JPH0414623B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a composite heat insulating material used as a lining material for the main body or door of a refrigerator. The composite heat insulating material of the present invention is a heat insulating material having a structure in which urethane foam and a sheet of polyolefin resin or styrene resin are firmly adhered. [Conventional technology] The main body and doors of refrigerators are made of baked-on stainless steel or steel plates, and are coated with acrylonitrile-butadiene-styrene copolymer, which is a styrene resin, to prevent rust on the structural base material (outer frame) and to form shelves. It is equipped with a lining material obtained by vacuum forming, pressure forming, or forming using a combination of vacuum and pressure forming (hereinafter, these forming methods are collectively referred to as differential pressure forming) from a composite (commonly known as "ABS") sheet. . Furthermore, attempts have been made to use polypropylene lining materials with excellent surface gloss and low water absorption in place of ABS lining materials. In order to improve the heat insulation properties of refrigerators, it has been proposed to interpose urethane foam between the baking-painted stainless steel plate, which is the structural base material of the refrigerator, and the lining material, but it is difficult to obtain such a laminated structure. When a polyolefin resin sheet is used as the lining and exterior material, it is necessary to strengthen the adhesion between the polyolefin resin sheet and the urethane foam, which is a heat insulating material. For this purpose, the interior and exterior materials, which have been differential pressure molded in advance, and the urethane foam are laminated using liquid acrylic adhesive or epoxy adhesive, and then this laminated material is baked with adhesive applied to the inside. This is done by inserting and crimping the coated stainless steel into a structural base material (formwork), but a method that involves multiple steps would be expensive. Therefore, as shown in FIG.
It is preferable to use an on-site construction method in which a multi-layered structure in which the formwork 1, the urethane foam 4' and the lining material 2 are integrated is manufactured by injecting the foam, followed by foaming and curing. Furthermore, it is possible to apply an organic solvent-based adhesive to the polyolefin resin sheet in advance, let it dry, and then bond it to the urethane foam, which is an insulating material. Unfavorable for work environment. Furthermore, before differential pressure molding a polyolefin sheet, it is necessary to wipe off dust adhering to the surface of the sheet with a cloth or the like. As a way to solve this,
This problem can be solved by kneading an antistatic agent into the resin of the sheet material and using a sheet made of this, but the method of kneading the antistatic agent into the resin,
The antistatic function cannot be imparted to the sheet unless the sheet is stored for 30 to 50 days after forming the sheet before the antistatic function is imparted to the surface of the sheet.
On the other hand, it is necessary to take care to ensure that the sheet storage period is not affected by dust, which is not a good idea. The present inventors have studied various coating-type adhesive compositions that satisfy the required performance when manufacturing laminated structure insulation materials of urethane foam and ABS or urethane foam and polypropylene by on-site construction methods, and first We provided a composite heat insulating material with a structure in which a molded product of polyolefin resin or styrene resin and urethane foam were laminated with an adhesive containing the following components (A) and (B) (Japanese Patent Application No. 59-3800) issue). Adhesive composition: (A) Water-soluble or water-dispersible carboxyl group-containing polyolefin polymer (including neutralized products)
20-100% by weight (B) A water-soluble polymer consisting of an amphoteric compound obtained by modifying the tertiary nitrogen atom of a polymer consisting of the following components (a) to (c) with an amphoteric agent and having antistatic properties 80-0% by weight 20-40% by weight (c) Other hydrophobic vinyl monomers 0 to 20% by weight [However, in each formula, R ¹ is H or CH ₃ , R ² and R ³ are each an alkyl group having 1 to 2 carbon atoms, R ⁵
is an alkyl group having 1 to 18 carbon atoms, and A is an alkyl group having 2 to 6 carbon atoms.
