JPH0340700B2 - - Google Patents

Description

[Detailed description of the invention]

[] Object of the Invention The present invention relates to a laminate comprising a polyurethane foam and a molded product of a polyolefin composition. More specifically, (A) olefin polymer, (B)
A urethane polymer production reaction on the surface of a molded product of a mixture consisting of an organic compound having at least one unsaturated bond in the molecule and containing a hydroxyl group, (C) an organic peroxide, and (D) a glass fiber. The invention relates to a laminate consisting of a polyurethane foam obtained by simultaneously performing foaming and foaming, and a molded product of an olefinic polymer mixture, and its purpose is to provide a laminate with strong adhesion. It is. [] Background of the Invention At present, the insulation properties of polyurethane foam,
Due to its cushioning properties, polyurethane foam is used in various ways as a cushioning material for automobile parts such as instrument panels and armrests, and as a heat insulating material for home appliances such as electric refrigerators and air conditioners, and refrigerated trucks.
When polyurethane foam is used in such fields, it is often necessary that the polyurethane foam be firmly adhered to the base material or surface material of the product. If the base material is highly surface active, such as metal, wood, or ABS resin (acrylonitrile-butadiene-styrene three-dimensional copolymer resin), methods such as injection foaming, which is used in the production of polyurethane foam, may be used. If the urethane polymer formation reaction and foaming are performed simultaneously on the base material, a product (laminate) in which the polyurethane foam is firmly adhered to the base material can be easily obtained. However, since olefin polymers do not have polar groups in their molecules (so-called non-polar), they are chemically extremely inert polymers. It is not possible to use polymers as substrates or surfaces to produce laminates with polyurethane foams because of the extremely poor adhesion. Currently, when the urethane polymer formation reaction and foaming are performed simultaneously on the surface of the substrate by methods such as injection foaming, mold foaming, and spray foaming, and when the olefin polymer and polyurethane are in close contact with each other, olefin polymer A method has been proposed in which a primer whose main components are chlorinated polypropylene and polyolefin grafted with maleic anhydride is applied in advance to the surface of the combined molded product. However, this method of applying a primer not only adds one more step to the application process, but also increases costs because an expensive primer is used. [] Structure of the Invention Based on the above, the present inventors have conducted various searches to obtain a laminate by firmly adhering a polyurethane foam and an olefin polymer molded product without using a primer. (A) Olefin polymer, (B) "Organic compound having at least one unsaturated bond in the molecule and containing a hydroxyl group (hereinafter referred to as "hydroxyl compound"), (C) Organic peroxide and (D) glass fiber, the mixing ratio of the glass fiber in the total amount of the olefin polymer and the glass fiber is 5 to 40% by weight, and the olefin polymer and the glass fiber are The mixing ratio of the hydroxyl compound to 100 parts by weight is 0.1 to 50 parts by weight of the hydroxyl compound and 0.01 to 20 parts by weight of the organic peroxide. It was discovered that a laminate consisting of a polyurethane foam and a molded product of an olefinic polymer mixture obtained by simultaneously performing a formation reaction and foaming is a laminate having strong adhesion, and the present invention was achieved. did. [] Effects of the Invention The laminate obtained by the present invention, including its manufacturing method, exhibits the following effects (characteristics). (1) A molded product of an olefinic polymer mixture and a polyurethane foam can be directly and firmly adhered to each other without using a primer. (2) The urethane polymer production reaction and foaming can be simultaneously and easily carried out on the surface of a molded article of an olefinic polymer mixture as a base material by a commonly used method. (3) It is ideal as a core material for various parts that require high rigidity, and by applying the above coating, molded products with good oil resistance and high rigidity can be obtained. be able to. The laminate obtained by the present invention can be used in a wide variety of ways in order to exhibit the above-mentioned effects. Typical usage examples are shown below. (1) Automotive parts such as bumpers, instrument panels, armrests, door liners, seat bags, duct covers, etc. (2) Home appliance parts such as the interior and exterior