JPH08337691A - Protective composition for reducing chemical attack on plastics - Google Patents

Abstract

(57) PROBLEM TO BE SOLVED: To provide a composition and a polymer film which resist the swelling action of a polymer foam blowing agent on a styrene-based polymer. Also provided is a composite comprising a thermoplastic synthetic resin sheet such as HIPS, a polymer film, a polymer foam and an outer wall member. The polymer is derived from a monomer comprising at least three types of polymers and copolymers: polyolefins, ethylenically unsaturated aliphatic or cycloaliphatic hydrocarbon monomers, and monomers containing vinyl groups and carboxylic acid groups. And a synthetic block copolymer. The polymer film provides a suitable barrier for high impact polystyrene (HIPS), especially in refrigerator applications, where it is susceptible to chemical attack from polyurethane halogenated blowing agents.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to polymeric films used to protect plastics from attack by various chemicals. More specifically, the present invention provides
Three types of polymers: polyolefins; copolymers derived from monomers consisting of ethylenically unsaturated aliphatic or alicyclic hydrocarbon monomers and monomer compounds containing vinyl and carboxylic acid groups; styrene block copolymers, chemistry It relates to compositions that resist erosion from chemicals and polymeric films thereof.

[0002]

BACKGROUND OF THE INVENTION Typical refrigerator cabinets are outer metal cabinets, inner plastic cabinets, typically ABS (acrylonitrile-butadiene-styrene), or HIPS (high impact polystyrene) and insulating polymer foam cores, typically Made of polyurethane foam. The blowing agent for the polymeric foam is trapped within the cells of the foam. In the past, CFC-11 was commonly used commercially as a blowing agent. According to the Montreal Protocol, alternatives for CFC-11 and other "hard" halogenated hydrocarbons should be found. A proposed alternative for CFC-11 is a halogenated hydrocarbon containing at least one hydrogen atom, known as "soft" CFC, which has significantly less ozone depletion capacity than CFC-11. Have.

Some of the commonly proposed conventional blowing agent substitutes for insulating type foams used in refrigerator cabinets are 1,1-dichloro-1-fluoroethane (HCFC-141b), 1,1. -Dichloro-2,
2,2-trifluoroethane (HCFC-123) and 1,1,2,2-tetrafluoroethane (HFC-1)
34a). Since the blowing agent is trapped within the cells of the foam, many different types of HCFC diffuse out of the cell walls and come into contact with the internal plastic liner of the refrigerator and chemically attack the liner. It may cause blistering, sudden cracking, crazing, and loss of impact resistance, as well as stress whitening and / or dissolution. HCFC-141b and HCFC-1
Blowing agents such as 23 are considered chemically more aggressive than CFC-11 in eroding the inner plastic liner.

Some proposals have been made to protect the inner plastic liner from attack by polymer foam blowing agents. For example, U.S. Pat. No. 5,227,245 proposes to use a thermoplastic polyester resin which is primarily a homo- or copolymer of an aromatic dicarboxylic acid in an active hydrogen containing material. However, this polyester resin has poor compatibility with styrene resins, and therefore the protective polymer lacks the desired regrinding capability. During the manufacture of equipment cabinets, thermoplastic synthetic resin sheets, generally made from polystyrene compounds, are coextruded with or laminated to a barrier layer to form an inner liner, and excess liner material is Trimmed. The resulting trimmed scrap material is often compounded with virgin thermoplastic synthetic resin sheet material. For effective recycling of trim or scrap, the protective polymer film composition should be compatible with the thermoplastic synthetic resin sheet composition.

Another composition proposed as a layer between the foam and the thermoplastic sheet is US Pat. No. 4,70,4.
See No. 7,401, which suggests a two-layer film comprising an inner film containing a copolymer of ethylene and vinyl acetate and an outer film containing a copolymer of ethylene and acrylic acid. . However, the purpose of the outer film is to improve the adhesion between the polyurethane foam and the outer film, while the inner film effectively provides a stress relief layer with an inner thermoplastic synthetic resin sheet. U.S. Pat. No. 5,118,174 discloses a protective polymer film for preventing diffusion of an insulating foam blowing agent to a liner sheet and an adhesive for fixing a laminated protective polymer film layer to an outer wall of a cabinet. It is proposed to use both with layers. The proposed composition of the protective polymer film (barrier) is EVOH, Saran,
It was nylon, PET, PDT or the like. US Patent No. 5,
221,136 proposed adding a protective polymeric material to a thermoplastic synthetic resin sheet. This protective polymer (barrier) material is a block copolymer rubber 0-4
It consisted of a polymer or copolymer of ethylene or propylene containing 0%. Block copolymer rubbers were optionally functionalized with maleic anhydride, maleic acid or mixtures thereof to maximize the adhesion of the core material to the protective polymer (barrier) material.

[0006]

The object of the present invention is therefore to find a composition which has a good resistance to attack by polymer foam blowing agents on thermoplastic synthetic resin sheets. Also, this same composition should have both thermoformability and recyclability.

[0007]

The above problems are solved by the means according to the invention as claimed.

The present invention provides compositions for protecting thermoplastics from various polymeric foam blowing agents and polymeric films thereof. The compositions and polymer films are derived from a monomer derived from (a) a polyolefin, (b) an ethylenically unsaturated aliphatic or alicyclic hydrocarbon monomer, and a monomer compound containing a vinyl group and a carboxylic acid group. Copolymers, and polymers and blends or mixtures of copolymers comprising (c) styrene block copolymers.

Compositions containing a mixture of at least three polymers and copolymers are most preferably prepared from a mixture of high density polyethylene, a copolymer of ethylene methacrylic acid, and a synthetic block copolymer such as styrene-butadiene.

This polymer film composition can be extruded into a polymer film sheet and laminated to a thermoplastic synthetic resin sheet, or coextruded with a thermoplastic post synthetic resin to produce a thermoformable innerliner.
The thermoformable inner liner is thermoformed, trimmed and spaced inside the wall cabinet, and polymer foam is injected or injected between the liner and the wall cabinet.

The present invention also provides a composite, which comprises, in sequence, (i) a thermoplastic synthetic resin sheet, (ii) a polymer film, (iii) a polymer foam and (iv) an outer wall member.

Further provided is a method of making a thermoformable innerliner sheet. In the method, (A) a thermoplastic synthetic resin composition is co-extruded with a polymer film composition to produce a liner composed of a thermoplastic synthetic resin sheet bonded to a polymer film, and (B) a thermoplastic synthetic resin sheet. Laminating it on a polymer film, the polymer film and polymer film composition comprising (1) a polyolefin,
(2) a copolymer derived from a monomer comprising an ethylenically unsaturated aliphatic or alicyclic hydrocarbon monomer and a monomer compound containing a vinyl group and a carboxylic acid group,
And (3) Styrene block copolymer.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Referring to FIGS.
The present invention will be described.

Although the present invention is described below in the context of a refrigerator cabinet, it will be appreciated that the polymer film may also be used in other applications where it is desired to protect the plastic from chemical attack. Is.

The refrigerator of FIG. 1 has a cabinet consisting of an outer wall member 1, a thermoformed inner liner wall 2, and an in-situ foamed polymer foam insulation 3 between the thermoformed inner liner wall and the outer wall member. Become. In the conventional, non-limiting design, the cabinet forms a refrigerating space 4 and a freezing space 5.

The inner liner 2 is thermoformed into the desired shape, as shown in FIG. The inner liner 2 is a thermoformed product of the liner sheet 6, one embodiment of which is shown in FIG. After thermoforming to the desired shape, the innerliner wall 2 is placed within the outer wall member 1 at fixed intervals for injecting the polymer insulation foam by conventional in-situ foaming operations. In general, the outer wall member 1 and the inner liner wall 2 are physically joined by fitting a joint.

The polymer film according to the invention is substantially chemically inert towards the halogenated hydrocarbons used as blowing agents in the production of polymer foam. Polymer foam In-situ manufacturing, according to one embodiment of the invention, the surface of the polymer film is adjacent to and bonded to the foam. However, it is not essential that the polymer film according to the invention be adjacent to the foam. In FIG. 3, the polymer film is designated by the reference numeral 8.

