JPH0328459B2 - - Google Patents

Description

[Detailed description of the invention]

[) Object of the invention The present invention relates to an olefinic polymer mixture.
More specifically, (A) an olefin polymer, (B) an organic compound having at least one unsaturated bond in the molecule and containing a hydroxyl group, (C) an organic peroxide, and (D) an organic tin compound. The present invention relates to an olefin-based polymer mixture consisting of a tertiary amine-based compound and/or a tertiary amine-based compound, and provides these articles with extremely excellent adhesive properties when producing coated products, adhesives, and laminates of molded products thereof. The purpose is to [] Background of the Invention As is well known, olefin resins not only have excellent moldability, but also have excellent mechanical strength, heat resistance,
Because it has good properties such as solvent resistance and chemical resistance, it is widely manufactured industrially and used in many fields as a general-purpose resin. however,
Olefin resins are chemically extremely inactive polymeric substances because they do not have polar groups in their molecules (so-called non-polar). Furthermore, it not only has high solidity but also extremely low solubility in solvents, so when used in fields such as painting and adhesion, it has very low paintability and adhesiveness. As mentioned above, although olefin resins have excellent moldability and the above-mentioned properties, olefin resins are used in fields where good adhesiveness and paintability are required (for example, automobile parts, home appliance parts). The use of resin was naturally limited. In order to solve the problems of adhesion and paintability of olefin resins, various methods have been proposed for some time, such as those described below. (a) A method in which an olefin resin or a molded product thereof is surface-treated from the outside and modified by a physical or chemical method (hereinafter referred to as the "modification method"). (b) A method of adding other polymeric substances or additives to olefin resin (hereinafter referred to as "addition method"). Below, these methods will be explained in more detail and problems will be described. (1) Modification method This method includes "flame treatment method, plasma treatment method, ozone treatment method, corona discharge treatment method, and irradiation treatment method using ultraviolet rays or electron beams" [hereinafter referred to as "denaturation method (a)"]. and ``a method of treatment using a chromic acid mixture and a mineral acid such as concentrated sulfuric acid, and a method of grafting in the presence or absence of a crosslinking agent using a compound containing a polar group on an olefin resin or its molded product. Chemical treatment methods such as denaturation (hereinafter referred to as ``denaturation method (b)'')]. By these modification methods, chemically active sites rich in polar groups are provided on the surface of the olefinic resin or its molded product, and the surface is physically roughened. As a result, it is thought that the effects of improved paintability and adhesiveness can be obtained. However, in order to carry out this modification method (a), the shape of the molded object to be treated must be significantly limited, and furthermore, the treatment effect not only deteriorates significantly over time due to leaving it after treatment, but also In many cases, the degree of activation is not always sufficient. Moreover, it has disadvantages such as being economically disadvantageous because it requires various expensive processing equipment. In addition, among the modification methods (b), the treatment method using mineral acids not only tends to cause pollution due to the chemicals used, but also requires complicated post-treatment steps such as neutralization, water washing, and drying. be. Furthermore, chemical treatment methods such as grafting require a drying step, require careful consideration of monomer application, grafting atmosphere, etc., and require a relatively long grafting reaction time. Therefore, it has drawbacks such as not being suitable for continuous production. (2) Addition method This method is a so-called resin blend method in which a rubber substance and/or a resin containing a polar group is added to an olefin resin.
[hereinafter referred to as "addition method (a)"] and "method of adding additives such as fillers (e.g. calcium carbonate, barium sulfate, talc, clay, wood flour)" [hereinafter referred to as "addition method (b)"] ] can be mentioned. Among the addition methods (a), in the method of adding a rubber substance to an olefin resin, since the rubber substance is generally in the form of a lump, a continuous mixer (for example, Not only is it almost impossible to perform continuous kneading using an extruder, but the mechanical properties such as stiffness and hardness of the resulting mixture, as well as heat resistance, are significantly reduced, and processability is even worse. There are disadvantages such as a decrease in On the other hand, in the method of adding a polar group-containing resin to an olefin resin, the compatibility between the resin and the olefin resin is generally poor, so the mechanical properties (e.g. strength, Not only does the impact resistance decrease, but also it is difficult to obtain a uniform composition, and in extreme cases, delamination may occur. Furthermore, addition method (b) not only impairs the above-mentioned excellent properties of the olefin resin, but also reduces moldability, and the improvement effect on adhesiveness and paintability is extremely small. . As mentioned above, both the modification method and the addition method can improve paintability and adhesion to some extent, but each method has various drawbacks, so it is difficult to find a satisfactory improvement method. It's hard to say. Furthermore, as a method for imparting paintability and adhesion to the surface of olefin-based polymer molded products, we have developed polyolefin polymers in which chlorinated polypropylene or maleic anhydride is graft-polymerized onto the surface of the molded product before coating with paint or adhesive. A method has been developed to apply a primer using such as the main ingredients.