of coolers and refrigerators (3) Housing materials such as loop panels and insulation walls ( 4) Daily necessities and furniture such as dining tables, desk surfaces, furniture panels, kitchen cabinets, ice boxes, etc. (5) Freezer components such as interior materials for refrigerated trucks and freezer walls [] Specific description of the invention (A) Olefin polymer The olefinic polymers used in the present invention include ethylene homopolymers, propylene homopolymers, random or block copolymers of ethylene and propylene, and ethylene and/or propylene copolymers having at most 12 carbon atoms. Examples include random or block copolymers with other α-olefins (copolymerization ratio of α-olefins is at most 20% by weight). The molecular weight of these olefin polymers is generally
2 to 1 million, preferably 2 to 500,000,
Particularly suitable are olefin resins having a molecular weight of 50,000 to 300,000. In addition, low density (0.900 g/cm ³ ) to high density (0.980 g/cm ³ ) ethylene homopolymers, propylene homopolymers, random or block copolymers of ethylene and propylene, and copolymers of ethylene or propylene with other Random or block copolymers with α-olefins are preferred. These olefinic polymers are produced by using a catalyst system (so-called Ziegler catalyst) obtained from a transition metal compound and an organoaluminium compound, and by supporting a chromium compound (for example, chromium oxide) on a carrier (for example, silica). It is obtained by homopolymerizing or copolymerizing an olefin using the resulting catalyst system (so-called Phillips catalyst) or a radical initiator (eg, an organic peroxide). Furthermore, the present invention also includes modified polyolefins obtained by graft polymerizing these olefin polymers with a compound having at least one double bond (for example, an unsaturated carboxylic acid or a vinyl silane compound). The production methods for these olefin polymers and modified polyolefins are well known. These olefin polymers and modified polyolefins may be used alone or in combination of two or more. Furthermore, two or more of these olefin polymers and modified polyolefins may be used as a resin blend in any proportion. (B) Hydroxyl Compound The hydroxyl compound used in the present invention is an organic compound containing at least one unsaturated bond (double bond, triple bond) and having a hydroxyl group. Of these,
Typical organic compounds containing hydroxyl groups include alcohols with double bonds, alcohols with triple bonds, esters of monovalent or divalent unsaturated carboxylic acids and unsubstituted dihydric alcohols, and Examples include esters of saturated carboxylic acids and unsubstituted trihydric alcohols, esters of unsubstituted tetrahydric alcohols, and esters of unsubstituted pentahydric or higher alcohols. Among the alcohols having a double bond, preferred representative examples are those whose general formula is represented by the following formula [formula ()]. In formula (), R ¹ and R ² may be the same or different, and have a hydrogen atom or a carbon number of 1 to 24
hydrocarbon groups. Representative examples of desirable alcohols having a triple bond are those whose general formula is represented by the following formula [formula ()]. (R ³ −C≡C−R ⁴ −)OH () In the formula (), R ³ and R ⁴ may be the same or different, and have a hydrogen atom or a carbon number of 1 to 24
hydrocarbon groups. Further, the ester of an unsubstituted dihydric alcohol and an unsaturated carboxylic acid is an ester of a monovalent unsaturated carboxylic acid and an unsubstituted dihydric alcohol, and as a representative example of a preferable one, the general formula is the following formula [( ) is expressed by the following formula. In formula (), R ⁵ is an unsaturated hydrocarbon group having 2 to 24 carbon atoms, and R ⁶ is an unsaturated hydrocarbon group having 2 to 24 carbon atoms.
~24 hydrocarbon groups. Furthermore, the ester of an unsubstituted trihydric alcohol and an unsaturated carboxylic acid is an ester of a monovalent unsaturated carboxylic acid and an unsubstituted trihydric alcohol,
A typical example of a desirable one is one whose general formula is represented by the following formula [formula ()]. In formula (), R ⁷ is an unsaturated hydrocarbon group having 2 to 24 carbon atoms, and R ⁸ is an unsaturated hydrocarbon group having 2 to 24 carbon atoms.
~24 hydrocarbon groups. In addition, the ester of an unsubstituted tetrahydric alcohol and an unsaturated carboxylic acid is an ester of a monovalent unsaturated carboxylic acid and an unsubstituted tetrahydric alcohol, and a typical example of a preferable one is the general formula [() It is expressed by the following formula. In formula (), R ⁹ is an unsaturated hydrocarbon group having 2 to 24 carbon atoms, and R ¹⁰ is an unsaturated hydrocarbon group having 2 to 24 carbon atoms.
