these thermoplastic polyester resins to form a crystalline polyester resin because the heat resistance is further improved.

The ethylene-based polymer mixture in the present invention is a mixture of a copolymer (I) and a copolymer (II) described below.

(B) Copolymer (I) The copolymer (I) used in the present invention comprises at least ethylene and α, β-unsaturated monocarboxylic acid, α, β-unsaturated dicarboxylic acid, their anhydrides and half esters. It is a copolymer composed of at least one monomer selected from the group consisting of: Examples of the copolymer include the following polymers.

(1) Copolymer of ethylene and α, β-unsaturated monocarboxylic acid [hereinafter referred to as “ethylene copolymer (a)”] (2) Ethylene and α, β-unsaturated monocarboxylic acid ester The copolymer obtained by saponifying a part or all of the copolymer of (1) and performing a neutralization reaction such as demetallizing with an acid or the like [hereinafter, referred to as "ethylene-based copolymer (b ) "] And (3) a copolymer of ethylene with an α, β-unsaturated dicarboxylic acid, an anhydride thereof or a half ester thereof [hereinafter referred to as" ethylene-based copolymer (c) "] The copolymer (I) melts at a temperature of 150 ° C or lower,
It is desirable to have fluidity.

(1) Ethylene-based copolymer (a) The ethylene-based copolymer (a) is at least ethylene and α,
Being a copolymer with β-unsaturated monocarboxylic acid, in order to ensure the above-mentioned fluidity, a radical-polymerizable comonomer having a polar group (hereinafter referred to as “third component”)
Copolymerized with is preferable.

By copolymerizing this third component as a comonomer, a multicomponent copolymer having units derived from the monomer corresponding to the third component copolymerized in the ethylene-based copolymer (a) can be obtained [see below. The same applies to the case of the ethylene-based copolymer (b) to the ethylene-based copolymer (e)].

The α, β-unsaturated monocarboxylic acid that can be used for the production of the ethylene copolymer (a) generally has 3 to 20 carbon atoms, and particularly preferably 3 to 16 carbon atoms.
Representative examples include acrylic acid, methacrylic acid, crotonic acid, monoalkylmalates, monoalkylfumarates and the like.

The third component is a radically polymerizable vinyl compound containing a polar group, and examples thereof include unsaturated carboxylic acid esters, vinyl esters, and alkoxyalkyl (meth) acrylates.

The number of carbon atoms of the unsaturated cambonate ester is usually 4 to 40, and particularly preferably 4 to 20. As a typical example,
Those having good thermal stability such as methyl (meth) acrylate and ethyl (meth) acrylate are preferable, and those having poor thermal stability such as t-butyl (meth) acrylate cause foaming and are not preferable.

Furthermore, the alkoxyalkyl acrylate usually has at most 20 carbon atoms. Also, the number of carbon atoms in the alkyl group is 1.
To 8 (preferably 1 to 4), and the alkoxy group has 1 to 8 carbons (preferably 1 to 4).
It is desirable to have one). Representative examples of preferred alkoxyalkyl acrylates include methoxyethyl acrylate, ethoxyethyl acrylate and butoxyethyl acrylate. The vinyl ester generally has at most 20 carbon atoms (preferably 4 to 16 carbon atoms). Representative examples thereof include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate and the like.

In the ethylene copolymer (a), the amount of the third component is 25
It is preferable that the content is mol% or less, and particularly 2 to 20 mol%
Is preferred. The characteristics of the present invention are exhibited even if it exceeds 25 mol%, but it is not necessary to exceed 25 mol%, which is not preferable in terms of production and economy.

The bonding amount of the α, β-unsaturated monocarboxylic acid in the ethylene copolymer (a) is preferably 0.5 mol% or more and 25 mol% or less, and particularly preferably 1.0 mol% to 15 mol%. is there.