It is an alkylene group]. This composite heat insulating material is a material in which a urethane foam is firmly adhered to a polyolefin resin sheet or a styrene resin sheet, and is suitable for practical use as a refrigerator interior material. However, it was found that less than 10% of products had corners of vacuum-formed resin sheets with lower adhesive strength than other parts. We also proposed a composite heat insulating material in which a differential pressure molded product of 2-hydroxypropyl methacrylate grafted polypropylene sheet was used as the resin sheet molded product, and a urethane foam was directly adhered to this resin sheet (Japanese Patent Application No. 11749/1982). However, it has been found that the above-mentioned drawbacks are also more prevalent in this composite insulation material. The present invention provides a composite heat insulating material in which the resin sheet does not peel off even under harsher conditions by further improving the adhesive strength between the resin sheet and the urethane foam. [Means for solving the problem] The present invention uses a hydroxyl group-containing modified polyolefin sheet as a resin sheet, and uses a partially or completely neutralized water-soluble or water-dispersible carboxyl group-containing polyolefin as an adhesive. This provides a composite heat insulating material in which the resin sheet molded product and the urethane foam are firmly bonded. That is, the present invention provides a composite heat insulating material having a structure in which a hydroxyl group-containing modified polyolefin resin molded article and a urethane foam are laminated with an adhesive containing the following components (A), (B) and (C). This is what we provide. Adhesive composition: (A) Partially or completely neutralized water-soluble or water-dispersible carboxyl group-containing polyolefin
20-100% by weight (B) Other water-soluble polymers with antistatic properties
80 to 0% by weight (C) Fluorine surfactant 0 to 1% by weight (Resin sheet) In the present invention, the hydroxyl group-containing modified polyolefin of the resin sheet material is prepared by adding 0.1 to 20% by weight of a hydroxyl group-containing monomer to the polyolefin. It is obtained by graft polymerization, and radical polymerization initiators such as organic peroxides and azobutyroisonitrile are used during graft polymerization (Japanese Patent Application Laid-open Nos. 154732-1987 and 58-1982).
185633, 58-185244). The above-mentioned hydroxyl group-containing monomer is an unsaturated organic compound containing a hydroxyl group, such as an ester of an aliphatic polyhydric alcohol and an unsaturated fatty acid, or an unsaturated alcohol, among which acrylic acid or methacrylic acid and an aliphatic Preference is given to esters with alcohols such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and their methacrylates. Other hydroxyl group-containing monomers include the above-mentioned JP-A-58
- Crotonic acid ethylene glycol monoester, glycerol methacrylate, polymethylolalkane methacrylate disclosed in No. 157432,
2,6-dimethyl-4-octen-2-ol,
Examples include 2-propyne-1-ol. Polyolefins to be modified include non-polar polyolefins such as polyethylene, polypropylene, ethylene/propylene copolymer, polybutene-1, and styrene grafted polypropylene; ethylene/acrylic acid random copolymer, ethylene/propylene copolymer, etc.
Methacrylic acid random copolymer, acrylic acid grafted polyethylene, methacrylic acid grafted polyethylene, maleic anhydride grafted polyethylene,
Carboxyl group-containing polyolefins such as maleic anhydride-grafted polypropylene, maleic anhydride-grafted ethylene/vinyl acetate copolymer, itaconic acid-grafted polyethylene; vinylsilane-modified polypropylene, acryloxymethyltrimethoxysilane-grafted polypropylene, γ-glycidpropylmethylsilane grafted Examples include silane-modified polyolefins such as polypropylene. The hydroxyl group-containing modified resin is generally produced by a known method. For example, in graft copolymerization, an organic peroxide is added to a hydroxyl group-containing monomer to form a solution state.
