JP2005324486A - Laminate, heat-insulating container using this laminate and method for manufacturing them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate which shows outstanding heat-insulating effect, beautiful print properties free from impairing the sharpness of a print pattern formed on the surface, manufacturing process simplicity, manufacturing ease, lightweight properties and low cost, and a heat-insulating container using the laminate and a method for manufacturing the laminate and the heat-insulating container. <P>SOLUTION: In the laminate, a foamable heat-insulating coating layer 2 composed of an organic/inorganic hybrid composite or an organic/inorganic powder mixture and a foaming agent, is formed on a paper base material or a plastic base material 1. Further, a gas barrier coating layer 3 composed of the organic/inorganic hybrid composite is formed on the heat-insulating coating layer 2. Also, the heat-insulating container using the laminate and the method for manufacturing the laminate and the heat-insulating container are provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a laminate and a heat-insulating container having excellent heat insulating properties, and more specifically, a foamable heat-insulating coating layer is formed on a paper substrate or a plastic substrate, and further on the heat-insulating coating layer. The present invention relates to a laminate formed by forming a gas barrier coating layer on the substrate, a heat insulating container using the laminate, and a method for producing them. This laminated body and a heat insulating container using the laminated body are suitably used for industrial applications such as heat insulating paper cups, heat insulating cardboards, heat insulating paper trays, food applications and transportation materials, and further for building materials applications such as heat insulating wallpaper. Can also be used.

  Conventionally, as paper having heat insulation properties, heat insulating paper using aluminum in which an aluminum foil is pasted on a base paper or a coating liquid containing aluminum powder and ceramic is applied to the base paper has been used. Yes. Furthermore, a heat-insulating cardboard paper in which this heat-insulating paper is bonded to a cardboard base paper is also used.

  Such conventional heat-insulating paper and heat-insulating corrugated cardboard have high heat-insulating properties and are waterproof, and are widely used mainly for food packaging boxes or containers that require heat insulation.

  However, the insulating paper containing aluminum also has various problems as described below. First of all, in recent years of environmental protection, recycling of paper used for various purposes is increasing, but conventional heat insulating paper cannot be recycled as waste paper because it contains aluminum.

  Secondly, since conventional packaging boxes using aluminum-containing heat-insulating paper react with metal detectors, if a food storage box using this is used, metal foreign matter mixed in the stored food is metalized. It can no longer be detected by the detector.

Patent literature is described below.
JP 2001-278363 A Japanese Patent No. 3047763 JP 2003-31635 A Therefore, in order to solve the above problems, various heat insulating papers, paper heat insulating cups, and the like have been proposed. For example, a paper cup having a body part and a bottom part, and having a mouth edge part whose outer periphery is curled outward, and at least the material structure of the body member forming the body part is a base material mainly composed of paper. A paper heat insulating cup made of a laminated sheet in which a foamed resin layer and a low density polyethylene film are sequentially laminated on the outer side and a sealant layer is provided on the inner side of the base material has been proposed (see Patent Document 1). This paper heat insulating cup has been devised in terms of cost, polyethylene film material, laminated structure, etc., but (1) the printing layer is also foamed, resulting in reduced surface smoothness, ink cracking, etc. The problem is that the clearness of the printing applied to the surface is impaired and the printed expression with excellent cosmetics cannot be achieved. (2) Polyethylene film is a petroleum-derived material, and the paper conversion rate occupied by the paper base material as a paper container is reduced, making it difficult to treat as waste after use and increasing the environmental burden. (3) Since the heat insulation layer cannot be made too thick, there are problems such as poor heat insulation effect.

  Also, a paper cup main body, embossing is formed substantially entirely, and embossed paper covering and adhering to the side surface of the cup main body, and covering and sticking to the embossed paper. A heat insulating cup comprising a thin paper and a liner paper covering and sticking to the thin paper and a method for producing the same have been proposed (see Patent Document 2). This heat insulating cup is made by wrapping paper with embossing on the outside of the cup, and further wrapping paper on it as a printing layer. (1) The problem is that the weight of the heat-insulating cup is increased and the burden such as contribution is increased. (2) A problem that the weight of the heat insulating cup increases and the total amount of garbage increases. (3) There are cost problems.

  Further, a paper cup body comprising a body part and a bottom part, and having a mouth edge whose outer peripheral edge is curled outward, and an annular leg part formed at the joint part between the body part and the bottom part, and the outer part of the paper cup body A paper heat insulating cup that is configured to be fitted into a paper tube, and a lower portion of the paper tube body has a bent portion whose cross-sectional shape is bent in an inverted N shape, and the paper tube body is a paper cup body. The cylindrical leg is formed so that the annular leg portion is hidden when fitted into the paper cup body, and the front end portion of the paper cylinder body in which the bent portion is formed is the annular shape of the lower edge of the paper cup main body part. Paper insulation that is fixed to the outer surface of the leg, the upper end of the cylinder is fixed in contact with the lower edge of the mouth edge of the barrel, and a thermal insulation space layer is provided between the paper cup body barrel and the paper cylinder A cup (refer to Patent Document 3) and an outward curled part are formed on the upper edge of the cup, and the upper part of the body part is expanded to the outer diameter side. The upper part of the inner cup and the upper part of the body part are fitted to the outside of the inner cup step part, and the lower edge is inserted into the bottom edge together with the lower edge of the inner cup side. A paper heat insulating cup (see Patent Document 4) that forms a heat insulating gap between the inner cup and the like has been proposed.

  Each of the above-mentioned paper heat insulating cups is one in which a single-layer paper is wound around the outside of the cup as a printed layer and a heat insulating layer, and an air layer is provided between the two layers of the cup body and the paper to express heat insulation. These paper heat insulation cups have the following problems: (1) The air layer collapses when held by hand, and there is a risk that the heat insulation effect may be lost by directly touching the cup body. (2) Since a single-layer paper is wound around the outside of the cup as a printed layer and a heat insulating layer, a process of winding around the main body is necessary for manufacturing, and there are technical difficulties and high costs.

  The present invention has been made in order to solve the above-described conventional problems, and is excellent in heat insulation effect, excellent in printing beauty without impairing the sharpness of the printed pattern applied to the surface, and in a manufacturing process. SUMMARY OF THE INVENTION An object of the present invention is to provide a laminate, a heat insulating container using the laminate, and a method for producing them, which is simple, easy to manufacture, lightweight and inexpensive.

To achieve the above objectives, ie
The invention according to claim 1
A foamable heat-insulating coating layer composed of an organic / inorganic hybrid composite or organic / inorganic powder mixture and a foaming agent is formed on a paper substrate or plastic substrate, and on the heat-insulating coating layer, A laminate comprising a gas barrier coating layer formed of an organic / inorganic hybrid composite.

The invention according to claim 2
The organic / inorganic hybrid composite constituting the heat insulating coating layer hydrolyzes an inorganic alkoxide mixture containing an alkoxide of an alkaline earth metal and / or an alkoxide of a metal other than an alkaline earth metal by a sol-gel method, The laminate according to claim 1, wherein the laminate is a composite obtained by polycondensation.

The invention according to claim 3
2. The laminate according to claim 1, wherein the organic / inorganic powder mixture constituting the heat insulating coating layer comprises a polymer resin and an inorganic powder.

