JPS5926258A - Laminate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION ■Object of the Invention The present invention relates to a laminate with excellent adhesion. More specifically, (8) (1) modification of an olefin polymer obtained by treating the olefin polymer with (2) an organic compound having at least one unsaturated bond in the molecule and containing a hydroxyl group; This product relates to a laminate consisting of a compound and a 0-year-old reflex polymer, and not only has excellent adhesion, but also has excellent adhesion between the surface of the modified product and other substances (for example, a compound containing an isocyanate group). The object of the present invention is to provide a laminate with improved properties.

■ Background of the Invention As is well known, olefin polymers not only have excellent moldability, but also have good properties such as mechanical strength, heat resistance, solvent resistance, and chemical resistance, so they are widely manufactured industrially. It is used in many fields as a general-purpose resin. Because of these properties, olefin polymers have recently been developed for use in automobile parts such as hub bumpers, instrument grills, front grills, fenders, and headlight cases. However, since olefin polymers do not have polar groups in their molecules (so-called non-polar), they are chemically extremely inactive polymeric substances. Furthermore, not only is it highly crystalline, but its solubility in solvents is also extremely low, making it extremely difficult to use it in fields such as painting and adhesives.

As mentioned above, although olefin resins have excellent moldability and the above-mentioned properties, olefin polymers are used in fields where good adhesiveness is required (e.g. automobile parts, home appliance parts). Its use was naturally limited.

In order to solve the problems of adhesion and paintability of olefin polymers, various methods have been proposed for some time, such as those described below.

(a) A method in which an olefin polymer or a molded product thereof is surface-treated from the outside and modified by physical or chemical methods (hereinafter referred to as "modification method").

('b) A method of adding other polymeric substances or additives to the olefin polymer.

Hereinafter, among these methods, the modification method will be explained in more detail and problems will be described.

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 mixed solution of chromic acid and a mineral acid such as concentrated sulfuric acid, and a method of treatment using a mixed solution of chromic acid and a mineral acid such as concentrated sulfuric acid. A method of chemically processing such as crafting or chemical treatment in the presence of denatured substances (hereinafter referred to as ``denaturation method Q'')].

The Conella modification method imparts chemically active sites rich in polar groups to the surface of an olefin polymer or its molded product, and also physically roughens the surface. the result,
It is thought that the effect of improving 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 is significantly limited, and furthermore, not only is the treatment effect significantly reduced over time by leaving it after the treatment, but also the In many cases, the degree of oxidation 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 (1)), the treatment method using mineral acids not only makes it easy for the chemicals used to become a source of pollution, but also requires complicated post-treatment steps such as a neutralization step, a water washing step, and a drying step. is necessary. Furthermore, chemical treatment methods such as krafting require a drying process, 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.

Furthermore, as a method for imparting paintability and adhesion to the surface of olefin polymer molded products, olefins are graft-polymerized with chlorinated polypropylene or maleic anhydride on the surface of the molded product before coating with paint or adhesive. A method of applying a primer whose main component is a polymer or the like has been developed. However, the method of applying a primer increases the cost by adding one step of coating or adhesion.

An olefin polymer having good adhesion and paintability without impairing the properties and processability of the olefin polymer, including those described above.

Its modifications and mixtures have not yet been developed.

0111 Structure of the Invention In light of the above, the present inventors have conducted various searches to improve the adhesion of olefin polymers, and have found that (At(1)) in an olefin polymer (2) at least A modified product of an olefin-based polymer obtained by treating an organic compound having one unsaturated bond and a hydroxyl group (hereinafter referred to as a "hydroxyl-based compound") and an olefin-based polymer The inventors have discovered that not only does a laminate comprising:

(b) Effects of the invention If the laminate according to the invention is used, the following effects will be exhibited.

(1) An excellent coating or adhesive can be obtained without carrying out the above-mentioned modification of the surface as conventionally done.

(2) Since a paint having an isone anate group can be applied directly to the surface of a molded product without applying a brimer in advance, a coated product with good oil resistance can be obtained.

