JPS6055014A - Olefin polymer composition - Google Patents

Abstract

PURPOSE:The titled polymer composition excellent in adhesiveness, application property, etc., obtained by mixing an olefin polymer with an organic, hydroxyl group-containing, unsaturated compound, an organic peroxide and a styrene polymer, and treating the mixture at a specified temperature or below. CONSTITUTION:100pts.wt. olefin polymer such as polyethylene or polypropylene is mixed with 0.1-50pts.wt. organic compound havng at least one unsaturated bond and at least one hydroxyl group in the molecule (e.g., 3-hydroxy-1-propene), 0.01-20pts.wt. organic peroxide (e.g., dicumyl peroxide), and 0.5-30pts.wt. styrene-based polymer of an average MW of 1,000-400,000. This mixture is treated at a temperature at which the organic peroxide can decompose and which is below 400 deg.C to obtain the purpose olefin polymer composition.

Description

[Detailed description of the invention] [I] Purpose of the invention The present invention relates to olefinic polymer compositions.

More specifically, (A) olefin polymer, (B)
An organic compound having at least one unsaturated bond in the molecule and containing a hydroxyl group, a mixture of an olefin polymer consisting of (C) an organic peroxide and (3) a styrene polymer is an organic peroxide. is the temperature at which it decomposes,
This relates to an olefin-based polymer composition obtained by processing under cross-contact conditions at 400°C or less, and has extremely excellent adhesive properties when making painted products, adhesives, and laminates of its molded products. The purpose is to provide the following.

[■] Background of the Invention As is well known, olefin resins (olefin polymers) not only have excellent moldability, but also have high mechanical strength and
Because it has good properties such as heat resistance, solvent resistance, and chemical resistance, it is widely manufactured industrially and used in many fields as a general-purpose resin. However, from the outside, olefin resins are polymeric substances that are extremely chemically inert because they do not have polar groups in their molecules (so-called non-polar). Furthermore, not only is it highly crystalline, but it also has extremely low solubility in solvents, so when used in fields such as painting and adhesion, its paintability and adhesiveness are extremely low.

As mentioned above, although olefin resins have excellent moldability and the above-mentioned properties, they are used in fields where good adhesion and paintability are required (for example, automobile parts and home appliance parts). The use of olefin resins naturally had limitations.

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

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

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

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 and electron beams" [hereinafter referred to as [denaturation method (a)]
] and "method of treatment using a chromic acid mixture and mineral acids such as concentrated sulfuric acid, and the presence or absence of a crosslinking agent using a compound containing a polar group in the molded product of olefin resin." A method of chemical treatment such as grafting (hereinafter referred to as "denaturation method (b)") is mentioned below.

These modification methods impart chemically active sites rich in polar groups to the surface of molded products of olefinic resins, and also physically roughen the surfaces. 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 (,), the shape of the molded object to be treated is extremely 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 (b), the treatment method using mineral acids not only tends to cause the chemicals used to be a source of pollution, but also requires complicated post-treatment steps such as neutralization, water washing, and drying. be. Furthermore, even chemical treatment methods such as grafting require a drying step, and also rf! : Not only does it require careful consideration in the application of the body and the grafting atmosphere, but also the grafting reaction time is relatively long. Therefore, it has drawbacks such as not being suitable for continuous production.

As described above, although the modification methods can improve the paintability and adhesion to some extent, none of the methods can be said to be a satisfactory improvement method because they have various drawbacks.

Furthermore, as a method to impart paintability and adhesive properties to the surface of olefin polymer molded products, 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 containing I-lyolefin as a main component.

However, the method of applying a primer increases the cost by adding one step of coating or adhesion.

Including the above, olefin polymers, modified products and mixtures thereof that do not impair the above-mentioned properties and processability of olefin resins and have good adhesiveness and paintability have not yet been developed.

Based on these facts, the present inventors conducted various searches for producing an olefin polymer or olefin polymer mixture with excellent paintability and adhesive properties, and as a result, (4) Olefin polymer (B) molecule has at least one unsaturated bond in it,
We have discovered that an olefinic polymer mixture consisting of an organic compound containing a hydroxyl group and (C') an organic peroxide, which has the above-mentioned drawbacks, firmly adheres to various paints,
This was proposed previously (Japanese Patent Application No. 57-36502). However, the paintability of the resulting olefin polymer mixture
The adhesion and the adhesion between the polyurethane foam V and the polyurethane foam V are not always satisfactory.