The invention according to claim 4
The organic / inorganic hybrid composite composing the gas barrier coating layer is a polymer having an alkaline earth metal alkoxide and / or an inorganic alkoxide mixture containing a metal other than an alkaline earth metal and a hydrogen bond-forming group. The laminate according to any one of claims 1 to 3, wherein the laminate is a composite obtained from a resin, hydrolyzed by a sol-gel method, and polycondensed. .

The invention according to claim 5
In the laminate according to claim 3,
The polymer resin is an acrylic resin or an ethylene-vinyl acetate copolymer.

The invention according to claim 6
In the laminate according to claim 3,
The laminate is characterized in that the inorganic powder is a foamed silica particle obtained by baking a composite formed by hydrolyzing ethyl silicate alkoxysilane by a sol-gel method and polycondensation.

The invention according to claim 7 provides:
The laminate according to claim 2 or 4,
The organic-inorganic hybrid composite is a laminate obtained by hydrolyzing and polycondensing ethyl silicate alkoxysilane by a sol-gel method.

The invention according to claim 8 provides:
In the laminated body in Claim 4,
The polymer resin having a hydrogen bond-forming group is a laminate characterized by being polyvinyl alcohol or an ethylene-vinyl alcohol copolymer.

The invention according to claim 9 is:
A laminate comprising a printed pattern layer provided on the gas barrier coating layer of the laminate according to any one of claims 1 to 8.

The invention according to claim 10 is:
It is a heat insulation container characterized by using the laminated body of any one of Claims 1-9 for the container trunk | drum which comprises a container.

The invention according to claim 11 is:
A foamable heat-insulating coating coating solution consisting of an organic / inorganic hybrid composite or organic / inorganic powder mixture and a foaming agent is prepared on a base material or plastic base material and then applied and dried. Forming a gas barrier film formed by applying and drying a gas barrier film coating liquid comprising an organic / inorganic hybrid composite on the heat insulating film. It is the manufacturing method of the laminated body characterized.

The invention according to claim 12
The organic / inorganic hybrid composite constituting the heat insulating coating layer hydrolyzes an inorganic alkoxide mixture containing an alkoxide of an alkaline earth metal and / or an alkoxide of a metal other than an alkaline earth metal by a sol-gel method, It is a composite obtained by polycondensation, The manufacturing method of the laminated body of Claim 11 characterized by the above-mentioned.

The invention according to claim 13 is:
12. The method for producing a laminate according to claim 11, wherein the organic / inorganic powder mixture constituting the heat insulating coating layer comprises a polymer resin and an inorganic powder.

The invention according to claim 14 is:
The organic / inorganic hybrid composite composing the gas barrier coating layer is a polymer having an alkaline earth metal alkoxide and / or an inorganic alkoxide mixture containing a metal other than an alkaline earth metal and a hydrogen bond-forming group. 14. The production of a laminate according to any one of claims 11 to 13, wherein the laminate is a composite obtained by hydrolyzing the composition by a sol-gel method and polycondensing the resin. Is the method.

The invention according to claim 15 is:
In the laminated body in Claim 13,
The method for producing a laminate, wherein the polymer resin is an acrylic resin or an ethylene-vinyl acetate copolymer.

The invention according to claim 16 provides:
The laminate according to claim 13, wherein
In the method for producing a laminate, the inorganic powder is foamed silica particles obtained by firing a composite formed by hydrolyzing ethyl silicate alkoxysilane by a sol-gel method and polycondensation. is there.

The invention according to claim 17 provides:
The laminate according to claim 12 or 14,
The organic / inorganic hybrid composite is a composite obtained by hydrolyzing ethyl silicate alkoxysilane by a sol-gel method and polycondensing the composite.

The invention according to claim 18
In the laminated body in Claim 14,
The method for producing a laminate, wherein the polymer resin having a hydrogen bond-forming group is polyvinyl alcohol or an ethylene-vinyl alcohol copolymer.

The invention according to claim 19 is
The insulated container according to claim 10,
It is a manufacturing method of the heat insulation container characterized by performing a foaming process by heating a container trunk | drum at the temperature of 100 to 145 degreeC after a container shaping | molding.
<Action>
According to the present invention, an inorganic alkoxide mixture containing an alkoxide of an alkaline earth metal and / or an alkoxide of a metal other than an alkaline earth metal on a paper substrate or plastic substrate, for example, ethyl silicate alkoxysilane or the like is sol- A foamable heat-insulating coating layer comprising an organic / inorganic hybrid composite or polymer resin hydrolyzed by gel method and polycondensation, an organic / inorganic powder mixture comprising inorganic powder, and a foaming agent Further, as an inorganic alkoxide mixture containing an alkaline earth metal alkoxide and / or an alkoxide of a metal other than the alkaline earth metal on the heat insulating coating layer, for example, ethyl silicate alkoxysilane and polyvinyl alcohol Or ethylene-vinyl alcohol copolymer A composition comprising a polymer resin having an elementary bond-forming group is hydrolyzed by a sol-gel method, and a gas barrier coating layer comprising an organic / inorganic hybrid composite obtained by polycondensation is formed. Since it is a laminate, it has excellent heat insulating function of inorganic powder such as foamed silica particles contained in the heat insulating coating layer, and by applying foaming treatment with a foaming agent contained in the heat insulating coating layer, heat insulation The gas barrier coating layer provided on the coating layer prevents the foaming gas from leaking to the outside, and the foaming gas is contained in the heat insulating coating layer so that foaming is performed, so that the heat insulating property is further improved dramatically. And since the gas barrier coating layer has a certain degree of flexibility and strength in the foaming treatment, the coating layer foams uniformly by the foaming treatment, so there is little influence of stress on the ink, even after foaming. There can be obtained a laminate having excellent printing beauty without impairing the sharpness of the printed pattern applied to the surface, and a heat insulating container using the laminate.

  According to the present invention, a lightweight and inexpensive laminate that has an excellent heat insulation effect, excellent print cosmetics that do not impair the sharpness of a printed pattern applied to the surface, and that is easy to manufacture and easy to manufacture. The heat insulation container using a laminated body and those manufacturing methods can be provided.

  The laminate of the present invention and the heat insulating container using the laminate are suitably used for industrial uses such as heat insulating paper cups, heat insulating cardboards, heat insulating paper trays, food applications and transport materials, and further, building materials such as heat insulating wallpaper. Can also be used for applications.

  Hereinafter, a preferred embodiment of the present invention will be described with reference to the drawings.

  FIG. 1 is a cross-sectional view showing an example of the configuration of the laminate of the present invention. FIG. 2 is a cross-sectional view showing a configuration in which the foamed body shown in FIG. FIG. 3 is a cross-sectional view showing another example of the configuration of the laminate of the present invention.

  As an example of the laminate of the present invention, as shown in FIG. 1, an alkoxide of an alkaline earth metal and / or an alkoxide of a metal other than an alkaline earth metal is provided on a paper substrate or plastic substrate (1). An organic / inorganic powder mixture obtained by hydrolyzing an inorganic alkoxide mixture contained by a sol-gel method and polycondensating an organic / inorganic hybrid composite or polymer resin and an inorganic powder; A foamable heat insulating coating layer (2) comprising a foaming agent is formed, and an alkaline earth metal alkoxide and / or an alkoxide of a metal other than the alkaline earth metal is further formed on the heat insulating coating layer (2). Is obtained by hydrolyzing and polycondensing a composition comprising an inorganic alkoxide mixture containing hydrogen and a polymer resin having a hydrogen bond-forming group by a sol-gel method. A structure in which a printed pattern layer (4) is further provided on the surface of the laminate formed by forming a gas barrier coating layer (3) made of an inorganic hybrid composite, that is, on the gas barrier coating (3). It is a laminated body (10).