It depends on the method of reacting with polyolefin in a molten state or a suspended state. When the modified resin is a propylene-based resin, molecular chain scission occurs during modification, making it difficult to keep the MFR low, and the selection of the organic peroxide to be used is most important. The organic peroxide is appropriately selected from ketone peroxide, dialkyl peroxide, hydroperoxide, diazyl peroxide, peroxy ester, etc., and benzoyl peroxide is particularly preferred. In addition, a modified polyolefin resin into which the hydroxyl group-containing monomer has been introduced at a high concentration can be diluted with an unmodified resin such as polypropylene, polyethylene, polystyrene, etc. In particular, a modified propylene resin at a high concentration can be diluted with an unmodified resin. By diluting with propylene resin, the unit price of the resin can be lowered and extrusion moldability can also be improved. Furthermore, stabilizers, inorganic fillers, pigments, rubbers, etc. can also be blended within ranges that do not impede the effects of the invention. The amount of hydroxyl groups per 100 g of polyolefin in the resin sheet is 0.01 g or more, preferably
It is sufficient if it is 0.1g or more. Further, since this hydroxyl group-containing modified polyolefin is expensive, it is preferable to make the layer of the hydroxyl group-containing modified polyolefin thin (1 to 30% of the wall thickness) and use it as a laminate with another unmodified resin. Resins for sheet materials to be laminated include high-density polyethylene, low-density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-propylene copolymer,
Polyolefin resins such as propylene-butene copolymers; polystyrene, styrene-butadiene,
Styrenic resins include styrene block copolymer (so-called SBS), acrylonitrile-butadiene-styrene copolymer (so-called ABS), and high-impact polystyrene (so-called HIPS). These may be used alone or in combination of two or more. A stabilizer, an inorganic filler, a pigment, a rubber, etc. may be added to this resin. These resins are coextruded into a sheet together with the aforementioned carboxyl group-containing polyolefin, and if necessary, the front and/or back surfaces are subjected to corona discharge treatment to form a differential pressure molding sheet having a wall thickness of 0.3 to 4 mm. (Adhesive) (A) Salt obtained by partially or completely neutralizing the carboxyl groups of a water-soluble or water-dispersible carboxyl group-containing polyolefin with a neutralizing agent such as ammonia, alkanolamine, caustic soda, caustic potash, etc. 20-100 Weight% (B) Polymer with water-soluble antistatic function
80-0% by weight (C) Fluorine surfactant 0-1% by weight dissolved or dispersed in water. The carboxyl group-containing polyolefin polymer used as the raw material for component (A) above includes unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid, unsaturated polycarboxylic acid anhydrides such as maleic anhydride, and olefins such as ethylene. (meth) or by graft copolymerizing the carboxylic acid to a polyolefin.
It can be obtained by random copolymerization or graft copolymerization of an unsaturated carboxylic acid ester such as an acrylic acid alkyl ester with ethylene or a polyolefin, and then saponification. Specifically, examples thereof include ethylene/acrylic acid random copolymer, ethylene/methacrylic acid random copolymer, maleic anhydride grafted ethylene/vinyl acetate copolymer, and acrylic acid grafted polyethylene. In order to water-solubilize or water-disperse this carboxyl-containing polyolefin, it is necessary to add an alkaline aqueous solution such as ammonia, alkanolamine, or caustic soda to the carboxyl-containing polyolefin to make it water-solubilized or self-emulsify, or use other emulsifiers or protective colloids. A partially neutralized product or a completely neutralized product can be produced by a known method of water dispersion using, for example, water dispersion. Such neutralized products are available from Nippon Steel Chemical Co., Ltd. as Zaixen-A, Zaixen A-TH or Zaixen-AC (ammonia neutralized product, PH 7-10), Zaichsen-L (alkanolamine neutralized product, PH 8). ~
10), Zaixen-N (caustic soda neutralized product, pH8~
11), it is sold by Mitsui Petrochemical Industries, Ltd. under the trade name "Chemipearl S-100" and by Asahi Kasei Corporation under the trade name "Copolene L-4000". Up to 80% by weight, preferably 60 to 20% by weight of the neutralized product of component (A) may be replaced with the water-soluble polymer (B) having an antistatic function. Water-soluble polymer (B) having such antistatic performance