(Curl) Structure of the Invention Based on the above, the present inventors have conducted various searches for producing an olefin polymer or olefin polymer mixture (composition) with even better paintability and adhesive properties, and as a result, ( 4) Olefin polymer, (B) "has at least one unsaturated bond in the molecule,
and organic compounds containing hydroxyl groups (hereinafter referred to as "hydroxyl compounds") (Q organic peroxides, and (c) styrenic polymers containing styrene as a main component with an average molecular weight of 1,000 to 40,000 A composition obtained by treating a mixture of olefinic polymers at a temperature of 40° C. or less at which the organic peroxide decomposes, the composition is based on 100 parts by weight of the olefinic polymers. The proportions are 0.1 to 50 parts by weight of the hydroxyl compound, 0.01 to 20 parts by weight of the organic peroxide, and 0.5 to 30 parts by weight of the styrene polymer. The present invention was achieved based on the discovery that a polymer composition has extremely excellent adhesion with various paints, various substances, and polyurethane foam.

[■] Effects of the invention If the composition obtained by the present 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 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) By adding an inorganic filler, it is ideal as a core material for various parts that require high rigidity and shape stability, and by applying the coating described above, it has good oil resistance. It is possible to obtain a molded product that has both high rigidity and shape stability.

(4) Similar to (2), various materials (for example, wood,
Can be easily bonded to various metals).

(5) A laminate with column polyurethane foam can be created at the same time as foaming is carried out on the molded article by methods such as injection foaming.

The composition 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 panzers, instrument panels, armrests, door liners, seat covers, duct covers, etc. (2) Home appliance parts such as the interior and exterior of coolers and refrigerators (3) Roofs, grooves, insulation walls, etc. Housing materials (4)
Daily necessities such as dining tables, desk surfaces, furniture panels, kitchen cabinets, ice cube boxes, and furniture (5) Freezer components such as interior materials for refrigerated trucks and freezer walls [V] Detailed description of the invention (4) Olefin polymer The olefin polymers used in the present invention include ethylene homopolymers, propylene polymers, random or block copolymers of ethylene and zorogylene, and ethylene and γ or propylene with a large number of carbon atoms. Random or block copolymers with 12 other α-olefins (the copolymerization ratio of α-olefins is at most 20% by weight) can be mentioned. Among the larylefin-based polymers used in the present invention, "propylene homopolymers and copolymers containing propylene as a main component (50% by weight or more)" (hereinafter referred to as "propylene-based polymers") have a melt flow index of (JISK-6758
However, the temperature was 230℃ and the load was 2.16k1.
Measured under the conditions of 7, hereinafter referred to as MFIJ, is generally 0o.
o1-10g/l.

min, preferably 0.005 to 5.0g710 min, particularly 0.05 to 5.0g. Ojj / ], O minutes are preferred. In addition, "ethylene homopolymers and copolymers containing ethylene as a main component (50% by weight or more)"
(hereinafter referred to as "ethylene polymer"), its melt index (according to JISK-6760), the temperature is 1.
Measured at 90°C and a load of 2.16 kg, hereinafter referred to as 1'-M, T, J) is usually 5.0 to to.

g710 minutes, preferably 5.0 to 70 g/l, 0 minutes, and preferably 10 to 70 g/10 minutes. MFI is O,OOl,! 9/Propylene polymer or M・■・of less than 10 minutes is 5. If an ethylene polymer having a value of less than Og/10 minutes is used, the wire crosstalk described later will be difficult and the moldability will be poor. On the other hand, MFI is 10g/
l, propylene polymer or M, I for more than 0 minutes
When an ethylene polymer having a temperature of more than 100F/10 minutes is used, crosstalk and moldability are good, but various mechanical properties of the resulting composition are poor. It's good, low density (
0,900ji/cm3) to high density (0,9809
7 cm ) of ethylene homopolymers, propylene homopolymers, random or block copolymers of ethylene and propylene, as well as ethylene or propylene and other α-
Random or block copolymers with 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). The resulting catalyst system (so-called Philizzos catalyst) or radical initiator (e.g. organic peroxide)
It can be obtained by homopolymerizing or copolymerizing olefins using

Furthermore, the present invention also includes modified I olefins obtained by graft polymerizing a compound having at least one double bond (for example, an unsaturated carboxylic acid or a vinyl silane compound) to these olefin polymers.