  FIG. 2 shows a heat insulating foaming agent (not shown) contained in two heat insulating coating layers of the laminate (10) as one embodiment of the present invention illustrated in FIG. It is the laminated body (20) in which the expandable foam coating layer (2 ') was formed.

As another example of the structure of the laminate of the present invention, as shown in FIG. 3, the paper substrate or plastic substrate (1) of the laminate (10) as one embodiment of the present invention illustrated in FIG. ) On which a thermoplastic resin layer (5) having heat sealing properties is provided. The thermoplastic resin layer (5) having heat sealability functions as an adhesive layer when forming a molded body such as a container.

  Organic / inorganic hybrid obtained by hydrolyzing and polycondensing an inorganic alkoxide mixture containing an alkoxide of an alkaline earth metal and / or an alkoxide of a metal other than an alkaline earth metal used in the present invention. The composite (porous polymer) can be either (1) hydrolyzed and polycondensed by a sol-gel method of a mixture of an alkoxide of an alkaline earth metal and an alkoxide of a metal other than an alkaline earth metal, or (2) inorganic It is an organic / inorganic hybrid composite (porous polymer) obtained by blending an alkaline earth metal with an alkoxide or a hydrolysis product thereof by a sol-gel method and polycondensing it.

(1) Alkaline earth metal alkoxide The alkaline earth metal alkoxide used in the present invention is represented by the general formula: M ¹ (OR) m (where M ¹ is selected from the group consisting of Mg, Ca, Sr and Ba). At least one element, R is an alkyl group, preferably a lower alkyl group having 1 to 4 carbon atoms, and m is an integer corresponding to the valence of M ¹ ). Of these, alkoxides of Mg and / or Ca are preferable. Specific examples thereof include Mg (OCH ₃ ) ₂ , Mg (OC ₂ H ₅ ) ₂ , Ca (OC ₂ H ₅ ) ₂ , Mg [Al (Oi-C ₃ H ₇ ) ₃ ] _{2 and the} like. It is done.

(2) Alkoxide of metal other than alkaline earth metal The alkoxide of metal other than alkaline earth metal used in the present invention has the general formula: M ² (OR) _m (where M ² is Li, Na, Cu, Zn , B, Al, Ga, Y, Si, Ge, Pb, P, Sb, Ta, W, La, Nd, Ni, Zr and Ti are at least one element, and R is an alkyl Group, preferably a lower alkyl group having 1 to 4 carbon atoms, and m is an integer corresponding to the valence of M.). Specific examples are listed below.

(I) Alkoxysilane When M is Si (valence: 4), it is represented by Si (OR) ₄ . Examples of such alkoxysilanes include Si (OCH ₃ ) ₄ and Si (OC ₂ H ₅ ) ₄ . Of these, Si (OC ₂ H ₅ ) ₄ is preferable.

(B) Aluminum alkoxide When M is Al (valence: 3), it is represented by Al (OR) ₃ . Examples of such aluminum alkoxide include Al (OCH ₃ ) ₃ , Al (OC ₂ H ₅ ) ₃ , Al (On-C ₃ H ₇ ) ₃ , Al (Oi-C ₃ H ₇ ) ₃ , al (OC ₄ H _{9) 3} and the like.

(C) Titanium alkoxide When M is Ti (valence: 4), it is represented by Ti (OR) ₄ . Examples of such titanium alkoxide include Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (OC ₃ H ₇ ) ₄ , Ti (OC ₄ H ₉ ) ₄ , Ti (Oi-C _3). H ₇ ) _{4 and the} like.

(D) Zirconium alkoxide When M is Zr (valence: 4), it is represented by Zr (OR) ₄ . Examples of such zirconium alkoxide include Zr (OCH ₃ ) ₄ , Zr (OC ₂ H ₅ ) ₄ , Zr (Oi-C ₃ H ₇ ) ₄ , Zr (Ot-C ₄ H ₉ ) ₄ , _{Zr (O-n-C 4} H 9) 4 , and the like. Of these, Zr (OC ₃ H ₇ ) ₄ and Zr (Ot-C ₄ H ₉ ) ₄ are preferable.

As (e) Other alkoxides other _{alkoxides, Fe (OC 2 H 5)} 3, V (O-i-C 3 H 7) 4, Sn (OC 2 H 5) 4, Sn (O-i-C 4 _{H 9) 4, Sn (O} -t-C 4 H 9) 4, Li (OC 2 H 5) 3,
Examples include Be (OC ₂ H ₅ ) ₃ , B (OC ₂ H ₅ ) ₃ , P (OC ₂ H ₅ ) ₃ , P (OCH ₃ ) _{3 and the} like. The Ni [Al (O-i- C 3 H 7) 4] 2 , and the like as a bimetallic alkoxide.

(3) Compounding Ratio The compounding ratio (A / B molar ratio) of the alkaline earth metal alkoxide A and the metal alkoxide B other than the alkaline earth metal is preferably 1/1 to 1/10.

(4) Inorganic alkoxide The inorganic alkoxide includes both the alkoxide of the alkaline earth metal and the alkoxide of a metal other than the alkaline earth metal. Therefore, this inorganic alkoxide has the general formula: M (OR) _m (where M is Li, Na, Cu, Mg, Ca, Sr, Ba, Zn, B, Al, Ga, Y, Si, Ge, Pb, P, It is at least one element selected from the group consisting of Sb, Ta, W, La, Nd, Ni, Zr and Ti, R is an alkyl group, and m is an integer corresponding to the valence of M. ).

  As the alkoxide containing an alkaline earth metal alkoxide and / or an alkoxide of a metal other than the alkaline earth metal used in the present invention, an alkoxysilane composed of ethyl silicate is particularly preferable.

(5) Hydrolysis of alkoxide An alkoxide of an alkaline earth metal and an alkoxide of a metal other than the alkaline earth metal are mixed with a solvent. The concentration of the alkoxide of the alkaline earth metal + the alkoxide of the metal other than the alkaline earth metal is preferably 300 to 500 g / liter. The hydrolysis temperature is preferably 20 to 85 ° C, more preferably 20 to 30 ° C.

(6) Solation When a sol-gel method catalyst is added to the hydrolyzed alkaline earth metal alkoxide + metal alkoxide other than the alkaline earth metal as necessary and stirred for 0.5 to 2 hours, Decomposition is completed, and the reaction solution becomes sol, precipitate, emulsion, and the like. Examples of the sol-gel method catalyst include the following acid catalysts and base catalysts, which are preferably used in combination.

(I) Acid catalyst An acid catalyst is used for the hydrolysis reaction of an alkoxide of an alkaline earth metal and an alkoxide of a metal other than the alkaline earth metal. When the reaction solution is vigorously stirred during the hydrolysis, carbon dioxide in the air is taken in to generate carbonic acid, which acts as an acid catalyst. Therefore, it is not necessary to add an acid catalyst.

  Acid catalysts include (1) mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, (2) anhydrous mineral acids such as hydrogen chloride gas, (3) tartaric acid, phthalic acid, maleic acid, dodecyl succinic acid, hexahydrophthal Acid, methyl nadic acid, pyromellitic acid, benzophenone tetracarboxylic acid, dichlorosuccinic acid, chlorendic acid, phthalic anhydride, maleic anhydride, dodecyl succinic anhydride, hexahydrophthalic anhydride, methyl nadic anhydride, pyrone anhydride Examples thereof include organic acids such as merit acid, benzophenone tetracarboxylic anhydride, dichlorosuccinic anhydride, and chlorendic anhydride, and anhydrides thereof.