(3j (Similar to 2+, it can be easily bonded to various substances (e.g., wood, various metals) because of its strong adhesion with adhesives having isone anate groups.

(4) A laminate with polyurethane foam can be created at the same time as foaming is carried out on the molded product using a method such as injection foaming.

(5) The properties and physical properties of the olefin polymer that is the base material are not impaired in terms of wood quality.

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.

fl) Automotive parts such as bumpers, instrument panels, armrests, door liners, /-door bags, duct covers, etc. (2) Home appliance parts such as the interior and exterior of air conditioners and refrigerators (3) Residential equipment such as roof panels and insulation walls fee (t
l) Dining tables, desk surfaces, furniture panels, kitchen cabinets,
[] River parts furniture such as ice box (5) Refrigerated truck interior system, refrigeration) Parts of freezer such as φ wall Detailed description of the invention (5) For manufacturing the olefin polymer laminate in the present invention Examples of the olefinic polymers used in the invention include homopolymers of ethylene, homopolymers of propylene, random or block copolymers of ethylene and propylene, and copolymers of ethylene and/or propylene with other polymers having at most 12 carbon atoms. Examples include random or block copolymers with α-olefins (copolymerization ratio of α-olefins is at most 20% by weight). The molecular weight of these olefin polymers is generally from 20,000 to 1,000,000, preferably from 20,000 to 500,000.
Particularly suitable are olefin resins having a molecular weight of 50,000 to 300,000. Also, low density (0,900g/cA) to high density (0,
980 g/ca) of ethylene homopolymers, propylene homopolymers, random or block copolymers of ethylene and propylene, and random or block copolymers of ethylene or propylene with other α-olefins are preferred.

These olefinic polymers include a catalyst system (so-called Ziegler catalyst) obtained from a transition metal compound and an organoaluminum compound, and a carrier (eg.

Homopolymerization of olefins using catalyst systems (so-called Phillips catalysts) obtained by supporting chromium compounds (e.g., chromium oxide) on silica (silica) or radical initiators (e.g., organic peroxides) Or obtained by copolymerization.

Furthermore, the present invention also includes modified polyolefins obtained by graft polymerizing a compound having at least one double bond (for example, an unsaturated carboxylic acid, a vinylane compound) to the olefin polymer of Q Makofl et al. Noah Ru.

Regarding these olefin-based polymers and modified polyolefins, the manufacturing method of Sonera is well known.

These olefin-based monomers and modified polyolefins may be used alone or in combination of two or more. Furthermore, two or more types of stiff olefin polymers and modified polyolefins may be used as a resin binder in any proportion.

(2) Hydroxyl compound The hydroxy compound used in the present invention is a compound that has at least one unsaturated bond, a triple bond, or a triple bond, and also contains a hydroxyl group. Typical examples include alcohols with double bonds, alcohols with triple bonds, esters of -valent or divalent unsaturated carboxylic acids and unsubstituted dihydric alcohols, and unsaturated carboxylic acids and unsubstituted trihydric alcohols. Examples include esters with hydrohydric alcohols, esters with unsubstituted tetrahydric alcohols, and esters with unsubstituted five or more alcohols.

(1) Alcohol having a double bond As a representative example of a preferable alcohol, its general formula is the following formula [(
In formula (1), R1
and R2 may be the same or different, and are a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms.

Among these alcohols, representative examples of preferable alcohols include a mixture with 2,6-dimethyl-7-octen-2-olfomate, fluorenyl alcohol having 5 to 8 carbon atoms ([), 2-propen-1-ol, Alkashenol having 6 to 8 carbon atoms, 3,7-dimethyl-1,6-octacyen-3-ol, butene-2-diol-1,4
, 2,6-dimethyl-l-octene-3,8-diol and α-hydroxyethyloleyl 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 (II).

(R3-C-:C-R4-) OII (11
1II) In the formula, ■? 3 and R' may be the same or different, and are a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms.