However, with the method of applying primer,
The cost increases because the coating or adhesion process is added by one step. Including the above, without impairing the above-mentioned properties and processability of the olefin resin,
Olefinic polymers, modified products and mixtures thereof with good adhesion and paintability have not yet been developed. Based on these facts, the present inventors, in order to solve these drawbacks, (A) 100 parts by weight of an olefin polymer, (B) having at least one unsaturated bond in the molecule and having a hydroxyl group. Organic compounds contained
It was discovered that the paintability and adhesion of a molded product of a mixture consisting of 0.1 to 50 parts by weight and (C) organic peroxide 0.01 to 20 parts by weight were extremely excellent, and was previously proposed (Japanese Patent Application No. 57-36502). issue). However, in molded products of this mixture, the coating film adhesion was not satisfactory depending on the type of paint used, and there were cases where the coating was insufficient. [] Structure of the Invention Based on the above, the present inventors conducted various searches for producing olefin polymers and olefin polymer mixtures with excellent paintability and adhesive properties, and as a result, (A) olefin polymer Combined 100 parts by weight, (B) "Organic compound having at least one unsaturated bond in the molecule and containing a hydroxyl group (hereinafter referred to as "hydroxyl compound") 0.1
50 parts by weight, (C) 0.01 to 20 parts by weight of an organic peroxide, and (D) 0.05 to 10 parts by weight of an organotin compound and/or a tertiary amine compound. The present invention has been achieved based on the discovery that the coating material has no adhesive properties and adheres firmly regardless of the type of coating material. [] Effects of the invention If the mixture according to the invention is used, the following effects will be exhibited. (1) Excellent coatings or adhesives can be obtained without carrying out the above-mentioned modification of the surface as conventionally done. (2) Since a paint having an isocyanate group can be applied directly to the surface of a molded product without applying a primer in advance, a coated product with good oil resistance can be obtained. (3) Similar to (2), it can be easily bonded to various substances (for example, wood, various metals) because it firmly adheres to adhesives having isocyanate groups. (4) A laminate with polyurethane foam can be created at the same time as foaming is performed on the molded product using a method such as injection foaming. The mixture obtained by the present invention can be used in a wide variety of ways to achieve the above 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 7 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 has at least one unsaturated bond (double bond,
It is a compound that has a triple bond) and contains a hydroxyl group. Typical examples include alcohols with double bonds, alcohols with triple bonds, esters of mono- or divalent unsaturated carboxylic acids and unsubstituted dihydric alcohols, and esters of unsaturated carboxylic acids with unsubstituted dihydric alcohols. Examples include esters with hydrohydric alcohols, esters with unsubstituted tetrahydric alcohols, and esters with unsubstituted pentahydric or higher alcohols. (1) Alcohol having a double bond A typical preferred example of the alcohol is one whose general formula is represented by the following formula [Formula (1)]. In formula (), R ¹ and R ² may be the same or different, and each has a hydrogen atom or a carbon number of 1 to 24
hydrocarbon groups. Among these alcohols, representative examples of preferable alcohols include mixtures with 2,6-dimethyl-7-octen-2-olformate, alkenyl alcohols having 5 to 8 carbon atoms,
-propen-1-ol, alkadienol having 6 to 8 carbon atoms, 3,7-dimethyl-
1,6-octadien-3-ol, butene-2-diol-1,4,2,6-dimethyl-1-octen-3,8-diol and α
-Hydroxyethyl oleyl alcohol. (2) Alcohol having a triple bond A typical example of a desirable alcohol is one whose general formula is represented by the following formula [formula ()]. (R ³ -C≡C-R ⁴ )-OH...() In 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. Among these alcohols, representative examples of desirable alcohols include 2-propyn-1-ol,