  The amount of the acid catalyst used is preferably from 0.001 to 0.5 mol, particularly preferably from 0.005 to 0.3 mol, based on 1 mol of an alkoxide of an alkaline earth metal + alkoxide of a metal other than an alkaline earth metal. . If the amount is less than 0.001 mol, hydrolysis may be insufficient. If the amount exceeds 0.5 mol, the polycondensation reaction proceeds excessively, and the viscosity may increase excessively.

(B) Base catalyst The base catalyst is not only used as a catalyst for polycondensation reaction of alkoxides of alkaline earth metals and alkoxides of metals other than alkaline earth metals, but also its rapid crosslinking reaction and three-dimensional It acts as a catalyst for forming a network structure. As the base catalyst, either an inorganic base or an organic base may be used. Examples of the inorganic base include calcium hydroxide, potassium hydroxide, sodium hydroxide, lithium hydroxide, rubidium hydroxide, magnesium hydroxide, ammonia and the like. Examples of the organic base include primary amines, secondary amines, tertiary amines, polyamines, and amine complexes. Specific examples of organic bases include ethylenediamine, diethylenetriamine, ethanolamine, butylamine, triethylenetetramine, diethylaminopropylamine, N-aminoethylpiperazine, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine, tris. (Dimethylaminomethyl) phenol, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, polyamide resin, dicyandiamide, boron trifluoride / monoethylamine, menthanediamine, xylylenediamine, ethylmethylimidazole and the like.

  Of the basic catalysts, tertiary amines that are substantially insoluble in water and soluble in organic solvents (for example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine, etc.) and ammonia are more preferred, N, N-dimethylbenzylamine and ammonia are particularly preferred. In particular, when ammonia gas is used, a fine particle porous polymer can be obtained.

  The amount of the base catalyst used is preferably 0.002 to 1.5 mol with respect to 1 mol of the inorganic alkoxide (alkali earth metal alkoxide + alkali earth metal alkoxide). If it is less than 0.002 mol, the polycondensation reaction proceeds slowly, and if it exceeds 1.5 mol, the polycondensation reaction proceeds rapidly, so that the resulting porous polymer may be non-uniform. When a tertiary amine that is insoluble in water and soluble in an organic solvent is used as the base catalyst, the amount used is preferably 0.004 to 0.008 mol. In the case of other than tertiary amine, the amount is preferably 0.1 to 1.5 mol.

(7) Solvent As a hydrolysis solvent, a mixed solvent of water necessary for hydrolysis and an organic solvent soluble in water is used. Preferred organic solvents include methanol, ethanol, butanol, propanol, pentanol, hexanol, acetone, methyl ethyl ketone, and formamide.

  The amount of water used is 10 mol or less, preferably 1 to 10 mol, more preferably 2 to 8 mol, especially 1 mol relative to 1 mol of inorganic alkoxide (alkali earth metal alkoxide + alkali earth metal alkoxide). Preferably it is 3-7 mol. If the amount of water used is too small, hydrolysis of the alkoxide is slow and the condensation reaction is difficult to proceed. However, since hydrolysis proceeds gradually with moisture in the air, it is not always necessary to add water to the solvent. In particular, when using a highly hygroscopic alkoxide containing zirconium or the like, it is not necessary to add water. When the amount of water exceeds 10 moles, the acidic gas adsorption / decomposition characteristics of the resulting porous polymer are deteriorated.

(8) Polycondensation Various forms of porous polymers can be produced by gelling the sol, precipitate or emulsion (hereinafter simply referred to as sol or the like) of the hydrolysis product by polycondensation reaction. The gelation time can be freely adjusted in the range of several seconds to several hours depending on the amount of the base catalyst. In particular, it is preferable to increase the gelation time to several hours by adjusting the pH of the sol or the like to about 6 to 8 and reducing the amount of the base catalyst. The polycondensation temperature is preferably 20 to 85 ° C, more preferably 20 to 30 ° C.

(9) Drying The gel-like material is pulverized and dehydrated by heating at a temperature of 200 ° C. or lower, preferably 100 to 180 ° C., particularly 120 to 150 ° C. for 1 to 8 hours, to obtain a fine porous polymer. be able to. Moreover, it can also be set as a porous film by casting sol etc. and drying and removing a solvent.

  In addition to making the porous polymer fine particles, it can be attached to a substrate such as various plastic materials. In that case, a sol or the like is applied to the substrate and dried at a temperature of 200 ° C. or lower. In the case of a substrate that cannot keep up with the firing temperature, the firing step is omitted. In addition, when making a porous polymer adhere to base materials, such as a fiber material and a plastic material, it is preferable to add a silane coupling agent to a reaction liquid.

(10) Firing In order to maximize the function of the porous polymer, it is preferable to perform firing at a temperature of 550 ° C. or lower for 0.5 to 4 hours after drying. Specifically, 350 ° C. is preferable. A more preferable firing temperature is 400 to 500 ° C.

  Hereinafter, the laminate of the present invention will be described in the case of using ethyl silicate alkoxysilane as an inorganic alkoxide as an example.

  As illustrated in FIG. 1, the laminate of the present invention is obtained by hydrolyzing ethyl silicate alkoxysilane by a sol-gel method on a paper substrate or plastic substrate (1) and polycondensing it. Forming a foamable heat-insulating coating layer (2) comprising an inorganic hybrid composite, or an organic / inorganic powder mixture obtained by mixing a polymer resin and inorganic powder, and a foaming agent; Organic-inorganic hybrid composite obtained by hydrolyzing and polycondensing a composition comprising ethyl silicate alkoxysilane and a polymer resin having a hydrogen bond-forming group on the conductive coating layer (2) by a sol-gel method A laminate (1) in which a printed picture layer (4) is further provided on the surface of the laminate constituted by forming a gas barrier coating layer (3) comprising a product, that is, on the gas barrier coating (3). ) It is.

  As the polymer resin constituting the heat insulating coating layer (2), it is preferable to use an acrylic resin or an ethylene-vinyl acetate copolymer.

  The inorganic powder constituting the heat insulating coating layer (2) is not particularly limited as long as it is an inorganic powder excellent in heat insulating properties. In particular, the ethyl silicate alkoxysilane is hydrolyzed by a sol-gel method to form a polycondensation process. Foamed silica particles obtained by subjecting an organic / inorganic hybrid composite formed by bubbling an inert gas to a baking treatment in FIG. Other inorganic powders include powders such as sodium silicate, mullite, quartz, cristobalite, cortilite, and zircon.

  Moreover, as a foaming agent contained in the heat insulating coating layer (2), dinitrosopentamethylenetetramine (DPT), azodicarbonamide (ADCA), p-, which are generally used from the viewpoint of hygiene and ease of handling, are used. Examples thereof include a simple substance such as toluenesulfonyl hydrazide (TSH), hydrazodicarbonamide (HDCA), sodium hydrogen carbonate, 4,4 oxybisbenzenesulfonyl hydrazide (HDCA), or a mixture of two or more thereof.

  The foamable heat-insulating coating layer (2) obtained above has an excellent heat-insulating function such as foamed silica particles and a foaming treatment with a foaming agent contained in the heat-insulating coating layer (2). The gas barrier coating layer (3) provided on the layer (2) prevents the foaming gas from leaking to the outside, and the foaming gas is contained in the heat insulating coating layer (2) to cause foaming. Further improved dramatically.