The α, β-unsaturated monocarboxylic acid serves as a cross-linking reaction point with the ethylene-based copolymer (d) or the ethylene-based copolymer (e) described below and imparts adhesiveness to various wide-ranging base materials. It does not have to be in excess from either side. If the amount increases, the water absorption will increase, which not only adversely affects foaming during molding and water absorption after molding, but also adversely affects electrical properties, as well as manufacturing problems such as safety, separation and recovery, and economically. Is also disadvantageous and not preferable. On the other hand, if it is less than 0.5 mol%, there is no problem in terms of adhesion, but heat resistance becomes insufficient, which is not preferable.

(2) Ethylene-based copolymer (b) Furthermore, the ethylene-based copolymer (b) used in the present invention is one of the ester groups in the ethylene-based copolymer composed of ethylene and an unsaturated carboxylic acid ester. It is a copolymer obtained by saponifying a part or all of it and performing a neutralization reaction such as demetallizing treatment.

The unsaturated carboxylic acid ester usually has 4 to 40 carbon atoms, and particularly preferably 4 to 20 carbon atoms. Typical examples are methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, 2-methoxyethyl (meth).
Examples thereof include acrylate and diethyl fumarate.

The content of unsaturated carboxylic acid ester in the ethylene copolymer (b) is preferably 1 to 25 mol%. The saponification rate of the ester cannot be generally determined because it depends on the content of the ester, but the saponification rate is 0.5 to 20 mol% in terms of the carboxylic acid-containing unit in the copolymer after the neutralization treatment. Is preferred, with 1 to 15 mol% being particularly preferred.

The saponification reaction is a widely known method, for example, a mixed solvent of toluene and isobutyl alcohol (mixing ratio 50: 5).
It can be carried out by adding a copolymer containing NaOH and an ester group in (0) and refluxing for 3 hours. The saponification rate can be adjusted arbitrarily depending on the amount of NaOH. Furthermore, after precipitating this saponified product with water or alcohol and passing the solvent through it, one day and one night,
Vacuum dry at 50 ° C. Disperse this polymer in water,
Sulfuric acid is added thereto, and the mixture is stirred at 70 ° C. for 1 hour to carry out a demetalization treatment (= neutralization reaction) to obtain an ethylene copolymer (b).

(3) Ethylene Copolymer (c) Further, the ethylene copolymer (c) used in the present invention is ethylene and α, β-unsaturated dicarboxylic acid, its anhydride or its monoester. The above-mentioned copolymer (which may contain the third component) may be used. That is, ethylene and α, β-unsaturated dicarboxylic acid,
The anhydride thereof or the half ester thereof, or those obtained by directly copolymerizing these with the third component.

Examples of the third component include compounds of the same type as the ethylene copolymer (a).

When the ethylene-based copolymer (c) is produced by the direct copolymerization method, α, β-unsaturated dicarboxylic acid, its anhydride or its half ester is selected as the copolymerization comonomer.

The α, β-unsaturated dicarboxylic acid usually has a large number of carbon atoms.
20 are all, and particularly 4 to 16 are preferable.
It Typical examples of the dicarboxylic acid include maleic acid and phenylcarboxylic acid.
Malic acid, itaconic acid, citraconic acid, 3,6-endomethyi
Len-1,2,3,6-tetrahydro-cis-phthalic acid
Acid ) Is given.

As the α, β-unsaturated dicarboxylic acid half ester,
The number of carbon atoms is generally at most 40, especially 5 to 20. As a typical example thereof, one in which one of the carboxyl groups of the dicarboxylic acid is half-esterified by a typical example of the alcohol described below can be mentioned.
Typical examples of the alcohol include methanol, ethanol, propanol and butanol having at most carbon atoms.
There are 20 primary alcohols. Representative examples of half esters include maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monoisopropyl ester, maleic acid monobutyl ester, and itaconic acid monoethyl ester.

The amount of "α, β-unsaturated dicarboxylic acid or its half ester" (hereinafter referred to as "unsaturated dicarboxylic acid component") bound in the ethylene copolymer (c) is 0.5 mol% or more, 2
It is preferably 0 mol% or less. More preferably 1.0
~ 15 mol%.

(C) Copolymer (II) The copolymer (II) used in the present invention is a copolymer comprising at least a unit derived from acetylene and a acetylene-based unsaturated monomer containing a hydroxyl group or an epoxy group. Examples of the copolymer include the following polymers.