Aliphatic unsaturated alcohol having 6-24 carbon atoms, 3-methyl-1-butyn-3-ol,
3-methyl-1-pentyn-3-ol, 1
-hexyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, butyne-2-
Diol-1,4, hexyne-3-diol-2,5,3,4-dimethyl-1-pentyne-3,4-diol, 2,5-dimethyl-3
-hexyne-2,5-diol, 3,6-dimethyl-4-octyne-3,6-diol,
2,4,7,9-tetramethyl-3,6-diol, 1,1,4,4-tetraisopropyl-2-butyne-1,4-diol, 2,7
-dimethyl-octa-3,5-diyne-2,
7-diol and 2,3,8,9-tetramethyl-4,6-decadiyn-2,3,8,
9-tetraol is mentioned. (3) Esters of unsubstituted dihydric alcohols and unsaturated carboxylic acids The esters are esters of monovalent unsaturated carboxylic acids and unsubstituted dihydric alcohols, and preferred representative examples include the following general formula: It is expressed by the formula [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. Among these esters, representative examples of preferable ones include 2-hydroxyethyl acrylate, esters of polyhydric alcohols and aliphatic unsaturated monobasic acids (however, polyhydric alcohols have 3 to 10 carbon atoms). , having 2 to 4 hydroxy groups; aliphatic unsaturated monobasic acids have 3 to 4 carbon atoms) methacrylic acid-2-
Hydroxyalkyl (2 to 8 carbon atoms),
Crotonic acid ethylene glycol monoester, ethylene glycol aliphatic (carbon number is 8
~24) ester, acrylic acid hydroxypropyl ester, propylene glycol monofatty acid (8 to 24 carbon atoms) ester, ester of propylene glycol and fatty acid with 18 carbon atoms, alkylene glycol (4 to 24 carbon atoms) ) Fatty acid (6 to 24 carbon atoms) monoester, 2,2-dialkyl-1,3-
Propanediol monofatty acid (carbon number is 8~
24) esters and alkanes (50 carbons)
~60) Polyol fatty acids (18 carbons)
The following esters can be mentioned. (4) Esters of unsubstituted trihydric alcohols and unsaturated carboxylic acids The esters are esters of monovalent unsaturated carboxylic acids and unsubstituted trihydric alcohols, and representative examples of desirable ones have the general formula shown below. It is shown by the 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. Among these esters, typical examples of desirable ones include those having 3 to 10 carbon atoms, and 2 to 10 carbon atoms.
Esters of polyhydric alcohols having 4 hydroxyl groups and aliphatic unsaturated monobasic acids having 3 or 4 carbon atoms, glycerol methacrylate, alkanoic acids (8 to 18 carbon atoms) 3-
(methacryloyloxy)-2-hydroxypropyl, fatty acid glyceride with 6 to 24 carbon atoms, glycerin fatty acid (8 to 24 carbon atoms)
Acetic acid mixed ester, polymethylolalkane methacrylate, fatty acid (3 to 24 carbon atoms) ester of trimethylolalkane (2 or 3 carbon atoms), trimethylolbropane fatty acid monocarboxylic acid (6 to 24 carbon atoms)
) Ester mixed ester of trimethylolpropane or tetramethylolmethane, fatty acid (8 to 18 carbon atoms), and acrylic acid or methacrylic acid, 3-methyl-pentane-
1,3,5-triol mono- or difatty acid (8 to 24 carbons) ester, 16 carbons
Acrylates or methacrylates and alkanes of triols or condensates of ~18 alkanes or alkenes (50 to 60 carbon atoms)
) polyol fatty acid (18 carbon atoms) ester. (5) Ester of unsubstituted tetrahydric alcohol and unsaturated carboxylic acid The ester is an ester of monovalent unsaturated carboxylic acid and unsubstituted tetrahydric alcohol, and a typical preferred example thereof has the general formula shown below. It is expressed by [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. Typical preferred examples include polyhydric alcohols having 3 to 10 carbon atoms and 2 to 4 hydroxyl groups, aliphatic unsaturated monobasic acid esters having 3 or 4 carbon atoms, and hydroxyethylglycerin. Fatty acid ester with 18 carbon atoms, trimethylolpropane or tetramethylolmethane and 8 to 18 carbon atoms
mixed esters of three fatty acids and acrylic acid or methacrylic acid, polymethylolalkane methacrylate, pentaerythritol mono-, di- or tri-fatty acids (8 to 24 carbon atoms)
) esters, and alkanes (with 50 carbons)
~60) Polyol fatty acids (18 carbons)