Representative examples of desirable alcohols include 2-propyn-1-ol, aliphatic unsaturated alcohols having 9 to 24 carbon atoms, and 3-methyl-1-butyn-3-ol.
ol, 3-methyl-1-pentyn-3-ol, ■-
Hexin-3-ol, 3,5-dimethyl-1-hexyn-3-ol, butyne-2-diol-1,4, hexin-3-diol-2,5,3,4-dimethyl-1-
Pentyne-3,4-diol, 2,5-dimethyl-3-
Hexyne-2,5-diol, 3,6-cymethyl-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-
Mention may be made of dimethyl-octa-3,5-diyne-2,7-diol and 2,3,8,9-tetramethyl-4,6-zocadiyne-2,3,8,9-tetraol.

(3) Esters of unsubstituted dihydric alcohols and unsaturated carboxylic acids The esters are esters of monovalent unsaturated carboxylic acids and unsubstituted dihydric alcohols, and representative examples of preferred ones include the general formula: is expressed by the following formula ([1) formula].

R5-CGID\0-R'-0l-1 In the GID formula, R5 is an unsaturated hydrocarbon group having 2 to 24 carbon atoms, and R6 is a hydrocarbon group having 2 to 24 carbon atoms.

Among these esters, representative examples of preferable ones,
Acrylic acid-2-hydroxy, diethyl, ester of polyhydric alcohol and aliphatic unsaturated basic acid (however, polyhydric alcohol has 3 to IO carbon atoms and has 2 to 4 hydroxy groups. Aliphatic unsaturated-basic acids have 3 carbon atoms
-2-hydroxyalkyl methacrylate (2 to 8 carbon atoms), ethylene glycol monoester of crotonate, ethylene glycol fatty acid (8 carbon atoms)
~24) ester, acrylic acid hydroxypropyl ester, glopylene glycol monofatty acid (carbon number is 8
~24) 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 (8 to 24 carbon atoms) ester, and alkanes (carbon number 6 to 24) Examples include esters of polyol fatty acids (18 carbon atoms).

(4) Ester of unsubstituted trihydric alcohol and unsaturated carboxylic acid The ester is an ester of monovalent unsaturated carboxylic acid and unsubstituted trihydric alcohol, and a typical example of a desirable one has the general formula: This is expressed by the formula [GV formula].

In the formula, R7 is an unsaturated hydrocarbon group having 2 to 24 carbon atoms, and %R8 is a hydrocarbon group having 2 to 24 carbon atoms. It is the basis.

Among these esters, representative examples of desirable ones include:
Esters of polyhydric alcohols having 3 to 10 carbon atoms and 2 to 4 hydroxyl groups and aliphatic unsaturated acids having 3 and 4 carbon atoms, glycerol methacrylate, alkanoic acids (carbon (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 -1:, trimethylolalkane (
Trimethylolpropane Fatty acid monocarboxylic acid (6 to 24 carbon atoms) ester of fatty acid (3 to 24 carbon atoms), trimethylolpropane or tetramethylolmethane and fatty acid (3 to 24 carbon atoms) Mixed ester of acrylic acid or methacrylic acid (8 to 18 carbon atoms), 3-methyl-pentane-1,3,5-triol mono- or difatty acid (8 to 24 carbon atoms) ester, 16 carbon atoms Examples include acrylates or methacrylates of triols or condensates of ~18 alkanes or alkenes, and alkane (50 to 60 carbon atoms) polyol fatty acid (18 carbon atoms) esters.

(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 M].

9-CM\0-RIO-(OH)3 In the formula M, R9 is an unsaturated hydrocarbon group having 2 to 24 carbon atoms, and R1' is a hydrocarbon group having 2 to 24 carbon atoms. .

Representative examples of preferred ones include polyhydric alcohols having 3 to 10 carbon atoms and 2 to 4 hydroxyl groups, and 3-! ! or 4 aliphatic unsaturated basic acid esters, hydroquine ethylglycerin has 18 carbon atoms
fatty acid esters, trimethylolpropane or tetramethylolmethane, mixed esters of fatty acids with 8 to 18 carbon atoms and acrylic acid or methacrylic acid, polymethylolalkane methacrylate, pentaerythritol mono-, di-, or tri-fatty acids (carbon numbers are 8-24
) esters, and alkane (50 to 60 carbon atoms) polyol fatty acid (18 carbon atoms) esters.