(1) Saponified product obtained by saponifying a part or all of a copolymer of ethylene and vinyl ester [hereinafter referred to as "ethylene-based copolymer (d)"] (2) Ethylene and "hydroxyl group A copolymer with an ethylenically unsaturated monomer having "(hereinafter referred to as" hydroxyl compound ") or an" ethylenically unsaturated monomer having an epoxy group "(hereinafter referred to as" epoxy compound ") and the above-mentioned Multicomponent copolymer with three components [hereinafter referred to as "ethylene copolymer (e)" (1) Ethylene copolymer (d) Further, the ethylene copolymer used in the present invention is ethylene and vinyl. It can be produced by saponifying a part or all of the copolymer with the ester.

As the vinyl ester which is a comonomer component of the copolymer, the same type as the second component is preferably used, and vinyl acetate is particularly preferable.

Ethylene-based copolymer (d) by saponifying this copolymer
In the production of, the saponification method may be a commonly used method. The degree of saponification is usually 80% or more, preferably 85% or more, and particularly preferably 90% or more.

(2) Ethylene-based copolymer (e) Further, the ethylene-based copolymer (e) used in the present invention may be a copolymer of ethylene and a hydroxyl-based compound or an epoxy-based compound. It may be a multi-component copolymer with the third component.

Examples of the hydroxyl-based compound that is a comonomer component of the copolymer include hydroxyalkyl (meth) acrylate (the alkyl group usually has 1 to 25 carbon atoms) and α-alkenyl alcohol having 3 to 25 carbon atoms. . Typical examples of the hydroxyl compound include hydroxymethyl (meth) acrylate and hydroxymethyl (meth).
Acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate and allyl
l) I can give you alcohol.

Further, as a typical example of the epoxy compound, there can be mentioned one having a general formula represented by the following formulas [(II) and (III)].

Typical examples of the epoxy compounds represented by the formulas (II) and (III) include glycidyl methacrylate, glycidyl acrylate, α-methyl glycidyl acrylate, α-methyl glycidyl methacrylate, vinyl glycidyl ether, and allyl glycidyl ether. And methacrylglycidyl ether.

The copolymerization ratio of ethylene in this copolymer (II) is generally 30 to 99.5% by weight, preferably 30 to 99.0% by weight,
Especially, 35 to 99.0% by weight is preferable. Further, the copolymerization ratio of the hydroxyl compound is the ethylene copolymer (a).
For the same reason as above, usually 0.1-70% by weight, 0.5-70%
% By weight is preferred, with 0.5-60% by weight being particularly preferred.
Further, in the case of a multi-component copolymer, the copolymerization ratio of the third component is generally at most 69.9% by weight for the same reason as the ethylene copolymer (a), preferably 65% by weight or less, and particularly preferably It is preferably 60% by weight or less.

These proportions are incompatible with the ethylene used to produce the ethylene-based copolymer (a), the ethylene-based copolymer (c) and the ethylene-based copolymer (e) and the ethylene-based copolymer (b). Both the copolymer with saturated carboxylic acid ester and the copolymer with ethylene and vinyl ester used for producing the ethylene-based copolymer (e) are
Copolymerizing a comonomer (including the third component) that copolymerizes with ethylene in the presence of a chain transfer agent (eg, an organic peroxide) at a temperature of 120 to 260 ° C under a high pressure of 50 to 2500 kg / cm ^3. Can be manufactured by. This copolymerization method is a well-known method.

These ratios are based on the melt flow index (JIS) of the ethylene copolymer (a) or the ethylene copolymer (e).
According to K7210, measured under condition 4, hereinafter referred to as "MFR")
Is generally 0.01 to 1000 g / 10 minutes, preferably 0.05 to 500 g / 10 minutes, particularly preferably 0.1 to 500 g / 10 minutes. MF
When R is less than 0.01 g / 10 min ethylene-based copolymer,
Not only is it difficult to uniformly mix the mixture of the present invention, but also the moldability is poor.