Esther can be given. (6) Esters of unsubstituted pentahydric or higher alcohols and unsaturated carboxylic acids The esters are esters of monovalent unsaturated carboxylic acids and unsubstituted pentavalent or higher alcohols. The general formula is represented by the following formula [formula ()]. In formula (), n is 4 or more, and R ¹¹
is an unsaturated hydrocarbon group having 2 to 24 carbon atoms, and R ¹² is a hydrocarbon group having 2 to 60 carbon atoms. Typical preferred examples include polymethylolalkane methacrylate, sorbitol fatty acid diesters, esters of acrylic or methacrylic acid of sorbitol, esters of mannitol or mannitane with fatty acids (8 to 24 carbon atoms), and alkanes (50 carbon atoms). -60) polyol fatty acid (18 carbons) ester. (7) Other esters Other esters include esters of unsaturated dihydric carboxylic acids and unsubstituted polyhydric alcohols, and representative examples of preferred ones include:
The general formula is expressed by the following formula [formula ()]. 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 preferred ones include pentaerythritol or dipentaerythritol dibasic acids (maleic acid, adipic acid, sebacic acid, phthalic acid) fatty acids (carbon number is 8 to 24
) mixed ester, alkenyl (carbon number is 8)
~50 carbon atoms) succinic acid polyhydric alcohol ester and pentaerythritol alkenyl (carbon number is 51 to 100 carbon atoms) succinic acid ester. (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, , 5-dimethylhexane-2,5-hydroperoxide, diacyl peroxides such as benzoyl peroxide, and peroxyesters such as 2,5-dimethyl-2,5-dibenzoyl peroxyhexane. It will be done. (D) Organic tin compound Furthermore, examples of the organic tin compound used in the present invention include those represented by the following formula [formula ()]. In formula (), R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ may be the same or different and are hydrocarbon groups having at most 12 carbon atoms, and Y ¹ and Y ² may be the same or different and are carbon X ¹ is at most 18 monovalent or divalent carboxylic acids, derivatives (alkyl esters) of said carboxylic acids, alcohols, mercaptans, mercapto acids, and has an oxygen atom, a sulfur atom, and at most 4 carbon atoms. is a carboxylic acid group having a double bond, l is 0 or an integer from 1 to 20. Typical examples of this organic tin compound include monobutyl tin trimethyl malate, dibutyl tin dilaurate, a mixture of dibutyl tin dimalate and dibutyl tin dimethyl maleate, dibutyl tin dioctyl maleate, and tribenzyl・Tin and trimethyl malate are listed. (E) Tertiary amine compound The tertiary amine compound used in the present invention is a catalyst used in the curing reaction of urethane polyol and isocyanate. Typical examples include dimethylaminopropylamine, diethylaminopropylamine, tris(dimethylaminomethyl)phenol, tetraguanidine,
N,N-dibutylethanolamine, N-methyl-N,N-diethanolamine, 1,4-diazabicyclo(2,2,2)otane and 1,8-
An example is diazabicyclo(5,4,0)-7 undecene. (F) Mixing ratio In producing the mixture of the present invention, the mixing ratio of the hydroxyl compound to 100 parts by weight of the olefin polymer 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. The mixing ratio of hydroxyl compound to 100 parts by weight of olefin polymer is
If it is less than 0.1 part by weight, the effect of improving adhesion is insufficient. On the other hand, even if 50 parts by weight or more is used, no improvement in adhesion is observed depending on the amount used, and rather the original properties of the olefin polymer are impaired, which is not preferable. The mixing ratio of organic peroxide to 100 parts by weight of the olefinic polymer is 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, and especially
0.1 to 7 parts by weight is preferred. If the mixing ratio of the organic peroxide to 100 parts by weight of the olefinic polymer is 0.01 parts by weight or less, 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. Furthermore, the mixing ratio of the organotin compound and tertiary amine compound to 100 parts by weight of the olefin polymer is calculated as their total amount.
The amount is 0.005 to 10 parts by weight, preferably 0.02 to 5 parts by weight, and particularly preferably 0.05 to 3 parts by weight.