  On the other hand, the polymer resin having a hydrogen bond-forming group constituting the gas barrier coating layer (3) used in the present invention includes a polymer having a hydroxyl group and a derivative thereof (polyvinyl alcohol, polyvinyl acetal, ethylene-vinyl alcohol). Polymers, phenol resins, methylol melamine, etc. and their derivatives); polymers having carboxyl groups and their derivatives (single or co-polymer containing units of polymerizable unsaturated acids such as poly (meth) acrylic acid, maleic anhydride, itaconic acid). Polymers and esterified products of these polymers (vinyl esters such as vinyl acetate, homo- or copolymers containing units such as (meth) acrylic acid esters such as methyl methacrylate), etc.); polymers having ether bonds (poly Alkylene oxide, polyoxyalkylene glycol, A polymer having an amide bond (> N (COR) -bond (wherein R represents a hydrogen atom, an alkyl group which may have a substituent, or a substituent). N-acylates of polyoxazolines and polyalkylenimines having a good aryl group);> polyvinylpyrrolidone and derivatives thereof having NC (O) -bonds; polyurethanes having urethane bonds; polymers having urea bonds, etc. be able to.

  Among the polymer resins having a hydrogen bond-forming group, it is particularly preferable to use polyvinyl alcohol or an ethylene-vinyl alcohol copolymer in the present invention.

  For example, ethyl silicate alkoxysilane and polyvinyl alcohol are used as the gas barrier coating obtained by hydrolyzing and polycondensing ethyl silicate alkoxysilane and a polymer resin having a hydrogen bond-forming group by a sol-gel method. Taking the case as an example, the polycondensation mechanism is considered as follows. That is, first, the alkoxysilane is hydrolyzed by the acid acting as a hydrolysis catalyst. Next, protons are taken from the hydroxyl groups in the hydrolysis products by the action of the sol-gel method catalyst, the hydrolysis products are dehydrated and polycondensed with each other, and the hydroxyl groups of the hydrolysis products also dehydrate with the hydroxyl groups of polyvinyl alcohol. , A polycondensate having a three-dimensional network structure in which an inorganic part composed of a bond of Si—O—Si and polyvinyl alcohol are bonded to each other is generated.

  The paper base material as the base material (1) used in the present invention is paper made from fibers. It does not matter whether the fiber is a natural fiber or a synthetic fiber. Specific examples include liner base paper, art paper, and coated paper. Moreover, the base paper may be a corrugated cardboard in which a liner base paper is bonded to at least one of the front and back surfaces of the core paper formed in a corrugated shape. By using corrugated base paper as the base paper, air exists in the space formed between the corrugated core paper and the liner base paper to be bonded, and the heat insulation effect of the air can also be obtained. It becomes paper. Here, the corrugated cardboard may be manufactured by a known corrugating machine or the like.

Further, the plastic substrate as the substrate (1) used in the present invention is not particularly limited, but polyethylene terephthalate (PET), polyethylene terephthalate copolymer polyester film, polyethylene naphthalate (PEN), and the like. Polyolefin film such as polyester film, polyethylene film, polypropylene film, ethylene-propylene copolymer film, polystyrene film, nylon 66 film, nylon 6 film, polyamide film such as metaxylidenediamine copolymer polyamide film, polycarbonate film, poly Acrylic nitrile film,
Examples thereof include a polyimide film, a polyamideimide film, a polyvinyl alcohol film, an ethylene-vinyl alcohol copolymer film, a polyphenylene film, a polysulfone film, and a polyphenylene sulfide film. These may be stretched or unstretched as long as they have mechanical strength and dimensional stability. In particular, a polyethylene terephthalate (PET) film arbitrarily stretched in the biaxial direction from the viewpoint of heat resistance or the like is preferably used.

  The printed pattern layer (4) of the present invention is provided on the gas barrier coating layer (3) constituting the laminate. This printed pattern layer (4) is formed for practical use as a package or the like. For example, various pigments, extender pigments and additives such as plasticizers, desiccants, stabilizers, etc. are added to conventionally used ink binder resins such as urethane, acrylic, nitrocellulose, and rubber. It is a layer composed of ink. Among these, urethane and acrylic ink binder resins are preferably used as the ink binder resin because the ink film is relatively soft and easy to handle. Characters, pictures, and the like are formed by this printing. As a forming method, for example, a known printing method such as an offset printing method, a gravure printing method, a silk screen printing method, or a known coating method such as a roll coating, a knife edge coating, or a gravure coating can be used. The dry film thickness (solid content) of the printed pattern layer may be 0.1 to 2.0 μm.

  One or more layers of thermoplastic resin can be appropriately provided on at least one surface of the laminate of the present invention obtained above as necessary. Examples of the resin film that forms the thermoplastic resin layer include, but are not limited to, polyester films such as polyethylene terephthalate (PET) and polyethylene terephthalate copolymer polyester film and polyethylene naphthalate (PEN), polyethylene film Polyolefin film such as polypropylene film and ethylene-propylene copolymer film, Polystyrene film such as polystyrene film, nylon 66 film, nylon 6 film, metaxylidenediamine copolymer polyamide film, polycarbonate film, polyacrylonitrile film, polyimide film Polyamideimide film, polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, Phenylene film, polysulfone film, polyphenylene sulfide head films. These may be stretched or unstretched as long as they have mechanical strength and dimensional stability. In particular, a polyethylene terephthalate (PET) film arbitrarily stretched in the biaxial direction from the viewpoint of heat resistance or the like is preferably used.

Moreover, the heat seal resin layer (5) functioning as an adhesive layer when forming the molded body such as a container using the laminate of the present invention can be provided on the side that becomes the inner surface of the molded body. The heat seal resin constituting the heat seal resin layer may be a thermoplastic resin that can be extruded and can be melted by heat and fused to each other. Density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene -Polyolefin resin such as methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene or polypropylene, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc. Acid-modified polyolefin system modified with unsaturated carboxylic acid such as Fat, polyvinyl acetate resins, polyester resins, polystyrene resins, one or resin comprising more resins other like can be used. In the present invention, when two layers of the thermoplastic resin layer are formed using the resin as described above, it can be formed by combining the same kind of resins or different kinds of resins. For example, it may be formed using the same kind of polyethylene resin, or different kinds of polyethylene resin and ethylene-vinyl acetate copolymer or polyethylene resin and ethylene-methacrylic acid copolymer are used. It can also be formed.

  Among the above resins, it is particularly preferable to use linear (linear) low density polyethylene. The above-mentioned linear low density polyethylene has the advantage of improving impact resistance with less propagation of breakage because it has adhesiveness, and since the inner layer is always in contact with the contents, It is also effective for preventing deterioration of environmental stress cracking properties.

  Next, the manufacturing method of the laminated body of this invention at the time of using an ethylsilicate alkoxysilane as an example as an inorganic alkoxide is demonstrated.

  The method for producing a laminate of the present invention comprises an organic / inorganic hybrid composite obtained by hydrolyzing ethyl silicate alkoxysilane by a sol-gel method and polycondensation on a paper substrate or plastic substrate (1), Alternatively, an insulative coating layer that can be foamed is prepared by mixing an organic / inorganic powder mixture obtained by mixing a polymer resin and inorganic powder and a foaming agent, and applying and drying the coating layer ( 2), and a composition comprising ethylsilicatealkoxysilane and a polymer resin having a hydrogen bond-forming group is hydrolyzed on the heat insulating coating layer (2) by a sol-gel method. A method for producing a laminate comprising preparing a gas barrier coating layer (3) by preparing a gas barrier coating solution comprising an organic / inorganic hybrid composite obtained by condensation, and applying and drying the coating solution. .