(6) Esters of unsubstituted 5 or more alcohols and unsaturated carboxylic acids The esters are esters of monovalent unsaturated carboxylic acids and unsubstituted 5 or more alcohols. , the general formula is represented by the following formula C (VD formula).

R11-Cα71) \ 0- R'' -(OH) n (In the VD formula, n is 4 or more, R'' is an unsaturated hydrocarbon group having 2 to 24 carbon atoms, and R12 is an unsaturated hydrocarbon group having 2 to 24 carbon atoms. 2 to 60 hydrocarbon groups.

Typical examples of desirable ones include polymethylolalkane methacrylate, nlubitol fatty acid diester, ester of acrylic or methacrylic acid of sorbitol, mannitol or manethane and fatty acid (having 8 carbon atoms).
~24 carbon atoms) and alkanes (50 carbon atoms)
-60) polyol fatty acid (18 carbon atoms) ester.

(7) Other esters and other esters include esters of unsaturated dihydric carboxylic acids and unsubstituted polyhydric alcohols, and preferred representative examples include the following general formula [C%IID formula]
I can't give you what is represented by .

1 RI3(v]D \ C-(OH) I (In the VID formula, in is 1 or more, R13 is an unsaturated hydrocarbon group having 2 to 50 carbon atoms, and R14 is an unsaturated hydrocarbon group having 2 to 50 carbon atoms. 100 hydrocarbon groups.

Preferred representative examples include pentaerythritol or diventaerythritol dibasic acids (maleic acid,
Adipic acid, cepatic acid, phthalic acid) fatty acids (8 to 24 carbon atoms) mixed esters, alkenyl (8 carbon atoms)
-50 carbon atoms) succinic acid polyhydric alcohol tester and pentaerythritol alkenyl (carbon number is 51 to too carbon atoms) succinic acid ester.

The modified product of the present invention is produced by treating the above-mentioned olefin polymer compound with a hydroquine compound. Organic peroxides are usually used to carry out this treatment.

O Organic peroxide The organic peroxide used in this treatment is generally used as an initiator in radical polymerization and as a crosslinking agent for polymers, and preferably has a half-life of 1 minute or more at 100°C. A temperature of 130° C. or higher is preferable. If the above temperature is below 100℃, it is not only difficult to handle, but also difficult to use.
Since there is no l, the car is not heavy. Representative examples of preferred organic peroxides include ketone peroxides such as l,■-bis-tertiary-butylperoxy-3,3,5-trimethylchlorohexane, dialkyl peroxides such as dicumyl peroxide, 2.5-di)1-methylhexane-2,
Examples include hydroperoxides such as 5-hydroperoxide, diacyl peroxides such as benzoyl peroxide, and peroxy esters such as 2.5-dimethyl-2,5-dibenzoylperoxyhexane.

In carrying out this treatment, the organic peroxide alone may be used, or an organic tin compound and/or a tertiary amine compound may be used in combination.

Examples of organic tin compounds include those represented by the following formula [alpha formula].

In the R46R4B 1 aID formula, R4fi, In47, R48 and R49 may be the same or different, and have at most 12 carbon atoms.
Yl and Y2 may be the same or different, monovalent or divalent carboxylic acids having at most 18 carbon atoms, derivatives (alkyl esters) of the carboxylic acids, alcohols, mercaptans, X is mercaptoic acid
+ is an oxygen atom, a sulfur atom, and a carboxylic acid group having at most 4 carbon atoms and a double bond; l is 0 or an integer from 1 to 20;

Typical examples of these organic tin compounds include motuputyl tin trimethyl malate, dibutyl tin dilaurate, a mixture of dibutyl tin cimarate and dibutyl tin dimethyl maleate, dibutyl tin dioctyl maleate, and tribenzyl.・Tin and trimethyl malate are listed.