~24 hydrocarbon groups. Further, esters of unsubstituted pentavalent or higher alcohols and unsaturated carboxylic acids are esters of monovalent unsaturated carboxylic acids and unsubstituted pentavalent or higher alcohols, and representative examples of desirable ones include:
The general formula is expressed by the following formula [formula ()]. In the formula (), n is the above, R ¹¹ is an unsaturated hydrocarbon group having 2 to 24 carbon atoms,
R ¹² is a hydrocarbon group having 2 to 60 carbon atoms. In addition, other esters include esters of unsaturated dihydric carboxylic acids and unsubstituted polyhydric alcohols, and preferred representative examples include those whose general formula can be represented by the following formula [formula ()]. can give. In formula (), m is 1 or more, and R ¹³
is an unsaturated hydrocarbon group having 2 to 50 carbon atoms, and R ¹⁴ is a hydrocarbon group having 2 to 100 carbon atoms. Representative examples of these hydroxyl compounds include the specification of Japanese Patent Application No. 57-36502 and "Handbook of Existing Chemical Substances" (Kagaku Kogyo Nippo Co., Ltd.,
Published in 1974) Supervised by the Chemical Safety Division, Basic Industries Bureau, Ministry of International Trade and Industry, 2nd edition, pages 25, 27 to 28
Pages, pages 50 to 55 and pages 57 to 57
It is described on page 58. Among the hydroxyl compounds used in the present invention, representative examples of suitable ones include 3-
Hydroxy-1-propene, 4-hydroxy-
1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene,
3-hydroxy-2-methyl-1-propene,
Cis-5-hydroxy-2-pentene, trans-5-hydroxy-2-pentene, cis-
1,4-dihydroxy-2-butene, trans-1,4-dihydroxy-2-butene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxyethyl Crotonate, 2,3,4,5,6-pentahydroxyhexyl acrylate, 2,3,4,5,6-pentahydroxyhexyl methacrylate, 2,
Examples include 3,4,5-tetrahydroxypentyl acrylate and 2,3,4,5-tetrahydroxypentyl methacrylate. (C) Organic peroxide Furthermore, the organic peroxide used in the present invention is generally used as an initiator in radical polymerization and a crosslinking agent for polymers, and has a half-life of 1 minute or more at 100°C or more. A temperature of 130°C or higher is particularly preferred.
If the above-mentioned temperature is below 100°C, it is not only difficult to handle, but also the effect of using it is not very noticeable, so it is not desirable. Representative examples of preferred organic peroxides include ketone peroxides such as 1,1-bis-tertiary-butylperoxy-3,3,5-trimethylcyclohexane, dialkyl peroxides such as dicumyl peroxide, Hydroperoxides such as 2,5-dimethylhexane-2,5-hydroperoxide, diacyl peroxides such as benzoyl peroxide, and po-oxyesters such as 2,5-dimethyl-2,5-dibenzoyl peroxyhexane. can give. (D) Glass fiber The glass fiber used in the present invention usually has a single fiber diameter of 0.5 to 20 microns, particularly preferably 0.5 to 15 microns.
It is undesirable to use glass fibers with a single fiber diameter of less than 0.5 microns because they may break during kneading and molding. On the other hand, if the diameter exceeds 20 microns, it is difficult to improve the rigidity of the resulting mixture, which is not preferred. Further, the cut length is generally 0.03 to 15 mm, and preferably 0.05 to 10 mm.
It is not preferable to manufacture the mixture using glass fibers with a cut diameter of less than 0.03 mm because it is difficult to improve the stiffness of the resulting mixture. On the other hand, if the diameter exceeds 15 mm, it is not preferable because it may break during kneading and molding. The glass fibers used in the present invention are commonly used as fillers or reinforcing agents in the rubber industry and synthetic resin industry, and include vinyl acetate resins, silane compounds, or titanate compounds. It is also possible to use a material that has been subjected to a coupling treatment. In addition, so-called milled glass fibers manufactured by grinding these glass fibers can also be used. (E) Mixing ratio In producing the mixture of the present invention, the mixing ratio of glass fiber in the total amount of olefinic polymer and glass fiber is 5 to 40% by weight, preferably 5 to 35% by weight, particularly Ten
~35% by weight is preferred. If the mixing ratio of the glass fibers in the total amount of the olefin polymer and the glass fibers is less than 5% by weight, the stiffness of the resulting mixture cannot be improved. On the other hand, if more than 30 parts by weight is mixed, moldability will be poor when producing a molded product, and even if a molded product is produced, the appearance of the molded product will not be good. In addition, the mixing ratio of the hydroxyl compound to the total amount of olefin polymer and glass fiber of 100 parts by weight is 0.1 to 50 parts by weight,
The amount is preferably 0.2 to 30 parts by weight, particularly preferably 0.3 to 20 parts by weight. If the mixing ratio of the hydroxyl compound to 100 parts by weight of the olefin polymer and glass fiber is 0.1 part by weight or less, the effect of improving adhesion is insufficient. On the other hand, even if 50 parts by weight or more was used, no improvement in adhesion was observed depending on the amount used.