  Hereinafter, an example of adjustment of the above-described heat insulating coating liquid will be described.

  For example, the heat insulating coating liquid is adjusted to a viscosity of 200 cps or less by dissolving an acrylic resin or ethylene-vinyl acetate copolymer in water while stirring. The resin blending amount is preferably 30 to 80 parts by weight with respect to 100 parts by weight of the aqueous solution coating solution. When the resin amount is more than 80 parts by weight, the foaming property is excellent, but the coating is easily cracked or peeled off.

  Examples of the blowing agent include dinitrosopentamethylenetetramine (DPT), azodicarbonamide (ADCA), p-toluenesulfonyl hydrazide (TSH), hydrazodicarbonamide (HDCA), sodium hydrogen carbonate, 4,4 oxybisbenzenesulfonyl hydrazide. A foaming agent selected from a single substance such as (HDCA) or a mixture of two or more thereof is appropriately considered in the range of 0.1 to 1.0 part by weight with respect to 100 parts by weight of the aqueous coating solution. To select.

  The inorganic powder is not particularly limited as long as it has a heat insulating function, but ethyl silicate alkoxysilane is a sol as an inorganic alkoxide mixture containing an alkoxide of an alkaline earth metal and / or an alkoxide of a metal other than an alkaline earth metal. -Foamed silica particles obtained by baking an organic / inorganic hybrid composite formed by hydrolyzing by a gel method and bubbling an inert gas in the polycondensation process are preferably used. Other inorganic powders include inorganic powders such as sodium silicate, mullite, quartz, cristobalite, cortilite, and zircon. For example, the above-mentioned expanded silica particles are dispersed and mixed in the range of 10 to 20 parts by weight, preferably 10 parts by weight, with respect to 100 parts by weight of the aqueous coating solution. When the mixing amount of the expanded silica particles is more than 20 parts by weight, cracks and peeling easily occur.

In addition, according to the heat insulation requested | required, said foamed silica particle can also be remove | excluded. That is, as an inorganic alkoxide mixture containing an alkoxide of an alkaline earth metal and / or an alkoxide of a metal other than an alkaline earth metal, an organic alkoxide obtained by hydrolyzing and polycondensing ethyl silicate alkoxysilane by a sol-gel method It can also be set as the heat insulation film coating liquid which consists of an inorganic hybrid composite (porous polymer), said acrylic resin or ethylene-vinyl acetate copolymer, and a foaming agent.

  The heat-insulating film coating solution prepared as described above is applied onto a paper substrate or plastic substrate and dried by heating at a temperature of 100 ° C. for 60 seconds to form a heat-insulating film having a film thickness in the range of 50 to 100 μm. Form.

  The above heat-insulating coating layer can be formed by applying the coating solution prepared as described above by dip coating, flow coating, curtain coating, spin coating, spray coating, bar coating or the like.

  Next, an example of a gas barrier film coating solution will be described.

  Solvent organic / inorganic hybrid composition using polyvinyl alcohol or ethylene-vinyl alcohol copolymer as polymer resin having ethyl silicate alkoxysilane and hydrogen bond forming group as inorganic alkoxide as gas barrier coating liquid. -A gas barrier film coating solution comprising an organic / inorganic hybrid composite (composite polymer) obtained by hydrolysis and polycondensation by a gel method is prepared.

  First, an ethyl silicate alkoxysilane hydrolyzate is prepared by dissolving ethyl silicate in an organic solvent and adding water and a catalyst to prepare the hydrolyzate. And the gas barrier film coating liquid is prepared by mixing polyvinyl alcohol or ethylene-vinyl alcohol copolymer in solution with the hydrolyzed liquid. Ethyl silicate, polyvinyl alcohol or ethylene-vinyl alcohol copolymer, sol-gel method catalyst, acid, water, and organic solvent are mixed and the polycondensation reaction gradually proceeds in the coating solution.

  The blending amount of ethyl silicate is preferably in the range of 10 to 30 parts by weight with respect to 100 parts by weight of the gas barrier coating solution.

  Examples of the organic solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol and the like. The type of the organic solvent is appropriately selected, and isopropyl alcohol is particularly preferable. The blending amount of the organic solvent such as isopropyl alcohol is preferably in the range of 30 to 50 parts by weight with respect to 100 parts by weight of the total gas barrier coating liquid.

  The added amount of water may be added in the range of 30 to 50 parts by weight with respect to 100 parts by weight of the total gas barrier coating liquid. At water additions within this range, ethyl silicate becomes a substantially linear and amorphous polymer. Furthermore, polar groups (OH groups) are partially present in the polymer molecule obtained, and the molecular cohesive energy is high. When the amount of water added exceeds 50 parts by weight, the polymer obtained from ethyl silicate becomes spherical particles, and the spherical particles are three-dimensionally cross-linked to become a low-density porous polymer. The gas barrier property cannot be improved. On the other hand, when the amount of water added is less than 30 parts by weight, the hydrolysis reaction hardly proceeds.

  The acid is used as a hydrolysis catalyst such as ethyl silicate. As the acid, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid and organic acids such as acetic acid and tartaric acid are preferable. The amount of acid used may be in the range of 0.1 parts by weight with respect to 100 parts by weight of the total gas barrier coating liquid.

  The concentration of the polyvinyl alcohol or ethylene-vinyl alcohol copolymer that has been dissolved in advance is preferably 5%.

  5% polyvinyl alcohol or ethylene-vinyl alcohol copolymer is mixed with the ethyl silicate hydrolyzate obtained above. The mixing ratio (ethyl silicate hydrolyzate: polyvinyl alcohol or ethylene-vinyl alcohol copolymer solution) is preferably 1: 1. If the ethyl silicate hydrolyzate has a mixing ratio larger than twice that of the polyvinyl alcohol or ethylene-vinyl alcohol copolymer solution, the hardness increases and a foaming effect cannot be obtained sufficiently. Moreover, when the mixing amount of the ethylsilicate hydrolyzate is smaller than 1: 1, the water resistance is lowered.

  In the gas barrier coating, since the silicon in the composite polymer layer is bonded to atoms of other metals through oxygen, the adhesive strength is sufficiently large and there is no fear of peeling. The thickness of the gas barrier coating is about 1 to 10 μm, preferably about 1 to 5 μm.

  The gas barrier coating layer can be formed by applying the coating solution prepared as described above by dip coating, flow coating, curtain coating, spin coating, spray coating, bar coating or the like.

  Finally, when the gas barrier film coated with the coating liquid is heated at 80 ° C. to 100 ° C. for 30 seconds to 60 seconds, a laminate firmly bonded to the heat insulating film layer is obtained.

  In addition, it can be set as the coating liquid which can be hardened | cured by ionizing radiation by adding a commercially available photoinitiator to a coating liquid. Moreover, it can be set as the thermosetting coating liquid by adding a thermal reaction initiator (For example, dibenzoyl peroxide, tert-butyl perbenzoate, azobisisobutyronitrile, etc.) to a coating liquid. Furthermore, an initiator for initiating an ionic polymerization reaction may be added to the coating solution. When such a reaction initiator is added, the addition amount is preferably about 0.5 to 2% by weight.