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. Additionally, 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 a compound having at least one unsaturated bond (double bond, triple bond) and containing 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 esters with unsubstituted trihydric alcohols, esters with unsubstituted tetrahydric alcohols, and esters with unsubstituted five or more alcohols.

Among alcohols having a double bond, preferred representative examples are those whose general formula is represented by the following formula [, (1)].

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.

A typical example of a desirable alcohol having a triple bond is one whose general formula is represented by the following formula ((In formula).

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

Furthermore, 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 as shown below. It is expressed by [Formula (A)].

In the measurement, R5 is an unsaturated hydrocarbon group having 2 to 24 carbon atoms, and R6 is a hydrocarbon group having 2 to 24 carbon atoms.

Further, 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, and a typical example of a desirable one has the general formula [ (■) Formula].

In the morning 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.

Furthermore, 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 preferred example thereof has the general formula shown below. It is expressed as a [closed expression].

In formula (a), R9 is an unsaturated hydrocarbon group having 2 to 24 carbon atoms, and R10 is a hydrocarbon group having 2 to 24 carbon atoms.

Furthermore, esters of non-wrinkling pentahydric or higher alcohols and unsaturated carboxyl acids and unsaturated carboxyl acids and unsubstituted trihydric or higher alcohols are representative examples of desirable ones. The general formula is expressed by the following formula [formula (b)].

In formula (b), n is 4 or more, R11 is an unsaturated hydrocarbon group having 2 to 24 carbon atoms, and R12 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 the following general formula [(6)
The following expression can be mentioned.

1 In formula (■), m is 1 or more, sb, and R has 2 carbon atoms.
~50 unsaturated hydrocarbon groups υ, and R14 is a hydrocarbon group having 2 to 100 carbon atoms.

Representative examples of these hydroxyl compounds include the specifications of Japanese Patent Application Nos. 57-36502 and 57-49065, and the "Existing Chemical Substances Book" (Kagaku Kogyo Nipposha, published in 1978) by the Ministry of International Trade and Industry. Supervised by Chemical Safety Division, Basic Industries Bureau, 2nd edition, pages 25, 27 to 2
8, pages 50 to 55, and pages 57 to 58.

Among the hydroxyl compounds used in the present invention,
Representative examples of suitable ones include 3-hydroxy-1-pronine, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene.
butene, 3-hydroxy-2-methyl-1-pro4,
Cis-5-hydroxy-2--! ! Trance, 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, 2,3,4.5-tetrahydroxy 4-antyl acrylate and 2.3.4.5 -Tetrahydroxy quanthyl methacrylate.

(0 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.
0°C or higher is preferable, especially 130°C IN,
h is preferred. If the above-mentioned temperature is 100° C. or lower, it is not only difficult to handle, but also the effect of using it will be unrecognizable, which is not desirable. Representative examples of suitable organic peroxides include monooxides such as 1,1-bis-tertiary-butyl-f-oxy-3,3,5-)limethylcyclohexane, and dicumyl oxide. Dialkyl tsya-oside, 2.5-
Hydrono-oxides such as dimethylhexane-2,5-nohedroba-oxide, diacyl peroxides such as benzoyl peroxide and 2,5-dimethyl-2,5-dibenzoyl/? - Peroxy esters such as oxyhexane.

(c) Styrenic polymer The molecular weight of the styrenic polymer used in the present invention is preferably 1,000 to 400,000, particularly preferably 1,000 to 300,000. When the molecular weight is 400,000 or more, miscibility with polyolefins is poor and dispersion during kneading is difficult. On the other hand, those with a molecular weight of 1000 or less have poor heat resistance. The styrenic polymer used in the present invention may be a styrene homopolymer, or may be a styrene homopolymer (copolymerization ratio is 4
(0 molar ratio or less) may be used. Other monomers include monoolefins (at most 8 carbons), diolefins (at most 8 carbons) and (meth)acrylic esters (at most 8 carbons) and acrylonitrile. Examples include polar group-containing vinyl compounds such as. The styrenic polymers may be used alone or in combination of two or more.