Also shown in FIG. 3 is a thermoplastic synthetic resin sheet 7, which is preferably in contact with and bonded to a polymer film 8. Optionally, a gloss cap 9 may also be provided which is provided inside the refrigerator cabinet to provide a pleasing aesthetic appearance. Therefore, in one embodiment according to the invention, i) a thermoplastic synthetic resin sheet 7, ii) a polymer film 8, iii) a polymer foam 3, sequentially from the innermost part to the outermost part of the refrigerator cabinet, And iv) A composite having an outer wall member 1 is provided.

The polymer film 8 and the thermoplastic synthetic resin sheet 7 together comprise a thermoformed innerliner 2 made from a thermoformable innerliner sheet 6.

In another embodiment of the present invention,
Also provided is a composite having a gloss cap 9 and a thermoformable inner liner sheet 6. Also, layer 1,
Additional layers may be disposed between any of the layers 3, 8, 7 and 9. For example, a thermal stress release layer or an adhesive layer may be provided.

In one embodiment, shown in FIG. 3, where the optional gloss cap 9 is present, the gloss cap 9 comprises 0.5-10% by weight of the thermoplastic synthetic resin sheet 6.
The thermoplastic synthetic resin sheet 7 comprises at least 50% by weight of the thermoformable inner liner sheet 6. The polymer film 8 is a thermoformable inner liner 6-4.
-50% by weight.

The layers described above can be of any desired thickness. In one embodiment of the invention, the polymer film 8 has a thickness of 0.001 to 0.050 inches (0.00251 to 0.00251).
The thickness of the thermoplastic synthetic resin sheet 7 is 0.015 to 0.30 inch (0.038 cm).
1 to 0.762 cm); and the optional gloss cap thickness 9 is 0.001 to 0.010 inches (0.
It is in the range of 00251 to 0.0254 cm). Polymer foam 3 typically has a thickness of 1 to 3 inches (2.54 to
7.62 cm).

Focusing on the composition of the individual layers, the polymer film 8 will first be described. The composition of the polymer film comprises at least three types of polymers and copolymers: a) a polyolefin, b) a monomer composed of an ethylenically unsaturated aliphatic or alicyclic hydrocarbon monomer and a monomer compound containing a vinyl group and a carboxyl group. It consists of a mixture of derivatized copolymers and styrene block copolymers.

The polyolefin of the polymer film composition includes homopolymers or copolymers of ethylene, propylene or butylene. Examples include polypropylene, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDP).
E) (melt index 1-10 and density 0.935
~ 0.970), high molecular weight high density polyethylene (melt index 0.05-1.0 and density 0.935-
0.970), and ethylene vinyl alcohol. As used herein, the term "high density polyethylene" means a melt index range of 0.05 to 10 and a density of 0.93.
It is meant to include high density polyethylene having 5 to 0.970.

HDPE materials polymerize ethylene using so-called Ziegler-Natta coordination catalysts which provide a linear (unbranched) narrow molecular weight distribution of HDPE or using the Phillip process which produces a broad molecular weight distribution. It can be manufactured by The HDPE material can be produced by polymerizing ethylene at high pressure and temperature using a free radical catalyst, in this case a branched polyethylene (density = 0.910-0.934 g / cc).
Is obtained. The LLDPFE material can be prepared from ethylene and a small amount of α-, β-ethylenically unsaturated C ₃ -C ₁₂ -alkene under Ziegler-Natta conditions, in which case substantially linear, but α- Low density polyethylene with alkyl side chains from olefin components (density =
0.88 to 0.935 g / cc) is obtained. Preferred in this polyethylene group are all high density polyethylenes as described above.

An example of HDPE is Quantu
m; from Cincinnati, Ohio) to Quantum ^TM LM-61
87 and LT-6194-69 [melt index (MI) = 0.
2] Commercially available HDPS; HDPS commercially available from Solvay, Solvay ^™ A 60-70-162 (MI =
0.7), F 621 S (MI = 1), J 60-500-C147 (MI =
6), T60-500-119 (MI = 6), T50-200-01 (MI =
1.7), A60-70-119 (MI = 0.7), 660-24-144
(MI = 0.25); Mobil ^TM HMA 034 (MI = 5) and N
CX-013 (MI = 0.7); Chevron ^TM 9659 (MI = 0.
7) HDPE; and Phillips ^™ EHM 6006 (MI = 1).

The a) polyolefins may optionally be modified by functionalizing the polyolefins with unsaturated carboxylic acids or functional derivatives thereof or another monomer containing vinyl functional groups. For example, polyethylene or any other polyolefin includes acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and ascorbic acid, their acid anhydrides, acid amides, epoxy group-containing compounds, hydroxyethyl group-containing esters, and It can be functionalized by graphing on an olefin polymer backbone compound such as a metal acrylate salt. Such functionalized polyolefins can improve the adhesion of foam insulation to polymer films and to polymer films to thermoplastic synthetic resin sheets.

The copolymer b) used in the polymer film composition is derived from at least two monomers, one of which is an unsaturated aliphatic or cycloaliphatic hydrocarbon and the other of which is a vinyl group or a carboxyl group. Contains an acid group. The ethylenically unsaturated aliphatic or cycloaliphatic hydrocarbon monomer is preferably only one double bond in the case of aliphatic hydrocarbons and only two double bonds in the case of cycloaliphatic hydrocarbons. Have. Examples of said hydrocarbons include the monomers used to make said polyolefins, such as ethylene, propylene, butylene and their copolymers. The preferred hydrocarbon monomer is ethylene.

Any compound containing both vinyl groups and carboxylic acid groups is suitable as another monomer compound used to prepare the b) copolymer. Examples of such compounds include, but are not limited to, the structural formula:

[0030]

Embedded image

[Wherein R ₁ , R ₂ and R ₃ independently of one another are hydrogen, a C ₁ -C ₄ -alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. ,
And n is an integer of 0 to 8]. R ₁ is preferably hydrogen or a methyl group, and n
Is 0. Thus, the monomer preferably consists of methacrylic acid or acrylic acid, and more preferably methacrylic acid.

The amount of monomeric compound units containing vinyl groups and carboxylic acid groups depends on the resistance of polymer films prepared in the absence of copolymers, for example polyolefins and styrene block copolymers alone or polyolefins, styrene block copolymers and polystyrene compounds only. This is an effective amount for improving the blistering property. Examples of suitable amounts are in the range 4% to 20% by weight. An amount of 9 to 12% by weight, based on the weight of the copolymer, has been found to be quite effective for improving the resistance of the polymer film to blister of thermoplastics. However, any amount of monomeric compound can be used and optimized in terms of cost reduction and maximization of blistering resistance.

Examples of some commercially available copolymers are:
DuPont (EI Dupont de Nemours, Wilmington, Dela
ware) commercially available Nucrel ^TM 1202 HC, 31001, 0407, 090
2 and 0930.

B) Copolymers can be prepared by copolymerizing the individual monomers with one another to form a heteroic or block copolymer. The hydrocarbon monomer and the monomer compound containing vinyl and carboxylic acid groups, when polymerized, formed the backbone of the copolymer. Thus, the hydrocarbon monomer will copolymerize through its ethylenic unsaturation with the ethylenic unsaturation present in the vinyl groups of the monomer compound.

The third compound of the polymer film composition is a styrene block copolymer. Suitable styrene block copolymers are generally synthetic block copolymer rubbers. Representative examples are styrene-butadiene diblock copolymer, styrene-ethylene-propylene diblock copolymer, styrene-ethylene / butylene-
Includes styrene triblock copolymers, and star block copolymers. Each of these styrene block copolymer rubbers includes maleic anhydride, maleic acid,
Acrylic acid, methacrylic acid, fumaric acid, itaconic acid, acid amides, compounds containing epoxy groups, such as glycidyl acrylate and glycidyl methacrylate, esters containing hydroxyethyl groups, such as 2-hydroxyethyl methacrylate and polyethylene glycol monoacrylate, and It may be functionalized with metal salts such as sodium acrylate, sodium methacrylate and zinc acrylate, and mixtures thereof, or any of the compounds mentioned above. Functionalization of the rubber copolymer improves the adhesion of the polymer film to the foam.