It may be cationic, anionic, nonionic, or amphoteric, and is not particularly limited, as long as it has ionic properties so that it can be uniformly mixed with component (A). Specific examples include polyethyleneimine, poly(ethyleneimine-urea), ethyleneimine adducts of polyamine polyamides, and nitrogen atom-containing cationic or amphoteric polymers. This nitrogen-containing water-soluble polymer can be obtained by homopolymerizing nitrogen-containing monomers or by copolymerizing these monomers with other copolymerizable monomers. Specific examples of nitrogen-containing monomers include the following. Here, in each formula, R ¹ is hydrogen or a methyl group,
R ² and R ³ are each a lower alkyl group (especially,
_C1 to _C4 , especially _C1 to _C2 ), ^R4 is a saturated or unsaturated alkyl group or benzyl group having 1 to 22 carbon atoms, X
is the quaternized counteranion of N (for example,
Halide (especially chloride)), A has 2 to 6 carbon atoms
represents an alkylene group. These nitrogen-containing water-soluble polymers having an antistatic function can be obtained by homopolymerizing these quaternary (amphoterized) nitrogen-containing monomers B, D, D', H, H', H, CH', or It can be obtained by copolymerizing these quaternary nitrogen-containing monomers with other vinyl monomers. In addition, tertiary nitrogen-containing monomers A, C, H, and T can be homopolymerized or copolymerized with other monomers, and then tetramerized with a cationizing agent such as alkyl halide, dimethyl sulfate, or benzyl halide monochloroacetic acid ester. It goes without saying that it can be made to exist in the polymer by grading or amphoterizing with an amphoteric agent such as monochloroacetic acid (salt), propanesultone, propiolactone, etc. The polymer (B) having this antistatic effect needs to be water-soluble, but it is not desirable that it be excessively water-soluble. Therefore, this tertiary to quaternary nitrogen-containing polymer is preferably a copolymer with a hydrophobic monomer. As a hydrophobic monomer,
Examples include styrene or its core or side chain substituted products, acrylic or methacrylic acid esters, vinyl halides, and others. A particularly suitable nitrogen-containing water-soluble polymer (B) is an acrylic polymer obtained by copolymerizing the following components (a) to (c). (a) Monomers A to F 20 to 40% by weight 60-80% by weight [wherein R ¹ is H or a methyl group, R ⁵ is a C ₁ -C ₁₈ alkyl group] (c) Other hydrophobic vinyl monomers 0-20% by weight Most suitable The water-soluble acrylic polymer is one in which the monomer (a) is the above monomer. This water-soluble acrylic polymer is available from Mitsubishi Yuka Fine Co., Ltd. as ST-1000, ST-1100, ST-1300,
It is sold under the product name ST-3000. Next, the fluorine-based surfactant as component (C) may be cationic, anionic, nonionic, or amphoteric; for example, C ₈ F ₁₇ COONH ₄ C ₈ F ₁₇ SO ₃ K C ₈ F ₁₇ SO ₂ NHC ₃ H ₆ N (CH ₃ ) ₃ I C ₈ F ₁₇ CH ₂ CH ₂ N (CH ₃ ) ₃ Cl C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) C ₂ H ₄ O (C ₂ H ₄ O) nH C ₉ F ₁₉ CH ₂ CH ₂ ( _{C2H4O )} nH and so on. Among these, anionic and amphoteric surfactants are more preferred than cationic surfactants, and nonionic surfactants are most preferred. As a commercially available fluorine-based surfactant, a cationic one from Sumitomo 3M Co., Ltd.
134, 135'', and the nonionic ones are ``Florado 170C, 430, 431''.
The anionic ones are “Florado 95, Florado 98, Florado
The cationic perfluoroalkyltrimethylammonium salt is the product name "Surflon 121" from Asahi Glass Co., Ltd., and the amphoteric perfluoroalkyl betaine is the product name "Surflon 131", and the nonionic perfluoroalkyl betaine is the product name "Surflon 131". Perfluoroalkyl polyether polyols are sold under the trade names "Surflon 141 and Surflon 145," anionic perfluoroalkyl carboxylates are sold under the trade names "Surflon 111," and perfluoroalkyl phosphate esters are sold under the trade names "Surflon 112." These are used by dissolving them in water, a mixture of water and an alcohol such as ethanol or isopropanol, or a mixture of water, butyl cellosolve and alcohol.The adhesive is an aqueous solution or dispersion with a concentration of 0.1 to 10% by weight. It is useful to apply an antistatic agent to the side opposite the adhesive side of the sheet. Such antistatic agent may be the same as the adhesive described above, or may be a combination of other antistatic polymers. For example, it may be the water-soluble antistatic polymer (B) mentioned above.Also, this water-soluble antistatic polymer (B) may contain an anionic surfactant, a cationic surfactant, or an amphoteric surfactant. , nonionic surfactants such as lauryl aminopropionate sodium salt, stearyltrimethylammonium chloride, 1-hydroxyethyl-2-undecyl-2-imidazoline/ethylene oxide adduct, nonylphenol/ethylene oxide adduct, lauryl sulfate. It may also contain antistatic agents such as ate tetrium salts and fluorine-based surfactants. (Manufacture of composite insulation materials) Having antistatic function containing these components (A), (B), and (C). The aqueous adhesive solutions 2a and 2c are rolled,
Apply a coating of 0.01 to 1.0 to at least the back side of the sheet 2b that will be bonded to the urethane by brushing, spraying, etc.