In producing the mixture of olefinic polymers of the present invention, it may be made of an olefinic polymer, a hydroxyl compound, an organic peroxide, and a styrene polymer; Adhesion can be further improved by mixing a tertiary amine compound.

(g) Organotin compound Furthermore, examples of the organic tin compound used in the present invention include those represented by the following formula [(■) formula].

15R17 In formula (■), R, R, R and R may be the same or different and are hydrocarbon groups having at most 12 carbon atoms, and Yl and Y2 may be the same or different and may have at most 12 carbon atoms. 18 monovalent or divalent carboxylic acids, derivatives (alkyl esters) of said carboxylic acids, alcohols, mercaptans, and mercapto acids. t is an integer from 1 to 20.

Typical examples of these organic tin compounds include monobutyl 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.

(About Tertiary Amine Compound) The tertiary amine compound used in the present invention is one that is used as a catalyst in the curing reaction of urethane polyol and isocyanate.

Typical examples include dimethylaminozologylamine,
Diethylaminopropylamine, tris(dimethylaminomethyl)phenol, tetraguanidine, N,N-dibutylethanolamine, N-methyl-N,N-jetanolamine, 1,4-diazabicyclo(2,2,2)
Othane and 1,8-diazabicyclo(5,4,0)
-7 unde 7in can be given.

The composition of the present invention obtained as described below may be used as it is, but an inorganic filler as described later may be further added during tri-blending or melt mixing as described later, and the composition obtained An inorganic filler may also be blended. By incorporating this inorganic filler, the rigidity of the composition can be improved.

(G) Inorganic filler The inorganic filler used in the present invention is commonly used in the synthetic resin and rubber industries, and is
Those that do not decompose at 00°C (see below) are preferably used. The inorganic fillers include metals such as aluminum, copper, iron, lead and nickel, oxides of these metals and metals such as magnesium, calcium, barium, zinc, zirconium, molybdenum, silicon, antimony and titanium, and their water. It is broadly classified into compounds such as hydrates (hydroxides), sulfates, carbonates, silicates, their double salts, and mixtures thereof. Typical examples of the inorganic optical filler include the metals mentioned above, aluminum oxide (alumina), its hydrates, calcium hydroxide, lead oxides such as lead white, magnesium carbonate, calcium carbonate, basic magnesium carbonate, White carton, asbestos, mica, shirasu balloon, talc, glass fiber, glass powder, glass peas, clay, diatomaceous earth, silica, wollastonite, iron oxide, antimony oxide, titanium oxide (titania), lithopone, pumice powder, aluminum sulfate, calcium sulfate (such as gypsum), zirconium silicate, zirconium oxide, barium carbonate, barium sulfate, dolomite, molybdenum disulfide and iron sand. Among these inorganic fillers,
The powdered material has a diameter of 1 mm or less (preferably 0.5 m).
m or less) is preferable. In addition, in fibrous materials,
The diameter is 1 to 500 microns (preferably 1 to 200 microns) and the length is 01 to 67 nrIL (preferably 0.1
~5 mm) is desirable. Furthermore, it is preferable that the diameter of the flat plate be 2 mm or less (preferably 1 mm or less).

Mixing ratio In producing the mixture of the present invention, 1. OO parts by weight The mixing ratio of the hydroxyl compound to the diolefin polymer is 0.1 to 50 parts by weight, preferably 0.2 to 30 parts by weight, and particularly preferably 03 to 20 parts by weight.

If the mixing ratio of the hydroxyl compound to 100 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, the effect of improving adhesion depending on the amount used is not observed, and rather the original properties of the olefin polymer are impaired, which is not preferable.

However, the mixing ratio of organic peroxide to 100 parts by weight of olefin polymer is 0.01 to 20 parts by weight, and 0.
．． 05 to 10 parts by weight is desirable, and 01 to 7 parts by weight is suitable. 1. ' If the mixing ratio of the organic peroxide to O0 parts by weight of the olefin polymer is less than 0.01 parts 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 weight parts, the excellent mechanical properties originally possessed by the polymer will deteriorate, which is undesirable in any case.

The mixing ratio of the styrene polymer to 100 parts by weight of the polyolefin is 0.5 to 30 parts by weight, particularly 1.
0 to 25 parts by weight is preferred. If the mixing ratio of the styrene polymer to the polyolefin is 0.5 parts by weight or less, there is almost no modification effect.