To produce the mixture of the present invention, the above copolymer (I) is used.
The copolymer (II) and the foaming agent are uniformly mixed within the range of the mixing ratio to be described later, but the copolymer (I) and the above-mentioned copolymer (I) are mixed by further mixing the reaction accelerator described below. A good mixture can be obtained by promoting the crosslinking of the polymer (II).

(D) Reaction Accelerator The reaction accelerator used in the present invention is widely known as a curing agent for epoxy resins, and a typical example thereof is "Epoxy Resin" edited by Hiroshi Kakiuchi (Shokodo, 1979). Issue)
26 to 29, 32 to 35, 109 to 128, 185 to 188, 330 and 331.

Typical examples of this reaction accelerator include primary, secondary or tertiary amines represented by formula (IV), acids, alkaline compounds and ammonium salts represented by formula (V). .

In the formulas (IV) and (V), R ⁶ , R ⁷ , R ⁸ and R ⁹
May be the same or different and each is a hydrogen atom, a hydrocarbon group selected from an alkyl group having 1 to 32 carbon atoms, an aryl group, an alkaryl group and an aralkyl group, but not all hydrogen atoms at the same time. X is a halogen atom. In these formulas, the carbon number of R ⁶ to R ⁹ is 12
Not more than one hydrocarbon group is preferred. Further, X is preferably a chlorine atom or a bromine atom.

Typical examples of the reaction accelerator include ethanolamine, diethanolamine, triethanolamine, dimethylamine, diethylamine, n-propylamine, isopropylamine, n-butylamine, N, N-dimethylaminoethanol, N, N-diethylaminoethanol. , Morpholine, biperidine, pyridine, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminomethacrylate, N, N-diethylaminoethyl acrylate, trimethylamine, triethylamine, tri-n-butylamine, N, N-dimethylbenzylamine, Tertiary amines such as hexamethylenetetramine, triethylenediamine, N, N-dimethylpiperazine and N-melethylmorpholine, acidic compounds such as p-toluenesulfonic acid and potassium hydroxide, or alkalis. Compounds and trimethylbenzylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride and cetyltrimethylammonium halide ammonium salt such as chloride, zinc chloride and the like more. Especially, N, N-dimethylbenzylamine and p-toluenesulfonic acid are preferable.

In producing the mixture of the present invention, a copolymer composed of ethylene and α, a monomer having a β-unsaturated dicarboxylic acid group as the copolymer (I), that is, ethylene and α,
An anhydride of β-unsaturated dicarboxylic acid or an ethylene-based multi-component copolymer consisting of these and the third component is used, and ethylene (E) and an ethylenically unsaturated monomer containing an epoxy group are used as the copolymer (II). Which is a copolymer of ethylene and a monomer represented by the above formula (I) or (II) or an ethylene-based multi-component copolymer comprising the third component and the above-mentioned reaction. When no accelerator is used, the copolymer (I) and the copolymer (II) are not crosslinked, and a good mixture cannot be obtained. In this case, by mixing (mixing) an organic compound or polymer having a boiling point of 150 ° C. or higher and having a hydroxyl group (—OH group) or a carboxyl group (—COOH group), the copolymer ( I) can be crosslinked with the copolymer (II). Examples of the polymer include ethylene and α, β-unsaturated monocarboxylic acid, α, β among the ethylene copolymer (a), the ethylene copolymer (b), and the ethylene copolymer (c). -Copolymers with monomers selected from the group consisting of unsaturated dicarboxylic acids and their half esters (these copolymers may be ethylene-based multicomponent copolymers containing a third component), ethylene and vinyl acetate The above ethylene-based copolymer (a) is added to the saponified product of the copolymer, the copolymer of ethylene and hydroxyalkyl (meth) acrylate, and the copolymer containing ethylene or propylene as a main component (including homopolymer). And grafting the α, β-unsaturated monocarboxylic acid, α, β-unsaturated dicarboxylic acid or anhydride thereof used in the production of the ethylene copolymer (c). Thus, the modified olefin polymer obtained can be mentioned. Further, as the organic compound, ethylene glycol, polyethylene glycol, propylene glycol,
Examples include glycerin and polypropylene glycol.