An advantageous styrene block copolymer is Firestone Tire and Rubber (Fireston).
"Stereon ^TM 8 available from e Tire and Rubber Company)
40A "," Finaclear ^TM 520 "commercially available from Fina of Houstone, Texas," Styrolux ^TM 684 D "which is a star block styrene butadiene block copolymer commercially available from BASF, respectively, styrene-butadiene block. The copolymer “Styrolux ^™ 268
6 ”and“ Styrolux ^TM 2689 ”and Shell Oil Company (Sh
"Kraton ^TM 1101D" and "Kraton ^TM 1101D" commercially available from Dell Oil Company).

The polymer film composition is, according to one embodiment according to the invention: a) a polyolefin 35-90.
% By weight, b) greater than 2.5% by weight, but 3
Less than 0% by weight, and c) styrene block copolymer 5
-25% by weight.

Advantageously, this embodiment contains a) 40 to 85% by weight of polyolefin, b) 5 to 20% by weight of copolymer and c) 10 to 20% by weight of styrene block copolymer. B) Copolymer 30 on polymer film
It is possible to use amounts greater than wt%, but to obtain synergistic swell resistance results only in polymer film compositions when greater than 2.5 wt% but less than 30 wt% copolymer is used. It turned out to be possible. The synergistic effect observed in improving the swelling resistance of the thermoplastic synthetic resin sheet will be illustrated in more detail in the following examples.

The polymer film may optionally contain other polymers and copolymers in addition to the above three types of polymers and copolymers. For example, a fourth polymer of a different type of polyethylene or high impact styrene polymer or copolymer may be used. A suitable example of high impact polystyrene is "ES 5350" commercially available from BASF.

The polystyrene is preferably about 150,0.
It is a high molecular weight polymer having a number average molecular weight of greater than 00 g / mol.

The polymer film is produced by compounding the individual polymer components in, for example, an extruder, a twin screw extruder, an FCM or a Banbury mixer in an amount corresponding to the desired weight percent of the components in the polymer film. You can The individual polymers and copolymers are melted and extruded through a die, then cooled and chopped into pellets for subsequent processing into sheets or films.

The optional additional high impact polystyrene polymer added to the polymer film composition is a well known material which is a rubber modified polystyrene, ie a polystyrene modified with an elastomer such as polybutadiene or styrene-butadiene polymers. Good. This material is, for example, Modern Plastics Encyclopedia , McGraw-Hi
ll, p. 72 (1983-1984). The rubber-modified polystyrene used in the thermoplastic synthetic resin sheet or as an optional additional component in the polymer film can be prepared in a number of different ways. Rubber-modified polystyrene is a polystyrene in which rubber particles are dispersed in a polystyrene matrix by polymerizing a styrene monomer in the presence of a rubber polymer, and each of the rubber particles is aggregated inside the particle and surrounded by a rubber phase gap. It can be produced by forming a high impact polystyrene having a morphology of occlusion. The size of the rubber particles is typically 1 to 5 μm. Another method is to polymerize a styrene monomer in the presence of a styrene block copolymer rubber such as styrene-butadiene to form a core-shell morphology in which a polystyrene core is encapsulated by a rubber shell dispersed within a polystyrene matrix. You can Another method of making rubber-modified polystyrene is to melt a blend of polystyrene polymer and a copolymer of styrene-butadiene to form small particles dispersed as domains within a polystyrene matrix, with dimensions ranging from about 0.05 to 0.15 μm. Are formed.

Further, the styrene monomer is added in a size of 3 to 30.
Environmental stress crack resistant HIP prepared by polymerizing in the presence of butadiene polymer under certain reaction conditions well known to those skilled in the art to obtain rubber particles in the μm range.
S also exists.

The amount of high impact polystyrene, if used, is in the range of 10% to 40% by weight, based on the weight of the polymer film composition.

The thermoplastic synthetic resin sheet 7 can be manufactured from high impact polystyrene or acrylonitrile-butadiene-styrene (ABS) copolymer as described above. Impact-resistant polystyrene, as described above, can optionally be prepared by polymerizing styrene monomers in the presence of a rubber polymer. ABS copolymers can also be prepared, optionally in the presence of rubber polymers. The amount of rubber in HIPS or ABS is in the form of particles in the range 5 to 35, preferably 5 to 20, usually 5 to 15% by weight. The rubber particles in the HIPS are generally at least 2 μm, preferably at least 5 μm, generally 10 μm.
It has a weight average diameter of less than or equal to μm. High gloss polystyrene (medium impact) is produced when the styrene block copolymer particles are less than 1 μm as described in US Pat. No. 4,513,120.

The optional gloss cap layer 9 may be disposed on the exterior surface of the thermoplastic synthetic resin sheet and is made of medium impact high gloss polystyrene.

Thermoformable inner liner sheet 6
Can be produced by coextrusion or lamination techniques. The techniques for applying films to thermoplastic sheets by laminating or coextrusion techniques are well known to those skilled in the art of making composite materials. Such film construction technology is
For example, U.S. Pat. Nos. 3,960,631 and 4,0
05,919, 4,707,401 and 4,196,
No. 950. In coextrusion technology,
Co-extruding the thermoplastic synthetic resin composition with the polymer film composition through a sheet die and onto a chill roll,
An inner liner sheet having a layer of a thermoplastic synthetic resin composition sheet heat sealed to a polymer film is formed. Those skilled in the art will immediately recognize many coextrusion techniques applicable for the production of such innerliner sheets. For example, one such technique is to separately feed the polymer film composition and the thermoplastic synthetic resin sheet composition via a Dow or Welex feedblock. Alternatively, the individual materials can be separately fed to the multi-manifold die. In the laminating technique, a thermoplastic synthetic resin sheet material can be extruded, conveyed to a press roller where it is wound into a roll of polymer film and laminated through the roller to the thermoplastic synthetic resin sheet. The pressure is applied to the rollers and the extrudate is heated to keep it soft, thereby binding. Alternatively, instead of laminating, the surfaces of the polymer film and the thermoplastic synthetic resin sheet can be electrostatically treated to promote adhesion of the polymer film to the sheet.

The thermoformable inner liner sheet 6 is then thermoformed into a thermoformed inner liner sheet structure that fits the desired outer wall member. Thermoforming techniques are well known to those skilled in the art and generally include hot drawing methods. Examples of thermoforming techniques are male billow molding technology and female billow plug assist technology. The thermoformed innerliner sheet is then trimmed and assembled to the outer wall member with mating and spacing to create a gap between the innerliner and the outer wall member for in situ foaming of the insulation material. Therefore, a composite having the following layers in sequence i) a thermoplastic synthetic resin sheet, ii) a polymer film, iii) a polymer foam and iv) an outer wall member is formed.

Suitable polymers are foams that are foamed in-situ or that are laminated or contacted to the cabinet outer wall and inner liner. For example, thermoplastic polymer foams such as polyethylene, polypropylene, or polystyrene foams can be utilized.
However, the polymer foam is advantageously a thermosetting polymer, for example a polyisocyanate-based foam, more advantageously a polyurethane and / or polyisocyanurate foam. These forms are
It is advantageous because it is in the form of fine cells, closed cells, is dimensionally stable, and can be foamed in situ. Polyisocyanate-based foams can be prepared by mixing an organic polyisocyanate with a polyol composition under reaction conditions, where the polyol composition comprises a polyol having at least two isocyanate-reactive hydrogens, a foaming agent. It contains components such as agents, catalysts and optionally surfactants.

Referring to the polyol component, there are polyols having at least 2 reactive hydrogens. Examples of preferred polyols are polyhydroxy compounds having a functionality of 2-8, more preferably 3-8 and an average hydroxyl number of 150-850, more preferably 350-800. Although it is possible to use polyols having hydroxyl numbers outside this range, it is advantageous for the average hydroxyl number with respect to the total amount of polyol used to be in the range 150 to 850.

Examples of polyols are polythioether polyols, polyesteramides, and hydroxyl group-containing polyacetals, hydroxyl group-containing aliphatic polycarbonates, amine-terminated polyoxyalkylene polyether polyols, and preferably polyesters. Includes polyols, polyoxyalkylene polyether polyols, and graft dispersed polyols. Further, combinations of the above polyols can be used as long as the combination has an average hydroxyl number within the range.