If the total mixing ratio of the organotin compound and the tertiary amine compound to 100 parts by weight of the olefinic polymer is less than 0.005 parts by weight,
Poor effect. On the other hand, even if more than 10 parts by weight is added, the effect will not be improved and, on the contrary, it may cause adverse effects such as bleeding. (G) Production of mixture and molded product In order to produce the mixture of the present invention, the olefinic polymer, hydroxyl compound, organic peroxide, and organic tin compound and/or tertiary amine compound are mixed in the above-mentioned mixing ratio. It is sufficient to mix the mixture uniformly so that it is within the range of . 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. The mixture may also consist of an olefinic polymer, a hydroxy compound, and an organic peroxide, but depending on the purpose of use of the mixture, these mixed components may be further supplemented with stabilizers against oxygen, heat and ultraviolet rays, and metal deterioration. inhibitor, flame retardant,
Additives such as colorants, electrical property modifiers, fillers, antistatic agents, lubricants, processability modifiers, and tack modifiers may be mixed as long as they do not impair the properties of the mixture of the present invention. You may. This mixture may be dry blended 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 melt kneading above,
If carried out at high temperatures, the olefinic polymer may deteriorate. However, it must be carried out at a temperature at which the organic peroxide used to graft polymerize the olefin polymer and hydroxy compound 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. (H) Coating and adhesion method Apply a coating material having an isocyanate group to the surface of the molded product obtained as described above to a thickness of 1 to 500 mm.
The object of the present invention can be achieved by uniformly applying the coating to a micron size (when dry). The application method is not a special method, and it is sufficient to apply a method that is generally used on the surface of metal or synthetic resin molded objects. Typical methods include applying with a spray gun and applying with a brush. Examples include a method of coating using a roll coater, and a method of coating using a roll coater. According to the present invention, it is possible to obtain a molded article that not only has excellent adhesion and gloss on the coated surface, but also has excellent weather resistance and gasoline resistance, such as in the case of urethane coating, so it is possible to obtain automotive parts. It can be applied to etc. It is also suitable for metallizing, laminating different materials, etc. on the coated film having isocyanate groups. Next, for bonding with an adhesive, an adhesive having an isocyanate group (for example, a solvent-based urethane adhesive, a water-based vinyl urethane adhesive) is applied to the surface of the obtained molded product, and the adhesive surface is coated with an adhesive having an isocyanate group. The adhesive body of the present invention can be obtained by bonding shapes of substances that can be bonded with an adhesive. These substances include metals (e.g. aluminum, iron, copper, and their alloys);
Glass, paper, fibers, wood, leather, rubbers (e.g., neoprene rubber, urethane rubber, butadiene rubber, natural rubber), polar group-containing resins (e.g., ABS resin, polyester, polyamide,
Examples include polyacrylonitrile and the above-mentioned olefin polymers. Shaped objects include thin objects (for example, foils, papers, films), sheet-like objects, board-like objects, plate-like objects, pipe-like objects, rod-like objects, container-like objects, spherical objects, and box-like objects. , and others with complex shapes. Furthermore, it is not limited to two layers, and multiple layers are also possible. Furthermore, as for polyurethane foam, 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. In manufacturing this laminate, no special equipment or special method is required. That is, foaming methods such as injection foaming, mold foaming, and spray foaming that are commonly used in the field of polyurethane foam production may be applied. Furthermore, polyols used as raw materials for polyurethane foam,
The isocyanate compound, the blowing agent, etc. do not need to be special, and any commonly used ones may be used without any limitation. In addition, when performing the above-mentioned coating, adhesion, and lamination, the conventional methods
In the preceding step, the surface of the molded product may be cleaned or degreased. The main purpose of this is to remove surface stains caused by oils and fats, eliminate variations in adhesion, and further improve adhesion. Specific examples include wiping off using an organic solvent such as isopropyl alcohol, toluene, or trichlene, or for large molded items, immersing the molded item in such an organic solvent under heating, or treating it with heated steam. I can give you a method. These degreasing and cleaning steps can be similarly applied to the molded product obtained according to the present invention. Furthermore, the same effects as before can be expected without being affected in any way. [] Examples and Comparative Examples The present invention will be explained in more detail below using 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-
According to 6758, temperature is 230℃ and load is 2.16
Measured under Kg conditions. In addition, for the paint film peel strength test, a strip of 10 mm wide was cut out from the test piece.
After forcibly peeling off a portion of the coating film from one end of the specimen, a tensile tester used for tensile testing of plastics was used at a tensile speed of 50 mm/min, a peeling angle of 180 degrees, and a temperature of 20 degrees Celsius. Paint film peeling strength (g/10mm) when the paint film is peeled off under the following conditions:
And so. Furthermore, gasoline resistance is achieved by using NT on the coating surface.