  Using the laminate of the present invention obtained above, it can be suitably used for industrial applications such as heat insulating paper cups, heat insulating cardboards, paper trays, food applications and transport materials, and can also be used for wallpaper.

  For example, as a heat insulating cup, as shown in FIG. 4, at least a body part of a paper cup having a mouth part (43) having a body part (41) and a bottom part (42) and having a peripheral edge of the opening part curled outward is formed. An example of the heat insulation cup (40) which used the laminated body of this invention for the trunk | drum member is shown. FIG. 5 shows an enlarged cross-sectional view of the region A of the trunk member. As shown in FIG. 5, the body member has a printed pattern layer (4) / gas barrier coating layer (3) / heat insulating coating layer (2) / paper substrate layer (1) / PET film layer (6) from the surface side. ) / An example in which the sealant layer (5) is composed of a laminated body (41) sequentially laminated.

  By subjecting the heat insulating cup (40) to a heat foaming treatment, a foaming agent (not shown) contained in the heat insulating coating layer (2) of the heat insulating cup (40) is foamed, and a part of the body member of FIG. As shown in the enlarged cross section of the region A, the heat insulating film layer (2) forms the foam heat insulating film layer (2 '), whereby the heat insulating property is further improved.

The heating and foaming treatment conditions may be about 140 ° C. for about 3 minutes, depending on the type of foaming agent used. The heat insulating coating layer (2) having a thickness in the range of 50 to 100 μm foams and expands in the range of 100 to 400 μm. By performing foaming treatment with the foaming agent contained in the heat insulating coating layer, the gas barrier coating layer provided on the heat insulating coating layer is prevented from leaking the foaming gas to the outside, and the foaming gas is contained in the heat insulating coating layer. Since the foam is contained and foamed, the heat insulation is further improved dramatically. In the foaming process, the gas barrier coating layer (3) has a certain degree of flexibility and strength, so that the coating layer foams uniformly by the foaming process, so that there is little influence of stress on the ink, and after foaming. Even if it exists, the heat insulation container excellent in the printing cosmetics which does not impair the clearness of the printed pattern (4) given to the surface is obtained.

  Further, as shown in FIG. 7, half of the thickness of the laminated sheet (41) is removed from the front end by a predetermined length inside the joint (B) of the body (41) of the paper cup shown in FIG. The paper end face protection (44) is applied so that the other half is folded back so that the removal side is inside, so that the contents contained in the paper end face are not directly touched. Further improve.

  Specific examples of the present invention will be described below.

  First, foamed silica particles were prepared in advance as an inorganic powder by the following method.

  Tetraethoxysilane tetramer (ethyl silicate 40, manufactured by Colcoat Co.) and ethanol were mixed and stirred at 25 ° C. for 3 minutes, 2N hydrochloric acid and water were added, and the mixture was stirred at 25 ° C. for 1 hour. Further, N, N dimethylbenzylamine dispersed in ethanol was added to this solution, gelled while bubbling an inert gas, and allowed to stand at 50 ° C. for 1 hour to obtain a white solid. The alcohol was removed, and the solid was dried, coarsely pulverized and pulverized. The powder was heated and dried at 150 ° C. for 1 day, and then baked at 500 ° C. for 2 hours to obtain powdered expanded silica particles.

  Based on the formulation a shown below, the foamed silica particles obtained above are further added to a paste-like mixture obtained by mixing a foaming agent with an acrylic resin while adding water, and the mixture is stirred and mixed. A heat insulating film coating solution was obtained. This coating liquid was applied with an applicator using polyethylene laminated paper as a base material, and dried by heating at a temperature of 100 ° C. for 60 seconds to form a heat-insulating coating layer having a white gloss of 100 μm.

  Next, ethyl silicate 40 (colcoat) based on the following blending c prepared in advance in a PVA solution obtained by dissolving polyvinyl alcohol (PVA) in a mixed solvent of isopropyl alcohol and water based on the blending b shown below. A hydrolyzate consisting of isopropyl alcohol, hydrochloric acid (HCl) and water was added and stirred and mixed to prepare a colorless and transparent gas barrier coating solution.

  The gas barrier film coating solution obtained above is already applied onto the heat insulating film layer in which the heat insulating film layer is formed on the polyethylene laminated paper base material, and is heated at a temperature of 100 ° C. in a blow drying oven. Heat treatment was performed for 2 seconds to form a colorless transparent and glossy gas barrier coating film having a coating thickness of 2 μm to obtain a laminate of the present invention.

  The laminated body obtained above was molded into a cup, subjected to a heat foaming treatment at a temperature of 140 ° C. for 3 minutes, and the heat insulating coating layer was foamed to produce a heat insulating cup of the present invention.

  As a result of pouring hot water of 95 ° C. into the heat insulation cup of the present invention obtained above and the heat insulation uncoated cup as a comparison, the outer surface temperature of the heat insulation cup of the present invention was measured as a result of measuring the container outer surface temperature after 3 minutes. While it was 69.9 degreeC, the heat insulation uncoated cup outer surface temperature as a comparison was 80 degreeC.

<Combination ratio>
Formulation a
Acrylic resin 60.0 parts by weight Water 29.0 parts by weight Expanded silica particles 10.0 parts by weight
Foaming agent 1.0 part by weight Total 100.00 parts by weight Formulation b
Polyvinyl alcohol (PVA) 2.50 parts by weight Water 44.96 parts by weight Isopropyl alcohol 20.11 parts by weight Formulation c
Ethyl silicate 40 (manufactured by Colcoat Co.) 6.26 parts by weight Isopropyl alcohol 12.02 parts by weight Hydrochloric acid (HCl) 0.01 parts by weight
Water 14.14 parts by weight Total 100.00 parts by weight

  According to the mixing ratio shown below, the laminate and the heat insulating cup of the present invention were obtained in the same manner as in Example 1 except that the acrylic resin was changed to an ethylene-vinyl acetate copolymer in the mixing a.

  As a result of pouring hot water of 95 ° C. into the heat insulation cup of the present invention obtained above and the heat insulation uncoated cup as a comparison, the outer surface temperature of the heat insulation cup of the present invention was measured as a result of measuring the container outer surface temperature after 3 minutes. While it was 71.7 degreeC, the heat insulation uncoated cup outer surface temperature as a comparison was 80 degreeC.

<Combination ratio>
Formulation a
Ethylene-vinyl acetate copolymer 60.0 parts by weight Water 29.0 parts by weight Expanded silica particles 10.0 parts by weight
Foaming agent 1.0 part by weight Total 100.00 parts by weight Formulation b
Polyvinyl alcohol (PVA) 2.50 parts by weight Water 44.96 parts by weight Isopropyl alcohol 20.11 parts by weight Formulation c
Ethyl silicate 40 (manufactured by Colcoat Co.) 6.26 parts by weight Isopropyl alcohol 12.02 parts by weight Hydrochloric acid (HCl) 0.01 parts by weight
Water 14.14 parts by weight Total 100.00 parts by weight

  According to the blending ratio shown below, the laminate and the heat insulating cup of the present invention were obtained in the same manner as in Example 1 except that the blending ratio of the acrylic resin in blending a was changed from 60% by weight to 80% by weight.