On the other hand, if it exceeds 30 parts by weight, the mechanical properties of the resulting composition will deteriorate due to poor compatibility.

In addition, when either of the above-mentioned organotin compounds and tertiary amine compounds are used together, the mixing ratio of these to 100 parts by weight of the olefin polymer is generally at most 10 parts by weight as a total amount. , 7 parts by weight or less, particularly preferably 5 parts by weight or less. 100
The total amount of organotin compound and tertiary amine compound is 10 parts by weight of the olefin polymer.
Even if it is added in excess of parts by weight, the adhesion may not be further improved, or it may cause adverse effects such as bleeding. Furthermore, when an inorganic filler is blended, the proportion of the inorganic filler in the composition is at most 90 parts by weight, preferably 1 to 85 parts by weight, and particularly preferably 2 to 80 parts by weight.

Even if an attempt is made to blend the composition so that the proportion of the inorganic filler in the composition exceeds 90% by weight, it is difficult to obtain a homogeneous composition, and even if it is obtained, the rigidity will be low. However, other mechanical properties of the composition are degraded.

(f') Production of mixtures and compositions To produce the mixtures of the present invention, olefinic polymers,
A hydroxyl compound, an organic peroxide, a styrene polymer, or these together with an organic tin compound and/or a tertiary amine compound may be uniformly mixed within the above-mentioned mixing ratio. To produce this mixture, a part of the mixture components is mixed in advance to produce a so-called master patch, and this master patch and the remaining mixture components are prepared to form the mixture into the above-mentioned formulation components. May be manufactured.

Further, the mixture may be composed of an olefin polymer, a hydroxy compound, an organic peroxide, a styrene polymer, or an organic tin compound and/or a tertiary amine compound, depending on the intended use of the mixture. Depending on the mixture, these components may also contain oxygen, heat and UV stabilizers, metal deterioration inhibitors, flame retardants, colorants, electrical property modifiers, fillers, antistatic agents, lubricants, processability modifiers. Additives such as tack improvers and adhesion modifiers may be mixed in as long as they do not impair the properties of the mixture of the present invention.

This mixture can be produced by melt-kneading using a mixer commonly used in the olefin polymer industry, such as a scree extruder, a Banbury mixer, a kneader, and a roll mill. . At this time, a more uniform composition can be produced by triblending in advance using a mixer such as a Henschel mixer, and then melting and kneading the resulting mixture.

This melt crossing must be carried out at a temperature at which the organic peroxide used decomposes. If the temperature is lower than this, the hydroxyl compound will not completely graft polymerize to the olefin polymer, and a composition with good adhesion will not be obtained. Undesirable due to residual presence. On the other hand, 400
If the temperature is exceeded, the olefin polymer may deteriorate. From the above, although it differs depending on the type of organic peroxide used, this melt mixing is generally carried out at 150 to 400°C, and preferably carried out at 160 to 300°C.

(6) Molding method The composition thus produced is processed into various molded products by processing methods commonly used in the field of olefin polymers, such as extrusion molding, injection molding, and press molding. Bye.

At this time, it is necessary to conduct the reaction at a temperature higher than the temperature at which the modified olefin polymer (graft product) 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 natural that the reaction must be carried out at a temperature below which decomposition occurs.

(L) Coating method The purpose of the present invention is achieved by uniformly coating the surface of the molded product obtained as described above with a coating material having an isocyanate group to a thickness of 1 to 500 microns (when dry). It is possible to produce a coated product that exhibits the following properties. The application method is not a special method; 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 the surface using a roll coater or the like.

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.

In addition, it is also suitable for metal lysing, laminating different materials, etc. by utilizing the applied coating film having isocyanate groups.

Next, regarding adhesion using an adhesive, an adhesive having an isocyanate group (for example,
solvent-based urethane adhesive, water-based vinyl urethane adhesive)
The adhesive body of the present invention can be obtained by applying the adhesive and adhering a shape of a substance that can be adhered to the adhesive surface using the adhesive.