g/m ² (solid content) and dried (see Figure 2). Adhesive resin films 2a, 2 thus obtained
The resin sheet having c on the front and back surfaces or on the back side to be bonded to urethane is subjected to normal differential pressure molding and shaped into a shape suitable as a refrigerator lining material. This shaped sheet 2 is perforated with a urethane solution 4 injection port 5 if necessary, and is inserted into a stainless steel or aluminum formwork 1, which is the outer structural base material of the refrigerator, as shown in Fig. 1. . Next, from the injection port 5, a two-component foaming urethane solution is poured into the cavity 4 formed by the mold 1 and the lining material 2.
The polyurethane foam 4' and the lining material 2 are injected into the lining material 2 and are injected into the lining material 2 to form a multi-layered lining material having a heat insulating property. Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that parts and percentages in the examples are based on weight. Example of producing a sheet Example 1 5 kg of polypropylene (MFR 0.8 g/10 minutes, density 0.91 g/cm ³ ) and 90 xylene were put into a reactor with an internal volume of 200 mm, and after purging the system with nitrogen, the reactor was heated to 120 mm with stirring. The temperature was raised to 0.degree. C., and polypropylene was dissolved in xylene. Separately, 400 g of benzoyl peroxide and 1 kg of 2-hydroxypropyl methacrylate were dissolved in 10 g of xylene and fed into the reactor above over 2 hours. After the supply, the temperature was kept at 120°C for 5 hours while stirring to complete the polymerization.
After the reaction, the mixture was cooled to 60°C and the product was precipitated with a large amount of acetone. After the product was filtered, it was thoroughly washed with acetone and dried in a vacuum drier to obtain 2-hydroxypropyl methacrylate-modified polypropylene. The 2-hydroxypropyl methacrylate content of this product was determined to be 1.4% by weight by infrared spectroscopy. 100 parts by weight of the obtained modified polypropylene, 2,
0.1 part by weight of 6-di-t-butyl-p-cresol,
After 0.05 parts by weight of calcium stearate was mixed in a Henschel mixer, the mixture was extruded at 230°C in an extruder having a diameter of 40 mm and L/D 28, and was pelletized after cooling with water.
The obtained modified polypropylene pellets (MFR4.2/10 minutes) were extruded into a sheet at 210°C, treated with corona discharge, and cooled to obtain a sheet with a wall thickness of 1.6 mm. Example 2 Polyethylene (MFR20
g/10 minutes, density 0.956g/ ^cm3 ) 5Kg xylene 70
was dissolved in a nitrogen atmosphere at 120°C with stirring. Separately, 500 g of benzoyl peroxide and 1 kg of 2-hydroxyethyl methacrylate were dissolved in xylene 10, and this was fed over 2 hours. Furthermore, keep stirring at 120℃ for 5 hours,
After completing the polymerization and cooling to 60°C, the product was precipitated with a large amount of acetone. After separating the product by filtration, it was thoroughly washed with acetone and dried in a vacuum dryer.
-Hydroxyethyl methacrylate modified polyethylene was obtained. The 2-hydroxyethyl methacrylate content of this product was 1.3% by weight. 50 parts by weight of the obtained modified polyethylene, 50 parts by weight of polyethylene (MFR 1.5 g/10 minutes, density 0.952 g/cm ³ ), 2,6-di-t-butyl-p-cresol
After mixing 0.1 part by weight in a Henschel mixer,
It was extruded into pellets at 200°C using an extruder. The MFR of this modified pellet was 4.1 g/10 minutes. The modified pellets are extruded into a sheet at 200℃, corona discharge treated on both sides, cooled, and thickened.