As used herein and in the claims, the term "polyester polyol" means a small amount of unreacted polyol remaining after the production of the polyester polyol and / or non-esterified polyester added after the production of the polyester polyol. Contains a polyol (eg, glycol). The polyester polyol may contain up to about 40% by weight free glycol.

The polyester polyols preferably have an average functionality of about 1,8-8, preferably about 1.8-5, more preferably about 2-3. These hydroxyl numbers are
It ranges from about 15 to 750, preferably from about 30 to 550, more preferably from about 150 to 500, and their free glycol content generally ranges from 0 to 40 of the total polyester component.
It is preferably from 2 to 30, more preferably from 2 to 15% by weight.

Such polyester polyols include, for example, organic dicarboxylic acids having 2 to 12 carbon atoms, including aromatic and aliphatic acids, and 2 to 12, preferably 2 to 6 carbon atoms. Can be prepared from polyhydric alcohols, preferably diols.

An example of a suitable polyester polyol is P
It is derived from ET scrap and is sold under the trade name "Chadol ^TM 170, 336" by Chardonol.
A, 560, 570, 571 and 572 "and from Freeman Chmical under the trade name" Freol ^TM 30-21.
Commercially available at 50 ". Examples of suitable DNT-derived polyols are" Terate ^™ 202, 203, 204, 2541 and 254A "polyols commercially available from Cape Industries. Phthalic anhydride-derived polyols. Is BASF
Trade name "Pluracol ^TM polyol 9118" from the company and "Stepanol ^TM P from the Stepan Company"
S-2002, PS-2402, PS-2502A, PS-2502, PS-2522, PS-285
2, PS-2852A, PS-2552 and PS-3152 ”.

The polyoxyalkylene polyether polyols obtainable by known methods are also advantageous for use as polyhydroxyl compounds. For example, polyether polyols use as catalysts alkali metal hydroxides such as sodium or potassium hydroxide or sodium methylate, sodium ethylate, or potassium ethylate or potassium isopropylate and preferably from 2 to 8, preferably. Is an anionic polymerization with the addition of at least one initiator molecule containing 3 to 8 reactive hydrogens, or a cation using Lewis acid such as antimony pentachloride, boron trifluoride etherate or bleaching earth as a catalyst. It can be prepared by polymerization from one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene group. Any suitable alkylene oxide, such as 1,3-propylene oxide, 1,2- and 2,3-butylene oxide, amylene oxide, styrene oxide, and preferably ethylene oxide and 1,2-propylene oxide and their oxides. Mixtures of can be used. The polyalkylene polyether polyols can be prepared from further starting materials such as tetrahydrofuran and alkylene oxide-tetrahydrofuran mixtures, epihalohydrins such as epichlorohydrin and also aralkylene oxides such as styrene oxide. The polyalkylene polyether polyol may have either primary or secondary hydroxyl groups. These polyether polyols include polyoxyethylene glycol, polyoxypropene glycol, polyoxybutylene glycol, polytetramethylene glycol, block copolymers such as polyoxypropylene and polyoxyethylene glycol, poly-1,2-oxybutylene. And polyoxyethylene glycol, combinations of poly-1,4-tetramethylene and polyoxyethylene glycol, and copolymer glycols prepared from blends or sequential additions of two or more alkylene oxides. Polyalkylene polyether polyols can be prepared by any known method, such as 1859 Wurtz and "Encyclopedia of Chmical Techn".
ology ”Vol. 7, pp. 257-265, Interscience Publisher
s, Inc. (1951) publication or the method described in US Pat. No. 1,922,459.
Preferred polyethers are ethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-.
Heptanediol, hydroquinone, resorcinol glycerol, glycerin, 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, pentaerythritol, 1,2,6-hexanetriol, α-
Alkylene oxide addition products of polyhydric alcohols such as methyl glucoside, sucrose and sorbitol. The term "polyhydric alcohol" also includes compounds derived from phenols such as 2,2-bis (4-hydroxyphenyl) propane, commonly known as bisphenol A.

Suitable organic amine starting materials include aliphatic and cycloaliphatic amines and mixtures thereof having at least one primary amino group, preferably two or more primary amino groups, and The most advantageous are diamines. Specific, but non-limiting examples of aliphatic amines are 1-1
2, a monoamine having preferably 1 to 6 carbon atoms,
For example, methylamine, ethylamine, butylamine, hexylamine, octylamine, decylamine and dodecylamine; aliphatic diamines such as 1,2-diaminoethane, propylenediamine, 1,4-diaminobutane, 1,6-diaminohexane, 2, 2-dimethyl-
3,3-propanediamine, 2-methyl-1,5-pentanediamine, 2,5-dimethyl-2,5-hexanediamine, and 4-aminomethylocta-1,8-diamine, and amino acid-based polyamines. For example lysine methyl ester and cystine dimethyl ester; cycloaliphatic monoamines having 5 to 12, preferably 5 to 8 carbon atoms in cycloalkyl, such as cyclohexylamine and cyclooctylamine and preferably 6 to 13 Cycloaliphatic diamines having carbon atoms, such as cyclohexylene diamine, 4,4'-, 4,2'- and 2,2'-diaminocyclohexylmethane and mixtures thereof; 6-1
Aromatic monoamines having 8 carbon atoms such as aniline, benzylamine, toluidine and naphthylamine and aromatic diamines preferably having 6 to 15 carbon atoms such as phenylenediamine, naphthylenediamine, fluorenediamine, diphenylene. Diamines, anthracene diamines, and preferably 2,4- and 2,6-
A mixture of toluylenediamine and 4,4 '-, 2,4'- and 2,2'-diaminodiphenylenemethane, and aromatic polyamines such as 2,4,6-triaminotoluene, polyphenyl-polymethylene-polyamine, And a mixture of diamine diphenylmethane and polyphenyl-polymethylene-polyamine. Preference is given to ethylenediamine, propylenediamine, decanediamine, 4,4'-diaminophenylmethane, 4,4'-diaminocyclohexylmethane and toluylenediamine.

Suitable initiator molecules also include alkanolamines such as ethanolamine, diethanolamine,
Includes N-methyl- and N-ethyldiethanolamine and triethanolamine + ammonia.

As a suitable polyol,
Polymer-modified polyols, especially so-called graft polyols, are mentioned. Graft polyols are well known to those skilled in the art and one or more vinyl polymers, preferably acrylonitrile and styrene, in situ in the presence of a polyether or polyester polyol, especially a polyol containing a small amount of natural or derived unsaturation. It is produced by polymerizing. The method for producing such a graft polymer is described in U.S. Pat. No. 3,652,639.
Column 5 and Examples, U.S. Pat. No. 3,823,201, Columns 1-6 and Examples, U.S. Pat. No. 4,690,956
Columns 2-8 of the specification and examples and US Pat. No. 4,
No. 524,157, all of which are provided by reference.

Non-graft polymer modified polyols are also advantageous, for example they are polyisocyanates with alkanolamines and are described in US Pat. Nos. 4,293,470, 4,296,213 and 4,374,209. Polyols as taught in U.S. Pat. No. 4,38,38
Dispersions of polyisocyanates containing ancillary urea groups as taught in US Pat. No. 6,167, and also containing biuret linkages as taught in US Pat. No. 4,359,541. It is manufactured by reacting in the presence of a polyisocyanurate dispersion. Another polymer modified polyol has a particle size of less than 20 mm,
It can be produced by in-situ reduction of the polymer, preferably to less than 10 mm.

Blowing agents which can be used are chemically active blowing agents which react chemically with isocyanates or another formulation ingredient to generate a gas for blowing, and are gaseous at the exothermic blowing temperature or In addition to physically active blowing agents that require little reaction with the foam components to provide the blowing gas. By physically active blowing agent is meant a gas that is thermally unstable and decomposes at high temperatures.

Examples of chemically active blowing agents are preferably those which react with isocyanates to generate a gas such as CO ₂ . Suitable chemically active blowing agents are 46-300.
Includes, but is not limited to, mono- and polycarboxylic acids having a molecular weight of, salts of those acids, and tertiary alcohols.

Water is preferably used as cocatalyst.
Water reacts with organic isocyanates to generate the actual blowing agent, CO ₂ . However, water consumes isocyanate groups, so an equimolar excess of isocyanate must be used to replenish the consumed isocyanate.