(E) Blowing Agent The blowing agent used in the present invention decomposes in the temperature range of 80 to 250 ° C., and the blowing agent itself and the gas generated by the decomposition are the above-mentioned copolymer (I) and copolymer. There is no particular limitation as long as it does not react with any of the combination (II), but a decomposition temperature of 110 ° C. or higher is particularly desirable, and 130 ° C. or higher is particularly preferable. Suitable blowing agents include organic blowing agents such as dinitropentamethylenetetramine, azobisisobutyronitrile, azodicarbonamide, paratoluenesulfonyl hydrazide and hydrazine. Further, in the above temperature range, an inorganic compound (for example, sodium bicarbonate) and an organic acid (for example, salicylic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, stearic acid, lauric acid) or boric acid which satisfy the above conditions A foaming agent in combination with can also be used.

In producing the mixture of the present invention, only these foaming agents may be used as the foaming agent, but the effect can be further enhanced by further using the foaming agent and the foaming auxiliary together. It cannot be unconditionally specified because it depends on the type of foaming agent used, but examples of azodicarbonamide foaming aids include zinc white (zinc oxide), tribasic lead sulfate, urea, and zinc stearate. Examples of the blowing agent aid for dinitrosopentamethylenetetramine include salicylic acid, phthalic acid, boric acid, and urea resin.

(E) Mixing ratio In producing the mixture of the present invention, the mixing ratio of the copolymer (I) in the total amount of the copolymer (I) and the copolymer (II) is 1 to 99% by weight. 5 to 95% by weight is preferable, and 10 to 90% by weight is particularly preferable. Even when the mixing ratio of the copolymer (I) in the total amount of the copolymer (I) and the copolymer (II) is less than 1% by weight or more than 99% by weight, the viscosity is maintained during foaming. Poor, no good molded product can be obtained.

In addition, the sum total (total amount) of the carboxyl group and the carboxylic acid anhydride group of the copolymer (I) in the mixture: the copolymer (I
The ratio of I) to the total amount (total amount) of hydroxyl groups and epoxy groups is 0.2: 1 to 5: 1 in molar ratio, and 0.3: 1
To 3: 1 are preferred, and 0.5: 1 to 2: 1 are preferred.

Further, the total amount of the copolymer (I) and the copolymer (II)
The mixing ratio of the foaming agent to 100 parts by weight is 0.1 to 50 parts by weight, preferably 0.3 to 50 parts by weight, and more preferably 0.5 to 45 parts by weight. If the mixing ratio of the foaming agent is less than 0.1 parts by weight based on 100 parts by weight of the total amount of the copolymer (I) and the copolymer (II), the amount of foaming is too small to obtain a foam. On the other hand, 50
If it exceeds the weight part, a good foam cannot be obtained because the viscosity of the mixture cannot be maintained.

When a reaction accelerator is added, the mixing ratio is 100% of the total amount of the copolymer (I) and the copolymer (II).
Generally, at most 5.0 parts by weight relative to parts by weight, 0.0
1 to 5.0 parts by weight is preferable, and 0.01 to 2.0 parts by weight is particularly preferable. Even if the reaction accelerator is blended in an amount of more than 5.0 parts by weight, the low-temperature cross-linking promoting effect is exhibited, but not only the cross-linking adhesion inhibiting effect by the reaction promoting agent itself may occur, but the reaction promoting agent may also form a molded article. It is not preferable because it causes bleeding on the surface and a good molded product cannot be obtained.

Furthermore, when the above-mentioned organic compound and / or polymer having a hydroxyl group or a carboxyl group is blended in producing the mixture of the present invention, the mixing ratio thereof is such that the copolymer (I) and the copolymer (II) are mixed. Total amount of
Usually at most 20 parts by weight per 100 parts by weight,
20 parts by weight is preferable, 0.5 to 20 parts by weight is preferable, and 1.0 to 15 parts by weight is particularly preferable.

(G) Preparation of Mixture In preparing the mixture of the present invention, a filler (for example, calcium carbonate, talc, mica) can be achieved by uniformly mixing the above polymer and the foaming agent. , Additives such as stabilizers for heat, light and oxygen, flame retardants, plasticizers, nucleating agents, colorants (pigments) and antistatic agents may be further added depending on the intended use of the mixture. Good.