A 1.6 mm sheet was obtained. Example 3 Polypropylene (PP) powder (MFR0.8
g/10 minutes, density 0.91 g/cm ³ ), 100 parts by weight, 4 parts by weight of 2-hydroxypropyl methacrylate, and 3 parts by weight of benzoyl peroxide were mixed in a Henschel mixer, and then mixed in an extruder with a diameter of 40 mm and L/D 28. The mixture was extruded into a sheet at 230°C, treated with corona discharge on both sides, and then cooled to obtain a sheet with a thickness of 1.6 mm. Example 4 () Resin for glossy surface layer: MFR2.0g/10
A crystalline propylene homopolymer with a residual amount of 99% by weight after extraction with boiling heptane was used. () Resin used for deep drawing layer: 40% by weight of crystalline propylene-ethylene block copolymer with ethylene content of 5% by weight, MFR of 0.5g/10 minutes, boiling heptane extraction residue of 98% by weight, and density of 0.950g/cm. ³ ,
A composition consisting of 40% by weight of polyethylene with an MFR of 0.6g/10 minutes and 20% by weight of talc having a particle size of 1.5μ was kneaded using an extruder, extruded into a strand, and cut into pellets. () Resin on the side to be bonded to urethane: The 2-hydroxypropyl methacrylate grafted polypropylene pellets obtained in Example 1 were used. The resin pellets for the deep drawing layer shown in () above have a diameter of 90.
The resin for the glossy layer () and the 2-hydroxypropyl methacrylate grafted polypropylene () were each extruded separately into a 40 mm diameter extruder at 230°C using a 700 mm width extruder. The same die was fed at 230 using a machine. The temperature of the die was 230°C. The molten sheet extruded from the die was sequentially cooled and solidified using three rolls each having a width of 700 mm, and then subjected to corona discharge treatment to obtain a sheet for vacuum forming. The temperatures of the rolls were 80°C, 95°C, and 100°C starting from the roll closest to the die, and the rotational speed of the rolls was 1.5 m/min. The total sheet thickness was 1.6 mm, the glossy surface layer was 0.25 mm, the deep drawing layer (intermediate layer) was 1.10 mm, and the thickness of the modified polypropylene layer, which was the adhesive layer with urethane, was 0.25 mm. Example 5 Polypropylene “Mitsubishi Noblen” manufactured by Mitsubishi Yuka Co., Ltd.
MA-8" (trade name) as the surface gloss layer, 2-hydroxyethyl methacrylate grafted polyethylene obtained in Example 2 as the urethane adhesive layer resin,
Coextruded at 230℃, wall thickness 1.6mm (surface gloss layer 1.56mm)
A multilayer sheet with a thickness of 0.04 mm and an adhesive layer of 0.04 mm was obtained. Example 6 () Resin for glossy surface layer: MFR2.0g/10
A crystalline propylene homopolymer with a residual amount of 99% by weight after extraction with boiling heptane was used. () Resin for deep drawing layer (urethane adhesive layer): Polypropylene “Mitsubishi Noblen MH-6”
66 parts 2-hydroxypropyl acrylate grafted polypropylene obtained in Example 3 20 parts Styrene-butadiene-styrene copolymer 4 parts Polystyrene 10 parts The deep-drawn layer resin of () above was heated at 230°C using an extruder with a diameter of 90 mm. The resin was supplied to a two-layer multi-manifold die with a width of 700 mm, and the resin for the glossy surface layer () was supplied to the same die at 230°C using an extruder with a diameter of 40 mm. The temperature of the die was 230°C. The molten sheet extruded from the die was sequentially cooled and solidified using three rolls with a width of 700 mm, and then subjected to corona discharge treatment to obtain a two-layer vacuum forming sheet. The temperature of the rolls varies from 80℃ to 95℃ starting from the roll closest to the die.