Rather, it is not preferable because the original properties of the olefin polymer are impaired. Furthermore, the mixing ratio of organic peroxide to the total amount (total sum) of olefinic polymer and glass fiber of 100 parts by weight is 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, and especially 0.1 parts by weight.
~7 parts by weight is preferred. The mixing ratio of organic peroxide to the total amount (sum) of 100 parts by weight of olefin polymer and glass fiber is
If it is less than 0.01 part by weight, not only the effect of improving adhesion is low, but also the durability of the adhesion strength of the mixture is reduced. On the other hand, if the amount exceeds 20 parts by weight, the excellent mechanical properties originally possessed by the polymer will deteriorate, which is undesirable in any case. (F) Production of mixture and molded product To produce the mixture of the present invention, the olefin polymer, hydroxyl compound, organic peroxide, and glass fiber are uniformly mixed within the above mixing ratio range. do it. In producing this composition, a part of the mixed components may be mixed in advance to produce a so-called masterbatch, and this masterbatch and the remaining mixed components may be mixed to produce the above-mentioned blended components. good. Further, the mixture may be composed of an olefinic polymer, a hydroxyl compound, a glass fiber, and an organic peroxide, but depending on the purpose of use of the mixture, these mixed components may further include:
Additions such as oxygen, heat and UV stabilizers, metal deterioration inhibitors, flame retardants, colorants, electrical property modifiers, fillers, antistatic agents, lubricants, processability modifiers and tack modifiers. Agents may be mixed as long as they do not impair the properties of the mixture of the present invention. The mixture may be prepared by dry blending using mixers commonly used in the olefinic polymer industry such as Henschel mixers, Banbury mixers, kneaders, roll mills, and screw extruders. It can also be produced by melt-kneading using a mixer. At this time, a more uniform mixture can be obtained by dry blending in advance and then melt-kneading the resulting mixture. In the case of the above melt-kneading, if carried out at a high temperature, the olefin polymer may deteriorate. However, the graft polymerization between the olefinic polymer and the hydroxyl compound must be carried out at a temperature at which the organic peroxide used is decomposed. From the above, although it differs depending on the type of organic peroxide used, this melt-kneading is generally performed at 160%
Performed at ~300°C. Various molded articles may be produced from the composition thus produced by processing methods commonly used in the field of olefin polymers, such as extrusion molding, injection molding, and press molding. At this time, it is necessary to carry out the process at a temperature higher than the temperature at which the composition (graft material) obtained as described above melts. However, if the reaction is carried out at a considerably high temperature, the olefinic polymer may deteriorate, so it is a matter of course that the reaction must be carried out at a temperature below which decomposition occurs. (F) Production of laminate The laminate of the present invention can be produced by simultaneously carrying out the urethane polymer production reaction and foaming on the surface of the molded product obtained as described above. The production of this laminate does not require special equipment or special methods, such as injection foaming, mold foaming, and spraying, which are commonly used in the field of polyurethane foam production. A foaming method such as a foaming method may be applied. Furthermore, polyols used as raw materials for polyurethane foam,
The isocyanate compound, blowing agent, etc. do not need to be special, and any commonly used ones may be used.
There are no limitations. [] EXAMPLES AND COMPARATIVE EXAMPLES The present invention will now be described in more detail with reference to Examples. In addition, in the examples and comparative examples, melt
The index (hereinafter referred to as "MI") is JIS K-
According to 6760, temperature is 190℃ and load is 2.16
Measured under Kg conditions. In addition, the melt flow index (hereinafter referred to as "MFI") is based on JIS K-6758.