After making a cross cut with a cutter at an angle of 30 degrees and immersing each test piece in gasoline at room temperature (approximately 20°C) for 24 hours, changes in the coating surface were observed. Also, for water resistance, a cross cut was made in the same way as the gasoline resistance test piece, and after each test piece was immersed in 40°C lukewarm water for 240 hours, changes in the coating surface were observed. Furthermore, the adhesive strength was determined by cutting out a molded product of the olefin polymer mixture into short strips of 10 cm x 2 cm, and applying adhesive to the ends of the strips in a 3 cm x 2 cm area. A molded product of the olefin polymer composition obtained in the example or comparative example, a copper plate, or a piece of wood was attached to this adhesive part, and the tensile shear stress at breakage was It was measured. 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 upper and lower molded parts of the sample were held between the crosshead of a tensile tester, and the tensile speed was set at 5 mm/cm in the direction perpendicular to the contact surface.
The sample was pulled under conditions of 10 minutes, and the strength when the sample broke was measured and defined as adhesion strength (Kg/cm ² ). In the Examples and Comparative Examples, the olefin polymer, rubber-like material, talc, and the like as compounding components were used as shown below. [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. [Low-density ethylene homopolymer] Furthermore, as an olefin-based polymer, the density
A low density ethylene homopolymer (hereinafter referred to as "LDPE") having a weight of 0.917 g/cm ³ and an MI of 5.1 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. [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. [Organic tin compounds] As organic tin compounds, dibutyl tin malate [hereinafter referred to as "compound (1)]" and dibutyl tin laurate [hereinafter referred to as "compound (2)]"
It was used. [Tertiary amine compound] Furthermore, as a tertiary amine compound, 1.4-
Diazabicyclo[2.2.2]octane [hereinafter referred to as "compound (3)"] was used. Examples 1 to 12, Comparative Examples 1 to 4 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. One side of each specimen thus obtained was coated with a two-component urethane paint (manufactured by Nippon P Chemical Co., Ltd., trade name: R).
Two types of -2572R-263 enamel were sprayed using a spray gun to a thickness of 35 to 40 microns for a paint film peeling test. Next, heat drying was performed at a temperature of 90° C. for 30 minutes. After leaving the sample at room temperature for one day and night, a peel strength test of the coating film of each sample was conducted. The results are shown in Table 2. Furthermore, each was tested for gasoline resistance and water resistance. The results are shown in Table 2. In addition, in these tests, the state of change in the coating film is shown below. 〇 No change at all, △ Partial peeling, × Fully peeling After cutting the above-mentioned flat specimen into short pieces of 10 cm x 2 cm, a two-component cold-curing solvent-based polyurethane adhesive (Konishi) was applied. Using a two-component curing water-based vinyl urethane adhesive (manufactured by Chuo Rika Kogyo Co., Ltd., product name, RIKABOND CR-100), cut it into short pieces of the same size. Samples of the resin parts used in each of the Examples and Comparative Examples [hereinafter referred to as "(A)"],
After gluing together a copper plate [1 mm thick, hereinafter referred to as "(B)"] or wood (lauan wood, 5 mm thick, hereinafter referred to as "(C)") and leaving it at room temperature for 24 hours, the adhesive strength was determined. The results are shown in Table 3. Two test specimens obtained as described above were fixed in parallel at a distance of 1 cm, and polyurethane foam was injected between them by the injection foaming method. generated.
Insulvac #20, a product of Instaform Inc. (USA), was used as an injection foaming device and a polyurethane foam stock solution (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 3 will be added. ”.

【table】

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[Table] From the results of the above examples and comparative examples, when the mixture obtained according to the present invention is molded into a molded product, and the surface of the molded product is coated with urethane, urethane adhesive, and urethane foamed, It is clear that not only the peel strength, adhesive strength and adhesion strength are improved, but also the oil resistance and water resistance of the coating film are excellent. Furthermore, it is clear that the strength of these compounds is greatly improved by adding only a small amount of an organic tin compound and/or a tertiary amine compound.

Claims (1)

[Scope of Claims] 1 (A) 100 parts by weight of an olefin polymer, (B) an organic compound having at least one unsaturated bond in the molecule and containing a hydroxyl group
0.1 to 50 parts by weight, (C) 0.01 to 20 parts by weight of an organic peroxide, and (D) 0.05 to 10 parts by weight of an organic tin compound and/or a tertiary amine compound.