The temperature was 100°C, and the rotation speed of the rolls was 1.5 m/min. The total sheet thickness is 1.6mm,
The glossy layer on the front and back is 0.2mm each, and the deep drawing layer is 1.4mm.
It was hot. Example 7 Vinyltrimethoxysilane/ethylene random copolymer 40 parts 2-hydroxyethyl methacrylate grafted polyethylene obtained in Example 2 20 parts Low density polyethylene 50 parts The above resin composition was extruded into a sheet at 200°C,
The mixture was sequentially cooled and solidified using three rolls, and then subjected to corona discharge treatment to obtain a vacuum forming sheet with a wall thickness of 1.6 mm. Example 8 (for comparison) () Resin used for gloss layer: MFR2.0g/10 minutes,
A crystalline propylene homopolymer with a residual amount of 99% by weight after extraction with boiling heptane was used. () Resin for deep drawing layer (intermediate layer): 40% by weight of crystalline propylene-ethylene block copolymer with 5% ethylene content, 0.5g/10 min MFR, 98% by weight remaining after extraction with boiling heptane, and density
0.950g/ ^cm3 , MFR0.6g/10min polyethylene
A composition consisting of 40% by weight of talc and 20% by weight of talc having a particle size of 1.5μ was kneaded using an extruder, extruded into strands, and cut into pellets. The resin pellets for the deep drawing layer shown in () above have a diameter of 90.
The resin was supplied to a three-layer multi-manifold die with a width of 700 mm at 230° C. using a 40 mm diameter extruder, and the resin for the glossy layer in () was supplied to the same die at 230 mm using an extruder with a diameter of 40 mm. The temperature of the die was 230°C. The molten sheet extruded from the die has a width of 700 mm.
The mixture was sequentially cooled and solidified using a book roll, and then subjected to corona discharge treatment to obtain a three-layer vacuum forming sheet. The temperature of the rolls varies from 80℃ to 95℃ starting from the roll closest to the die.
The temperature was 100°C, and the rotation speed of the rolls was 1.5 m/min. The total sheet thickness is 1.6mm,
Each gloss layer was 0.20 mm and the deep draw layer was 1.20 mm. Example 9 (for comparison) Polypropylene “Mitsubishi Noblen” manufactured by Mitsubishi Yuka Co., Ltd.
MA-8" (trade name) was extruded into a sheet at 230°C, and then subjected to corona discharge treatment to obtain a sheet with a wall thickness of 1.6 mm. Manufacturing example of acrylic antistatic polymer of component (B) N, N -dimethylaminoethyl methacrylate
80 parts (0.5 mol), 50 parts (0.5 mol) of methyl methacrylate, and 200 parts of isopropyl alcohol were placed in a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, and after purging with nitrogen gas, , 0.9 part of 2'-azobisisobutyronitrile was added as a polymerization initiator, and the polymerization reaction was carried out at 80°C for 4 hours. Next, add 60 parts of monochloroacetic acid soda, and add 80 parts of sodium monochloroacetate.
After reaction (amphomerization) at ℃ for 6 hours, water was added while distilling off isopropyl alcohol to obtain an aqueous solution with a solid content of 35%. This acrylic polymer (hereinafter referred to as "ST") is is included in the molecular chain. Example 1 An ammonia-neutralized product of carboxyl group-containing polyolefin "Zaikusen A-TH" manufactured by Nippon Steel Chemical Co., Ltd. was applied to both sides of the three-layered sheet obtained in Example 1.