<Combination ratio>
Formulation a
Acrylic resin 80.0 parts by weight Water 29.0 parts by weight
Foaming agent 1.0 part by weight Total 100.00 parts by weight Formulation b
Polyvinyl alcohol (PVA) 2.50 parts by weight Water 44.96 parts by weight Isopropyl alcohol 20.11 parts by weight Formulation c
Ethyl silicate 40 (manufactured by Colcoat Co.) 6.26 parts by weight Isopropyl alcohol 12.02 parts by weight Hydrochloric acid (HCl) 0.01 parts by weight
Water 14.14 parts by weight Total 100.00 parts by weight 95 ° C. hot water was poured into the heat-insulated cup of the present invention obtained above and a heat-insulated uncoated cup as a comparison, and the outer surface temperature of the container after 3 minutes was measured. As a result, the outer surface temperature of the heat insulation cup of the present invention was 71.0 ° C, whereas the heat insulation uncoated cup outer surface temperature as a comparison was 80 ° C.

  As a comparative example of the present invention, only a heat insulating film composed of the blend a of Example 1 was formed in the same manner as in Example 1, and a laminate without forming a gas barrier film was prepared.

  As a result of pouring hot water of 95 ° C. into the heat insulation cup obtained above and the heat insulation uncoated cup as a comparison, the outer surface temperature of the container after 3 minutes was measured. As a result, the outer surface temperature of the heat insulation cup of the present invention was 75.1. In contrast, the outer surface temperature of the heat-insulated uncoated cup as a comparison was 80 ° C.

  As a result of Examples 1-4, the heat insulation cup using the laminated body of the present invention has a cup outer surface temperature difference of 5 ° C. or more with a conventional heat insulation uncoated cup, and is excellent in heat insulation effect. It was also confirmed that even after the foaming treatment, the printing beauty of deteriorating the sharpness of the printed pattern applied to the cup surface is excellent. The laminate of the present invention and the heat insulating container using the laminate are suitably used for industrial uses such as heat insulating paper cups, heat insulating cardboards, heat insulating paper trays, food applications and transport materials, and further, building materials such as heat insulating wallpaper. Can also be used for applications.

It is sectional drawing which shows an example of a structure of the laminated body of this invention. It is sectional drawing which shows the structure of the laminated body after performing the heat foaming process to the laminated body of this invention. It is sectional drawing which shows the other example of a structure of the laminated body of this invention. It is a front view of the heat insulation cup which showed the partial cross section of the cup main body using the laminated body of this invention. It is the expanded sectional view which expanded and showed the cup trunk | drum (FIG. 4 area | region A) of the heat insulation cup shown in FIG. It is the expanded sectional view which expanded and showed the cup trunk | drum (FIG. 4 area | region A) after performing the heat foaming process to the heat insulation cup shown in FIG. It is explanatory drawing which expanded and showed the junction part (FIG. 4B area | region) of the heat insulation cup shown in FIG.

Explanation of symbols

10, 20, 30 ... Laminate 1 ... Paper base material layer (or plastic base material layer)
2 ... heat insulating coating layer 2 '... heat insulating foam coating layer 3 ... gas barrier coating layer 4 ... printed pattern layer 5 ... sealant layer 6 ... thermoplastic resin layer 40 ...・ Insulating cup 41 ... trunk 42 ... bottom 43 ... mouth edge 44 ... end face protection

Claims (19)

  A foamable heat-insulating coating layer composed of an organic / inorganic hybrid composite or organic / inorganic powder mixture and a foaming agent is formed on a paper substrate or plastic substrate, and on the heat-insulating coating layer, A laminate comprising a gas barrier coating layer made of an organic / inorganic hybrid composite.   The organic / inorganic hybrid composite constituting the heat insulating coating layer hydrolyzes an inorganic alkoxide mixture containing an alkoxide of an alkaline earth metal and / or an alkoxide of a metal other than an alkaline earth metal by a sol-gel method, The laminate according to claim 1, which is a composite obtained by polycondensation.   The laminate according to claim 1, wherein the organic / inorganic powder mixture constituting the heat insulating coating layer is composed of a polymer resin and an inorganic powder.   The organic / inorganic hybrid composite composing the gas barrier coating layer is a polymer having an alkaline earth metal alkoxide and / or an inorganic alkoxide mixture containing a metal other than an alkaline earth metal and a hydrogen bond-forming group. The laminate according to any one of claims 1 to 3, which is a composite comprising a resin, obtained by hydrolyzing and polycondensing the composition by a sol-gel method. In the laminate according to claim 3,
The laminated body, wherein the polymer resin is an acrylic resin or an ethylene-vinyl acetate copolymer. In the laminate according to claim 3,
A laminate in which the inorganic powder is foamed silica particles obtained by firing a composite formed by hydrolyzing ethyl silicate alkoxysilane by a sol-gel method and polycondensation. The laminate according to claim 2 or 4,
A laminate in which the organic / inorganic hybrid composite is a composite obtained by hydrolyzing and polycondensing ethylsilicate alkoxysilane by a sol-gel method. In the laminated body in Claim 4,
A laminate comprising the resin having a hydrogen bond-forming group being polyvinyl alcohol or an ethylene-vinyl alcohol copolymer.   A laminate comprising a printed pattern layer provided on the gas barrier coating layer of the laminate according to any one of claims 1 to 8.   The heat insulation container characterized by using the laminated body of any one of Claims 1-9 for the container trunk | drum which comprises a container.   A foamable heat-insulating coating coating solution consisting of an organic / inorganic hybrid composite or organic / inorganic powder mixture and a foaming agent is prepared on a base material or plastic base material and then applied and dried. Forming a gas barrier film formed by applying and drying a gas barrier film coating liquid comprising an organic / inorganic hybrid composite on the heat insulating film. The manufacturing method of the laminated body characterized.   The organic / inorganic hybrid composite constituting the heat insulating coating layer hydrolyzes an inorganic alkoxide mixture containing an alkoxide of an alkaline earth metal and / or an alkoxide of a metal other than an alkaline earth metal by a sol-gel method, It is a composite obtained by polycondensation, The manufacturing method of the laminated body of Claim 11 characterized by the above-mentioned.   The method for producing a laminate according to claim 11, wherein the organic / inorganic powder mixture constituting the heat insulating coating layer comprises a polymer resin and an inorganic powder.   The organic / inorganic hybrid composite composing the gas barrier coating layer is a polymer having an alkaline earth metal alkoxide and / or an inorganic alkoxide mixture containing a metal other than an alkaline earth metal and a hydrogen bond-forming group. 14. The production of a laminate according to any one of claims 11 to 13, wherein the laminate is a composite obtained by hydrolyzing the composition by a sol-gel method and polycondensing the resin. Method. In the laminated body in Claim 13,
The method for producing a laminate, wherein the polymer resin is an acrylic resin or an ethylene-vinyl acetate copolymer. The laminate according to claim 13, wherein
A method for producing a laminate, wherein the inorganic powder is foamed silica particles obtained by firing a composite formed by hydrolyzing ethyl silicate alkoxysilane by a sol-gel method and polycondensation. The laminate according to claim 12 or 14,
A method for producing a laminate, wherein the organic / inorganic hybrid composite is a composite obtained by hydrolyzing ethyl silicate alkoxysilane by a sol-gel method and polycondensing. In the laminated body in Claim 14,
The method for producing a laminate, wherein the resin having a hydrogen bond-forming group is polyvinyl alcohol or an ethylene-vinyl alcohol copolymer. The insulated container according to claim 10,
A method for producing a heat-insulating container, wherein after the container is molded, a foaming treatment is performed by heating the container body at a temperature of 100 ° C or higher and 145 ° C or lower.

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