Physically active foaming agents are exothermic foaming temperatures or below,
It preferably boils below 500 ° C. The most advantageous physical blowing agents are those that have an ozone depletion capacity of 0.05 or less. Examples of physically active blowing agents are volatile non-halogenated hydrocarbons having 2 to 7 carbon atoms, such as alkanes, alkenes, cycloalkanes having up to 6 carbon atoms, dialkyl ethers, cycloalkylene ethers and Ketones; Hydrochlorofluorocarbons (HCFCs); Hydrofluorocarbons (HFCs); Perfluorinated hydrocarbons (HFCs); Fluorinated ethers (HF)
C) and degradation products.

Examples of volatile non-halogenated hydrocarbons are linear or branched alkanes such as butane, isobutane,
2,3-dimethylbutane, n- and isopentane and technical grade pentane mixtures, n- and isohexane, n-
And isoheptane, n- and isooctane, n- and isoheptane, n- and isooctane, n- and isononane, n- and isodecane, n- and isoundecane,
And n- and isododecane. Further, specific examples of alkenes are 1-pentene, 2-methylbutene, 3-methylbutene, and 1-hexene, and specific examples of cycloalkanes are cyclobutane, preferably cyclopentane,
Cyclohexane or mixtures thereof, special examples of linear or cyclic ethers are dimethyl ether, diethyl ether, methyl ethyl ether, vinyl methyl ether, vinyl ethyl ether, divinyl ether, tetrahydrofuran and furan, and special ketones. Examples are acetone, methyl ethyl ketone and cyclopentanone. The preferred alkanes are cyclopentane, n- and isopentane, n-hexane, and mixtures thereof.

Any hydrofluorocarbon blowing agent can be used in the present invention. Preferred hydrofluorocarbon blowing agents are 1-chloro-1,2-difluoroethane; 1-chloro-2,2-difluoroethane (14
2a); 1-chloro-1,1-difluoroethane (14
2b); 1,1-dichloro-1-fluoroethane (14
1b); 1-chloro-1,1,2-trifluoroethane; 1-chloro-1,2,2-trifluoroethane;
1,1-dichloro-1,2-difluoroethane; 1-chloro-1,1,2,2-tetrafluoroethane (124
a); 1-chloro-1,2,2,2-tetrafluoroethane (124); 1,1-dichloro-1,2,2-trifluoroethane; 1,1-dichloro-2,2,2- Trifluoroethane (123); and 1,2-dichloro-
1,1,2-Trifluoroethane (123a); Monochlorodifluoromethane (HCFC22); 1-Chloro-
2,2,2-trifluoroethane (HCFC-133
a); gem-chlorofluoroethylene (R-1131
a); Chloroheptafluoropropane (HCFC-2
17); Chlorodifluoroethylene (HCFC-11
22); and transchlorofluoroethylene (HC
FC-1131). The most preferred hydrochlorofluorocarbon blowing agent is 1,1-dichloro-1-fluoroethane (HCFC-141b).

Suitable hydrofluorocarbons, perfluorinated hydrocarbons and fluorinated ethers are difluoromethane (HFC-32); 1,1,1,2-tetrafluoroethane (HFC-134a); 1,1,2, 2-Tetrafluoroethane (HFC-134); 1,1-Difluoroethane (HFC-152a); 1,2-Difluoroethane (HFC-142); Trifluoromethane; Heptafluoropropane; 1,1,1-Trifluoroethane;
1,1,2-trifluoroethane; 1,1,1,2,2
-Pentafluoropropane; 1,1,1,3-tetrafluoropropane; 1,1,2,3,3-pentafluoropropane; 1,1,1,3,3-pentafluoro-n-
Butane; hexafluorocyclopropane (C-21
6); Octafluorocyclobutane (C-318); Perfluorotetrahydrofuran; Perfluoroalkyltetrahydrofuran; Perfluorofuran Perfluoro-propane, -butane, -cyclobutane, -pentane,
-Cyclopentane, and -hexane, -cyclohexane, -heptane, and -octane; perfluorodiethyl ether; perfluorodipropyl ether; and perfluoroethylpropyl ether.

Decomposition type, physically active blowing agents which evolve gas upon pyrolysis include pecanfluores, amine / carbon dioxide complexes, and alkyl alcoholate compounds, especially methyl and ethyl formates.

The total and relative amounts of blowing agent depend on the desired foam density, the type of hydrocarbon, and the amount and type of additional blowing agent used. Typical polyurethane foam densities for rigid polyurethane insulation applications are:
0.5 pcf-10 pcf, preferably 1.2-3.5 p
It is in the range of the free rising density of cf. The weight of all blowing agents is from 0.05 to 45 with respect to 100 parts by weight of polyol having at least 2 isocyanate-reactive hydrogens.
Parts by weight.

Catalysts which significantly accelerate the reaction of compounds containing hydroxyl groups with modified or unmodified polyisocyanates can be used. Examples of suitable compounds are also cure catalysts that function to reduce stick time, increase green strength, and prevent foam shrinkage. Suitable curing catalysts are organometallic catalysts, preferably organotin catalysts, although iron such as lead, titanium, copper, mercury, cobalt, nickel, iron, vanadium, antimony and manganese can also be used. . Here way of example tin as the metal, but a suitable organometallic catalyst has the _{formula: R n Sn [X-R} 1 -Y] 2 [ wherein, R C ₁ -C ₈ - alkyl or aryl group , R ¹ is a C ₀ -C ₁₈ -methylene group, optionally substituted or branched with a C ₁ -C ₄ -alkyl group, Y
Is a hydrogen atom or a hydroxy group, preferably a hydrogen atom, X is ^{methylene, -S -, - SR 2 COO} -, - SO
OC -, - O ³ S- or a -OOC-, wherein R ² is C
_1- C ₄ -alkyl group, n is 0 or 2, provided that when X is a methylene group, R ¹ is C ₀ ]. Tin (II) acetate, octane tin (II),
Tin (II) ethylhexanoate and tin laurate (I
I); Dialkyl of organic carboxylic acids having 1 to 32 carbon atoms, preferably 1 to 20 carbon atoms (1 to 8)
C) Tin (IV) salts such as diethyltin diacetate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dihexyltin diacetate and dioctyltin diacetate. Other suitable organotin catalysts are organotin alkoxides and mono- or polyalkyl (1-8C) tin (IV) salts of inorganic compounds such as butyltin trichloride, dimethyl- and diethyl- and dibutyl- and dioctyl- and diphenyl. -Tin oxide, dibutyltin dibutoxide, di (2-ethylhexyl) tin oxide, dibutyltin dichloride, and dioctyltin dioxide. However, preference is given to tin catalysts having a tin-sulfur bond which is hydrolysis resistant, for example dialkyl (1-20C) tin dimercaptides including dimethyl-, dibutyl- and dioctyltin dimercaptides.

Tertiary amines also promote urethane bond formation and are triethylamine, 3-methoxypropyldimethylamine, triethylenediamine, tributylamine, dimethylbutylamine, N-methyl-, N-ethyl- and N-cyclohexylmorpholine, N-. , N, N ',
N'-tetramethylethylenediamine, N, N,
N ', N'-tetramethylbutanediamine or -hexanediamine, N, N, N'-trimethylisopropylpropylenediamine, pentamethyldiethylenetriamine, tetramethyldiaminoethylether, bis (dimethylaminopropyl) urea, dimethylpiperazine, 1-
Methyl-4-dimethyl braided ethylpiperazine, 1,2
-Dimethylimidazole, 1-azabicyclo [3.3.
0] octane and preferably 1,4-diazacyclo [2,2]
2,2] octane, and alkanolamine compounds such as triethanolamine, triisopropanolamine, N-methyl- and N-ethyl-diethanolamine and dimethylethanolamine.