These materials include metals (e.g. aluminum, iron, copper, and their alloys), glass, paper, textiles, wood, leather,
Rubbers (e.g. neoprene rubber, urethane rubber,
butadiene rubber, natural rubber), polar group-containing resins (for example, ABS resin, polyester, polyamide, polyacrylonitrile, and the above-mentioned olefin polymers). In addition, shaped objects include thin objects (for example, foils, papers, films), sheet-like objects, board-like objects, plate-like objects, tube-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 commonly used in the field of polyurethane foam manufacturing such as injection foaming, mold foaming, and spray foaming may be used. Furthermore, the polyols, isocyanate compounds, blowing agents, etc. used as raw materials for 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 article may be cleaned or degreased in the previous step. This mainly removes surface dirt caused by oil and fat, eliminates variations in adhesion, and even improves adhesion.
= The purpose is to ascend. Specific examples include a method of wiping off using an organic solvent such as inzologyl alcohol, toluene, or trichlene; or, for large molded products, immersion in such an organic solvent under heating, or wiping with heated steam. There are ways to process it.

These degreasing and cleaning steps can be similarly applied to the molded product obtained according to the present invention. moreover,
It will not be affected in any way and you can expect the same effects as before.

[VI) 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 paint film peeling strength test was conducted by cutting out a test piece on a strip with a width of 10 mm, and after forcibly peeling off a portion of the paint film from one end of the test piece. The coating film was peeled off using a tensile testing machine used in plastic tensile testing, etc., at a tensile speed of 50 mm/min, a peeling angle of 180 degrees, and a temperature of 20 degrees Celsius. It was defined as peel strength (g/10 nun). To test the adhesive strength, a molded product of the olefin polymer mixture was cut into 10 cm x 26 m strips, and adhesive was applied to the ends of the 3 cm x 2 m strips. A molded article of the olefin polymer composition obtained in the Example or Comparative Example was attached to this adhesive part, and the mixture was pulled at a pulling speed of 50 mm/min and a temperature of 20°C. The tensile shear stress at fracture was measured.

Furthermore, the adhesion strength between the molded product and the polyurethane foam was determined by injecting the polyurethane foam between flat test pieces arranged in parallel at 1 crn intervals using the foaming method, and then using the sandwich-shaped test pieces. 1 cm x 1
A sample was cut to a size of cm, the upper and lower molded parts of the sample were held between the crosshead of a tensile tester, and the sample was pulled in a direction perpendicular to the contact surface at a tensile speed of 5 cylinders/min. The strength when broken was measured and defined as adhesion strength (kg/ff12).

In addition, in the Examples and Comparative Examples, the following ingredients were used as the olefin polymer, hydroxy compound, organic peroxide, organic tin compound, tertiary amine compound, and styrene polymer. .

[Propylene homopolymer]

Density as olefin polymer is 0.900!9/cr
A zorogylene homopolymer (hereinafter referred to as [pp(t)J]) having n3 and an MFI of 1.0 g/10 minutes was used.

[Block zolopyrene copolymer]

Mata, the content of ethylene as an olefin polymer is 1
2.0 weight, A・tsu MFI is 2.0Ei/10
Propylene-ethylene block copolymer with a density of 0.9009/cm3 [rpp(2)
J) was used.

[High-density ethylene homopolymer]

Furthermore, as an olefin polymer, the density is 0.961.
A high-density ethylene homopolymer (hereinafter referred to as rf (DPF, 1)) was used, which had a weight ratio of 20 g/cm and M and L of 20 g/10 min.

[Hydroxyl compound]

As hydroxyl-based compounds, 2-hydroxyethyl acrylate [hereinafter referred to as "compound prisoner"] and 2-hydroxyzorobyl methacrylate [hereinafter referred to as "compound (B)"]
] was used.

[Organic peroxide]

As organic peroxides, benzoyl oxide (hereinafter referred to as "BPO") and dicumyl oxide (hereinafter referred to as "DCP") were used.

[Styrenic polymer]

As the styrene polymer, styrene homopolymer with an average molecular weight of about 2,000 [hereinafter referred to as r PS (1) J] and styrene homopolymer with an average molecular weight of about 250,000 [hereinafter referred to as 1'-PS (2) J] are used. I used ``say''.

[Organic tin compound]

As an organic tin compound, dibutyl tin laurate [
Hereinafter, [referred to as compound (1)] was used.

[Tertiary amine compound]

Furthermore, as a tertiary amine compound, 1,4-diazabicyclo(2,2,2)octane [hereinafter [compound (2)]
” was used.