(solid content concentration approximately 30%, pH approximately 8), Sumitomo 3M's cationic fluorine-based surfactant "Florad"
430” (product name, viscosity at 25℃ 15000CPS, specific gravity 1.1)
A 4% by weight aqueous dispersion of 100 parts by weight to 0.5 parts by weight in terms of solid content was applied to each sample at a solid content of 0.6 g/m ² and air-dried. Using a vacuum/pressure forming machine, this sheet is made into approximately 180
Guided into a heated filter set at ℃, and compressed air (5.0Kg/cm ² )
Plug assist molding was carried out using a combination of pressure and reduced pressure (-600 mmHg) (drawing ratio H/D = 1/1). The release properties of the sheet were good, and the plug was easily separated from the sheet. After drilling an injection port in a part of this shaped sheet, this sheet is inserted into a stainless steel frame that is the frame of the refrigerator body, and then the space (cavity) formed by the frame and the shaped sheet is inserted. When a two-component foaming urethane solution "HM-1510" (trade name) manufactured by Polyurethane Kagaku Kasei Co., Ltd. was injected into the space from the injection port, foaming started after 10 seconds, and after 1 minute, the space was filled with urethane. Completely filled with foam.The density of this urethane foam is 0.05g/cm ³
It was hot. Repeat the same operation 20 times and prepare 20 samples.
I got one. After 24 hours, the flat and corner portions of the sheet to which the urethane foam had been adhered were cut out, and the adhesion between the urethane foam and the sheet was measured. on the other hand,
Another sheet (not bonded with urethane) that had been vacuum formed in the same manner as above was partially cut out, and the ash adhesion on the surface of the sheet was examined. The results are shown in Table 1. Adhesion: After separating the urethane foam from the sample piece by hand, use a knife to touch the sheet with the remaining urethane.
100 squares were cut into pieces, adhesive tape was then pasted onto the squares, and when the adhesive tape was vigorously peeled off from the sheet, the residual urethane foam squares remaining on the sheet side were examined. Ash adhesion: × - Adhesive even at a height of 5 km or more △ - Adhesive at a height of 3 to 5 cm ○ - Adhesive or no adhesion at a height of 3 cm or less. Examples 2 to 15, Comparative Examples 1 to 3 Urethane foam/sheet laminated heat insulating materials were obtained in the same manner as in Example 1 except that the coating agent was changed as shown in Table 1. This laminated heat insulating material was evaluated in the same manner as in Example 1. The results are shown in Table 1.

【table】

[Table] Examples 16 to 21, Comparative Examples 4 to 5 Instead of using the layered sheet obtained in Example 1 as a sheet for differential pressure molding, the sheets obtained in Examples 2 to 9 were used, and the sheet surface side Coating agent “ST-1100”
A urethane foam/sheet laminated heat insulating material was obtained in the same manner as in Example 4, except that . The physical properties of this product are shown in Table 2.

【table】 [Brief explanation of drawings]

FIG. 1 is a sectional view showing one embodiment of the present invention;
FIG. 2 is a sectional view of the sheet. In the figure, 1 is a stainless steel frame, 2 is a sheet for differential pressure molding (lining material), 2a is a coating agent layer, 2c is an adhesive layer, 3 is a cavity, 4' is a urethane foam,
5 is an injection port.

Claims (1)

[Scope of Claims] 1. A hydroxyl group-containing modified polyolefin resin molded product and urethane foam contain the following components (A), (B) and
Composite insulation material with a structure laminated with an adhesive containing component (C). Adhesive composition: (A) Partially or completely neutralized water-soluble or water-dispersible carboxyl group-containing polyolefin
20-100% by weight (B) Other water-soluble polymers with antistatic properties
0 to 80% by weight (C) Fluorine surfactant 0 to 1% by weight 2 Component (B) is a polymer consisting of the following components (a) to (c) whose tertiary nitrogen atoms are modified with an amphoteric agent. The composite heat insulating material according to claim 1, which is an amphoteric compound. 20-40% by weight 60 to 80% by weight (c) Other hydrophobic vinyl monomers 0 to 20% by weight [However, in each formula, R ¹ is H or CH ₃ , and R ² and R ³ are each alkyl having 1 to 2 carbon atoms Group, R ⁵
is an alkyl group having 1 to 18 carbon atoms, and A is an alkyl group having 2 to 6 carbon atoms.
It is an alkylene group]. 3. The composite heat insulating material according to claim 1, wherein component (A) is an ammonia salt, an alkanol amici salt, or an alkali metal salt of an ethylene/acrylic acid copolymer. 4. The composite heat insulating material according to claim 1, wherein the fluorine-based surfactant is a nonionic surfactant.