The mixing method is an extruder, mixing roll, kneader, roll mill, ordinarily used in the field of thermoplastic resins.
There is a method of kneading a polymer used in a molten state by using a mixer such as a Banbury mixer and a continuous mixer, but the mixture obtained in advance is mixed by using one of these mixers, and the obtained mixture is the same kind or another kind. A more uniform mixture can be obtained by mixing using a mixer. Further, a more uniform mixture can be obtained by dry-blending with a mixer such as a drum tumbler and a Henschel mixer before the mixing, and further melt-kneading the resulting mixture. Further, a so-called masterbatch may be produced by previously mixing a part of these mixed components, and the obtained masterbatch (mixture) may be mixed with the remaining mixed components. At this time, it is desirable to mix the foaming agent with the copolymer (I) and the copolymer (II) in advance to produce pellets, and to mix the remaining mixed components with the obtained mixture. Alternatively, the foaming agent and the copolymer (II) or the foaming agent and the copolymer (I) and the copolymer (II) may be mixed in advance, and the resulting mixture may be mixed with the remaining mixing components. .

During the melt-kneading, it is necessary that the copolymer (I) and the copolymer (II) as the mixing components do not substantially crosslink (when they are crosslinked, the resulting mixture is processed as described later). It is not preferable because not only the moldability is deteriorated, but also the desired shape of the formed product or the heat resistance is lowered when the molded product is crosslinked). From this fact, the temperature of melt kneading depends on the kinds and blending amounts of the copolymer (I) and the copolymer (II) used and the presence or absence of addition of the reaction accelerator, but at room temperature (20
℃) to 150 ℃ is desirable, 140 ℃ or less is suitable.

As a measure of this "substantially no cross-linking", the diameter of the total amount of the above-mentioned copolymer (I) and copolymer (II) in the mixture is "after extraction treatment in boiling toluene for 3 hours,
Residue of 0.1 μm or more ”(hereinafter referred to as“ extraction residue ”)
Is generally 15% by weight or less, preferably 10% by weight or less, and most preferably 5% by weight or less.

(H) Manufacture of Laminate The laminate of the present invention comprises a resin layer essentially consisting of a thermoplastic polyester resin (hereinafter referred to as “A layer”) and a foamed layer described below (hereinafter referred to as “B layer”). And is obtained by joining these layers. For joining, any known method (for example, coextrusion molding method, extrusion coating method, dry laminating method, extrusion laminating method) may be adopted. Among these methods, the extrusion laminating method in which the foamed body (B layer) of the ethylene-based polymer mixture obtained in advance is melt-extruded when the A layer is melt-extruded is preferable. The molding temperature is equal to or higher than the softening point of the component of each layer, but may be equal to or lower than the decomposition temperature. For these reasons,
80 to 350 ° C. is desirable, and 120 to 300 ° C. is particularly preferable.

When melt extruding the A layer, an adhesive layer that easily adheres to the B layer,
For example, ethylene-vinyl acetate copolymer, maleic acid,
A layer such as a modified polyolefin obtained by graft-copolymerizing fumaric acid, itaconic acid or an acid anhydride thereof with an olefin polymer (hereinafter referred to as "C layer") is used by interposing it between the B layer and the layer. This makes it possible to obtain a laminate having high adhesive strength.

The structure of the laminate is not limited to the three-layer structure in which the two layers consisting of the A layer and the B layer and the C layer are interposed between the A layer and the B layer as described above, but also the B layer / A layer / B Layer, A layer / B layer / A layer, B layer
A combination such as / C layer / A layer / C layer / B layer or A layer / C layer / B layer / C layer / A layer may be appropriately used depending on the intended use of the laminate.

Further, the thickness of each layer can be arbitrarily selected so as to meet the purpose of use of the laminate, economy, quality and the like. The thickness of the A layer is generally 50 μm to 5 mm (preferably 50 μm to 3 mm). Furthermore, for layer B, it is usually 50μ
m to 3 cm (preferably 50 μm to 2 cm).
When the C layer is provided, its thickness is generally 5 to 100.
μm (preferably 5 to 80 μm).