Measurements were made at a temperature of 230°C and a load of 2.16 kg. Furthermore, the adhesion strength between the molded product and the polyurethane foam was determined by forming the polyurethane foam between flat test pieces arranged in parallel at 1 cm intervals by an injection foaming method. A sample was cut to a size of 1 cm, and the molded parts above and below the sample were held between the crosshead of a tensile tester and pulled at a tensile speed of 5 mm/min in the direction perpendicular to the contact surface, causing the sample to break. Measure the strength when
It was defined as adhesion strength (Kg/cm ² ). In Examples and Comparative Examples, mixed components such as an olefin polymer, hydroxyl compound, glass fiber, organic peroxide, rubbery material, and talc having the following physical properties were used. [Propylene homopolymer] Density is 0.900 g/cm ³ as an olefin polymer
A propylene homopolymer [hereinafter referred to as "PP(1)"] having the following properties and an MFI of 4.0 g/10 minutes was used. [Block propylene copolymer] Also, as an olefin polymer, the ethylene content is 12.0% by weight, and the MFI is 2.0g/10
A propylene-ethylene block copolymer (hereinafter referred to as "PP(2)") having a density of 0.900 g/cm ³ and a density of 0.900 g/cm 3 was used. [High-density ethylene homopolymer] Furthermore, as an olefin polymer, the density
A high-density ethylene homopolymer (hereinafter referred to as "HDPE") having a weight of 0.961 g/cm ³ and an MI of 20 g/10 minutes was used. [Ethylene-propylene copolymer rubber] As a rubber material, the ethylene content is 72% by weight, the MFI is 0.8g/10min, and the density is
Ethylene-propylene copolymer rubber (hereinafter referred to as "EPR") having a weight of 0.86 g/cm ³ was used. [Glass Fiber] As the glass fiber, a glass fiber (hereinafter referred to as "GF") having a single fiber diameter of 11 microns and a cut length of 3 mm was used. [Talc] Talc with an average particle size of 2.0 microns was used. [Hydroxyl compound] As a hydroxyl compound, 2-hydroxyethyl acrylate [hereinafter referred to as "compound (A)"],
2-hydroxypropyl methacrylate [hereinafter referred to as "compound (B)"] and 3,6-dimethyl-
4-octyne-3,6-diol [hereinafter referred to as “compound
(C)” was used. [Organic peroxide] Benzoyl peroxide (hereinafter referred to as "BPO") and dicumyl peroxide (hereinafter referred to as "DCP") were used as organic peroxides. Examples 1 to 10, Comparative Examples 1 to 7 The components whose amounts are shown in Table 1 were mixed in advance for 10 minutes using a super mixer. Each mixture obtained was processed using a vented extruder (diameter
Pellets were manufactured while kneading using a 50 mm). Each pellet obtained was injection molded using a 5 oz. injection molding machine at a temperature of 230°C.
A flat specimen (120 x 150 mm, 2 mm thick) was prepared. Two test pieces thus obtained were fixed in parallel with an interval of 1 cm between them, and polyurethane foam was produced between them by injection foaming. The equipment for injection foaming and the stock solution of polyurethane foam were Insulvac #20 manufactured by Instaform (USA) (foaming ratio: 40 times). After being left for 24 hours after injection, the adhesion strength of each specimen to the polyurethane foam was measured. The results are shown in Table 1. In addition, in this test, if the adhesion strength is too strong and failure does not occur at the interface between the molded part and the polyurethane foam, and the polyurethane foam suffers cohesive failure, the "cohesive failure" column in Table 1 will be added. ”.

【table】

[Table] In Comparative Example 7, normal strands could not be obtained during kneading, and collection was impossible. Comparative Example 8 A composition consisting of 80 parts by weight of PP(1) and 20 parts by weight of GF was injection molded in the same manner as above to produce a flat specimen. Spray a thermosetting polypropylene primer (manufactured by Nippon P Chemical Co., Ltd., product name RB-291, ○ modified primer) onto one side of this specimen uniformly using a spray gun to a film thickness of 13 to 15 microns. 30 at a temperature of 90℃ after attaching
Drying was performed by heating for a minute. Then, a polyurethane foam was produced on the primer-coated surface by the injection foaming method in the same manner as described above. The adhesion strength of this specimen was measured and found to be 2.0 Kg/cm ² .

Claims (1)

[Scope of Claims] 1 (A) Olefin polymer (B) Organic compound having at least one unsaturated bond in the molecule and containing a hydroxyl group (C) Organic peroxide and (D) Glass It is a mixture consisting of fibers, and the mixing ratio of the glass fibers in the total amount of the olefin polymer and the glass fibers is 5 to 40% by weight,
The mixing ratio of the hydroxyl group-containing organic compound to 100 parts by weight of the total amount of the olefin polymer and glass fiber is 0.1 to 50 parts by weight,
Furthermore, the amount of organic peroxide is 0.01 to 20 parts by weight in a molded product of a mixture of polyurethane foam and olefinic polymer obtained by simultaneously carrying out a urethane polymer production reaction and foaming on the surface of a molded product of the mixture. A laminate consisting of.