First, tertiary amine compounds are used as catalysts in the curing reaction of urethane polyols and isocyanates. Typical examples include dimethylaminopropylamine, diethylaminopropylamine, tris(dimethylaminomethyl)phenol,
Tetraguanidine, N,N-dibutylethanolamine, N-methyl-N,N-jetanolamine, 1.4-
Examples include diazabicyclo(2,2,2)otane and 1,8-diazabicyclo(5,4,0)-7unzecene.

0 Production of treated product In producing the treated product of the present invention, the proportion of the hydroxyl compound used relative to 100 parts by weight of the olefin polymer is 0.1 to 50 parts by weight, preferably 0.2 to 30 parts by weight. , particularly preferably 0.3 to 20 parts by weight. 1
If the ratio of the hydroxyl compound to 0.00 parts by weight of the olefin polymer is less than 0.1 parts 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.

Further, the usage ratio of organic peroxide to 100 parts by weight of olefin polymer is 0.01 to 20 parts by weight, and 0.01 to 20 parts by weight.
．． 05 to 10 parts by weight is desirable, and particularly preferably 01 to 7 parts by weight. If the proportion of the organic peroxide used is less than 0.01 parts by weight relative to 100 parts by weight of the olefin polymer, not only the effect of improving adhesion is low, but also the durability of the adhesion strength of the modified product 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.

When using the organotin compound and/or tertiary amine compound in producing the modified product of the present invention, 1
The ratio of kneading to 0.00 parts by weight of the oleene-based polymer is at most 10 parts by weight, preferably 5 parts by weight or less.

To produce the modified product of the present invention, an olefin polymer,
The hydroxyl compound and the organic peroxide, or these and the organic tin compound and/or the tertiary amine compound may be uniformly mixed so that the proportions used are within the above-mentioned range. In producing this modified product, a part of the mixed components is mixed in advance to produce a so-called masterbatch, and this masterbatch and the remaining mixed components are produced to produce the modified product so that the above-mentioned compounded components are obtained. You may.

To produce this modified product, triblending may be performed 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 such as the following. At this time, a more uniform mixture can be obtained by triblending in advance and further melt-kneading the resulting mixture.

In the case of the above melt-kneading 9, if carried out at a high temperature, the olefin 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, this melt-kneading is generally carried out at 160 to 300°C, although it varies depending on the type of organic peroxide to be used.

Various molded products may be produced from the composition thus produced by processing methods such as extrusion molding and press molding which are commonly used in the field of olefin polymers. 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 olefin polymer may deteriorate, so it is a matter of course that the reaction must be carried out at a temperature below which decomposition occurs.

Production of a laminate The modified product obtained as described above and the olefin polymer described above are processed into a laminate using various lamination methods that are generally used in the production of olefin polymer laminates. can be manufactured.

This lamination method uses two types of extruders.

A coextrusion method in which the olefin polymer and the modified product are extruded using separate extruders and brought into close contact with each other.The modified product or olefin polymer is preformed into a film or sheet with a thickness of 5 microns to 5 microns, and this film is Or, the so-called extrusion lamination method in which the sheet is laminated onto a film or sheet of an olefinic polymer or modified product extruded from an extruder, using two types of rolls, and from one of the rolls, a film or sheet of the modified product is laminated.
A so-called stamping method in which an olefin polymer film or sheet is fed from another roll and pressed while applying heat, and a method in which a modified product and an olefin polymer film or sheet are formed in advance and then vacuum formed together. Another example is a film insert injection molding method in which a pre-formed modified film or sheet is laminated simultaneously with injection molding of an olefin polymer.

Note that if this laminate is produced at a considerably high temperature, the olefin polymer and the modified product may deteriorate, so the production is carried out at 300° C. or lower in the same manner as above. In addition, the olefinic polymer used to produce the 9-modified laminate and the olefinic polymer used to produce the laminate may be different, but they may be of the same type. Preferably.