Polyisocyanurates are used to prepare polyisocyanurates (PIR) and PUR-PIR foams based on the process according to the invention. Suitable polyisocyanurate catalysts are generally alkali metal salts of organic acids having 1 to 8 carbon atoms, preferably 1 or 2 carbon atoms, such as sodium salts, preferably potassium salts and ammonium salts. , Formic acid, acetic acid, salts of propionic acid or octanoic acid, and tris (dialkylaminoethyl)-, tris (dimethylaminopropyl)
-, Tris (dimethylaminobutyl)-and the corresponding tris (diethylaminoalkyl) -s-hexahydrotriazine. However, (trimethyl-2-hydroxypropyl) ammonium formate, (trimethyl-2-hydroxypropyl) -ammonium octanoate, -potassium acetate, -potassium formate and tris (dimethylaminopropyl) -s-hexahydrotriazine are , Is a commonly used polyisocyanurate catalyst. Suitable polyisocyanurate catalysts are generally based on 100 parts by weight of the total polyol.
1 to 10 parts by weight, preferably 1.5 to 8 parts by weight are used.

Examples of suitable surface-active agents are compounds which serve to maintain the homogenization of the starting materials and which can also adjust the cell structure of the plastic. Specific examples are salts of sulfonic acids, for example fatty acids such as oleic acid or stearic acid, salts of dodecylbenzene- or dinaphthylmethanesulfonic acid, and ricinoleic acid; foam stabilizers,
For example, siloxane oxyalkylene copolymers and other organopolysiloxanes, oxyethylated alkyl-phenols, oxyethylated fatty alcohols, paraffin oils, castor oil esters, ricinoleic acid esters, funnel oils and peanut oils, and foam control agents such as paraffins, fatty alcohols. , And dimethylpropyl siloxane. Surfactants are generally used in amounts of 0.01 to 5 parts by weight, preferably 1.5 to 8 parts by weight, based on 100 parts by weight of the total polyol.

Examples of suitable flame retardants are tricresyl phosphate, tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, and tris (2,3-dibromopropyl) phosphate.

In addition to the halogen-substituted phosphates mentioned above, inorganic or organic flameproofing agents such as red phosphorus, aluminum oxide hydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate (Exolit ^™ ) and calcium sulphate, foaming Graphite or cyanuric acid derivative, such as melamine, or a mixture of two or more flame retardants, such as ammonium polyphosphate and melamine, and optionally corn starch, or ammonium polyphosphate, melamine, and expandable graphite and / or optionally aromatic. Group polyesters can also be used to make the polyisocyanate polyaddition products flameproof. The flame retardant is generally 100% of the total amount of polyol.
2 to 50 parts by weight, preferably 1.5 to 2 parts by weight
It can be used in 5 parts by weight.

Any flame retardant compound is tetrakis (2-
Chloroethyl) ethylenephosphonate, pentabromodiphenyloxide, tris (1,3-dichlorophenyl) phosphate, tris (β-chloroethyl) phosphate, molybdenum trioxide, ammonium molybdate, tricresyl phosphate, 2,3-dibromopropanol, hexabromo Cyclododecane, dibromoethyldibromocyclohexane, dibromoethyldibromocyclohexane, tris (2,3-dibromopropyl) phosphate, tris (β-chloropropyl) phosphate, and melamine.

Organic polyisocyanates include virtually all known aliphatic, cycloaliphatic, araliphatic and preferably aromatic polyvalent isocyanates. Specific examples include: alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene group, such as 1,
12-dodecane diisocyanate, 2-ethyl-1,4
-Tetramethylene diisocyanate, 2-methyl-1,
5-pentamethylene diisocyanate, 1,4-tetramethylene diisocyanate and preferably 1,6-hexamethylene diisocyanate; cycloaliphatic diisocyanates,
For example, 1,3- and 1,4-cyclohexanediisocyanate and any mixtures of these isomers, 1-isocyanate-3,3,5-trimethyl-5-isocyanate methylsiloxane (isophorone diisocyanate), 2,4- and 2 , 6-Hexahydrotoluene diisocyanate and the corresponding isomer mixture, 4,4 '
-, 2,2'-, and 2,4'-dicyclohexylmethane diisocyanate and the corresponding isomer mixtures and preferably aromatic diisocyanates and polyisocyanates such as 2,4- and 2,6-toluene diisocyanate and the corresponding isomers Mixture, 4,4'-, 2,4'-,
And 2,2'-diphenylmethane diisocyanate and the corresponding isomer mixtures, 4,4'- and 2,4'-diphenylmethane diisocyanate mixtures, and polyphenylene polymethylene polyisocyanates (polymer MD
I), and mixtures of polymeric MDI and toluylene diisocyanate. The organic di- and polyisocyanates can be used individually or in the form of mixtures.

Frequently also so-called modified polyvalent isocyanates, ie products obtained by partial chemical reaction of organic diisocyanates and / or polyisocyanates, are used. Examples of these include diisocyanates and / or polyisocyanates containing ester groups, urea groups, biuret groups, allophanate groups, carbodiimide groups, isocyanurate groups and / or urethane groups. Specific examples are organic, in particular aromatic polyisocyanates, such as low molecular weight diols, which contain urethane groups and have an NCO content of 33.6 to 15% by weight, preferably 31 to 21% by weight, based on the total weight. Triol, dialkylene glycol, trialkylene glycol, or 150
4,4'-diphenylene methane diisocyanate or 2,4- and 2,6-toluene diisocyanate modified with polyoxyalkylene glycols having a molecular weight of up to 0, which can be used individually or as a mixture Examples of di- and polyoxyalkylene glycols are diethylene glycol, dipropylene glycol, polyoxyethylene glycol, polyoxypropylene glycol and polyoxypropylene polyoxyethylene glycol or -triol. Based on the total weight, 25 to 9% by weight, preferably 21 to 14% by weight, of NCO groups and polyester polyols and / or preferably polyether polyols as described below: 4,
4'-diphenylmethane diisocyanate, 2,4'-
Also suitable are prepolymers containing NCO groups made from mixtures of 4,4'-diphenylmethane diisocyanate, 2,4- and / or 2,6-toluene diisocyanate or polymeric MDI. Furthermore, for example, 4,
Based on 4'- and 2,4'- and / or 2,2'-diphenylmethane diisocyanate and / or 2,4'- and / or 2,6-toluene diisocyanate,
33.6-15% by weight, based on the total weight, preferably 31-
Liquid polyisocyanates containing carbodiimide groups with an NCO content of 21% by weight have also proved suitable. Modified polyisocyanates are organic polyisocyanates, optionally with one another or unmodified, such as 2,4'- and 4,4'-diphenylmethane diisocyanate, polymeric MDI, 2,4'- and / or 2,6.
-May be mixed with toluene diisocyanate.

The foam produced had a closed cell structure and a residual amount of blowing agent. Polyisocyanate-based foams are formed by foaming in a high pressure mixing head equipped with a nozzle for introducing the foam or foaming component into the cavity formed by the fitting of the outer wall member and the inner liner sheet.

[0080]

【Example】

Example 1 This example demonstrates the synergistic effect of ethylene-methacrylic acid copolymer on blistering time.

Sheets of polymer film were tested for their effectiveness against chemical attack on high impact polystyrene sheets. The protective polymer film components set forth in Table 1 below were prepared by compounding the individual components in a single screw extruder at 200 ° C. The strand exiting the circular die was cooled in a water bath and then chopped into pellets. Some of these pellets were placed between two polyester films and placed in a hydraulic press.
The film was pressed between plates heated to 7 ° C. (350 F) to produce a 0.002 inch (0.00508 cm) thick film. The polyester film was removed from the test film. Similarly, ES7100HI
Approximately 0.03 inch (0.0762) from PS pellets
cm) thick sheets were produced. The test film and E
Place the S7100 together between the polyester films,
Again using a hydraulic press, 0.03 inch (0.07 inch)
A 62 cm thick laminate was produced. A circular test piece with a diameter of 16 mm was cut out from the laminate using a cork borer.

Glass bottle with screw stopper (height 70 mm, diameter 2
0 mm), and HCFC141b is partially about 6 cm ³
Was filled. A circular test piece was placed on top of the bottle and the test film side was exposed to HCFC141b. Screw a chemical resistant plastic stopper with a 12 mm diameter hole into the bottle,
HCFC 141b was contained. The effect of HCFC141b diffusion through the test film was measured by HIPS ES
The 7100 layers were monitored for chemical attack.
The time at which blister of the HIPS ES 7100 layer occurs was recorded and the results are summarized in Table 1 below. The time below the range indicates the time when blisters did not develop, and the time above the range indicates the time when blisters occurred. The bottle was kept at 350 ° C. for the duration of the test.