[Inorganic filler]

As inorganic fillers, calcium carbonate (hereinafter referred to as "caco5") having an average particle size of 10 microns, Merck (density 2.79/crn3) having an average particle size of 2.0 microns,
), mica with an average particle size of 7 microns (aspect ratio 30), barium sulfate (hereinafter referred to as rBaSO4J) with an average particle size of 2.2 microns, and average particle size of 0.1
antimony trioxide (hereinafter referred to as "5b203")
), aluminum powder (hereinafter referred to as "At powder") with an average particle size of 70 microns, iron sand with an average particle size of about 100 microns, and gypsum with an average particle size of 4.8 microns.

Examples 1-16. Comparative Examples 1 to 4 The ingredients whose amounts are shown in Table 1 were mixed in advance for 10 minutes using a Suhar mixer. , further blending 01 parts by weight of compound (2)]. Each of the obtained mixtures was passed through a vented extruder (diameter 4.0
tm) was used to produce pellets while melting and kneading at 230°C.
A flat specimen (120 x 150 mm, thickness 2
(key) was created.

A two-component urethane paint (manufactured by Nippon B Chemical Co., Ltd., trade name R-257) was applied to one side of each specimen thus obtained using a spray gun to a thickness of 35 to 40 microns for a paint film peeling test. I sprayed it. Then, heat drying was performed at a temperature of 90° C. for 30 minutes. After leaving it at room temperature for one day and night, the peel strength test of the coating film of each sample was measured. The results are shown in Table 2.

In addition, after cutting the above-mentioned flat specimen into a short piece of 10 crn x 2 crn, a two-component cold-curing solvent-based polyurethane adhesive (manufactured by Konishi Co., Ltd., trade name, Pound
KU-10) was used to cut out the same size of the resin part test piece used in each example or comparative example, and after leaving it at room temperature for 24 hours, the adhesive strength was measured. It was measured. The results are shown in Table 2.

Two test pieces obtained as described above were fixed in parallel at a distance of 1 m, and Je IJ urethane foam was produced between them by injection foaming.

The equipment for injection foaming and the raw solution for polyurethane foam are manufactured by Instaform Inc. (USA) under the trade name Insulpack-1.
1-20 (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 so strong that no breakage occurs at the interface between the molded product part and the polyurethane foam part, and the polyurethane foam suffers cohesive failure, the "cohesive failure" column in Table 2 will be added. ”.

113- Table 2 (Part 1) Table 2 (Part 2) The flexural modulus of the composition obtained in Example 1 (
(measured according to ASTM D-790) is 11.00
However, the flexural modulus of the composition obtained in Example 8 was 35.000 kg/crn2. In addition, in Example 9, 28,000 kg/cm
2, and in Example 10 it is 33,000 kg7cm2
Met. Furthermore, in Example 13, 41,000 kg
/m, and in Example 14 it was 32,000 kl? /1
yn2, 23,000 kg/cm in Example 15
It was 2. In addition, in Example 16, 68.000 kl
It was i/crn2.

From the results of the above Examples and Comparative Examples, it is clear that the composition obtained by the present invention has excellent adhesion to paints having incyanate groups, adhesion to other substances using urethane adhesives, and adhesion to polyurethane foam. It is clear that not only the properties are greatly improved, but also the rigidity (flexural modulus) is greatly improved by adding an inorganic filler.

Patent applicant: Showa Denko Co., Ltd. Representative Patent Attorney Kikuchi Sei -

Claims (1)

[Scope of Claims] (A) an olefin polymer; (B) having at least one unsaturated bond in the molecule;
and an organic compound containing a hydroxyl group, (C) an organic peroxide, and Q)) a mixture of an olefinic polymer consisting of a styrene polymer whose main component is styrene with an average molecular weight of 1 + 1 (100,000 to 40,000). It is a composition obtained by treating at a temperature of 400 ° C. or lower, which is the temperature at which the organic peroxide decomposes, and the mixing ratio with respect to 100 parts by weight of the olefin polymer is hydroxyl group-containing. An olefin polymer composition comprising 01 to 50 parts by weight of an organic compound, 1 to 20 parts by weight of an organic peroxide, and 05 to 30 parts by weight of a styrene polymer.