An olefin polymer and a hydroquine compound, or a mixture of these and an organotin compound and/or a tertiary amine compound when producing the above-mentioned modified product, and an olefin polymer used when producing a laminate. Each can be produced without the addition of other ingredients, but depending on the intended use of the laminate, additional stabilizers against oxygen, heat and ultraviolet light, metal deterioration inhibitors, flame retardants,
Additives such as colorants, electrical property modifiers, fillers, antistatic agents, slipping agents, processability modifiers, and tack modifiers are added to the laminates of the present invention (in particular, the olefinic polymer base). They may be mixed as long as they do not impair their properties.

[F] Coating and adhesion method A coating material having an isocyanate group is uniformly applied to the surface of the molded product obtained as described above to a thickness of 1 to 500 microns (when dry). can be manufactured. The application method is not a special method, and it is sufficient to apply the method generally applied to the surface of metal or synthetic resin Q molded objects. Typical methods include application using a spray gun, brush application, etc. Examples include a coating method using a roll coater, and a coating method 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 types of materials, etc. on the applied coating film having incyanate groups.

Furthermore, for bonding with adhesives, adhesives having isocyanate groups (for example,
The adhesive body of the present invention can be obtained by applying a solvent-based adhesive, a urethane adhesive, or a water-based vinyl urethane adhesive, and adhering a shaped object of a substance that can be adhered with the adhesive to the adhesive surface.

These materials include metals (e.g. aluminum, iron, copper, and their alloys), glass, paper, textiles, wood, leather,
Rubbers (e.g. neobrane rubber, urethane rubber,
butadiene rubber, natural comb), polar group-containing resins (for example, ABS resin, polyester, syramide, polyacrylonitrile, and the above-mentioned olefin polymers). In addition, shaped objects include thin objects (for example, foils, paper frames, films), sheet-like objects, board-like objects, plate-like objects, pipe-like objects, rod-like objects, container-like objects, spherical objects, box-shaped objects, I wonder if there are other things with complicated shapes. Furthermore, the number of layers is not limited to two, and multiple layers are also possible.

Regarding polyurethane foam, a laminate can be produced by simultaneously carrying out a urethane polymer production reaction and foaming on the surface of a molded product.

The production of this laminate does not require any special equipment or may be carried out using any special method. That is,
Foaming methods commonly used in the field of polyurethane foam manufacturing such as injection foaming, mold foaming, and spray foaming may be used. Further, the polyol, isocyanate compound, blowing agent, etc. used as the thick phase of the polyurethane foam do not need to be special materials, and any commonly used materials may be used without any limitation.

In addition, in performing the above-mentioned coating, adhesion, and lamination, in the conventional method, the surface of the molded product may be cleaned or degreased in the previous step. 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 with an organic solvent such as isopropyl alcohol/L/, toluene, or trichlene, or immersing large molded items in such an organic solvent under heating, or wiping with heated steam. There are ways to process it. In the laminates obtained according to the invention, these degreasing and cleaning steps can be similarly applied.

Furthermore, the same effects as before can be expected without being affected in any way.

CV[l Examples and Comparative Examples The present invention will now be explained in more detail with reference to Examples.

In addition, in the examples and comparative examples, the melt index (hereinafter referred to as rM, 1.J) is JISI Gu-676.
According to 0, the temperature is 190℃ and the load is 2.16
It was measured under the conditions of k. In addition, the melt flow index (hereinafter referred to as 11VIFIJ) is based on JIS K-6.
According to 758, the temperature is 230 °C and the load is 2.1
Measured under G K90 conditions. In addition, the paint film peeling strength test was performed by cutting out a gold sample on a strip with a width of 10 mm.
After forcibly peeling off a portion of the coating film from one end of the specimen, it was tested using a tensile tester used in tensile testing of plastics at a tensile rate of 50 cylinders/min, a peeling angle of 180 degrees, and a temperature of 20 degrees. The coating film was peeled off under conditions of .degree. Furthermore, the adhesive strength of the molded product of the olefin polymer mixture was 10 (1n).
Cut into a short piece of ×2 ctn, and add 3 cm to the end.
Adhesive was applied to the X 2 ctn area. A molded product of the olefin polymer composition obtained in the example or comparative example, a copper plate, or a piece of wood chips is attached to this adhesive part, and the tensile shear stress at the time of breakage is determined by pulling at a pulling speed of 50 mm/min. 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 m intervals using an injection foaming method. A sample was cut to a size of 1 cTn x 1an, and the upper and lower molded parts of the sample were held between the crosshead of a tensile tester and stretched at a tensile speed of 5 mm/min in the direction perpendicular to the contact surface.
The strength when the sample breaks is measured and the adhesion strength (K
q/cJ).