(J) Foamed layer and its manufacturing method The foamed layer (namely, B layer) of this invention foams the mixture which consists of a copolymer (I) and a copolymer (II) 1.1 to 60 times. Examples of the foaming method include the following methods that are generally used.

(1) A method in which a foaming agent is decomposed in an extruder to obtain a foam-molded article having a target shape depending on the shape of a die.

(2) A method of forming a target shape product without decomposing the foaming agent, and then heating to decompose the foaming agent to obtain a foam.

(3) A method in which a foaming agent is partially foamed in an extruder to form a target shape, and then heated to decompose the foaming agent to obtain a foam having a final target shape.

(4) A method in which the mixture is heated under pressure with a press or the like, returned to normal pressure, and press-foamed.

(5) A method of forming the mixture into beads and molding it into a mold having a desired shape.

(6) A method of obtaining a foam by gas-pressurizing the mixture into an extruder.

(7) A method of foaming during coextrusion of the thermoplastic polyester resin and the mixture.

The expansion ratio is 1.1 to 60 times, preferably 1.2 to 60 times, and more preferably 1.5 to 50 times. Foaming ratio is 1.1
If it is less than double, the heat insulating property is poor. On the other hand, it is difficult to manufacture a product exceeding 60 times, and even if obtained, the rigidity is poor and the shape cannot be retained.

[Examples and Comparative Examples]

Hereinafter, the present invention will be described in more detail with reference to Examples.

The thermoplastic polyester resin used in Examples and Comparative Examples and the copolymer (I) and the copolymer (II)
The physical properties and mixing ratio of the foaming agent of the mixture are shown below.

[(A) Thermoplastic polyester resin]

As the thermoplastic polyester resin, polyethylene terephthalate (hereinafter referred to as "PETP") having an intrinsic viscosity (measured under the above conditions) of 0.8 and polybutylene terephthalate (hereinafter referred to as "PBTP") having an intrinsic viscosity of 1.0 were used. .

[(B) Foam of Ethylene Copolymer Mixture]

As the foam of the ethylene copolymer mixture, the foam obtained as described below was used.

MFR of the ethylene is 300 g / 10 min - acrylic acid copolymer (density 0.954 g / cm ^3, copolymer ratio 20% by weight of acrylic acid, hereinafter referred to as "EAA") and vinyl copolymer fraction acetate 28 wt%
A saponified product obtained by saponifying an ethylene-vinyl acetate copolymer having a saponification degree of 97.5%, MFR 75 g
/ 10 minutes, density 0.951 g / cm ³ , hereinafter referred to as “saponified material”] [mixing ratio 50:50 (weight ratio)] was foamed, and a foaming ratio of 20 times [hereinafter referred to as “ "Foam (I)"], a mixture of an ethylene-methacrylic acid copolymer having an MFR of 200 g / 10 minutes (density: 0.950 g / cm ³ , methacrylic acid copolymerization ratio: 25% by weight) and the saponification degree. A mixture having a mixing ratio of 50:50 (weight ratio)] and a foaming ratio of 10 times (hereinafter referred to as “foam (II)”), MFR of 212 g /
10 minutes of terylene-ethyl acrylate-maleic anhydride terpolymer (ethyl acrylate copolymerization ratio 3
0.7% by weight, maleic anhydride copolymerization ratio 1.7% by weight, hereinafter referred to as "EAM") and ethylene-methylmethacrylate-hydroxymethacrylate terpolymer (Methylmethacrylate copolymer) having MFR of 123 g / 10 min. A mixture having a polymerization ratio of 20.7% by weight and a hydroxymethacrylate copolymerization ratio of 11.7% by weight (a mixing ratio of 50:50 (weight ratio)) was foamed to give a foamed product having a foaming ratio of 5.0 times [hereinafter referred to as "foamed (II
I) ”] and MFR of 105 g / 10 minutes Ethylene-methyl methacrylate-maleic anhydride terpolymer (copolymerization ratio of methyl methacrylate 20.5% by weight, copolymerization ratio of maleic anhydride 3.1% by weight) ) And ethylene-methyl methacrylate-glycidyl methacrylate terpolymer (copolymerization ratio of methyl methacrylate 18.6% by weight, copolymerization ratio of glycidyl methacrylate 12.7% by weight) (mixing ratio 30:70 (weight ratio)) A foam having a foaming ratio of 2.0 times (hereinafter referred to as "foam (I
V) ”]].