The following is a description of all components used and listed in Table 1: Quantum ^™ LM 6187 is a high density polyethylene commercially available from Quantum.

Stereon ^™ 840a is a styrene-butadiene rubber copolymer commercially available from Firestone.

Nucrel ^™ 0903 is a DuPont (EI Dupon
is an ethylene-methacrylic acid copolymer containing 9% by weight of methacrylic acid, based on the weight of the copolymer, commercially available from T. de Nemours.

Finaclear ^™ 520 is a styrene-butadiene diblock copolymer available from Fina.

ES 5350 is a high impact polystyrene available from BASF.

[0088]

[Table 1]

The high density polyethylene used alone provides good protection against chemical attack on the HIPS layer as shown by the high swell time of 48-50 hours in Sample 1. However, pure high density polyethylene film is commercially unsuitable as a protective film because it does not adhere to HIPS thermoplastic sheets. Therefore, for commercial application it is necessary to add components such as block styrene / butadiene copolymers to improve adhesion. However, as shown in Sample 2, with only 15% addition of styrene-butadiene block copolymer, the blistering time drops sharply from 48-50 hours to 8-16 hours.

The 100% composition of Nucrel in the sample 3, which is an ethylene methacrylic acid copolymer, also showed a chemical attack on the HIPS thermoplastic layer, as indicated by the 30-32 hours to swell time. It provided good resistance to it. Also, ethylene copolymers of acrylic or methacrylic acid provide polyurethane foam attachment. However, pure Nuc
Rel does not provide as good blistering resistance as high density polyethylene film (Sample 1). And, as expected and as shown in Samples 4 and 5, the addition of the block styrene / butadiene copolymer resulted in "Nucre
The time to blistering in the l "ethylene-methacrylic acid copolymer was reduced.

The composition of Sample 2 (8-16 hours) containing rubber and high density polyethylene was treated with rubber and "Nucrel".
The combination of the compositions of Samples 4 or 5 (20-24 hours) containing OH is expected to provide the final composition with a time to blistering anywhere between 8-16 hours and 20-24 hours. Was done. However, quite unexpectedly, this combination had the opposite effect, synergistically increasing the time to blistering as shown in samples 6-8. The combination of ethylene-methacrylic acid copolymer, high-density polyethylene and styrene-butadiene block copolymer in Sample 6 is more than a two-component composition that could result by itself while maintaining the amount of block styrene-butadiene copolymer at the same weight percent. Beyond the value, the time until blistering was further increased. As shown by samples 7 and 8,
A reduction of the amount of ethylene-methacrylic acid copolymer to 20% by weight or also a slight reduction of the styrene-butadiene block copolymer results in a composition of pure high-density polyethylene with a slightly closer swell time. In all cases the advantage of enhanced adhesion was achieved by the incorporation of styrene-butadiene block copolymers.

As already mentioned, the polymer film composition may optionally contain high impact polystyrene polymers. Samples 9-13 show the effect of the copolymer on polymer film compositions containing high impact polystyrene. Blends of high impact polystyrene, high density polyethylene and styrene block copolymers show chemical attack on high impact polystyrene thermoplastic synthetic resin sheet layers as shown in Samples 9, 11 and 12 with short blistering times. Does not provide adequate protection against. However, the addition of ethylene-methacrylic acid copolymer improved the time to blistering even in compositions containing high impact polystyrene. This was also amazing. That's because ethylene
This is because in the composition containing the methacrylic acid copolymer, the relative proportion of the high density polyethylene, which itself provides good swell resistance, is reduced. Moreover, the blistering resistance nevertheless increased.

Example 2 Sheets of polymer film were tested for their effectiveness against chemical attack on high impact polystyrene sheets. The same method of making and testing the laminate as described in Example 1 was used in this example as well.

The following components were used to make the polymer film: Nucrel ^™ 0903 is an ethylene-methacrylic acid copolymer.

Finaclear ^™ 520 is a styrene-butadiene diblock copolymer.

Quantum ^™ LM 6187 is a high density polyethylene.

ES 5350 is a high impact polystyrene.

[0098]

[Table 2]

The results for Sample 1, in which no polymer film is present, show that the HIPS ES 7100 layer has only about 2-3.
It was shown that swelling occurred within the range of time. In sample 2, which used pure high density polyethylene as the protective layer, blistering occurred in 50-52 hours. However, as already mentioned, a protective film containing pure pure high density polyethylene is not commercially useful. When some high-density polyethylene film was blended with some styrene block copolymers, as in Sample 3, the time to blistering was drastically reduced to 16-18 hours. However,
The incorporation of styrene block copolymer particles was necessary to promote adhesion between the polymer film and the HIPS thermoplastic synthetic resin sheet. As shown in Sample 4, incorporation of a small amount of ethylene methacrylic acid copolymer into the polymer film in an amount of 2.5% by weight, based on the weight of the polymer film, further reduced the time to blistering. did. At first glance, this copolymer is generally considered to adversely affect the protective action of the polymer film.

Surprisingly, as shown in Sample 5, the addition of additional ethylene methacrylic acid copolymer to the polymer film composition dramatically increased the time to blistering from 8-16 hours to 44-45 hours. Increased. Therefore,
Amounts of ethylene-methacrylic acid copolymer above 2.5% by weight are effective to synergistically increase the time to blistering. This unexpected increase in blistering time continued until the amount of ethylene-methacrylic acid copolymer reached 30% by weight, based on the weight of the polymer film, as shown in Sample 9, at which point the blistering time was It decreased to 26-28 hours. Nevertheless, the blistering time in Samples 9-11 using an amount of copolymer greater than 30% by weight was comparable to that of Sample 1, in which the amount of the copolymer was 0 or 2.5.
It was still higher than in 3 and 4. Therefore, there is no limit to the amount of ethylene-methacrylic acid copolymer that can be added to the polymer film composition to improve blistering time. However, for cost reasons and to achieve optimum synergistic effect, the amount of the copolymer is
Advantageously more than 2.5% by weight and less than 0% by weight, based on the weight of the polymer film composition.

Samples 12-19 and Samples 1-11 differ in that the former contained an additional component, impact resistant polystyrene, in the polymer film composition. A comparison of Sample 12 and Sample 13 shows that the addition of high impact polystyrene reduces blistering time somewhat. Also in this case, sample 1
As shown in 3, no improvement was observed when only 2.5 wt% ethylene-methacrylic acid copolymer was added to the polymer film composition. However, as shown in Sample 4, the addition of 5% by weight Nucrel copolymer doubles the blistering time, increases to 10% by weight, stabilizes to 20% by weight and then again exceeds 30% by weight. Diminished. Thus, the addition of Nucrel surprisingly improved the blistering time of this composition even when adding high impact polystyrene, which has a detrimental effect on the protective action of the polymer film.

Example 3 In this example, the effect of different types of ethylene-vinyl acid copolymers was tested on blister resistance to adjacent HIPS on polymer films. Blistering times were tested for the different compositions listed in Table 3 using the same procedure as described in Examples 1 and 2 above. Quantum LM-618
7 (high density polyethylene) 65% by weight and Finaclear 520
(Styrene-butadiene block copolymer rubber) 15
To a polymer film composition consisting of wt% was added 20 wt% of different types of Nucrel ethylene-vinyl acid copolymer. The different types of Nucrel copolymers were: Nucrel 1202HC contains 12% by weight methacrylic acid with a melt index of 2; Nucrel
31001 contains 10% by weight acrylic acid with a melt index of 1.3; Nucrel 0407 contains 4% by weight of methacrylic acid with a melt index of 7;
Nucre 0902 contains 9% by weight acrylic acid with a melt index of 2; Nucrel 0903 contains 9% by weight of acrylic acid with a melt index of 3.

[0103]

[Table 3]

The results of the experiments carried out above show that methacrylic acid has a much better effect than acrylic acid, but acrylic acid still produced some resistance to the blistering action of 141b. In addition, only 4% by weight of methacrylic acid, relative to the weight of the ethylene-methacrylic acid copolymer, continued to provide resistance to the blistering effect of 141b.
A more optimal amount is in the range above 4% by weight as shown in samples 4 and 5.