In the Examples and Comparative Examples, the following ingredients were used as the olefin polymer, rubbery material, and sludge.

[Propylene homopolymer]

As an olefin polymer, the density is 0.90 (1/crl
and MFI is 4. A propylene homopolymer (hereinafter referred to as rPP(1)J) having a og/lo content was used.

[Globylene-ethylene block copolymer] Also, as a propylene-ethylene block copolymer, the ethylene content is 12.0% by weight, and the MFI is 2.0% by weight. (L9/
10 minutes, the density is 0.900 g/cr/l, and the alpropylene-ethylene block copolymer [r P P
(2) Say J) 'fl: I used it.

[Low density ethylene homopolymer]

Furthermore, as an olefin polymer, the density is 0.9179.
/cal and M, 1. is 5.1g/10
low-density ethylene homopolymer (IT, D P
EJ) was used.

〔talc〕

Talc with an average particle size of 280 microns was used.

[Hydroxyl compound]

As the hydroxyl compounds, 2-hydroxyethyl acrylate (hereinafter referred to as compound agent) and 2-hydroxypropyl methacrylate (hereinafter referred to as "compound 0") were used.

[Organic peroxide]

As the organic peroxides, benzoyl peroxide (hereinafter referred to as "BPO") and dicumyl peroxide (hereinafter referred to as rDCPj) were used.

[Organic tin compound]

As the organic tin compounds, dibutyl tin malate [hereinafter referred to as "compound (1)"] and dibutyl tin laurate [hereinafter referred to as [compound (2)]] were used.

[Tertiary amine compound]

Furthermore, as a tertiary amine compound, 1. ．． 4-DiazabicycloC2,2,23octane [hereinafter referred to as “compound (3
)” was used.

Examples 1 to 12, Comparative Examples 1 to 4 As the modified products, the ingredients 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
50 mm) was used to produce pellets while kneading. The pellet of the modified product thus produced is T-
A film with a width of 20 on (thickness: 30 microns) was produced at a temperature of 230° C. using a die film forming machine (diameter: 25 cylinders, die width: 27 m).

In addition, a propylene homopolymer with a density of 0.9009/crd [MFI 2.0g/10min, hereinafter rPP
(a) J], the density is 0.900,! i'/c
Propylene-ethylene block copolymer [M
FI2.0, 9/10 min, 1 ft/7 containing right j,
16.0. ii, hereinafter referred to as "PP(b)"] and a density of 0.900 g/crd.
Ethylene block copolymer (Ml'i'I 2.7g
/10 minutes, ethylene content 15.0% by weight] 75 parts by weight and talc 2Si with an average particle size of 20 microns
The mixture with part i [hereinafter referred to as rPP (hereinafter referred to as OJ)] was heated to a width of 30 mm at a temperature of 220°C using an extruder with a diameter of 40 mm (for forming a sheet with a width of 400 mm).
cm sheets (2 mm thick) were produced. This sheet f: Cut to a length of 2° (1), 30 pieces x 20
A sheet with a size of cm was obtained.

The films of the modified products thus produced and the sheets of olefinic polymers whose types are shown in Table 2 were molded using the 2-ton stamping machine shown in FIG. The samples shown as figures were prepared. In FIG. 1, 1 is a feed roll, and 2 is a take-up roll. Further, 3 is an olefin polymer sheet. Furthermore, 4 is a film of the modified product,
Further, 5 is a core side mold, and 6 is a cavity side mold. Further, in FIG. 2, 7 is a sheet of an olefin polymer, and 8 is a film of a modified product. The width of the sample shown in this figure is 130 mm and the length is 13 mm.
0 mm, height is 30 mm, and thickness is 2 wm.
It is. In this way, samples for measuring physical properties shown below were manufactured (Examples 1, 4 to 12).