Examples 1 to 4 and Comparative Examples 1 and 2 Thermoplastic polyester resins each type of which is shown in Table 1 for forming the A layer were prepared using an extruder (diameter 65 mm) equipped with a T-die. Extrusion was performed at a resin temperature of 280 ° C., and a sheet was formed by a roll pressure bonding method. At this time, in order to form the layer B at the inlet of the pressure-bonding roll, the foamed product of the above-mentioned ethylene copolymer mixture whose type is described in Table 1 is laminated, and the thermoplastic polyester resin sheet is heated by the heat pressure of the roll. Was heat-laminated to prepare a sheet (width 300 mm) whose thickness is shown in Table 1.

In order to evaluate the heat insulating property of the obtained sheet, the thermal conductivity was measured using a thermal conductivity meter (manufactured by Showa Denko KK, rapid thermal conductivity meter model QTM type). The results are shown in Table 1.

Each of the sheets thus obtained was subjected to pressure-air vacuum forming using a roll continuous thermoforming machine (model Asaken Kenkyusha, model name FLX-02 type, oven type, double-sided infrared heating system), and a container (diameter 100 mm , Depth of 50 mm). In order to evaluate the heat resistance of the obtained containers, the oven temperature was set to 230 ° C with an oven grill range (Toshiba Electric Co., model ER-630SF), these containers were left in the oven for 20 minutes, and The appearance change was visually observed. The results are shown in Table 1.

[Effect of the Invention] The laminate of the present invention exhibits the following effects (features).

(1) Utilizing the heat resistance property of the thermoplastic polyester resin, the thermal conductivity is low and the heat resistance is further improved.

(2) Therefore, it can be used as a container having excellent heat resistance, which is essential for heat resistance such as a microwave oven container and an oven oven container for oily foods.

Since the laminate of the present invention exhibits the above effects, it can be used in all industrial fields. Typical fields of use (uses) are shown below.

(1) As a heat insulating material, interior materials for building materials, automobiles, trains, ships, frozen food containers, and various pipe covers.

(2) As structural materials, walls of buildings, partitions, sandals, shoe soles, etc.

(3) As cushioning materials and electrical equipment, packaging materials for precision equipment such as cameras and packaging materials for foods.

(4) Others include levitating materials, cloth substitute materials, packing materials for various containers, covering materials for cables, various sports goods, and miscellaneous cargo such as toys.

Claims (1)

[Claims] 1. An (A) resin layer essentially consisting of a thermoplastic polyester resin, and (B) a foam layer obtained by foaming an ethylene-based polymer mixture 1.1 to 60 times. The ethylene-based polymer mixture comprises (1) At least ethylene and a monomer having at least one polar group selected from the group consisting of α, β-unsaturated monocarboxylic acids, α, β-unsaturated dicarboxylic acids, their anhydrides and half esters. A copolymer (I), and (2) a copolymer (II) comprising at least ethylene and an ethylenically unsaturated monomer having at least one polar group selected from the group consisting of a hydroxyl group or an epoxy group, The mixing ratio of the copolymer (I) in the total amount of the copolymer (I) and the copolymer (II) is 1 to 99% by weight.
However, the ratio of the total amount of carboxyl groups and carboxylic acid anhydride groups in the copolymer (I) to the total amount of hydroxyl groups and glycidyl groups in the copolymer (II) is a molar ratio.
0.2: 1 to 5: 1, the copolymerization ratio of ethylene in each of these copolymers is 30 to 99.5% by weight, and the copolymerization ratio of the monomer having a polar group is 0.1.
~ 70% by weight, a laminate.