An important issue to consider when making the composition as a protective polymer film is regrind / recycle performance. Provide a thermoformable innerliner sheet consisting of a thermoplastic formed sheet bonded to a protective film using either coextrusion or laminating methods. The sheet is then thermoformed and trimmed of excess.
This trimmed portion is recycled back to the extruder used to make the thermoplastic molded sheet, rather than discarded. The thermoplastic molded sheet is typically made from high impact polystyrene. Scrap and trim contain both high impact polystyrene and a protective film composed of a polyolefin, a copolymer and a styrene block copolymer, so that the unused virgin used to make the synthetic resin of the scrap and trim. Recycling back to high impact polystyrene materials introduces at least three different polymer compositions into the now virgin HIPS. As a result, it is also possible to adjust the mechanical properties of the thermoplastic synthetic resin sheet by adding the trim and scrap. In particular, the inventor has extruded 95% by weight of ES7 100 and 5% by weight of ES 7860 (both are high impact polystyrene commercially available from BASF) in a Brabender 3/4 inch single screw extruder. And injection molding with 28 tons of air burg having a barrel temperature of 2000 ° C. at an injection temperature of 8 seconds to obtain a thermoplastic synthetic resin of 0.
When producing a 125 inch plaque, it was found to have a Gardner impact strength of about 200 inch-lb. However, based on the weight of each polymer film composition, Nucrel 0903
20% by weight, Finaclear 520 15% by weight and Quantum LM
6187 ES with a polymer film composition consisting of 65% by weight
When 85% by weight of 7100 and 5% by weight of ES 7860 were added, the Gardner impact strength of the mixture decreased to 110 inch-lb. Thus, a scrap or trim virgin high impact polystyrene mixture, the total combination of which will contain 10% by weight of the polymer film composition, reduces the Gardner impact strength of the polymer film composition.

However, the Gardner impact strength is
It can be increased by adding a small amount of a block copolymer, preferably a styrene-butadiene copolymer, to a fresh high impact polystyrene mixture containing the polymer film composition. For example, adding 1% by weight of FINACLEAR 520 styrene-butadiene copolymer rubber to a mixture of virgin impact polystyrene and 10% by weight of a polymer film composition, the Gardner impact strength of a thermoplastic synthetic resin sheet is 290 inch-lb. Rose to. This value far exceeds the impact strength of virgin high impact polystyrene alone.

Accordingly, another subject of the present invention is the melt-blending of a high impact polystyrene composition with a thermoformable innerliner material, provided that the innerliner comprises a layer of thermoplastic synthetic resin sheet material and a polymer film. And combining the melt blend with an effective amount of a synthetic block copolymer rubber. In this case, an effective amount is the desired level of Gardner impact strength of a sheet of material made from the above ingredients, preferably 180 inch-lb, more preferably 250 inch-lb.
An amount considered sufficient to raise the Gardner impact strength in lbs. Examples of suitable amounts of styrene block copolymers are based on the weight of polymer film material and styrene block copolymer in the melt blend.
It is in the range of 0.5 to 2% by weight.

In this method, the styrene block copolymer is added separately to virgin high impact polystyrene and scrap and trim, rather than adding an additional amount of synthetic block copolymer rubber to the polymer composition. It has been found that increasing the amount of styrene block copolymer in the polymer film composition adversely affects the blistering resistance of the polymer film composition. Therefore, it is advantageous to add styrene block copolymers separately to virgin high impact polystyrene and scrap and trim and extrude them together to form a thermoplastic synthetic resin sheet material. The materials can be bonded to the polymer film composition either by coextrusion or lamination.

[Brief description of drawings]

FIG. 1 is a perspective view showing a cabinet of a refrigerator.

FIG. 2 is a perspective view of a thermoformed inner liner.

FIG. 3 is a cross-sectional view of a composite composed of an inner liner, a polymer foam and an outer wall member.

[Explanation of symbols]

1 outer wall member, 2 inner liner, 3 polymer foam heat insulator, 6 inner liner sheet, 7
Thermoplastic synthetic resin sheet, 8 polymer film,
9 gloss cap

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display area C08L 23/26 LCN C08L 23/26 LCN 53/02 LLY 53/02 LLY 75/04 NFX 75/04 NFX

Claims (16)

[Claims] 1. A composition for resisting the swelling action of a polymer foam blowing agent, which comprises (a) a polyolefin, (b) an ethylenically unsaturated aliphatic or alicyclic hydrocarbon monomer, and a vinyl group and a carboxylic acid group. A copolymer derived from a monomer comprising a monomer compound
And (c) a protective composition for reducing chemical attack on plastics, which comprises a styrene block copolymer. 2. Based on the weight of the composition, respectively: (a) 35% to 90% by weight of polyolefin, (b) more than 2.5% by weight and less than 30% by weight of copolymer, and (c) styrene block copolymer 5. The composition of claim 1 which comprises from 25% to 25% by weight. 3. The composition according to claim 1, which comprises (a) 40% by weight to 85% by weight of polyolefin, (b) 5% by weight to 20% by weight of copolymer, and (c) 10% by weight to 20% by weight of styrene block copolymer. Composition. 4. The styrene block copolymer comprises at least two different monomers comprising styrene, ethylene, butylene, or a conjugated double bond compound, even if they are functionalized with maleic acid or maleic anhydride, respectively. 4. A composition according to claim 1, 2 or 3 consisting of a block copolymer derived from 5. (a) At least one C _{2 to} C ₄ selected from the group consisting of ethylene, propylene and butylene.
A homopolymer or copolymer of olefinically unsaturated monomers, (b) at least one ethylenically unsaturated aliphatic hydrocarbon monomer selected from the group consisting of ethylene, propylene and butylene, and the group of acrylic acid and methacrylic acid. Copolymers derived from monomers selected from (c) styrene-butadiene diblock, styrene-ethylene-propylene diblock, styrene-ethylene /
A composition according to any one of claims 1, 2 or 3 consisting of a styrene block copolymer selected from the group consisting of butylene-styrene triblock and star block copolymers. 6. Further comprising high impact polystyrene,
The composition of claim 1. 7. The composition of claim 5, wherein the amount of high impact polystyrene is in the range of 10% to 40% by weight, based on the weight of the composition. 8. A polymer film mainly consisting of the composition according to any one of claims 1 to 6. 9. A thermoplastic synthetic resin sheet, (ii) a polymer film, (iii) a polymer foam and (iv) an outer wall member, which are successively formed, wherein the polymer film is mainly composed of those of claims 1 to 6. A composite comprising the composition according to claim 1. 10. The composite according to claim 8, wherein (i) the resin sheet is made of high-impact polystyrene and (iii) the polymer foam is made of polyurethane foamed with a blowing agent made of a halogenated hydrocarbon. 11. The resin sheet comprises 0.015 inch to 0.15 inch.
30 inches thick, polymer film 0.001 to 0.05 inches thick and polymer foam 1 to
The composite of claim 9 having a thickness of 3 inches. 12. The composite of claim 10, wherein the polymer is a film coextruded with a resin sheet. 13. The composite of claim 11, further comprising a gloss cap in contact with the side of the resin sheet opposite the polymer film. 14. A method for producing a thermoformable inner liner sheet, comprising: (A) a thermoplastic synthetic resin sheet bonded to a polymer film by coextruding the thermoplastic synthetic resin composition with a polymer film composition. A liner is manufactured and (B) a thermoplastic synthetic resin sheet is laminated on a polymer film, wherein the polymer film and the polymer film composition are (1) a polyolefin,
(2) a copolymer derived from a monomer comprising an ethylenically unsaturated aliphatic or alicyclic hydrocarbon monomer and a monomer compound containing a vinyl group and a carboxylic acid group,
And (3) a styrene block copolymer, which is a method for producing a thermoformable inner liner sheet. 15. The method of claim 14 comprising melting the individual compositions and feeding the individual compositions separately through a coextrusion feed block or a multi-manifold die. 16. A liner is thermoformed in a female billow plug assist or a male billow, trimmed and spaced inside the wall cabinet, and a polymer foam is injected between the liner and the wall cabinet. 16. The method of claim 15, which is or is injected.