After inserting P
(Example 2).

Using an extruder with a diameter of 40mm (for sheet forming with a T-die width of 400mm), the width is 30cm+ at a die temperature of 230℃.
A PP(a) sheet having a thickness of 500 μr'y was prepared. An extrusion laminate molding machine (1゛die
The modified product was laminated to a thickness of 50 μm using a die temperature of 260° C. to produce a laminate of the modified product and P P (a) sheet (Example 3).

Density is 0.9241/crl at die temperature of 230℃
A low density ethylene homopolymer (M, 1.5.(H
//10 minutes, a sheet (thickness: 500 microns) of "rLI" (hereinafter referred to as "I'i") was prepared. A laminate of the modified product and the LTPE sheet was produced in the same manner as in Example 3, except that the die temperature of the laminate molding machine was changed to 260° C. (Example 13).

Furthermore, pellets of P P (a) and P P (1)) were injection molded using a 5 oz injection molding machine at a temperature of 230°C, and flat samples (120 mm x 15
0 mm, thickness 2 mm).

In addition, two-component urethane ffaf'+ (manufactured by Nippon P Chemical Co., Ltd., product name R-2) was coated on one side of each specimen.
57. The enamel was sprayed using a spray gun to a thickness of 35 to 40 microns for the paint film peel test. Then, heat drying was performed at a temperature of 90° C. for 30 minutes. After being left at room temperature for one day and night, the coating film of each sample was tested for peel strength. 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.

○ No change at all, △ Partial peeling, × Fully peeling After cutting the above-mentioned flat specimen into a rectangular shape of 10 crn x 2 cn1, a two-component cold-curing solvent-based polyurethane adhesive (Konin) was applied. Manufactured by the company, product name, Bond KU-
10) was used to cut a sample piece of the resin part used in each Example or Comparative Example into short pieces of the same size.
Copper plate [thickness 1mm, hereinafter referred to as “(g)”]
0") or a wooden board (Lawanzaka, 5mm thick, hereinafter referred to as "0") and left at room temperature for 24 hours, then the adhesive strength was measured. The results are shown in Table 2. Shown below.

Two test pieces obtained as described above were fixed in parallel with an interval of 1α, and polyurethane foam was produced between them by injection foaming.

The equipment for injection foaming and the raw solution of polyurethane foam is a product name of Insulvac≠ manufactured by Instaform Co., Ltd.
20 were used (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 2. In addition, in this test, if the adhesion strength is too strong and failure does not occur at the interface between the molded product part and the polyurethane foam part, and the polyurethane foam suffers cohesive failure, 1 cohesive failure is indicated in the column of adhesion strength in Table 2. ”.

From the results of the above Examples and Comparative Examples, the laminate obtained by the present invention not only exhibits strong adhesion to urethane paints, but also has excellent gun stain resistance (oil resistance) since no primer is used. Furthermore, by using urethane adhesives, it is possible to bond with many other materials, and laminates with urethane foam can be manufactured using conventional methods such as injection foaming. It is clear that the adhesion is strong enough to break inside the urethane foam (cohesive failure) as shown in the examples. Due to their fragility, urethane coatings, foams, laminates, etc. are widely used in fields where they are used (e.g., automobile parts, home appliance parts, residential use, daily necessities, furniture, insulation parts). is clear.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of a stamping molding apparatus used in producing laminates from films of modified products and sheets of olefinic polymers used in Examples and Comparative Examples of the present invention. Moreover, FIG. 2 is a sectional view of the obtained laminate (sample). Patent applicant Showa Denko K.K. agent Patent attorney Sei Kikuchi

Claims (1)

[Scope of Claims] (AJ) An olefin polymer obtained by treating (1) an olefin polymer with (2) an organic compound having at least one unsaturated bond in the molecule and containing a hydroxyl group. A laminate consisting of a modified polymer and an olefin polymer.